(12) United States Patent (10) Patent No.: US 9,028,856 B2 Reid Et Al

USOO9028856B2

(12) United States Patent (10) Patent No.: US 9,028,856 B2 Reid et al. (45) Date of Patent: May 12, 2015

(54) SYNERGISTIC PESTICIDE COMPOSITIONS (52) U.S. Cl. CPC ...... A0IN 65/22 (2013.01); A0IN 25/006 (71) Applicant: Bayer CropScience LP, Research (2013.01); A0IN 43/40 (2013.01); A0IN 51/00 Triangle Park, NC (US) (2013.01); A0IN 43/56 (2013.01); A0IN 47/02 (2013.01); A0IN 47/22 (2013.01); A0IN 53/00 (72) Inventors: Byron L. Reid, Raleigh, NC (US); (2013.01); A0IN 31/14 (2013.01); A0IN3706 Robert B. Baker, Cary, NC (US); (2013.01); A0IN37/10 (2013.01); A0IN 65/12 Nanggang N. Bao, Raleigh, NC (US); (2013.01); A0IN 31/16 (2013.01); A0IN 37/42 Deborah A. Koufas, Clayton, NC (US); (2013.01); A0IN 43/08 (2013.01); A0IN 43/78 Gerald J. Kent, Northfield, NH (US); (2013.01); A0IN 43/88 (2013.01) Peter Baur, Schondorf am Ammersee (58) Field of Classification Search (DE) CPC ...... A01N 65/12: A01N 61/00 See application file for complete search history. (73) Assignee: Bayer Cropscience LP, Research Triangle Park, NC (US) (56) References Cited (*) Notice: Subject to any disclaimer, the term of this U.S. PATENT DOCUMENTS patent is extended or adjusted under 35 U.S.C. 154(b) by 189 days. 3,042,706 A * 7/1962 Price et al...... 560,124 4,320,139 A 3, 1982 Takei et al. (21) Appl. No.: 13/733,007 (Continued) (22) Filed: Jan. 2, 2013 FOREIGN PATENT DOCUMENTS (65) Prior Publication Data AU 2007314150 B2 5, 2008 AU 2007341647 B2 T 2008 US 2013/O183390A1 Jul.18, 2013 (Continued) Related U.S. Application Data OTHER PUBLICATIONS (62) Division of application No. 12/410,840, filed on Mar. Third Party Observation for application No. EP200907268.99 mailed 25, 2009, now Pat. No. 8,404,260. Feb. 27, 2013. (60) Provisional application No. 61/163,206, filed on Mar. (Continued) 25, 2009, provisional application No. 61/072,778, filed on Apr. 2, 2008. Primary Examiner — Patricia A Leith (51) Int. Cl. (74) Attorney, Agent, or Firm — Miles & Stockbridge PC AOIN 65/12 (2009.01) (57) ABSTRACT AOIN 6L/00 (2006.01) AOIN 6.5/22 (2009.01) The present invention relates to compositions that include a AOIN 25/00 (2006.01) combination of one or more pesticides and one or more adju AOIN 43/40 (2006.01) VantS. (Continued) 6 Claims, 57 Drawing Sheets

UW Synergy with Deltamethrin against Aedes aegypti mosquito 100 cassessesssssssssssssss

8 O

6 O

4 O -- Deltamethrin (1%) 2 O --Deltamethrin (1%) + UV

O r O O2 0.4 O6 O8 1 12 Time (hr) US 9,028,856 B2 Page 2

(51) Int. Cl. JP 10-167906 A 6, 1998 AOINSI/00 (2006.01) JP 2003-55119 A 2, 2003 AOIN 43/56 2006.O1 JP 2004-51631 A 2, 2004 (2006.01) JP 2004-507478 A 3, 2004 AOIN 47/02 (2006.01) JP 2006-525258. A 11, 2006 AOIN 47/22 (2006.01) RU 2O35861 * 5, 1995 AOIN 53/00 (2006.01) W SSA 33 AOIN3L/4 (2006.01) WO Of 40446 6, 2001 AOIN37/06 (2006.01) WO O2, 17721 A2 3, 2002 AOIN37/10 (2006.01) WO O2/O982.30 12/2002 AOIN3L/6 (2006.01) WO 03.01.1031 2, 2003 AOIN 37/42 2006.O1 WO O3O45877 A1 6, 2003 (2006.01) WO 2004/098290 A1 11, 2004 AOIN 43/08 (2006.01) WO 2005OO9129 A1 2/2005 AOIN 43/78 (2006.01) WO 2005058O38 A1 6, 2005 AOIN 43/88 (2006.01) WO 2005099.453 A1 10, 2005 WO 2006/079079 A1 T 2006 WO 2006/089.747 A2 8, 2006 (56) References Cited WO 2007O18659 A1 2/2007 WO 2008/037379 4/2008 U.S. PATENT DOCUMENTS WO 2008052263 A1 5.2008 WO 2008080541 A1 T 2008 4.674.445 A * 6/1987 Cannelongo ...... 119,651 4.888,174 A * 12/1989 Farquharson et al...... 514.89 OTHER PUBLICATIONS 5,047,424 A 9, 1991 Puritch et al. 5,334,585 A * 8, 1994 Derian et al...... 514,74 International Search Report Based on Application No. PCT/US2009/ 5,346,699 A * 9, 1994 Tiernan et al...... 424/405 038349 Mailed May 11, 2009. 5,472,712 A 12/1995 Oshlacket al. Written Opinion Based on Application No. PCT/US2009/038349 5,759,569 A * 6/1998 Hird et al...... 424/443 Mailed May 11, 2009. 5,798,112 A 8, 1998 Heitz et al. International Preliminary Reporton Patentability Based on Applica $998. A 121 Veroy tion No. PCT/US2009/038349 Mailed October 5, 2010. 6,071,538 A 6/2000 Milstein et al...... 424/464 Third Party Observation to Published European Patent Application 6,177.465 B1 ck 1/2001 Tanaka No. 2271210 based on EPO9726899.9-1454 2271210 PCT, 6,337,078 B1 1/2002 Levy ...... 424/406 US2009038349 mailed Mar. 7, 2013 6,352,704 B1 3/2002 Nicholson et al. males Mar?, 6,395,765 B1 5/2002 Etchegaray Ralph B. Mar. et al., “Synergists for DDT Against Insecticide-Resis 6,500,416 B2 12/2002 Hofer et al. tant House Flies,” Journal of Economic Entomology, 1952, vol. 45, 7,198,800 B1 4/2007 Ko No. 5, pp. 851-860. 7,368,123 B1 5, 2008 Tabuchi et al. Notice of Rejection dated Sep. 3, 2013, issued in Application No. 7,728,011 B2 6/2010 Sirinyan et al. 2011-503045 and English translation thereof. 7,799,737 B2 9/2010 Rosenfeldt et al. European Search Report based on Application No. 09 726 899.9; 2002.0137632 A1 9, 2002 Kawai search completed Oct. 4, 2012. 2002/0177526 A1 11, 2002 Chen et al. Merial MSDS Frontline Top Spot (Oct. 23, 2001). 2003/0194419 A1 10/2003 Sun et al. Ciba TINUVIN 292 Data Sheet (Oct. 2000). 2004O161441 A1 ck 8/2004 Sirinyan et al. Raymond C. Rowe et al., eds., Handbook of Pharmaceutical 2005/02444452006/0029632 A1A1* 11/20052/2006 AndersonHenshaw ...... 424/405 Excipixcipients (5th5th ed. 20062006), pp. 30-31, 79-80,79-80,236-237, 236-237, 414-415,494414-415, 494 2006, O166898 A1 7, 2006 Chen 495,505-506, 2006/0252728 A1 1 1/2006 Sirinyan et al. Sarfaraz K. Niazi, ed., Handbook of Pharmaceutical Manufacturing 2006/0288955 A1* 12/2006 Albright et al...... 119,655 Formulations: Liquid Products (vol. 3) (2004), ch.5 “Formulation 2007/0020304 A1 1/2007 Tamarkin et al. Considerations of Liquid Products', pp. 51-58. 2007/O155797 A1 7/2007 Andersch et al. Sartaraz K. Niazi, Handbook of Preformulation: Chemical, Biologi 2007/0298967 A1 12/2007 Kelley cal, and Botanical Drugs (2007); pp. 266, 365. 2008. O146445 A1 6/2008 De Kerpel et al. Hanne Hjorth Tonnesen, ed., Photostability of Drugs and Drug For 2009/0163582 A1 6/2009 Wang et al. mulations (2nd ed.) (2004); pp. 315-316. 2010.0099.717 A1 4/2010 Vermeer et al. Loyd V. Allen, Jr., et al., eds., Pharmaceutical Dosage Forms and Drug Delivery Systems (8th ed.) (2005); pp. 92-141. FOREIGN PATENT DOCUMENTS Mark Gibson, ed., Pharmaceutical Preformulation and Formulation: CN 1433696. A 8, 2003 A Practical Guide from Candidate Drug Selection to Commercial DE 101 17676 10, 2002 Dosage Form (2004); pp. 203-204, 544-546. EP O235979 A1 9, 1987 Beatrice M. Magnusson et al., “Veterinary drug delivery: potential for EP 1112687 A2 T 2001 skin penetration enhancement.” Advanced Drug Delivery Reviews 50 GB 2002635 2, 1979 (2001) 205-227. JP 54-28.818 A 3, 1979 The National Formulary (25th ed.): The Official Compendia of Stan JP 62-56401 A 3, 1987 dards (vol. 1); pp. 1045-1049, 1073-1074, 1168-1170. JP O8151308 * 6/1996 JP 10167906 A * 12/1996 * cited by examiner U.S. Patent May 12, 2015 Sheet 1 of 57 US 9,028,856 B2

Benzenepropanoic acid (5%) Synergy with Imidacloprid against Argentine Ant

100 “ters 80 -0-midacloprid (0.5%) 60 -Himidacloprid (0.5%) BpA (5%) -A-BpA (5%) 40 20

O f O 5 10 15 20 25 Time (hours) Figure 1

Benzenepropanoic acid (1%) Synergy with Imidacloprid against Susceptible German Cockroach 100 YYYYYYYYY. Hay

80 -0-Imidacloprid (0.5%) 60 --Imidacloprid (0.5%) BpA (1%) 5 -A-BpA (1%) e 40 SS 20

O O 5 10 15 20 25 Time (hours)

Figure 2 U.S. Patent May 12, 2015 Sheet 2 of 57 US 9,028,856 B2

Oleic Acid (1%) Synergy with imidacloprid against Susceptible German cockroach 100 as

80 -0-midacloprid (0.5%) e -H-Imidacloprid (0.5%) + Oleic Acid (1%) (s 60 -A-Oleic Acid (1%) O e 40 SS 20

O r O 5 10 15 20 25 Time (hours)

Figure 3

Oleic Acid (0.1%) Synergy with Imidacloprid against Argentine Ant

1OO s -0-imidacloprid (0.5%) -Himidacloprid (0.5%) + Oleic Acid (0.1%) -A Oleic Acid (0.1%)

O 5 1O 15 2O 25 Time (hours) Figure 4 U.S. Patent May 12, 2015 Sheet 3 Of 57 US 9,028,856 B2

Methyl Oleate (5%) Synergy with imidacloprid against Argentine Ant 100 - Hy S 80 5 9 60 -0-midacloprid (0.5%) e -Himidacloprid (0.5%) + Methyl Oleate (5%) 40 -A-Methyl Oleate (5%) O iss 20 O O 5 10 15 20 25 Time (hours) Figure 5

Methyl Oleate (1%) Synergy with imidacloprid against Susceptible German cockroach (T164 Strain) 100 far-Hy

80 60 O e 40 SS -0-mi (0.5%

20 -A-Methyl--Imi E. Oleate -- My (1%) Oleate (1%) O O 5 10 15 20 25 Time (hours)

Figure 6 U.S. Patent May 12, 2015 Sheet 4 of 57 US 9,028,856 B2

Methyl Linoleate (1%) Synergy with imidacloprid against Argentine Ant 100 " -e-Imi (0.5% o -Himi E. + M. Linoleate (1%) 80 A Methyl Linoleate (1%) e 60 s 40 SS 20

O O 5 10 15 20 25 Time (hours)

Figure 7

Methyl Linoleate (1%) Synergy with imidacloprid against Susceptible German Cockroach 100 assassy

80 60 O e 40 SS -0-mi (0.5%) 20 --Imi (0.5%) + Methyl Linoleate (1%) -A-Methyl Linoleate (1%) O O 5 10 15 20 25 Time (hours)

Figure 8 U.S. Patent May 12, 2015 Sheet 5 of 57 US 9,028,856 B2

Methyl Palmitate (5%) Synergy with Imidacloprid against Argentine Ant 100 smassamo- . S 80 X 5 -0-midacloprid (0.5%) s 9 60 -H-Imidacloprid (0.5%) + Methyl Palmitate (5%) -A-Methyl Palmitate (5%) s 40 e SS 20 O O 5 10 15 20 25 Time (hours) Figure 9

Methyl Palmitate (5%) Synergy with Imidacloprid against Susceptible German Cockroach

S 80 C 3 6O -0-mi (0.5%) S. --Imi (0.5%) + Methyl Palmitate (5%) E -A-Methyl Palmitate (5%) 40 O

SS 20 O O 5 10 15 2O 25 Time (hours) Figure 10 U.S. Patent May 12, 2015 Sheet 6 of 57 US 9,028,856 B2

BHA (1%) Synergy with Imidacloprid against Argentine Ant 100 assassssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssss -0-mi (0.5%) 80 -Himi (0.5%) + BHA (1%) e -A BHA (1%) 60 O e 40 SS 20

O I 5 10 15 20 25 Time (hours)

Figure 11

BHA (5%) Synergy with Imidacloprid against Susceptible German Cockroach (T164 strain)

100 -

80 -0-mi (0.5%) -Himi (0.5%) + BHA (5%)

a 40 SS 20

O O 5 10 15 20 25 Time (hours)

Figure 12 U.S. Patent May 12, 2015 Sheet 7 Of 57 US 9,028,856 B2

BHT (0.1%) Synergy with imidacloprid against Argentine Ant 100 fossssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssoxy -0-mi (0.5%) 80 --Imi (0.5%) BHT (0.1%) -A-BHT (0.1%)

O 5 10 15 20 25 Time (hours)

Figure 13

BHT (1%) Synergy with Imidacloprid against Susceptible German cockroach 100 peoxy -0-mi (0.5%) 8 O -Himi (0.5%) BHT (1%) -A-BHT (1%)

6 O

4 O

2 O

O O 5 10 15 20 25 Time (hours)

Figure 14 U.S. Patent May 12, 2015 Sheet 8 Of 57 US 9,028,856 B2

TBHQ (0.1%) Synergy with imidacloprid against Susceptible German cockroach (T164 strain) 100 xy -0-midacloprid (0.5%) s 80 - --Imidacloprid (0.5%) + TBHQ (0.1%) -A-TBHQ (0.1%)

O 5 10 15 20 25 Time (hours)

Figure 15

TBHQ (1%) Synergy with imidacloprid against Argentine Ant 100 foyer

-0-midacloprid (0.5%) 80 --Imidacloprid (0.5%) + TBHQ (1%) -A-TEBHQ (1%) 60

O 5 10 15 20 25 Time (hours)

Figure 16 U.S. Patent May 12, 2015 Sheet 9 Of 57 US 9,028,856 B2

Diphenyl Methane (1%) Synergy with Imidacloprid against Argentine Ant 100 -0-midacloprid (0.5%) 80 -HImidacloprid (0.5%) Diphenyl Methane (1%) -A-Diphenyl Methane (1%) 60 O e 40 SS 20

O O 5 10 15 20 25 Time (hours)

Figure 17

Diphenyl Methane (5%) Synergy with Imidacloprid against Susceptible German Cockroach

80 -0-midacloprid (0.5%) --Imidacloprid (0.5%) Diphenyl Methane (5%) 60 -A-Diphenyl Methane (5%)

4 O

2 O

O O 5 10 15 20 25 Time (hours) Figure 18 U.S. Patent May 12, 2015 Sheet 10 Of 57 US 9,028,856 B2

Tritylchloride (1%) Synergy with imidacloprid against Argentine Ant

-0-Imidacloprid (0.5%) 80 -HImidacloprid (0.5%) + Tritylchloride (1%) -A-Tritylchloride (1%) 60 O e 40 SS 20

O O 5 10 15 20 25 Time (hours)

Figure 19

Tritylchloride (0.1%) Synergy with Imidacloprid against Susceptible German cockroach (T164 strain) 100 assssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssy 80 -0-midacloprid (0.5%) 2. -Himidacloprid (0.5%) + Tritylchloride (0.1%) 60 — -A-Tritylchloride (0.1%)

e SS

O 5 10 15 20 25 Time (hours)

Figure 20 U.S. Patent May 12, 2015 Sheet 11 Of 57 US 9,028,856 B2

Dibutyl Sebacate (1%) Synergy with Imidacloprid against Susceptible German Cockroach

100 --- Hassss 80 -0-midacloprid (0.5%) e -HImidacloprid (0.5%) DBS (1%) s 60 -A-DBS (1%) & 40 SS 20

O O 5 10 15 20 25 Time (hours)

Figure 21

Dibutyl Sebacate (0.1%) Synergy with Imidacloprid against Argentine Ant 100 assassssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssss -0-midacloprid (0.5%) 80 — -H-Imidacloprid (0.5%)

e RS 10A s O e SS

O 5 10 15 20 25 Time (hours) Figure 22 U.S. Patent May 12, 2015 Sheet 12 Of 57 US 9,028,856 B2

& S & & SS : & x

& S

Figure 23 a

UW Synergy with Deltamethrin against

Aedes aegypti mosquito

--Deltamethrin (1%) s

- --Deltamethrin (1

O2 0.4 0.6 0.8 12

Time (hr)

Figure 23 c U.S. Patent May 12, 2015 Sheet 13 Of 57 US 9,028,856 B2

UW Synergy with Deltamethrin against Argentine Ant

100 -

80 - e 60 s 40 SS -0-Deltamethrin (1%)

20 - --Deltamethrin (1%) + UV O icci O 5 10 15 20 25 30 35 Time (minutes)

Figure 24

UW Synergy with Deltamethrin against Bait Averse German Cockroach (IHOP Strain)

100 YYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYyalas

80 e s 60 & 40 --Deltamethrin (1%) SS --Deltamethrin (1%) + UV 20

O O.O 0.2 0.4 O.6 O.8 1.O Time (hr)

Figure 25

U.S. Patent May 12, 2015 Sheet 15 Of 57 US 9,028,856 B2

UW Synergy with Deltamethrin against Odorous House Ant

100 asssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssss

80 e 60 t O a 40 SS 20 -0-Deltamethrin (1%) --Deltamethrin (1%) + UV O O.O 0.5 1.O 1.5 2.0 2.5 Time (hr)

Figure 27 b

UW Synergy with Deltamethrin against Red Imported Fire Ant

100 as c

80 s 60 & 40 -0-Deltamethrin (1%) SS --Deltamethrin (1%) + UV 20

O O.OO 0.20 0.40 O.60 O.80 1.00 1.20 Time (hr)

Figure 28 U.S. Patent May 12, 2015 Sheet 16 Of 57 US 9,028,856 B2

UW Synergy with Deltamethrin against German Cockroach (Monheim strain)

100 assasssssssssssssssssssssssssssssssssssssssssss Husssssssssssssssssssssssssssss

80 60 t & SS 40 -0-Deltamethrin (1%) 20 --Deltamethrin (1%) + UV w

O O 5 10 15 20 25 Time (minutes)

Figure 29

UW Synergy with Thiamethoxam against Argentine Ant

100 xyleux's is 80 U 60 40 & -0-thiamethoxam 0.01% SS 20 --thiamethoxam 0.01% + UV

O f O 5 10 15 20 25 Time (hours)

Figure 30 U.S. Patent May 12, 2015 Sheet 17 Of 57 US 9,028,856 B2

UW Synergy with Thiamethoxam against Odorous House Ant 100 assass -0-thiamethoxam 0.1% g 80 -- thiamethoxam 0.1% + UV 5 9 e s s e SS

O 5 10 15 20 Time (hours)

Figure 31

UVSynergy with Thiamethoxam against Susceptible German Cockroach (Monheim) 100 as X S 80 s O

9 60 2 -0 thiamethoxam 1% 40 --thiamethoxam 1% + UV

SS 20

O y s y O.O 0.5 1.O 1.5 2.0 2.5 3.0 Time (minutes)

Figure 32 U.S. Patent May 12, 2015 Sheet 18 Of 57 US 9,028,856 B2

UVBLocker Synergy with Resmethrin against Aedes aegypti 100 xxxxxxxxxxxxxxxx sasau-Hasssssssssssssssssssss - 80 O 60 -0-Resmethrin (0.5%) 3 40 -- Resmethrin (0.5%) + UV SS 20 O O 0.2 0.4 0.6 0.8 12 Time (hr) Figure 33

UVBLocker Synergy with Resmethrin against Culex quinquefasciatus 100 as -0- Resmethrin (0.5%)

80 -- Resmethrin (0.5%) + UV O E O O SS

O O.5 1 1.5 2.5 Time (hr) Figure 34 U.S. Patent May 12, 2015 Sheet 19 Of 57 US 9,028,856 B2

UW Synergy with Permethrin against Aedes Aegypti

100 -rayalalasa-axes

80 e s 60 s -0-Permethrin (0.5%) 40 -- Permethrin (0.5%) + UV 20

O O.O 0.2 0.4 O.6 0.8 1.O 1.2 Time (hr)

Figure 35

UVSynergy with Permethrin against Argentine Ant

e &s -0-Permethrin (0.5%) 40 -- Permethrin (0.5%) + UV 20

O s f y f r O.OO O.05 O. 10 O. 15 0.20 O.25 0.30 O.35 Time (hour)

Figure 36 U.S. Patent May 12, 2015 Sheet 20 Of 57 US 9,028,856 B2

UW Synergy with Permethrin against a Bait Averse Strain of German Cockroach (IHOP)

100 xxyyxxyyxxyyxxyyyyyyyyyyyyyyyyyyyyyyyyy xy

80 60 O -0-Permethrin (0.5%) a 40 - SS -- Permethrin (0.5%) + UV s 20

O O.O 0.2 0.4 O.6 O.8 1.O 1.2 Time (hour)

Figure 37

UVSynergy with Permethrin against Odorous House Ant

100 xxxxxxxxxxxxsassissau-H-uxxxxxxxxxxxxxy

80 e s 60

& 40 -0-Permethrin (0.5%) SS -- Permethrin (0.5%) + UV 20

O f r y f f O.O 0.2 0.4 0.6 O.8 1.O 1.2 Time (hour)

Figure 38 U.S. Patent May 12, 2015 Sheet 21 Of 57 US 9,028,856 B2

UW Synergy with Permethrin against Red Imported Fire Ant

60 -0-Permethrin (0.5%) 40 -- Permethrin (0.5%) + UV

0.2 0.4 O.6 0.8 1.O 1.2 Time (hour)

Figure 39

UW Synergy with Permethrin against susceptible German cockroach (Monheim)

100 a.

80 60 -e-Permethrin (0.5%) — 40 -- Permethrin (0.5%) + UV |

Time (hours)

Figure 40 U.S. Patent May 12, 2015 Sheet 22 Of 57 US 9,028,856 B2

Compound A Synergy with Fipronil (0.001% AI) against Argentine Ant 100 as-s-s-s------O-Fiproni (0.001%) 80 -HFiproni (0.001%) + Compound A (1%) 5 A Fipronil (0.001%) + Compound A (0.1%) 5 6O -O-Compound A (1%) -H Compound A (0.01%)

g 40 SS

O - O.O O.5 1.O 15 2.O 2.5 3.0 3.5 4.0 4.5 5.O Time (hours)

Figure 41

UW Synergy with Fipronil against Aedes Aegypti

80 -

60 O O e 40 – --fipronilp (.01%( 6) SS --fipronil (.01%) + UV 2O

O crococci O 5 1O 15 2O 25 Time (hours)

Figure 42 U.S. Patent May 12, 2015 Sheet 23 Of 57 US 9,028,856 B2

UW Synergy with Fipronil against Argentine Ant

100 -acy y

se 60 s a 40 -0-fipronil (.001%) SS --fipronil (.001%) + UV 20

O O 5 10 15 20 25 Time (hours)

Figure 43

UW Synergy with Fipronil against Culex quinquefasciatus

1OO 80 -0-fipronil (.01%) 2. --fipronil (.01%) + UV s 60 s a 40 SS 20

O O 5 10 15 20 25 Time (hours)

Figure 44 U.S. Patent May 12, 2015 Sheet 24 Of 57 US 9,028,856 B2

UW Synergy with Fipronil against Odorous House Ant

100 feeysessssssssssssssssssssssssssssssssaaa- evey

80 e s 60 s a 40 SS -0-fipronil (.001%) 20 --fipronil (.001%) + UV O O 5 10 15 20 25 Time (hours)

Figure 45

UW Synergy with Fipronil against Red Imported Fire Ant

100 yuhy

80 e s 60 s a 40 SS 20 -0-fipronil (.01%) w --fipronil (.01%) + UV O O 5 10 15 20 25 Time (hours)

Figure 46 U.S. Patent May 12, 2015 Sheet 25 Of 57 US 9,028,856 B2

Figure 47

UW Synergy with Fipronil against Susceptible German Cockroach (Monheim strain) 100 -

-0-fipronil (.001%) 80 - -- fipronil (.001%) + UV 6 O

4. O

20 -

O 5 10 15 20 25 Time (hours)

Figure 48 U.S. Patent May 12, 2015 Sheet 26 Of 57 US 9,028,856 B2

Compound A Synergy with Ethiprole (0.01% AI) against Argentine Ant

60 -0-Ethiprole (0.01%) --Ethiprole (0.01%) + Compound A (1%) -A-Ethiprole (0.01%) + Compound A (0.1%) 40 -O-Compound A (1%) -O-Compound A (0.1%)

O.O O.5 1.0 1.5 2.0 2.5 3.0 3.5 Time (hours)

Figure 49

UW Synergy with Ethiprole against Aedes aegypti

-O-Ethiprole (0.01%) -o-Ethiprole (0.01%) + UV

O 5 10 15 20 25 Time (hours)

Figure 50 U.S. Patent May 12, 2015 Sheet 27 Of 57 US 9,028,856 B2

UW Synergy with Ethiprole against Argentine Ant

100 -rayaa-0xxxxs

80 e 60 s --Ethiprole (0.01%) 40 SS -0-Ethiprole (0.01%) + UV 20

O O.O 0.2 0.4 O.6 0.8 1.O 1.2 Time (hour)

Figure 51

UW Synergy with Ethiprole against Housefly

100

80 e is 60 s a 40 SS 20 --Ethiprole (0.01%) s -o-Ethiprole (0.01%) + UV O k O 5 10 15 20 25 Time (hours) Figure 52 U.S. Patent May 12, 2015 Sheet 28 Of 57 US 9,028,856 B2

UW Synergy with Ethiprole against Odorous House Ant

80 s 60 s 40 --Ethiprole (0.01%) SS -0-Ethiprole (0.01%) + UV 20

O O.O 0.5 10 15 2.0 2.5 Time (hours) Figure 53

UW Synergy with Ethiprole against Red Imported Fire Ant 100 assssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssso-Ossasssssssssssssssss

80 e s 60 & --Ethiprole (0.01%) SS 40 -0-Ethiprole (0.01%) + UV 20

O O 0.5 1 1.5 2 2.5 3 3.5 Time (hours)

Figure 54 U.S. Patent May 12, 2015 Sheet 29 Of 57 US 9,028,856 B2

UW Synergy with Ethiprole against Susceptible German Cockroach (Monheim Strain) 100 cross-or 80 e E 60 -- Ethiprole (0.01%) -0-Ethiprole (0.01%) + UV S 40 &

O sm---s-rypay-pa-rayry O 5 10 15 20 25 Time (hours)

Figure 55

1. 9 C E NY LT50 :LT95 H

O S

Figure 56 U.S. Patent May 12, 2015 Sheet 30 Of 57 US 9,028,856 B2

Figure 58 U.S. Patent May 12, 2015 Sheet 31 Of 57 US 9,028,856 B2

Performance Enhancement of EcoPCO ACU by Compound A against German Cockroaches UTC EcoPCOACUG. O.1% EcoPCO ACU 0.1% + Compound A G 1.0% 100 - Compound Ad 1.0% asssssssss

8 O 4.6OO

2 O -

O 0.5 2 4. 24 Exposure (hours) Figure 59

Performance Enhancement of Kicker by Compound A - House Cricket on Tile, 9110/2007 (Pyrethrins G0.006% = 0.125 fl oz Kickerigal) 100 - ...... ------EUTC Kicker - O.OO6% Kicker + Compound A- 0.1% 80 H. S. Compound A- 0.1%

d e s Na a 40

O - O.25 O.5 O.75 2 24 Exposure (hours) Figure 60 U.S. Patent May 12, 2015 Sheet 32 Of 57 US 9,028,856 B2

Performance Enhancement of Kicker by Compound A - German Cockroach on Tile, 915/2007 Kicker at 0.006% = 0.125 fl ozlgal

80 - Š Š

e SO = Š S Š S S. s s S Š S S S.

0.25 0.5 "spun on 1 2 24

Figure 61

3-Cyfluthrin and UV Block synergy against Argentine Ant 100 YYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYYye YYYYYYYYYYYYYYYs 80 e

60 & 40 -0-B-Cyfluthrin (.001%) 20 -- B-Cyfluthrin (.001%) + UV

O : r r r O 1 2 3 4. 5 6 7 Time (hours)

Figure 62 U.S. Patent May 12, 2015 Sheet 33 Of 57 US 9,028,856 B2

3-Cyfluthrin and UV Block synergy against bait averse German cockroach (IHOP)

1OO

80 e s 60 s 40 SS 20 -0-B-Cyfluthrin (.001%) -- B-Cyfluthrin (.001%) + UV O O 5 10 15 20 25 Time (hours)

Figure 63

3-Cyfluthrin and UV Block synergy against susceptible German cockroach (Monheim)

100 ray-0-0-e-usssssssssssssssssssssssssssssssssssssssssssssssss

60 & 40 -0-3-Cyfluthrin (.001%) SS -- B-Cyfluthrin (.001%) + UV

O 0.2 0.4 O.6 O.8 1 Time (hr)

Figure 64 U.S. Patent May 12, 2015 Sheet 34 of 57 US 9,028,856 B2

3-Cyfluthrin and UV Block synergy against Odorous House Ant

80 -0-3-Cyfluthrin (.001%) 60 --B-Cyfluthrin (.001%) + UV b 40 SS 20 O O 5 10 15 20 25 Time (hours) Figure 65

UW Synergy with Bendiocarb against Aedes aegypti

100 xxyyxxxHxxxyyyyyyyyyyyyyyyy

80 e 60 & 40 -0-bendioCarb 0.1% SS --bendiocarb 0.1% + 20 UV

O O 10 20 30 40 50 60 70 Time (minutes)

Figure 66 U.S. Patent May 12, 2015 Sheet 35 of 57 US 9,028,856 B2

UW Synergy with Bendiocarb against Argentine ant

100 xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxy, as x's

s 60 s -0-bendiocarb 0.001% 40 SS --bendiocarb 0.001% + UV 20

O O 10 20 30 40 50 60 70 Time (minutes)

Figure 67

UW Synergy with Bendiocarb against Culex quinquefasciatus 100 easy c

80 -0-bendiocarb 0.1%

£ 60 --bendiocarb 0.1% + UV t t O 40 SS 20

O O 10 20 30 40 50 60 70 Time (minutes)

Figure 68 U.S. Patent May 12, 2015 Sheet 36 of 57 US 9,028,856 B2

UW Synergy with Bendiocarb against Odorous House Ant 100 cy-ce

80 is 60 s -0-bendiocarb 0.001% 40 SS --bendiocarb 0.001% + UV 20

O O 10 20 30 40 50 60 70 Time (minutes)

Figure 69

UW Synergism with Carbaryl against Aedes aegypti

1OO

80 e 60 t O a 40 SS 20

O O 5 10 15 20 25 Time (hr) -0- Carbary (0.1%) -- Carbary (0.1%) + UV Figure 70 U.S. Patent May 12, 2015 Sheet 37 Of 57 US 9,028,856 B2

UW Synergism with Carbaryl against Argentine Ant 100 focus--cy

80 £ 60 -0- Carbary (0.01%) --Carbary (0.01%) + UV 2 40 SS 20

O O 10 20 30 40 50 60 70 Time (minutes)

Figure 71

UW Synergism with Carbaryl against Odorous House Ant 100 assasssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssss

-- Carbary (0.01%) 60 -0- Carbary (0.01%) + UV O 40 SS 20

O O 0.5 1 1.5 2 2.5 3 3.5 Time (hours)

Figure 72 U.S. Patent May 12, 2015 Sheet 38 of 57 US 9,028,856 B2

UW Synergism with Carbaryl against Red Imported Fire Ant 100 YYYYYYYYYYYYYYYYYYYYYYYYYYYYYHe-Huy

8 O

6 O -- Carbary (0.05%) 4. O -- Carbary (0.05%) + UV 2 O

O O 10 20 30 40 50 60 70 Time (minutes)

Figure 73

UW Synergism with Carbaryl against susceptible German Cockroach (Monheim) 100 assass -0- Carbary (0.05%)

8 O -- Carbary (0.05%) + UV

6 O

4. O

2 O

O O 5 10 15 20 25 Time (hours)

Figure 74 U.S. Patent May 12, 2015 Sheet 39 Of 57 US 9,028,856 B2

UW Synergy with Clothianidin against Argentine Ant

100 as xy is 80 5 -0- clothianidin 0.1% Q 60 2 - clothianidin 0.1% + UV 40 O d SS 20

O O 1 2 3 4 5 6 Time (hours)

Figure 75

UW Synergy with Clothianidin against Odorous House Ant 100 - or

s 80 U 60

40 e -0- Clothianidin 0.1% & 20 - -- clothianidin 0.1% + UV

O f r s O 5 10 15 20 25 30 Time (hours)

Figure 76 U.S. Patent May 12, 2015 Sheet 40 of 57 US 9,028,856 B2

UW Synergy with Clothianidin against Susceptible German Cockroach (Monheim)

5 E O O e -0- clothianidin 0.1% s -- clothianidin 0.1% + UV SS 20 -

O r O.O O.5 1.O 15 2.0 2.5 3.0 3.5 4.0 4.5 Time (hours) Figure 77

Compound A Synergy with tidacloprid 0.5%. At against Odoros House An

08: -

8 - s --innidacoprici (0.5

3 8 - iridaciopic: {0.5% + 3opoid. A 3% --iridaciopric 0.5% + Cenpound: A G 1%

4 - --Congou: A 3) s SS 2 -

- 5 5. 2. 25 Time hours) Figure 78 U.S. Patent May 12, 2015 Sheet 41 of 57 US 9,028,856 B2

Compound A Synergy with imidacioprid (0.1% A) against Ocofous Hose At

-- micaciopric G.3% SS. 60 -- midaciogrid R0.3% + ongound. A 1%;W. v t - Eidaciopric R. 3% + Coigeund A (0.1% sS 40 - Corpoid. A 1%

O 5 5 2. 5 Time hours

Figure 79

UW Synergy with imidacloprid against Aedes aegypti

80 -0-midacloprid (1%) 60 --Imidacloprid (1%) + UV

O s d SS

Time

Figure 80 U.S. Patent May 12, 2015 Sheet 42 of 57 US 9,028,856 B2

UW Synergy with imidacloprid against Argentine Ant

1OO 80 -0-midacloprid (0.5%) --Imidacloprid (0.5%) + UV e 60 s a 40 SS 20

O O 5 10 15 20 25 Time (hr)

Figure 81

UW Synergy with imidacloprid against Bait Averse German cockroach (IHOP strain)

100 as

-0-midacloprid (0.5%) --Imidacloprid (0.5%) + UV e w s O e SS

O 5 10 15 20 25 Time (hours) Figure 82 U.S. Patent May 12, 2015 Sheet 43 of 57 US 9,028,856 B2

UW Synergy with imidacloprid against Susceptible German cockroach (Monheim strain) 100 -

80 - 60 t O 2 40 SS 20 - -0-Imidacloprid (0.5%) -- Imidacloprid (0.5%) + UV O - O 5 10 15 20 25 Time (hr) Figure 83

UW Synergy with imidacloprid against Odorous House Ant

100 ye-yy 80 e -0-midacloprid (0.1%)

iss 60 --Imidacloprid (0.1%) + UV a 40 SS 20

O O 5 10 15 20 25 Time (hr)

Figure 84 U.S. Patent May 12, 2015 Sheet 44 of 57 US 9,028,856 B2

UW Synergy with Imidacloprid against Red Imported Fire Ant

-0-midacloprid (0.5%) --Imidacloprid (0.5%) + UV

O.5 1.O 15 2.O 2.5 Time

Figure 85

-- 0.8%. Berdiccai in ethyiacetate be 3.9%. Bediocarb + & Congolic A : ethyiacetate -- C.2%. Berdiccart + % Sebacic acic dioenzyl ester in ethyiacetate H. Beidiccart + & 4-Hydroxy-2.2,8,8-iatariethylpipeficine in ethylacetate not dissoiwabe -- .2%. Besidiocart in cyclohexafone - as C.: Besidiccart 's Conoc A : cyclohexa: one

3. 9. 5 3. 2 3. 4.

Figure 86 U.S. Patent May 12, 2015 Sheet 45 of 57 US 9,028,856 B2

H. : 8 Sedioca, H.C. 3, Beridiocas + 8% Corpound. A ecs - Eise as Si2. Eiwaliwa i. i. 833 - 8 evatis 3

8 s s 6 s c 4. s s 2

Figure 87

as Eakia; --O, 9% Bendiocast + ; %Copo Fid A -- Sa Beat cease re-8 seca eya?e 2 --. Bardicca; - % cleriyaye 3

* 60

O SO Se S. 20

s' 5 3. 1. R 4. g 15 3'

Figure 88 U.S. Patent May 12, 2015 Sheet 46 of 57 US 9,028,856 B2

-ass. 8 Bendocar --O. & Bendiocasio - 1% Compound A O. start - 8 servative 4 saC.'s Bendicast - 8 servatives B. & Sexs. eyes

8O S "t, 80

O O S. & 20

g 5 3' 1. 3' 15 33 t A. 1.

Figure 89

- . , 3e.caf H-O. '8, 3edicas + 3 Corpou 8 A. 3.36 Beascar + 3 cerate a r). & Beta - eyaye S -- 1: Eerocar + i & dervative 8

8O s is SO

40 C s iss 20

O g 5 3' t 2. t 15 3. 1. 1.

Figure 90 U.S. Patent May 12, 2015 Sheet 47 of 57 US 9,028,856 B2

H. & Eiga? --0. & Sesii cara + i & Co pound A -- eitka - sease --. Becars -- ce:3 e -- . seriocar + , ceiyaye 9

res 88

4 C &s 20

g 5' 3. 2 al g 15 3. A.

Figure 91

as . Bedioca H. C. Bediocash + i & Compound A H 3.1% Belicario + 's desivae sh. Seca - % disfiya: We 8 -- Eediocar + is eyale 9

is 8.

o 40 e SSs 28

5' 3. 2 A. 1. g 15 3'

Figure 92 U.S. Patent May 12, 2015 Sheet 48 of 57 US 9,028,856 B2

aa, Sass HQ.1%, Sediocari + 1% Connoit A --O, & Bensiocarx - ?:, Gerspo: ---. Serliotar - Rasc:

8 O

s O

4. | 2

9." 15 3. 1. 2 A. 9 15 3. 2 4.

Figure 93

as 'SeScas --O.'s Bendiocary + '& Compound: A --0.1% Bersiocaria + 1 % Gerapot si-O. 8% Bedocsa -- 8 Paso

18 -

SO 3 O SS 20

9 t5 3O' t 2 9 15" 3. 2

Figure 94 U.S. Patent May 12, 2015 Sheet 49 of 57 US 9,028,856 B2

s: 80 t S 60 s to 3G s s 20 s

in from 35 SC on gazed tie in from 350 SC on Englazed tile "5" A. -5 --.3% : age F3xF acetae --0.1% in: alone with acetone in mediately afterwards --with % Compound A in acetone immediately afterwards -e-.1% im: alone with acetone day ate: --with : % compound A. s. acetone day ate: Figure 95

s E. S. s 4 e

s - A if R from OSC on gazed tile Etiki from 8 SC on Linglazed tile 5 4. i5 4. .02% age with aeria -8.82% is a one with acetone in heciately afte: saids --with 1% Compound A in acetoire immediately afterwards -be 3.82% i? a one with acetone day iate? --witt % contid A is acetone day later

Figure 96 U.S. Patent May 12, 2015 Sheet 50 of 57 US 9,028,856 B2

> 0 radarr; s 80 is2 60 s 40 5 2. SS as EW on glazed tiles as EW o: unglazed tile acetoe on 5" h 4 d 5' 4 5 1 a

--Q.04% Cyfistria alone : SS EE - Rii; 28 BS 292 He-y: as BS 29. Figure 97

> OO 80 is 60 5 40

5 2. SS - as ENO glazed tiles as E. & Englazed tie acete is 5' 4 5' 4 15 1. A

-- (.304% Cyfi thrin alone HH SS wit .2% BS 292 Hy: A BS 29

Figure 98 U.S. Patent May 12, 2015 Sheet 51 of 57 US 9,028,856 B2

O - 2 80 - t : S 60 -

ss & se 2 e 2 – s

d 2d 3. 4d d 2d 3. did 2d 3d 4d .25 inidacopic 0.02%. Fipoii (, , Eisigote -- rsecticide alone H-secticice - a BS 292 secticide +3.2% BS 232 secticise + - 8 S 22 Figure 99

OC 80 8O 3 40 S 2O

O 5" Ah c 15 1. 4th c . Eedicar 0.1% trinidacioprid

is sects as: H. : :S 2S2 . , 2%. S. 23. it: , K S 22

Figure 100 U.S. Patent May 12, 2015 Sheet 52 of 57 US 9,028,856 B2

1 O.

23 | 2

15" 4th 15' 1 4. 5 h 4. O2. Biocarp 9.02%. Ethipole 9.002%. Inidaciopid

r-- insacticide aiore H witi & Compound A -- with G.2% Copcu. A - - - with 0.04% Corpound A

Figure 101

48 | 28

5' h 2,5% linidaciopFict

-- insecticids alone H with 1% Corpo rid. A -- with 3.2% Campaud A --with 0.04% Cornpoint. A

Figure 102 U.S. Patent May 12, 2015 Sheet 53 of 57 US 9,028,856 B2

2 CO - -- ...... 8 E S 8) e 46 e 20 & O - 5 15 1. 4 15 4 5' . A 1: 6. imidacioprid ... entiaca 0.82%. Ethiprote ... etarrehir -0 secticide gazed tie H secticide + i. 9%. BLS 292 gazed tie) -- secticice itingazed tie -- is sectic:ce + i. 9. BLS 292 in-gazec tie Figure 103

6 O

O -

15" 5' . . . 15' 5' 18 8.3% iridaciopid . Betics 0.02%. Ethipole 0.02 stars

H secticide gazed tie H secticids + : , ELS 2S2 gazed tie is surgiside gasaei is be tissciitive - 3% ELS 292 targaz st: its Figure 104 U.S. Patent May 12, 2015 Sheet 54 Of 57 US 9,028,856 B2

2 OO

S 60 a 40 -1

St 20C 4 4 a. as s ... irida caprid ... erica .2% Ethieroe ... argi 15 1 15 S' 4 5 1. A 1

-- insecticice (glazed tile H insscicide + 1 3& Compound: A glazed tie -- insecticise (us glazed tile -- insecticide + 1 % Composind. A sunglazed tie) Figure 105

4. 2O

, Eridaciopsid Beach C.2s, Etiprote test 5 5' 5 a 1: 15" 1

--3 secticide Egiazed tile HH secticide + 1 % Colponi A glazec i.e. -h-secticide (Englazed tie -- insectic:ce - 3, CorpcEnd A taigazed tie Figure 106 U.S. Patent May 12, 2015 Sheet SS Of 57 US 9,028,856 B2

OO 80 3. 60 40 SS. 20

1. 2 1. 2 d d S. Fetti Fetis

-- sectice are -- it: : SS 292 - 3.2% SS 292 -- it 3.48 BS 29.

Figure 107

O 80 60 3 40 e SS 20

O 1. 2 h 1. 2 h Feiti 8 Feir

-- secticide acne H- it is BS 292 - it .2% BS 292 -- with .348 BS 292

Figure 108 U.S. Patent May 12, 2015 Sheet 56 of 57 US 9,028,856 B2

00 s E 80 2 60

s 40 t 85 20 t SS O 15' 30" 1 2 4 15' 30" 2 4 15' 3" 1 2 4 1 0.25% AS 334 BSE 286 i., SY 296 secticide ade His SS 2S2 wit, 0.2%, BS 232 Wii Oak, BS 23. SS 292 ace Figure 109

100 - 80 2 60

Cs 4 8 20 t SS C 15' 30" 2 4 15' 30" 2 15. 38' 2 25 AS: 33 S. 26 Y 2960 -- secticise aise Hit 8S 292 it, O.2% BS 292 Hi- a B.S. 9 BS 29 as e

Figure 110 U.S. Patent May 12, 2015 Sheet 57 Of 57 US 9,028,856 B2

>00

s E 80 2 60

s 40 C 8 20 S s 0 5' 38' 2 A: i: 5' 30 1 2 4 1 5' 38' 1 2 4: 1 3.25% A8S 833 BSN: 2360 E. BY 2960 Secticice are H SS 29 O. BS 29 a ES 292 SS 29 gate

Figure 111 US 9,028,856 B2 1. 2 SYNERGISTC PESTICDE COMPOSITIONS observed as shown infra. While certain components in pesti cide formulations may be provided for the protection of the This application is a Divisional of U.S. application Ser. No. active pesticidal ingredient against photodegradation, the 12/410,840, filed Mar. 25, 2009, the contents of which is present invention provides an effective pesticidal composi incorporated by reference herein in its entirety, which claims tion, with embodiments that demonstrate a reduction in the priority to U.S. Provisional Application No. 61/163,206, filed amount of pesticide necessary to kill pests by up to 10% or more in a given application. Further, the present invention Mar. 25, 2009 and U.S. Provisional Application No. 61/072, provides methodology for increasing the kill spectrum of a 778, filed Apr. 2, 2008. particular pesticide. FIELD OF THE INVENTION 10 In one embodiment, the present invention provides a pes ticidal composition comprising a pesticide; and an adjuvant, The present invention relates to compositions that include wherein the composition provides an observed kill rate that a combination of one or more pesticides and one or more exceeds an expected kill rate, the expected kill rate calculated adjuvants. using the formula: E-X-Y-CXXY)/100, wherein E is the 15 expected kill rate; X is efficacy expressed as % of untreated BACKGROUND OF THE INVENTION control of the pesticide; and Y is efficacy expressed as % of untreated control of the adjuvant. Pesticides include any Substance or mixture of Substances In a further embodiment, the amount of adjuvant is an used for preventing, controlling, or lessening the damage amount effective to increase the rate of cuticle penetration. caused by a pest. A pesticide may be a chemical Substance, In a further embodiment, the amount of adjuvant is an biological agent such as a virus or bacteria, antimicrobial, or amount effective to decrease the amount of pesticide required a disinfectant. Pests include insects, plant pathogens, weeds, to achieve a certain kill rate, by at least around 10%. In a mollusks, birds, mammals, fish, nematodes such as round further embodiment, the amount of adjuvant is an amount worms, and microbes. effective to decrease the amount of pesticide required to Insecticides are a category of pesticides for the control of 25 achieve a certain kill rate, by at least around 20%. In a further insects, namely ovicides or Substances that kill eggs, larvi embodiment, the amount of adjuvant is an amount effective to cides or substances that kill larvae, or adulticides or sub decrease the amount of pesticide required to achieve a certain stances that kill adult insects. Pesticides also include miti kill rate, by at least around 30%. cides, acaricides, mulluscides, nematicides, and other In a further embodiment, the pesticide has a log P value of varieties of agents. 30 about <2.0. In a further embodiment, the pesticide has a log P Pesticides are used for a variety of applications, including value of between about >2.0 and about <4.0. In a further crop treatments, animal treatments, treatments for substrates embodiment, the pesticide has a log Pvalue of about >4.0. Such as wood or other Surfaces, and treatment of home infes In one embodiment, the pesticide is selected from one or tations. The choice of pesticide typically depends on a variety more of abamectin, acephate, acetamiprid, acrinathrin, alany of factors, including the type of pest, the type of application, 35 carb, aldicarb, allethrin, alpha-cypermethrin, aluminium the likelihood of contact with humans or other animals, the phosphide, amitraz, azadirachtin, azamethiphos, azinphos porosity of the substrate, and the like. ethyl, azinphos-methyl, bendiocarb, benfuracarb, benSultap, In one application, namely crop protection, there is a need beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, to eliminate or Substantially reduce crop damage caused by bioallethrin S-cyclopentenyl isomer, bioresmethrin, bistriflu insects, while at the same time, lessening the environmental 40 ron, borax, buprofezin, butocarboxim, butoxycarboxim, impact caused by pesticide use. cadusafos, calcium cyanide, calcium polysulfide, carbaryl, In another application, namely insecticidal control, there is chlorantraniliprole, carbofuran, carbosulfan, cartap, chlore a need to provide effective insecticidal control in a home or thoxyfos, chlorfenapyr, chlorfenVinphos, chlorfluaZuron, business while avoiding concentrations of insecticides that chlormephos, chloropicrin, chlorpyrifos, chlorpyrifos-me might be harmful to humans or other animals. One Such 45 thyl, chromafenozide, clothianidin, cyantraniliprole, couma application includes protecting wood products from termite phos, cryolite, cyanophos, cycloprothrin, cyfluthrin, cyhalo damage, with a preference for using agents that are less toxic thrin, cypermethrin, cyphenothrin, cyromazine, dazomet, than current common products such as copper/chromefar deltamethrin, demeton-S-methyl, diafenthiuron, diazinon, senic (CCA) applications. dichlorvos, dicrotophos, dicyclanil, diflubenZuron, For these and other reasons, it would be advantageous to 50 dimethoate, dimethylvinphos, dinotefuran, disulfoton, ema provide compositions that enhance the efficacy of insecti mectin, emamectin benzoate, empenthrin, endosulfan, esfen cides. Valerate, ethiofencarb, ethion, ethiprole, ethoprophos, ethyl enedibromide, etofemproX, etoxazole, famphur, fenitrothion, SUMMARY OF THE INVENTION fenobucarb, fenoxycarb, fenpropathrin, fenthion, fenvalerate, 55 fipronil, flonicamid, flucycloxuron, flucythrinate, flufenoxu In one embodiment, the present invention provides a pes ron, flumethrin, formetanate, formetanate hydrochloride, fos ticidal composition comprising a pesticide and an adjuvant, thiazate, furathiocarb, gamma-cyhalothrin, halofenozide, wherein the composition provides a synergistic kill rate. In heptachlor, heptenophos, hexaflumuron, hydramethylnon, accordance with one embodiment of the present invention, hydroprene, imidacloprid, imiprothrin, indoxacarb, isofen the use of a free radical stabilizer is believed to change the 60 phos, isoprocarb, isopropyl O-(methoxyaminothiophospho permeability of an insect or plant cuticle to pesticides. An ryl)salicylate, isoxathion, lambda-cyhalothrin, lithium per adjuvant of the present invention is preferably present in a fluorooctane Sulfonate, lufenuron, magnesium phosphide, Sufficient amount so as to change the permeability of an insect malathion, mecarbam, mercurous chloride, metaflumizone, or plant cuticle, without being limited thereby, for example metam, metam-Sodium, methamidophos, methidathion, through destabilization. By providing a sufficient amount of 65 methiocarb, methomyl, methoprene, methothrin, methoxy an adjuvant according to the present invention to destabilize chlor, methoxyfenozide, metofluthrin, methyl isothiocyan the cuticle of an insect or plant, Synergistic effects have been ate, metolcarb, mevinphos, milbemectin, monocrotophos, US 9,028,856 B2 3 4 naled, naphthalenic compounds, nicotine, nitenpyram, nithi 6-tetramethylpiperidine, 1.2.2.6,6-pentamethyl-4-piperidi azine, novaluron, noviflumuron, omethoate, oxamyl, oxy nol, 4-hydroxy-2.2.6.6 tetramethylpiperidin-1-oxyl, demeton-methyl, parathion, parathion-methyl, pentachlo hindered amine light stabilizers, diphenyl methane, triphenyl rophenol, pentachlorophenyl laurate, permethrin, petroleum methane (Gomberg's trity1), triphenyl methyl chloride (trityl oils, phenothrin, phorate, phosalone, phosmet, phosphami chloride). BHA (butylated hydroxyanisole), BHT (butylated don, phosphine, pirimicarb, pirimiphos-methyl, prallethrin, hydroxytoluene), BHQ (butylated hydroxyquinone), TBHQ profenofos, propaphos, propetamphos, propoXur, prothiofos, (tertiary butyl dihydroxyquinone), methyl esters, including pymetrozine, pyraclofos, pyrethrins, pyridalyl pyridaben, long chain fatty acid esters such as, for example, methyl pyridaphenthion, pyrimidifen, pyriproxyfen, quinalphos, res oleate, methyl linoleate, methyl palmitate, ethyl esters, ethyl methrin, rotenone, Sabadilla, Silafluofen, Sodium cyanide, 10 oleate, dibenzyl maleate, ascorbic acid, retinol, grape seed Sodium pentachloro-phenoxide, spinetoram, spinosad, Sulco oil, roSVeratrol, benzenepropanoic acid, oleic acid, linoleic furon, Sulcofuron-sodium, Sulfluramid, Sulfotep, Sulfuryl acid, palmitic acid, omega-3-fatty acids, EPA, DHA, acetyl fluoride, sulprofos, tau-fluvalinate, tebufenozide, tebupirim salicylic acid, Salicylic acid, methyl salicylate, ibuprofen, fos, teflubenzuron, tefluthrin, temephos, terbufos, tetrachlor tetramethylsilane, trimethylsilane, and a Surfactant selected Vinphos, tetramethrin, theta-cypermethrin, thiacloprid, thia 15 from miranol or miritain. methoxam, thiodicarb, thiofanox, thiometon, thiosultap In still further an embodiment, the adjuvant is the com Sodium, tolfenpyrad, tralomethrin, transfluthrin, triazamate, pounds identified herein as Compound A or bis(1.2.2.6.6- triazophos, trichlorfon, triblumuron, trimethacarb, vamidot pentamethyl-4-piperidinyl)sebacate and methyl(1.2.2.6.6- hion, Xylylcarb, Zeta-cypermethrin, Zinc phosphide, beet pentamethyl-4-piperidinyl)sebacate. juice, D-limonene, cedarwood oil, castor oil, cedar oil, cin In one embodiment, the composition is for treating flying namon oil, citric acid, citronella oil, clove oil, corn oil, cot pests. In one embodiment, the composition is applied to tonseed oil, eugenol, garlic oil, geraniol, geranium oil, lauryl plants and further comprises a suitable carrier. In a further Sulfate, lemon grass oil, linseed oil, malic acid, mint oil, embodiment, the composition is applied to leaves of a plant, peppermint oil, 2-phenethyl propionate (2-phenylethyl pro to Soil adjacent to a plant, or directly to a plant root. In a pionate), potassium Sorbate, rosemary oil, sesame oil, sodium 25 further embodiment, the plant is a house plant, a bush, a tree, chloride, sodium lauryl Sulfate, soybean oil, and thyme oil. an ornamental or the plantis turfor grass. In one embodiment, In still further an embodiment, the pesticide is selected the pesticide is a virucide, bactericide, fungicide, plant from one or more of abamectin, acetamiprid, allethrin, alpha growth regulator, or herbicide. In one embodiment, the com cypermethrin, azadirachtin, bendiocarb, beta-cyfluthrin, position is designed for root application. In a further embodi bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, 30 ment, the composition is designed for spray application. bioresmethrin, borax, carbaryl, chlorantraniliprole, chlor In a further embodiment, the composition is applied to a fenapyr, chlorfluaZuron, chromafenozide, clothianidin, substrate to treat or prevent a pest infestation. In still further cyantraniliprole, cryolite, cyfluthrin, cyhalothrin, cyper an embodiment, the substrate is a wood product. In a further methrin, cyphenothrin, deltamethrin, diflubenZuron, dinote embodiment, the wood product is pressed wood, particle furan, emamectin, emamectin benzoate, esfenvalerate, 35 board, chip board, wafer board, plywood, wood laminated ethiprole, etofemproX, fenvalerate, fipronil, flonicamid, flucy material, freshly cut timber, lumber, and paper. In one cloXuron, flufenoXuron, flumethrin, gamma-cyhalothrin, embodiment, the composition further includes at least one of halofenozide, hexaflumuron, hydramethylnon, hydroprene, a diluent, emulsifier, melting agent, organic binding agent, imidacloprid, imiprothrin, indoxacarb, lambda-cyhalothrin, auxiliary solvent, processing additive, fixative, stability lufenuron, malathion, metaflumizone, methoprene, methoxy 40 enhancer, dye, color pigment, siccative, corrosion inhibitor, fenozide, nitenpyram, novaluron, noviflumuron, permethrin, anti-settlementagent, oranti-skinning agents. In one embodi phenothrin, prallethrin, propoXur, pymetrozine, pyrethrins, ment, the composition is applied by soaking the Substrate in pyriproxyfen, resmethrin, Silafluofen, spinetoram, spinosad, or with the composition, impregnating the Substrate with the tau-fluvalinate, tebufenozide, teflubenzuron, tefluthrin, tet composition, brushing the composition onto the Substrate, ramethrin, thiacloprid, thiamethoxam, transfluthrin, Zeta 45 spraying the composition onto the Substrate, or dipping the cypermethrin, D-limonene, cedarwood oil, castor oil, cedar Substrate into the composition. oil, cinnamon oil, citric acid, citronella oil, clove oil, eugenol, In one embodiment, the composition targets eggs, larvae, garlic oil, geraniol, geranium oil, lauryl Sulfate, lemon grass nymphs, or adults of pests. In one embodiment, the compo oil, malic acid, mint oil, peppermint oil, 2-phenethyl propi sition targets crawling pests, ants, arachnids, bed bugs, onate (2-phenylethyl propionate), potassium Sorbate, rose 50 beetles, centipedes, cockroaches, crickets, earwigs, fleas, mary oil, Sesame oil, sodium chloride, Sodium lauryl Sulfate, Scorpions, silverfish, spiders, termites, ticks, flying insects, Soybean oil, and thyme oil. flies, gnats, hornets, midges, mosquitoes, moths, wasps, plant In one embodiment, the adjuvant is a free radical scaven pests, aphids, armyworms, bagworms, cutworms, mealy ger. bugs, mites, nematodes, plant bugs, psyllids, Scale insects, In one embodiment, the adjuvant is in an amount So as to 55 thrips, or whiteflies. In still further an embodiment, the com provide negligible ability to function as a plasticizer. position targets Hemiptera; Delphacidae such as Laodelphax In one embodiment, the adjuvant is selected from one or striatellus, Nilaparvata lugens, Sogatella fircifera and the more dibasic esters, such as, for example sebacates, polyphe like; Deltocephalidae such as Nephotettix cincticeps, Nepho nyl methanes, food grade preservatives, fatty acid esters, anti tettix virescens and the like: Aphididae such as Aphis gos oxidants, vitamins, fatty acids, Surfactants, ibuprofen, tetram 60 sypii, Myzus persicae and the like; Pentatomidae Such as ethylsilane, trimethylsilane, Compound A (used herein to Nezara antennata, Riptortus clavetus, Eysarcoris lewisi, describe a mixture of bis(1.2.2.6,6-pentamethyl-4-piperidi Eysarcoris parvus, Plautia Stali, Halyomorpha mista and the nyl)sebacate and methyl(1.2.2.6,6-pentamethyl-4-piperidi like; Aleyrodidae Such as Trialeurodes vaporariorum, Bemi nyl)sebacate) at 1%), dimethyl sebacate, sebacic acid, sebacic sia argentifolii and the like; Coccidae Such as Aonidiella acid dibenzyl esters, sebacic acid-bis-(N-succinimidyl)ester, 65 aurantii, Comstockaspis perniciosa, Unaspis citri, Ceroplas bis(1-octyloxy-2.2.6,6-tetramethyl-4-piperidyl)sebacate, bis tes rubens, Icerva purchasi and the like; Tingidae; Psyllidae, (2.2.6,6-tetramethyl-4-piperidyl)sebacate), 4-hydroxy-2.2.6. and the like; Lepidoptera; Pyralidae such as Chilo suppres US 9,028,856 B2 5 6 salis, Cnaphalocrocis medinalis, Notarcha derogata, Plodia One embodiment of the present invention includes a interpunctella and the like: Noctuidae Such as Spodoptera method for controlling or preventing pest infestation, com litura, Pseudaletia separata, Thoricoplusia spp., Heliothis prising administering a composition as herein described. In a spp., Helicoverpa spp. and the like; Pieridae such as Pieris further embodiment, the composition provides a longer rapae and the like; Tortricidae Such as Adoxophyes spp., residual pesticidal effect than the combined residual pesti Grapholita molesta, Cydia pomonella and the like; Car cidal effects of the pesticide and the adjuvant when each is posinidae such as Carposina niponensis and the like; Lyo applied individually at a same concentration. In a further netiidae Such as Lyonetia spp. and the like; Lymantriidae Such embodiment, the composition is not phytotoxic but the pes as Lymantria spp., Euproctis spp., and the like; ticide, alone, is phytotoxic. 10 One embodiment of the present invention provides a Yponomeutidae such as Plutella xylostella and the like: method for treating or preventing a pest comprising: applying Gelechiidae such as Pectinophora gossypiella and the like; aan amount of pesticide at a locus together with an adjuvant, Arctiidae such as Hyphantria cunea and the like; Tineidae wherein the adjuvant is present in an amount Sufficient to Such as Tinea translucens, Tineola bisselliella and the like; stabilize the formation of free radicals, wherein the amount of Diptera, Calicidae such as Culex pipiens pallens, Culex tri 15 pesticide applied is at least about 10% less than expected. In taeniorhynchus, Culex quinquefasciatus and the like; Aedes other words, where an expected amount of pesticide is nec spp. Such as Aedes aegypti, Aedes albopictus and the like; essary to achieve an effect, the combination with an adjuvant Anopheles spp. Such as Anopheles sinensis and the like, Chi within the present invention provides for a synergistic reduc ronomidae; Muscidae such as Musca domestica, Muscina tion in the amount of pesticide necessary to achieve an stabulans and the like; Calliphoridae, Sarcophagidae; Fanni equivalent effect. idae; Anthomyiidae Such as Delia platura, Delia antiqua and One embodiment of the present invention is a method for the like: Tephritidae: Drosophilidae: Psychodidae: Taban increasing a kill spectrum of a pesticide comprising: provid idae; Simuliidae; Stomoxyidae; Agromyzidae, and the like; ing a pesticide at a locus together with an adjuvant, wherein Coleoptera; Diabrotica spp. Such as Diabrotica virgifera vir the adjuvant is present in an amount Sufficient to stabilize the gifera, Diabrotica undecimpunctata howardi and the like; 25 formation of free radicals. In one embodiment, the adjuvant Scarabaeidae Such as Anomala cuprea, Anomala rufocuprea destabilizes the cuticle of a plant or an insect. and the like; Curculionidae such as Sitophilus zeanais, Lis One embodiment of the present invention provides a pes SOrhoptrus Oryzophilus, Callosobruchuys chienensis and the ticidal composition consisting essentially of a pesticide that is like; Tenebrionidae such as Tenebrio molitor, Tribolium cas not an organophosphate and an adjuvant, wherein the com taneum and the like; Chrysomelidae Such as Oulema Oryzae, 30 position provides a synergistic kill rate. For Such embodi Aulacophora femoralis, Phyllotreta striolata, Leptinotarsa ments, additional formulation components are believed to not decemlineata and the like; Anobiidae: Epilachna spp. such as materially affect the basic and novel characteristics of the Epillachna vigintioctopunctata and the like; Lyctidae; Bostry invention. chidae; Cerambycidae; Paederus fiscipes; Blattodea such as One embodiment of the present invention provides a Blattella germanica, Periplaneta fuliginosa, Periplaneta 35 method for increasing the permeability of a pesticide to an americana, Periplaneta brunnea, Blatta Orientalis and the insector plant comprising exposing a cuticle of said insector like; Thysanoptera: Thrips palmi, Thrips tabaci, Franklin plant to an adjuvant wherein said adjuvant destabilizes said iella Occidentalis, Frankliniella intonsa and the like: cuticle of said insect or plant. Hymenoptera: Formicidae, Vespidae, bethylid wasp, Tenthre One embodiment of the present invention provides a dinidae Such as Athalia japonica, and the like; Orthoptera: 40 method for initiating a free radical reaction on insect or plant Gryllotalpidae, Acrididae, and the like: Aphaniptera: Cteno tissue thereby altering the permeability of biological mem cephalides felis, Ctenocephalides canis, Pulex irritans, branes in said tissue comprising: exposing said insector plant Xenopsylla cheopis, and the like; Anoplura: Pediculus tissue to an adjuvant that destabilizes the cuticle of said insect humanus corporis, Phthirus pubis, Haematopinus euryster or plant. nus, Dalmalinia ovis, and the like; Isoptera: Reticulitermes 45 The present invention includes combinations of one or speratus, Coptotermes formosanus, and the like; Acarina: more embodiments herein disclosed. Tetranychidae Such as Tetranychus urticae, Tetranychus kan Zawai, Panonychus citri, Panonychus ulmi, Oligonychus spp., BRIEF DESCRIPTION OF THE FIGURES and the like; Eriophyidae Such as Aculops pelekassi, Aculus Schlechtendali, and the like; Tarsonemidae such as Polyph 50 FIG. 1 is a graph illustrating the Synergy of a free radical agotarisonemus latus, and the like; Tenuipalpidae; Tuckerel stabilizer, benzenepropanoic acid, with an insecticide, imida lidae. Ixodidae Such as Haemaphysalis longicornis, Haema cloprid, against the Argentine ant, in terms of mortality (%) physalis flava, Dermacentor taiwanicus, Ixodes ovatus, overtime (hours). Diamonds representimidacloprid at a 0.5% Ixodes persulcatus, Boophilus microplus, and the like; Acar concentration, triangles represent benzenepropanoic acid at a idae Such as Trophagus putrescentiae, and the like: Epider 55 5% concentration, and squares represent a blend of imidaclo moptidae such as Dermatophagoides farinae, Dermatopha prid at a 0.5% concentration and benzenepropanoic acid at a goides ptrenyssnus, and the like; Cheyletidae such as 5% concentration. Cheyletus eruditus, Cheyletus malaccensis, Cheyletus FIG. 2 is a graph illustrating the Synergy of a free radical moorei, and the like; Dermanyssidae; Araneae Such as Chi stabilizer, benzenepropanoic acid, with an insecticide, imida racanthium japonicum, Latrodectus hasseltii, and the like; 60 cloprid, against the German cockroach, in terms of mortality Chilopoda: Thereuonema hilgendorfi, Scolopendra subspin (%) over time (hours). Diamonds representimidacloprid at a ipes, and the like; Diplopoda: Oxidus gracilis, Nedyopus 0.5% concentration, triangles represent benzenepropanoic tambanus, and the like; Isopoda: Armadillidium vulgare, and acid at a 1% concentration, and squares represent a blend of the like; Gastropoda: Limax marginatus, Limax flavus, and imidacloprid at a 0.5% concentration and benzenepropanoic the like: Nematoda: Pratylenchus coffeae, Pratylenchus fal 65 acid at a 1% concentration. lax, Heterodera glycines, Globodera rostochiensis, Meloid FIG. 3 is a graph illustrating the Synergy of a free radical ogyne hapla, Meloidogyne incognita, and the like. stabilizer, oleic acid, with an insecticide, imidacloprid, US 9,028,856 B2 7 8 against the German cockroach, in terms of mortality (%) over cide, imidacloprid, against the Argentine ant, in terms of time (hours). Diamonds represent imidacloprid at a 0.5% mortality (%) over time (hours). Diamonds representimida concentration, triangles represent oleic acid at a 1% concen cloprid at a 0.5% concentration, triangles represent BHA at a tration, and squares represent a blend of imidacloprid at a 1% concentration, and squares represent a blend of imidaclo 0.5% concentration and oleic acid at a 1% concentration. prid at a 0.5% concentration and BHA at a 1% concentration. FIG. 4 is a graph illustrating the Synergy of a free radical FIG. 13 is a graph illustrating the synergy of a free radical stabilizer, oleic acid, with an insecticide, imidacloprid, stabilizer, butylated hydroxy toluene (BHT), with an insecti against the Argentine ant, in terms of mortality (%) over time cide, imidacloprid, against the Argentine ant, in terms of (hours). Diamonds representimidacloprid at a 0.5% concen mortality (%) over time (hours). Diamonds representimida tration, triangles represent oleic acid at a 0.1% concentration, 10 and squares represent a blend of imidacloprid at a 0.5% cloprid at a 0.5% concentration, triangles represent BHT at a concentration and oleic acid at a 0.1% concentration. 0.1% concentration, and squares represent a blend of imida FIG. 5 is a graph illustrating the synergy of a free radical cloprid at a 0.5% concentration and BHT at a 0.1% concen stabilizer, methyl oleate, with an insecticide, imidacloprid, tration. against the Argentine ant, in terms of mortality (%) over time 15 FIG. 14 is a graph illustrating the synergy of a free radical (hours). Diamonds representimidacloprid at a 0.5% concen stabilizer, butylated hydroxy toluene (BHT), with an insecti tration, triangles represent methyl oleate at a 5% concentra cide, imidacloprid, against the German cockroach, in terms of tion, and squares represent a blend of imidacloprid at a 0.5% mortality (%) over time (hours). Diamonds representimida concentration and methyl oleate at a 5% concentration. cloprid at a 0.5% concentration, triangles represent BHT at a FIG. 6 is a graph illustrating the Synergy of a free radical 1% concentration, and squares represent a blend of imidaclo stabilizer, methyl oleate, with an insecticide, imidacloprid, prid at a 0.5% concentration and BHT at a 1% concentration. against the German cockroach, in terms of mortality (%) over FIG. 15 is a graph illustrating the synergy of a free radical time (hours). Diamonds represent imidacloprid at a 0.5% stabilizer, t-butyl hydroquinone (TBHQ), with an insecticide, concentration, triangles represent methyl oleate at a 1% con imidacloprid, against the Germancockroach, interms of mor centration, and squares represent a blend of imidacloprid at a 25 tality (%) over time (hours). Diamonds represent imidaclo 0.5% concentration and methyl oleate at a 1% concentration. prid at a 0.5% concentration, triangles represent TBHQ at a FIG. 7 is a graph illustrating the synergy of a free radical 0.1% concentration, and squares represent a blend of imida stabilizer, methyllinoleate, with an insecticide, imidacloprid, cloprid at a 0.5% concentration and TBHQ at a 0.1% concen against the Argentine ant, in terms of mortality (%) over time tration. (hours). Diamonds representimidacloprid at a 0.5% concen 30 FIG. 16 is a graph illustrating the synergy of a free radical tration, triangles represent methyl linoleate at a 1% concen stabilizer, t-butyl hydroquinone (TBHQ), with an insecticide, tration, and squares represent a blend of imidacloprid at a imidacloprid, against the Argentine ant, in terms of mortality 0.5% concentration and methyl linoleate at a 1% concentra (%) over time (hours). Diamonds representimidacloprid at a tion. 0.5% concentration, triangles represent TBHQ at a 1% con FIG. 8 is a graph illustrating the Synergy of a free radical 35 centration, and squares represent a blend of imidacloprid at a stabilizer, methyllinoleate, with an insecticide, imidacloprid, 0.5% concentration and TBHQ at a 1% concentration. against the German cockroach, in terms of mortality (%) over FIG. 17 is a graph illustrating the synergy of a free radical time (hours). Diamonds represent imidacloprid at a 0.5% stabilizer, diphenyl methane, with an insecticide, imidaclo concentration, triangles represent methyl linoleate at a 1% prid, against the Argentine ant, in terms of mortality (%) over concentration, and squares represent a blend of imidacloprid 40 time (hours). Diamonds represent imidacloprid at a 0.5% at a 0.5% concentration and methyllinoleate at a 1% concen concentration, triangles represent diphenyl methane at a 1% tration. concentration, and squares represent a blend of imidacloprid FIG. 9 is a graph illustrating the synergy of a free radical at a 0.5% concentration and diphenyl methane at a 1% con stabilizer, methyl palmitate, with an insecticide, imidaclo centration. prid, against the Argentine ant, in terms of mortality (%) over 45 FIG. 18 is a graph illustrating the synergy of a free radical time (hours). Diamonds represent imidacloprid at a 0.5% stabilizer, diphenyl methane, with an insecticide, imidaclo concentration, triangles represent methyl palmitate at a 5% prid, against the Argentine ant, in terms of mortality (%) over concentration, and squares represent a blend of imidacloprid time (hours). Diamonds represent imidacloprid at a 0.5% at a 0.5% concentration and methyl palmitate at a 5% con concentration, triangles represent diphenyl methane at a 5% centration. 50 concentration, and squares represent a blend of imidacloprid FIG. 10 is a graph illustrating the synergy of a free radical at a 0.5% concentration and diphenyl methane at a 5% con stabilizer, methyl palmitate, with an insecticide, imidaclo centration. prid, against the German cockroach, in terms of mortality (%) FIG. 19 is a graph illustrating the synergy of a free radical overtime (hours). Diamonds representimidacloprid at a 0.5% stabilizer, trityl chloride, with an insecticide, imidacloprid, concentration, triangles represent methyl palmitate at a 5% 55 against the Argentine ant, in terms of mortality (%) over time concentration, and squares represent a blend of imidacloprid (hours). Diamonds representimidacloprid at a 0.5% concen at a 0.5% concentration and methyl palmitate at a 5% con tration, triangles represent trityl chloride at a 1% concentra centration. tion, and squares represent a blend of imidacloprid at a 0.5% FIG. 11 is a graph illustrating the synergy of a free radical concentration and trityl chloride at a 1% concentration. stabilizer, butylated hydroxyanisole (BHA), with an insecti 60 FIG. 20 is a graph illustrating the synergy of a free radical cide, imidacloprid, against the German cockroach, in terms of stabilizer, trityl chloride, with an insecticide, imidacloprid, mortality (%) over time (hours). Diamonds representimida against the Susceptible German cockroach, in terms of mor cloprid at a 0.5% concentration, triangles represent BHA at a tality (%) over time (hours). Diamonds represent imidaclo 1% concentration, and squares represent a blend of imidaclo prid at a 0.5% concentration, triangles represent trityl chlo prid at a 0.5% concentration and BHA at a 1% concentration. 65 ride at a 0.1% concentration, and squares represent a blend of FIG. 12 is a graph illustrating the synergy of a free radical imidacloprid at a 0.5% concentration and trityl chloride at a stabilizer, butylated hydroxyanisole (BHA), with an insecti 0.1% concentration. US 9,028,856 B2 10 FIG. 21 is a graph illustrating the synergy of a free radical time (hours). Diamonds represent deltamethrin at a 1% con stabilizer, dibutyl sebacate, with an insecticide, imidacloprid, centration, and squares represent a blend of deltamethrin at a against the resistant German cockroach (T164 strain), in 1% concentration and Compound Aata 1% and Compound B terms of mortality (%) over time (hours). Diamonds represent at a 0.5% concentration. imidacloprid at a 0.5% concentration, triangles represent FIG. 28 is a graph illustrating the synergy of a combination dibutyl sebacate at a 1% concentration, and squares represent of free radical stabilizers, Compound A and Compound B, a blend of imidacloprid at a 0.5% concentration and dibutyl with an insecticide, deltamethrin, against the red imported sebacate at a 1% concentration. fire ant, in terms of mortality (%) over time (hours). Dia FIG. 22 is a graph illustrating the synergy of a free radical monds represent deltamethrin at a 1% concentration, and stabilizer, dibutyl sebacate, with an insecticide, imidacloprid, 10 against the Argentine ant, in terms of mortality (%) over time squares represent a blend of deltamethrin at a 1% concentra (hours). Diamonds representimidacloprid at a 0.5% concen tion and Compound A at a 1% and Compound B at a 0.5% tration, triangles represent dibutyl sebacate at a 0.1% concen concentration. tration, and squares represent a blend of imidacloprid at a FIG. 29 is a graph illustrating the synergy of a combination 0.5% concentration and dibutyl sebacate at a 0.1% concen 15 of free radical stabilizers, Compound A and Compound B, tration. with an insecticide, deltamethrin, against the German cock FIG. 23 a is a photograph of a pre-cut fiberglass screen roach (Monheim strain), in terms of mortality (%) over time coated with an aqueous solution of 1% deltamethrin with and (minutes). Diamonds represent deltamethrin at a 1% concen without a combination of Compound A, as used herein to tration, and squares represent a blend of deltamethrin at a 1% describe a mixture of bis(1.2.2.6,6-pentamethyl-4-piperidi concentration and Compound A at a 1% and Compound B at nyl)sebacate and methyl(1.2.2.6,6-pentamethyl-4-piperidi a 0.5% concentration. nyl)sebacate) at 1% and Compound B (2-(2H-Benzotriazole FIG.30 is a graph illustrating the synergy of a combination 2-yl)-4-methylphenyl, at 0.5%. of free radical stabilizers, Compound A and Compound B, FIG. 23 b is a photograph illustrating a petri dish that with an insecticide, thiamethoxam, against the Argentine ant, includes the screen shown in FIG. 23 a. and Aedes aegypti 25 in terms of mortality (%) over time (hours). Diamonds rep mosquitos. resent thiamethoxam at a 0.01% concentration, and squares FIG. 23 c is a graph illustrating the synergy of a combina represent a blend of thiamethoxam at a 0.01% concentration tion of free radical stabilizers, Compound A and Compound and Compound A at a 1% and Compound B at a 0.5% con B, with an insecticide, deltamethrin, against the Aedes centration. aegypti mosquito, interms of mortality (%) overtime (hours). 30 FIG.31 is a graph illustrating the synergy of a combination Diamonds represent deltamethrin at a 1% concentration, and squares represent a blend of deltamethrin at a 1% concentra of free radical stabilizers, Compound A and Compound B, tion and Compound A at a 1% and Compound B at a 0.5% with an insecticide, thiamethoxam, against the odorous house concentration. ant, in terms of mortality (%) over time (hours). Diamonds FIG.24 is a graph illustrating the synergy of a combination 35 represent thiamethoxam at a 0.1% concentration, and squares of free radical stabilizers, Compound A and Compound B, represent a blend of thiamethoxam at a 0.1% concentration with an insecticide, deltamethrin, against the Argentine ant, in and Compound A at a 1% and Compound B at a 0.5% con terms of mortality (%) over time (minutes). Diamonds repre centration. sent deltamethrin at a 1% concentration, and squares repre FIG. 32 is a graph illustrating the synergy of a combination sent a blend of deltamethrin at a 1% concentration and Com 40 of free radical stabilizers, Compound A and Compound B, pound A at a 1% and Compound B at a 0.5% concentration. with an insecticide, thiamethoxam, against the Susceptible FIG.25 is a graph illustrating the synergy of a combination German cockroach (Monheim Strain), in terms of mortality of free radical stabilizers, Compound A and Compound B, (%) over time (minutes). Diamonds represent thiamethoxam with an insecticide, deltamethrin, against the bait averse Ger at a 1% concentration, and squares represent a blend of thia man cockroach (IHOP strain), in terms of mortality (%) over 45 methoxam at a 1% concentration and Compound A at a 1% time (hours). Diamonds represent deltamethrin at a 1% con and Compound B at a 0.5% concentration. centration, and squares represent a blend of deltamethrin at a FIG.33 is a graph illustrating the synergy of a combination 1% concentration and Compound Aata 1% and Compound B of free radical stabilizers, Compound A and Compound B, at a 0.5% concentration. with an insecticide, resmethrin, against the Aedes aegypti FIG. 26 is a graph illustrating the synergy of a combination 50 mosquito, in terms of mortality (%) over time (hours). Dia of free radical stabilizers, Compound A and Compound B, monds represent resmethrin at a 0.5% concentration, and with an insecticide, deltamethrin, against Culex quinquefas squares represent a blend of resmethrin at a 0.5% concentra ciatus, in terms of mortality (%) over time (hours). Diamonds tion and Compound A at a 1% and Compound B at a 0.5% represent deltamethrin at a 1% concentration, and squares concentration. represent a blend of deltamethrin at a 1% concentration and 55 FIG.34 is a graph illustrating the synergy of a combination Compound A at a 1% and Compound B at a 0.5% concentra of free radical stabilizers, Compound A and Compound B, tion. with an insecticide, resmethrin, against Culex quinquefascia FIG. 27a is a photograph illustrating a glazed tile treated tus, in terms of control (%) over time (hours). Diamonds with an aqueous solution of deltamethrinata concentration of represent resmethrin at a 0.5% concentration, and squares 1% in combination with free radical stabilizers Compound A 60 represent a blend of resmethrin at a 0.5% concentration and at 1% and Compound B at 0.5%. The odorous house ant, Compound A at a 1% and Compound B at a 0.5% concentra Tapinoma sessile, is in contact with the tile, and its escape is tion. physically blocked, as shown in the photograph, by a column. FIG.35 is a graph illustrating the synergy of a combination FIG. 27 b is a graph illustrating the synergy of a combina of free radical stabilizers, Compound A and Compound B, tion of free radical stabilizers, Compound A and Compound 65 with an insecticide, permethrin, against the Aedes aegypti B, with an insecticide, deltamethrin, against the odorous mosquito, in terms of mortality (%) over time (hours). Dia house ant, Tapinoma sessile, in terms of mortality (%) over monds represent permethrin at a 0.5% concentration, and US 9,028,856 B2 11 12 squares represent a blend of permethrin at a 0.5% concentra FIG. 44 is a graph illustrating the synergy of a combination tion and Compound A at a 1% and Compound B at a 0.5% of free radical stabilizers, Compound A and Compound B, concentration. with an insecticide, fipronil, against Culex quinquefasciatus, FIG. 36 is a graph illustrating the synergy of a combination in terms of mortality (%) over time (hours). Diamonds rep of free radical stabilizers, Compound A and Compound B, resent fipronil at a 0.01% concentration, and squares repre with an insecticide, permethrin, against the Argentine ant, in sent a blend of fipronil at a 0.01% concentration and Com terms of mortality (%) over time (hours). Diamonds represent pound A at a 1% and Compound B at a 0.5% concentration. permethrin at a 0.5% concentration, and squares represent a FIG. 45 is a graph illustrating the synergy of a combination blend of permethrin at a 0.5% concentration and Compound of free radical stabilizers, Compound A and Compound B, 10 with an insecticide, fipronil, against the odorous house ant, in A at a 1% and Compound B at a 0.5% concentration. terms of mortality (%) overtime (hours). Diamonds represent FIG.37 is a graph illustrating the synergy of a combination fipronil at a 0.001% concentration, and squares represent a of free radical stabilizers, Compound A and Compound B, blend offipronil at a 0.001% concentration and Compound A with an insecticide, permethrin, against a bait averse strain of at a 1% and Compound B at a 0.5% concentration. German cockroach (IHOP strain), in terms of mortality (%) FIG. 46 is a graph illustrating the synergy of a combination over time (hours). Diamonds represent permethrin at a 0.5% of free radical stabilizers, Compound A and Compound B, concentration, and squares represent a blend of permethrin at with an insecticide, fipronil, against the red imported fire ant, a 0.5% concentration and Compound A at a 1% and Com in terms of mortality (%) over time (hours). Diamonds rep pound B at a 0.5% concentration. resent fipronil at a 0.01% concentration, and squares repre FIG.38 is a graph illustrating the synergy of a combination sent a blend of fipronil at a 0.01% concentration and Com of free radical stabilizers, Compound A and Compound B, pound A at a 1% and Compound B at a 0.5% concentration. with an insecticide, permethrin, against the odorous house FIG. 47 is a photograph illustrating a series of glazed tiles ant, in terms of mortality (%) over time (hours). Diamonds treated with an aqueous solutions of fipronil at 0.01, 0.001 represent permethrin at a 0.5% concentration, and squares and 0.0001% active ingredient (referred to herein as 'AI) represent a blend of permethrin at a 0.5% concentration and 25 were prepared with and without free radical stabilizers (a Compound A at a 1% and Compound B at a 0.5% concentra combination of Compound A at 1% and Compound B at tion. 0.5%) in acetone. Red imported fire ants (Solenopsis invicta) FIG. 39 is a graph illustrating the synergy of a combination are in contact with the tiles, and their escape is physically of free radical stabilizers, Compound A and Compound B, blocked, as shown in the photograph, by a column. with an insecticide, permethrin, against the red imported fire 30 FIG. 48 is a graph illustrating the synergy of a combination ant, in terms of mortality (%) over time (hours). Diamonds of free radical stabilizers, Compound A and Compound B, represent permethrin at a 0.5% concentration, and squares with an insecticide, fipronil, against the susceptible German represent a blend of permethrin at a 0.5% concentration and cockroach (Monheim strain), in terms of mortality (%) over Compound A at a 1% and Compound B at a 0.5% concentra time (hours). Diamonds represent fipronil at a 0.001% con tion. 35 centration, and squares represent a blend of fipronil at a FIG. 40 is a graph illustrating the synergy of a combination 0.001% concentration and Compound A at a 1% and Com of free radical stabilizers, Compound A and Compound B, pound B at a 0.5% concentration. with an insecticide, permethrin, against the Susceptible Ger FIG. 49 is a graph illustrating the synergy of a free radical man cockroach (Monheim Strain), in terms of mortality (%) stabilizer, Compound A, with an insecticide, ethiprole, over time (hours). Diamonds represent permethrin at a 0.5% 40 against the Argentine ant, in terms of mortality (%) over time concentration, and squares represent a blend of permethrin at (hours). Diamonds represent ethiprole at a 0.01% concentra a 0.5% concentration and Compound A at a 1% and Com tion, squares represent a blend of ethiprole at a 0.01% con pound B at a 0.5% concentration. centration and Compound A at a 1%, triangles represent a FIG. 41 is a graph illustrating the synergy of a free radical blend of ethiprole at a 0.01% concentration and Compound A stabilizer, Compound A, with an insecticide, fipronil, against 45 at a 0.1% concentration, X's represent Compound A, alone, at the Argentine ant, in terms of mortality/control (%) over time a 1% concentration, and asterisks ('s) represent Compound (hours). Diamonds represent fipronil at a 0.001% concentra A, alone, at a 0.1% concentration. tion, squares represent a blend of fipronil at a 0.001% con FIG.50 is a graph illustrating the synergy of a combination centration and Compound A at a 1%, triangles represent a of free radical stabilizers, Compound A and Compound B, blend offipronil at a 0.001% concentration and Compound A 50 with an insecticide, ethiprole, against Aedes aegypti mosqui at a 0.1% concentration, X's represent Compound A alone at tos, in terms of mortality (%) over time (hours). Diamonds a concentration of 1%, and asterisks represent Compound A represent ethiprole at a 0.01% concentration, and squares alone at a concentration of 0.01%. represent a blend of ethiprole at a 0.01% concentration and FIG. 42 is a graph illustrating the synergy of a combination Compound A at a 1% and Compound B at a 0.5% concentra of free radical stabilizers, Compound A and Compound B, 55 tion. with an insecticide, fipronil, against the Aedes aegypti mos FIG. 51 is a graph illustrating the synergy of a combination quito, in terms of mortality (%) over time (hours). Diamonds of free radical stabilizers, Compound A and Compound B, represent fipronil at a 0.01% concentration, and squares rep with an insecticide, ethiprole, against the Argentine ant, in resent a blend offipronil at a 0.01% concentration and Com terms of mortality (%) overtime (hours). Diamonds represent pound A at a 1% and Compound B at a 0.5% concentration. 60 ethiprole at a 0.01% concentration, and squares represent a FIG. 43 is a graph illustrating the synergy of a combination blend of ethiprole at a 0.01% concentration and Compound A of free radical stabilizers, Compound A and Compound B, at a 1% and Compound B at a 0.5% concentration. with an insecticide, fipronil, the Argentine ant, in terms of FIG. 52 is a graph illustrating the synergy of a combination mortality (%) over time (hours). Diamonds represent fipronil of free radical stabilizers, Compound A and Compound B, at a 0.001% concentration, and squares represent a blend of 65 with an insecticide, ethiprole, against houseflies, in terms of fipronil at a 0.001% concentration and Compound A at a 1% mortality (%) over time (hours). Diamonds represent and Compound B at a 0.5% concentration. ethiprole at a 0.01% concentration, and squares represent a US 9,028,856 B2 13 14 blend of Ethiprole at a 0.01% concentration and Compound A B-cyfluthrin (at a concentration of 0.001%), against the Ger at a 1% and Compound B at a 0.5% concentration. man Cockroach (IHOP), in terms of mortality (%) over time FIG. 53 is a graph illustrating the synergy of a combination (hours). of free radical stabilizers, Compound A and Compound B, FIG. 64 is a graph illustrating the synergy of a free radical with an insecticide, Ethiprole, against the odorous house ant, stabilizer Compound A (at a concentration of 1%) and Com in terms of mortality (%) over time (hours). Diamonds rep pound B (at a concentration of 0.5%), with the insecticide resent Ethiprole at a 0.01% concentration, and squares rep B-cyfluthrin (at a concentration of 0.001%), against the Ger resent a blend of Ethiprole at a 0.01% concentration and man cockroach (Monheim), in terms of mortality (%) over Compound A at a 1% and Compound B at a 0.5% concentra time (hours). tion. 10 FIG. 65 is a graph illustrating the synergy of a free radical FIG. 54 is a graph illustrating the synergy of a combination stabilizer Compound A (at a concentration of 1%) and Com of free radical stabilizers, Compound A and Compound B, pound B (at a concentration of 0.5%), with the insecticide with an insecticide, ethiprole, against the red imported fire B-cyfluthrin (at a concentration of 0.001%), against the Odor ant, in terms of mortality (%) over time (hours). Diamonds 15 ous House ant, in terms of mortality (%) over time (hours). represent Ethiprole at a 0.01% concentration, and squares FIG. 66 is a graph illustrating the synergy of a free radical represent a blend of Ethiprole at a 0.01% concentration and stabilizer Compound A (at a concentration of 1%) and Com Compound A at a 1% and Compound B at a 0.5% concentra pound B (at a concentration of 0.5%), with the insecticide tion. bendiocarb (at a concentration of 0.001%), against the Aedes FIG.55 is a graph illustrating the synergy of a combination aegypti, in terms of mortality (%) over time (minutes). of free radical stabilizers, Compound A and Compound B, FIG. 67 is a graph illustrating the synergy of a free radical with an insecticide, ethiprole, against the Susceptible German stabilizer Compound A (at a concentration of 1%) and Com cockroach (Monheim strain), in terms of mortality (%) over pound B (at a concentration of 0.5%), with the insecticide time (hours). Diamonds represent Ethiprole at a 0.01% con bendiocarb (at a concentration of 0.001%), against the Argen centration, and squares represent a blend of Ethiprole at a 25 tine ant, in terms of mortality (%) over time (minutes). 0.01% concentration and Compound A at a 1% and Com FIG. 68 is a graph illustrating the synergy of a free radical pound B at a 0.5% concentration. stabilizer Compound A (at a concentration of 1%) and Com FIG. 56 is a chart illustrating the time (minutes) required pound B (at a concentration of 0.5%), with the insecticide for various compositions (including the insecticide bendio bendiocarb (at a concentration of 0.001%), against the Culex 30 quinquefasciatus, in terms of mortality (%) over time. carb and various adjuvants) to provide knockdown (LT50 and FIG. 69 is a graph illustrating the synergy of a free radical LT95) of Culex quinquefasciatus (adults, 3 days old). stabilizer Compound A (at a concentration of 1%) and Com FIG. 57 is a continuation of FIG. 56 with the chart illus pound B (at a concentration of 0.5%), with the insecticide trating the time (minutes) required for various compositions bendiocarb (at a concentration of 0.001%), against the Odor (including the insecticide bendiocarb and various additional 35 ous House ant, in terms of mortality (%) over time (minutes). adjuvants) to provide knockdown (LT50 and LT95) of Culex FIG.70 is a graph illustrating the synergy of a free radical quinquefasciatus (adults, 3 days old). stabilizer Compound A (at a concentration of 1%) and Com FIG. 58 is a chart illustrating the effect of a EcoSmart IC pound B (at a concentration of 0.5%), with the insecticide treatments, alone or in combination with Compound A. carbaryl (at a concentration of 0.1%), against Aedes aegypti, against the German cockroach, measured in terms of mortal 40 in terms of mortality (%) over time (hours). ity (%) over time (hours). FIG.71 is a graph illustrating the synergy of a free radical FIG. 59 is a chart illustrating the performance enhance stabilizer Compound A (at a concentration of 1%) and Com ment of Compound A against the insecticide sold under the pound B (at a concentration of 0.5%), with the insecticide tradename Eco PCO ACU, also described as hexa-hydroxyls, carbaryl (at a concentration of 0.1%), against the Argentine measured in terms of mortality (%) versus exposure time 45 ant, in terms of mortality (%) over time (minutes). (hours). FIG.72 is a graph illustrating the synergy of a free radical FIG. 60 is a chart illustrating the performance enhance stabilizer Compound A (at a concentration of 1%) and Com ment of Compound A on the insecticide sold under the trade pound B (at a concentration of 0.5%), with the insecticide name Kicker, also described as a mixture of pyrethrins and carbaryl (at a concentration of 0.1%), against the Odorous piperonyl butoxide, measured in terms of mortality (%) ver 50 House ant, in terms of mortality (%) over time (hours). SuS exposure time (hours). FIG. 73 is a graph illustrating the synergy of a free radical FIG. 61 is a chart illustrating the performance enhance stabilizer Compound A (at a concentration of 1%) and Com ment of Compound A in combination with the insecticide pound B (at a concentration of 0.5%), with the insecticide sold under the tradename Kicker, also described as a mixture carbaryl (at a concentration of 0.1%), against the Red of pyrethrins and piperonyl butoxide at 0.006% against Ger 55 Imported Fire ant, in terms of mortality (%) over time (min man cockroaches. utes). Note that in the following figures, Compound A+Com FIG. 74 is a graph illustrating the synergy of a free radical pound B may be alternatively referred to as “UV Block” or stabilizer Compound A (at a concentration of 1%) and Com “BLS292. pound B (at a concentration of 0.5%), with the insecticide FIG. 62 is a graph illustrating the synergy of a free radical 60 carbaryl (at a concentration of 0.5%), against the German stabilizer Compound A (at a concentration of 1%) and Com Cockroach (Monheim), in terms of mortality (%) over time pound B (at a concentration of 0.5%), with the insecticide (hours). B-cyfluthrin (at a concentration of 0.001%), against the FIG. 75 is a graph illustrating the synergy of a free radical Argentine Ant, in terms of mortality (%) over time (hours). stabilizer Compound A (at a concentration of 1%) and Com FIG. 63 is a graph illustrating the synergy of a free radical 65 pound B (at a concentration of 0.5%), with the insecticide stabilizer Compound A (at a concentration of 1%) and Com clothianidin (at a concentration of 0.1%), against the Argen pound B (at a concentration of 0.5%), with the insecticide tine ant, in terms of mortality (%) over time (hours). US 9,028,856 B2 15 16 FIG. 76 is a graph illustrating the synergy of a free radical 0.1%), against Culex quinquefasciatus, in terms of percent stabilizer Compound A (at a concentration of 1%) and Com knockdown (%) over time (minutes, hours, and days). Com pound B (at a concentration of 0.5%), with the insecticide pounds evaluated include bendiocarb, alone or in combina clothianidin (at a concentration of 0.1%), against the Odorous tion with Compound A. Compound 1 (diethyl sebecate), House ant, in terms of mortality (%) over time (hours). Compound 2 (sebacic acid), or Compound 3 (sebacid acid FIG. 77 is a graph illustrating the synergy of a free radical dibenzyl ester). stabilizer Compound A (at a concentration of 1%) and Com FIGS. 89 and 90 are graphs illustrating repeated analyses pound B (at a concentration of 0.5%), with the insecticide of the Synergy of various adjuvants (eachata concentration of clothianidin (at a concentration of 0.1%), against the German 1%), with the insecticide bendiocarb (at a concentration of cockroach (Monheim), in terms of mortality (%) over time 10 0.1%), against Culex quinquefasciatus, in terms of percent (hours). knockdown (%) over time (minutes, hours, and days). Com FIG. 78 is a graph illustrating the synergy of a free radical pounds evaluated include bendiocarb, alone or in combina stabilizer Compound A (at a concentration of 1% or 0.1%), tion with Compound A. Compound 4 (sebecacid acid-bis-N- with the insecticide imidacloprid (at a concentration of succinimidyl)ester), Compound 5 (Bis(1-octyloxy-2.2.6.6- 0.5%), against the Odorous House ant, in terms of mortality 15 tetramethyl-4-piperidinyl sebecate), or Compound 6 (Bis(1- (%) over time (hours). 2.2.6.6-tetramethyl-4-piperidinyl sebecate). FIG. 79 is a graph illustrating the synergy of a free radical FIGS. 91 and 92 are graphs illustrating repeated analyses stabilizer Compound A (at a concentration of 1% or 0.1%), of the Synergy of various adjuvants (eachata concentration of with the insecticide imidacloprid (at a concentration of 1%), with the insecticide bendiocarb (at a concentration of 0.1%), against the Odorous House ant, in terms of mortality 0.1%), against Culex quinquefasciatus, in terms of percent (%) over time (hours). knockdown (%) over time (minutes, hours, and days). Com FIG.80 is a graph illustrating the synergy of a free radical pounds evaluated include bendiocarb, alone or in combina stabilizer Compound A (at a concentration of 1%) and Com tion with Compound A. Compound 7 (4-hydroxy-2.2.6.6- pound B (at a concentration of 0.5%), with the insecticide tetramethyl-4-piperidine), Compound 8 (1.2.2.6.6- imidacloprid (at a concentration of 1%), against Aedes 25 pentamethyl-4-piperidinol), or Compound 9 (4-hydroxy-2.2, aegypti, in terms of mortality (%) over time (hours). 6,6-tetramethyl-4-piperidin-1-oxyl). FIG. 81 is a graph illustrating the synergy of a free radical FIGS. 93 and 94 are graphs illustrating repeated analyses stabilizer Compound A (at a concentration of 1%) and Com of the Synergy of various adjuvants (eachata concentration of pound B (at a concentration of 0.5%), with the insecticide 1%), with the insecticide bendiocarb (at a concentration of imidacloprid (at a concentration of 0.5%), against the Argen 30 0.1%), against Culex quinquefasciatus, in terms of percent tine ant, in terms of mortality (%) over time (hours). knockdown (%) over time (minutes, hours, and days). Com FIG. 82 is a graph illustrating the synergy of a free radical pounds evaluated include bendiocarb, alone or in combina stabilizer Compound A (at a concentration of 1%) and Com tion with Compound A, anionic and nonionic Surfactants sold pound B (at a concentration of 0.5%), with the insecticide under the tradename GenapolRX 080, and lactate esters sold imidacloprid (at a concentration of 0.5%), against the bait 35 under the tradename Purasolv(R. EHC. adverse German cockroach, in terms of mortality (%) over FIG.95 is a graph illustrating the synergy of Compound A time (hours). (at a concentration of 1% in acetone), with the insecticide FIG. 83 is a graph illustrating the synergy of a free radical imidacloprid 35 SC (at a concentration of 0.1%), against stabilizer Compound A (at a concentration of 1%) and Com Culex quinquefasciatus, in terms of percent knockdown (%) pound B (at a concentration of 0.5%), with the insecticide 40 over time (minutes, hours, and days). The graph reflects data imidacloprid (at a concentration of 0.5%), against the Suscep points where the imidacloprid was applied neat (without tible German cockroach (Monheim strain), in terms of mor acetone), where acetone was added immediately afterward, tality (%) over time (hours). where Compound A in acetone was added immediately after FIG. 84 is a graph illustrating the synergy of a free radical ward, where acetone was added one day later, and where stabilizer Compound A (at a concentration of 1%) and Com 45 Compound A in acetone was added one day later. pound B (at a concentration of 0.5%), with the insecticide FIG.96 is a graph illustrating the synergy of Compound A imidacloprid (at a concentration of 0.1%), against the odor (at a concentration of 1% in acetone), with the insecticide ous house ant, in terms of mortality (%) over time (hours). deltamethrin 10 SC (at a concentration of 0.002%), against FIG. 85 is a graph illustrating the synergy of a free radical Culex quinquefasciatus, in terms of percent knockdown (%) stabilizer Compound A (at a concentration of 1%) and Com 50 over time (minutes, hours, and days). The graph reflects data pound B (at a concentration of 0.5%), with the insecticide points where the deltamethrin was applied neat (without imidacloprid (at a concentration of 0.5%), against the red acetone), where acetone was added immediately afterward, imported fireant, in terms of mortality (%) over time (hours). where Compound A in acetone was added immediately after FIG. 86 is a graph illustrating the synergy of various adju ward, where acetone was added one day later, and where vants, with the insecticide bendiocarb (at a concentration of 55 Compound A in acetone was added one day later. 0.1%), against Culex quinquefasciatus, in terms of percent FIG.97 is a graph illustrating the synergy of Compound A knockdown (%) over time (minutes, hours, and days). Dia (at concentrations of 0.04, 0.02, and 1%), with the insecticide monds represent bendiocarb in combination with 1% Com cyfluthrin (at a concentration of 0.004%), against Musca pound A in ethylacetate. Triangles represent bendiocarb in domestica, susceptible strain (WHO(N)), in terms of percent combination with 1% Sebasic acid dibenzyl ester in ethyl 60 knockdown (%) over time (minutes, hours, and days). The acetate. Squares represent bendiocarb and 1% 4-hydroxy-2, graph reflects data points where the cyfluthrin was applied 2.6,6-tetramethylpiperidine in ethyl acetate. Light circles neat (without acetone) onto glazed tiles and unglazed tiles, represent bendiocarb in cyclohexanone. Dark circles repre and where the cyfluthrin was applied as a solution in acetone sent bendiocarb and 1% Compound A in cyclohexanone. onto glazed tiles. FIGS. 87 and 88 are graphs illustrating repeated analyses 65 FIG.98 is a graph illustrating the synergy of Compound A of the Synergy of various adjuvants (eachata concentration of (at concentrations of 0.04, 0.02, and 1%), with the insecticide 1%), with the insecticide bendiocarb (at a concentration of cyfluthrin (at a concentration of 0.004%), against Musca US 9,028,856 B2 17 18 domestica, resistant strain (Reichswald), in terms of percent 0.01%), against Cimex lectularius, measured in terms of per knockdown (%) over time (minutes, hours, and days). The cent knockdown (%) over time (hours, and days). graph reflects data points where the cyfluthrin was applied FIG. 109 is a graph illustrating the synergy of Compound A neat (without acetone) onto glazed tiles and unglazed tiles, (at concentrations of 0.04, 0.2, and 1%) and a phthalic acid and where the cyfluthrin was applied as a solution in acetone diamide derivative (at a concentration of 0.25%), onto glazed tiles. spiromesifen (at a concentration of 1%) or a butenolide (at a FIG. 99 is a graph illustrating the effect of imidacloprid, concentration of 1%), against Cimex lectularius, measured in fipronil and ethiprole (all in an excipient Such as that sold terms of percent knockdown (%) over time (minutes, hours, under the tradename Lutrol) with and without Compound A. and days). against the American cockroach (Periplaneta americana) 10 FIG. 110 is a graph illustrating the synergy of Compound A after oral application, measured in terms of percent knock (at concentrations of 0.04, 0.2, and 1%) and a phthalic acid down (%) over time (days). diamide derivative (at a concentration of 0.25%), FIG.100 is a graph illustrating the synergy of Compound A spiromesifen (at a concentration of 1%) or a butenolide (at a (at concentrations of 0.04, 0.2, and 1%) and bendiocarb (at a 15 concentration of 1%), against Culex quinquefasciatus, mea concentration of 0.1%) and imidacloprid (at a concentration Sured in terms of percent knockdown (%) overtime (minutes, of 0.1%), against Culex quinquefasciatus, measured in terms hours, and days). of percent knockdown (%) over time (days). FIG. 111 is a graph illustrating the synergy of Compound A FIG. 101 is a graph illustrating the synergy of Compound A (at concentrations of 0.04, 0.2, and 1%) and a phthalic acid (at concentrations of 0.04, 0.2, and 1%) and bendiocarb (at a diamide derivative (at a concentration of 0.25%), concentration of 0.002%), ethiprole (at a concentration of spiromesifen (at a concentration of 1%) or a butenolide (at a 0.02%), and imidacloprid (at a concentration of 0.002%), concentration of 1%), against Musca domestica (Susceptible against Cimex lectularus, measured in terms of percent strain), measured in terms of percent knockdown (%) over knockdown (%) over time (minutes, hours, and days). time (minutes, hours, and days). FIG. 102 is a graph illustrating the synergy of Compound A 25 (at concentrations of 0.04, 0.2, and 1%) and imidacloprid (at DETAILED DESCRIPTION OF THE PREFERRED a concentration of 2.5%), against Acheta domesticus, mea EMBODIMENTS Sured in terms of percent knockdown (%) over time (minutes, hours, and days). Pesticidal compositions, methods for their preparation, FIG. 103 is a graph illustrating the synergy of Compound A 30 and methods for their use are described in more detail below. (at a concentration of 1%) and imidacloprid (at a concentra The present invention will be better understood with refer tion of 0.1%), bendiocarb (at a concentration of 0.1%), ence to the certain definitions. The fact that certain terms are ethiprole (at a concentration of 0.02%), or deltamethrin (at a defined herein, however, does not imply that those terms concentration of 0.002%) against Culex quinquefasciatus, on without specific definition are indefinite. Rather, all terms are glazed and unglazed tiles, measured in terms of percent 35 believed to be used within the accepted meaning in the art. knockdown (%) over time (minutes, hours, and days). Compound A, as used herein, describes a mixture of bis(1, FIG. 104 is a graph illustrating the synergy of Compound A 2.2.6,6-pentamethyl-4-piperidinyl)sebacate and methyl(1.2, (at a concentration of 1%) and imidacloprid (at a concentra 2.6,6-pentamethyl-4-piperidinyl)sebacate). tion of 0.1%), bendiocarb (at a concentration of 0.1%), Compound B, as used herein, describes (2-(2H-Benzotria ethiprole (at a concentration of 0.02%), or deltamethrin (at a 40 Zole-2-yl)-4-methylphenyl. The combination Compound concentration of 0.002%) against Musca domestica (Suscep A+Compound B is alternatively referred to herein as “UV tible strain (WHO(N)), on glazed and unglazed tiles, mea Block or as “BLS292. Sured in terms of percent knockdown (%) over time (minutes, Throughout the present specification, the term “insect' is hours, and days). used in the common meaning and, more phylogenically, FIG. 105 is a graph illustrating the synergy of Compound A 45 should be considered equivalent to the term “arthropod.” (at a concentration of 1%) and imidacloprid (at a concentra Thus, as used herein the term “insect, includes chelicerates, tion of 0.1%), bendiocarb (at a concentration of 0.1%), namely spiders, mites, Scorpions and related organisms char ethiprole (at a concentration of 0.02%), or deltamethrin (at a acterised by the presence of chelicerae, appendages just concentration of 0.002%), against Musca domestica (resis above/in front of the mouth; myriapods, namely millipedes tant strain (Reichswald), on glazed and unglazed tiles, mea 50 and centipedes and their relatives that have many body seg Sured in terms of percent knockdown (%) over time (minutes, ments, each bearing one or two pairs of legs; hexapods hours, and days). namely insects and three Small orders of insect-like animals FIG. 106 is a graph illustrating the synergy of Compound A with six thoracic legs; and crustaceans, which are primarily (at a concentration of 1%) and imidacloprid (at a concentra aquatic (a notable exception being woodlice) and are charac tion of 0.1%), bendiocarb (at a concentration of 0.1%), 55 terised by having biramous appendages. ethiprole (at a concentration of 0.02%), or deltamethrin (at a As used herein, a free radical stabilizer is a compound that concentration of 0.002%) against Blattella germanica (Sus reacts with a free-radical in an electron transfer process to ceptible), on glazed and unglazed tiles, measured in terms of produce a stable free radical. Examples include hindered percent knockdown (%) over time (minutes, hours, and days). amine light stabilizers, such as various sebacates; polyphenyl FIG. 107 is a graph illustrating the synergy of Compound A 60 methanes; food-grade preservatives; certain esters. Some of (at concentrations of 0.04.0.2, and 1%) and fenithrothion (at these free radical stabilizers are also UV absorbers, and can a concentration of 0.01%) or fenthion (at a concentration of enhance the useful lifetime of light-sensitive compounds 0.01%), against Culex quinquefasciatus, measured in terms when they are used in an environment that is exposed to of percent knockdown (%) over time (hours, and days). Sunlight. FIG.108 is a graph illustrating the synergy of Compound A 65 As used herein, a plasticizer is an additive that increases the (at concentrations of 0.04.0.2, and 1%) and fenithrothion (at plasticity or fluidity of the material to which it is added. A a concentration of 0.01%) or fenthion (at a concentration of plasticizer makes or keeps such material soft or pliable. US 9,028,856 B2 19 20 While not wishing to be bound to a particular theory, the logical outer side of the leafcuticle, normally exposed to the present inventors believe that the free radical stabilizer adju air, may be then contacted with a buffer (pH 7), with the vants of the present invention function by a direct action on receptor solution, and the desorption thereby started. The the pest to be controlled, namely through the insects cuticle, penetrated acid form of the test substance is dissociated by the or, when applied to a plant, through the plant cuticle. receptor and the desorption follows first-order kinetics. The The amount of free radical stabilizer necessary to penetrate desorption constant is proportional to the mobility of the the cuticle, for example the insect cuticle, is greater than the tracer in the cuticle. amount typically used as a preservative. After at least 2 times for determining this constant, the While not wishing to be bound to a particular theory, the desorption is then continued with a buffer which additionally present inventors believe that the adjuvants of the present 10 includes the test additive. Depending on the property of the invention function by destabilizing the pests, for example, additive there is then sorption of the additive in the cuticle insects or plants cuticle. Alternatively, the adjuvants of the and, depending on its activity as a plasticizer for the cuticle, present invention are believed to alter the permeability of the there is an increase in the mobility of the tracer within the cuticle, thus, allowing for a synergistic application of pesti cuticle. This is manifested in an increased desorption con cide. In this regard, a preferred amount of adjuvant will be that 15 stant, and the ratio of the slopes with additive to that without necessary to promote the free radical degradation in the additive describes the effect of the additive to act as a pen cuticle. This preferential amount, however, will change etrant at the level of the cuticle. The comparison of the aver depending on the pest, namely insector plant, and also on the age effect of different additives shows their effectiveness at active ingredient employed in conjunction with the adjuvant. acting as plant cuticle plasticizers. As will be demonstrated herein, the synergism achieved by Free Radical Stabilization the active ingredient and adjuvant is not predictable and, thus, As mentioned, in some embodiments of the present inven the synergism associated with the compositions of the present tion, the adjuvant functions as a free radical stabilizer. Certain invention is unexpected. In other words, there is no correla free radical stabilizers such as, benzophenones, piperidines, tion between the partition coefficient of any particular active or benzotriazoles, may be used in combination with pesti ingredient and the activity of that active ingredient with the 25 cides for the purpose of protecting the molecular integrity of adjuvant to achieve the synergism of the present invention. the active pesticidal compound(s) by preventing photolytic As used herein, a “partition coefficient' is defined as the breakdown of chemical bonds in the pesticide molecules. ratio of concentrations of an un-ionized compound between Observers note a beneficial effect of preserving the pesticidal Solutions of water and octanol. To measure the partition coef action for longer periods of time, either on storage or in situ ficient of ionizable solutes, the pH of the aqueous phase is 30 following application to a locus, as compared to the pesticide adjusted Such that the predominant form of the compound is presented without the mitigation of photolytic degradation un-ionized. The logarithm of the ratio of the concentrations of afforded by the UV blockers. Thus, free radical stabilizers the un-ionized solute in the solvents is referred to herein as may prevent a free radical reaction of photolytic energy with log P or log K ow. the pesticidal compounds themselves. As used herein, the adjuvants are described to affect the 35 The present invention is different in that it uses free radical cuticle of the targeted pest. As will be appreciated by those stabilizers to initiate a free radical reaction on insect or plant skilled in the art, there are distinct physical and chemical tissue, thereby altering the permeability of these biological differences between the cuticle of a plant pest and the cuticle membranes. The benefits of this use are surprising in that the of an insect pest. actions facilitate the movement of the pesticidal compound In the field, there are additives which act as penetrants at 40 across the biological membrane and on to a physiological site the level of the cuticle, which may be referred to as accelera of action inside the animal or plant. Therefore, in the present tor additives. See, for example, Schönherr and Baur, 1994, invention, the use of free radical stabilizers is presented in a Pesticide Science 42, 185-208. Accelerator additives pen Sufficient amount to destabilize the cuticle in insects or plants. etrate from the application into the plant cuticle and thereby By destabilizing the cuticle, the application of a pesticide at a increase the mobility of active Substances in the plant cuticle. 45 specific dose rate becomes unexpectedly much higher than Other additives such as polyethylene glycol, in contrast, act what is observed when the cuticle is not destabilized. That is, only in the spray covering (via the liquid phase) or act only as based on a particular dose applied, either to a pest or to a wetting agents, such as sodium dodecyl Sulphate, for locus, the percentage of effectiveness at reaching the physi example. There is an accepted test to determine the influence ological target site where the pesticide exerts its effects on the of additives on the penetration properties of other substances 50 pest is increased when the cuticle is destabilized. at the level of the plant cuticle. The mobility of the test Many of the adjuvants useful in the present invention are Substance in the cuticle is measured with and without an also UV stabilizers, which can contribute to the inhibition of additive, by way of a desorption method. The method is photodegradation of the pesticides. While protection against published in detail in the literature (Baur et al., 1997, Pesti chemical decomposition induced by light energy can some cide Science, 51, 131-152) and any deviations are within the 55 times be achieved by using specific compounds, the amount skill of the art. needed of Such chemicals to protect against decomposition is As a test Substance with the function of a tracer, a selection not indicative as to the amounts necessary to affect structural may be made of a radiolabelled weak organic acid. Plant integrity in an insect or plant cuticle, to thereby promote material may be used, such as enzymatically isolated leaf greater penetration of the pesticide into the organism. More cuticles of the top face of peach leaves from outdoor trees. 60 over, there is simply no indication that if a chemical acts as The cuticles may be installed in specially manufactured stain protectant to a pesticide against decomposition, that such a less steel diffusion cells. The tracer, in a citrate buffer at a pH chemical would have any affect on how that same chemical of 3 in the dissolved state, may be applied to the side origi would affect an insect or plant when administered with a nally facing the inside of the leaf. This inner side readily takes pesticide. Indeed, in cases where an adjuvant is provided to up the Small radioactive amount of the tracer in the undisso 65 reduce decomposition of a pesticide, by the time the pesticide ciated acid form. Subsequently this inner side may be covered is used in a locus and comes into contact with a plantorinsect, and maintained at 100% atmospheric humidity. The morpho that adjuvant may well be virtually exhausted or maybe even US 9,028,856 B2 21 22 completely gone. As such, the adjuvant would not be capable Representative insectides useful in the present invention of affecting the cuticle of the plant or insect when it is applied include pyrethrum type insecticides, such as pyrethrin; pyre with a pesticide. throids, such as deltamethrin, permethrin, B-cyfluthrin, In the compositions of the present invention, the use of an bifenthrin, and resmethrin, nicotinics, particularly chloroni additional attractant, namely a pheromone or a kairomone, 5 cotinyl compounds. Such as acetamiprid, imidacloprid, thia may be contraindicated. In such circumstances, the compo methoxam, clothianidin, acetamiprid, thiacloprid, and sition of the present invention need not include anattractant in dinotefuran; pyrazoles such as fipronil, ethiprole, and order to provide the Synergistic efficacy. tebufenpyrad; semicarbazones such as indoxacarb and The compositions of the present invention may be applied metaflumizone, phthalic acid diamides Such as flubendiamide to a variety of surfaces. As mentioned above, however, the 10 and (S)-3-chloro-N1-(2-methyl-4-1,2,2,2-tetrafluoro-1- adjuvants of the present invention are provided in amounts so (trifluoromethyl)ethylphenyl-N2-(1-methyl-2-methylsul as to destabilize the cuticle of the targeted insector plant. As fonylethyl)phthalamide; anthranilic acid amides Such as Such, when the compositions of the present invention are to be chloroanthraniliprole; organophosphates such as chlorpyri formulated into a paint composition, the formulation may be 15 fos, malathion, and diazinon; carbamates such as bendiocarb, adjusted so as to provide for the UV stabilization as previ carbaryl, and thiodicarb, ketoenoles Such as spirotetramat, ously described. Preferably, the composition is not presented spirodiclofen, and spiromesi?en; phthalic acid diamides Such in a paint formulation. as insecticides with an active ingredients from the antrhanilic The compositions of the present invention may be formu diamide class such as that sold by DuPont under the trade lated in a variety of application forms. As is appreciated in the name Rynaxypyr (hereinafter referred to a rynaxypyrfor ease art, encapsulation of materials for protection from environ of reference), and flubendiamide; IGRs such as methoprene, mental elements may include UV stabilization. Similar to pyriproxifen, triflumuron, hexaflumuron, noviflumuron, above, therefore, the adjuvants of the present invention are fenoxycarb; and other insecticides, such as abamectin, provided in amounts so as to destabilize the cuticle of the hydramethylnon, Sulfluramid, and spinosad. Representative targeted insect or plant. Preferably, the compositions of the 25 chlorinated hydrocarbons include aldrin, chlordane, chlorde present invention are not formulated in encapsulated form cone, DDT, dieldrin, endosulfan, endrin, heptachlor, with UV Stabilizers. hexachlorocyclohexane, gamma-hexachlorocyclohexane, The compositions of the present invention may be formu lindane, methoxychlor, mirex, pentachlorophenol, and TDE. lated with or without additional active ingredients. As one Representative organophosphorus insecticides include example, the composition may include an additional fungi 30 acephate, azinphos-methyl, bensulide, chlorethoxyfos, chlo cide. In this regard, preferably Such an additional component rpyrifos, chlorpyriphos-methylm diazinon, dichlorvos does not adversely impact the synergy of the pesticide and (DDVP), dicrotophos, dimethoate, disulfoton, ethoprop, adjuvant. In this regard, with respect to fungicides, there is a fenamiphos, fenitrothion, fenthion, fosthiazate, malathion, preference for avoiding wood stain and decay fungicides. methamidophos, methidathion, methyl-parathion, I. Pesticides 35 mevinphos, naled, omethoate, oxydemeton-methyl, par Pesticides are defined as chemicals used to kill pests. Pes athion, phorate, phosalone, phosmet, phostebupirim, pirimi ticides specifically include fungicides, herbicides, insecti phos-methyl, profenofos, terbufos, tetrachlorvinphos, tribu cides, and rodenticides. Pesticides are defined by the Federal fos, trichlorfon. Representative carbamates include aldicarb, Government in 40 CFR 152.3 as “any substance (or group of carbofuran, carbaryl, methomyl, and 2-(1-methylpropyl)phe structurally similar Substances if specified by the Agency) 40 nyl methylcarbamate. Representative pyrethroids include that will prevent, destroy, repel, or mitigate any pest, or that allethrin, beta-cyfluthrin, bifenthrin, cyfluthrin, deltamethrin, functions as a plant regulator, desiccant or defoliant within permethrin, resmethrin, Sumithrin, tetramethrin, tralom wording the meaning of FIFRA sec. 2 (a). Several types of ethrin, and transfluthrin. Representative plant toxin derived pesticides are described in more detail below. insecticides include derris (rotenone), pyrethrum, neem (aza A. Insecticides 45 dirachtin), nicotine, and caffeine. An insecticide is a pesticide used against insects in all Additional insecticides include cyclic ketoenols with developmental forms. They include ovicides and larvicides insecticidal and acaricidal properties. Such as those described used against the eggs and larvae of insects, respectively. in EP 528 156 A. WO95/01971, EP 647 637 A. WO Insecticides are commonly used in agriculture, medicine, 96/16061, WO 96/20196, WO 96/25395, WO 96/35664, WO industry, and for household use. 50 97/02243, WO 97/01535, WO 97/36868, WO 97/43275, WO There are several classes of agricultural insecticides. Sys 98/05638, WO 98/06721, WO 99/16748, WO 99/43649, WO temic insecticides are incorporated by treating plants such 99/48869, and WO 99/55673, each hereby incorporated by that insects ingest the insecticide while feeding on the plants. reference with regard to such teaching. Contact insecticides are toxic to insects brought into direct Certain pesticides are exempt from the requirements of the contact with the insecticide. Contact insecticides are com 55 FIFRA act (40 CFR 152.25(f)). They are commonly known as monly applied by aerosol distribution and, in some examples, minimum risk pesticides. Examples of these pesticides may remain in active form on treated Surfaces for extended includes castor oil (U.S.P. or equivalent), cedar oil, cinnamon periods of time. Natural insecticides, such as nicotine and and cinnamon oil, citric acid, citronella and citronella oil, pyrethrum, are made by plants as defense mechanisms cloves and clove oil, corn gluten meal, corn oil, cottonseed against insects. Inorganic insecticides are manufactured with 60 oil, dried blood, eugenol, garlic and garlic oil, geraniol, gera various metal salts, including arsenates, chromium, copper, nium oil, lauryl Sulfate, lemongrass oil, linseed oil, malic fluorine, and Sulfur. Inorganic insecticides are commonly acid, mint and mint oil, peppermint and peppermint oil, used for wood treatment, although quaternary ammonium 2-phenethyl propionate (2-phenylethyl propionate), potas salts and other compounds are replacing chromium and sium Sorbate, putrescent whole egg solids, rosemary and arsenates due to toxicity issues with the latter. Organic insec 65 rosemary oil, sesame (includes ground sesame plant) and ticides are synthetic chemicals. Most insecticides in use today sesame oil, Sodium chloride (table salt), Sodium lauryl Sul are organic insecticides. fate, soybean oil, thyme and thyme oil, and white pepper. US 9,028,856 B2 23 24 Numerous heterocycles, organotin compounds, benzoy TABLE 1-continued lureas and pyrethroids have insecticidal and acaricidal prop Likelihood of erties, for example, see WO93/22297, WO 93/10083, DE 2 Direct Insect 641 343 A, EP 347 488 A, EP 210 487 A, U.S. Pat. No. Cuticular 3.264,177, and EP 234 045A, each herein incorporated by Insecticide Class Examples Log P Penetration reference with regard to such teaching. carbamates bendiocarb 1.7 Slow Certain bacteria, fungi, and other biological material may carbaryl 2.8 intermediate be active as insecticides. When these biological insecticides thiodicarb 1.6 Slow are inactive against other organisms. Some are considered IGRS methoprene >6.O Fast 10 pyriproxifen 5.4 Fast more environmentally friendly than synthetic pesticides. trifumuron 4.9 Fast Examples include, but are not limited to, Bacillus Sphericus, hexaflumuron S.6 Fast Bacillus Subtilis, Bacillus cereus, or combinations of such noviflumuron 4.9 Fast material. fenoxycarb 4.1 Fast ketoenoles spirodiclofen 5.8 Fast The above-referenced exemplary insecticides may be char spiromesifen 4.6 Fast acterized as either (i) fast acting; (ii) intermediate acting; or 15 spirotetramate (iii) slow acting. As noted herein, the octanol-water partition other abamectin 4.4 Fast hydramethylnon 2.3 intermediate coefficient may be used to identify the cuticular penetration of Sulfuramid >6.8 Fast a particular active ingredient. One factor in the relative speed spinosad 2.8–5.2 Intermediate-Fast through which any insecticide acts is the insecticide's ability to cross the insect cuticle. A determining factor for cuticle penetration is Log Kow, also known as Log P. Log Kow (Log As noted, despite an active ingredient's characterization for P) is the octanol-water partition coefficient for a neutral mol cuticular penetration, the present invention provides an unex ecule. Log P is used hereinfurther, but, as noted above, the pected Synergism. As one example, an adjuvant of the present term is synonymous with Log Kow. As previously noted, the invention may allow for a decreased amount of active ingre cuticular penetration of any particular active ingredient as 25 dient for an equivalent effect for an active ingredient that is against a plant cuticle is not indicative of that same active already characterized as “fast.” Thus, mechanistically, ingredient’s ability to penetrate an insect cuticle. Further, as including physicochemically, the adjuvants of the present will be illustrated herein further, the base cuticular penetra invention provide cuticular penetration beyond any expected tion for an active ingredient does not provide a direct corre level. lation to the synergistic effect of the present invention. As 30 Certain insecticidal agents can be used to combat material such, the mechanism attributable to the synergistic effect of destroying insects and preserve technical materials, such as the adjuvant of the present invention is different from the wood products. They can also be used for soil treatment cuticular penetration achieved by compounds by measure against termite infestation. Representative insecticidal com ment of Log K ow. pounds used to treat Surfaces, specifically wood products, The cuticular penetration of a compound is classified as 35 "SLOW' when the compound has a Log P value of about include organophosphorus insecticides such as phoXim and <2.0. The cuticular penetration of a compound is classified as chloropyriphos, as well as those classified in the pyrethroid “FAST when it has a Log Pvalue of about >4.0. The cuticu series insecticides such as permethrin, deltamethrin, cyper lar penetration of a compound is classified as “INTERME methrin, fenvalerate, and cyfluthrin. Additional insecticides 40 include 1-(6-chloro-3-pyridylmethyl)-2-nitromethylene DIATE' when the Log Pvalue is between about 2.0 and about imidazolidine, 3-(6-chloro-3-pyridylmethyl)-2-nitromethyl 4.0. Log P values of representative insecticides from the ene-thiazolidine, 1-(6-chloro-3-pyridylmethyl)-2-ni various insecticide classes are shown below in Table 1. troimino-imidazolidine, 1-(6-chloro-3-pyridylmethyl)-2- TABLE 1. nitromethylene-tetrahydropyrimidine, and 3-(6-chloro-3- 45 pyridylmethyl)-2-nitromethylene-tetrahydro-2H-1,3- Likelihood of thiazine. Direct Insect B. Agricultural Chemicals Cuticular Any type of agricultural chemical, pesticide, or genetic Insecticide Class Examples Log P Penetration material, which results in a desired effect, may be considered pyrethrums pyrethrin 4.3 Fast 50 a pesticide for the present invention. Thus, the active compo pyrethroids deltamethrin 4.6 Fast permethrin 6.1 Fast nents can be herbicidal, insecticidal, bactericidal, Virucidal, B-cyfluthrin 5.9 Fast fungicidal, acaricidal, and the like as herein described. The bifenthrin 6.O Fast active components may be genetic material to be transfected resmethrin 5.4 Fast into a plant. chloronicotinyls imidacloprid O6 Slow 55 Plant Growth Regulators hiamethoxam O.1 Slow clothianidin 0.7 Slow Any compound that regulates plant growth can be included acetamiprid O.8 Slow in the compositions of the invention. As used herein, the hiacloprid 1.3 Slow phrase “plant growth regulator” includes chemicals that are dinotefuran O.S Slow designed to affect plant growth, development, or both. They pyrazoles fipronil 4.0 Fast ethiprole 2.90 Fast 60 are applied for specific purposes to affect specific plant ebufenpyrad 4.9 Fast responses. Although there is much scientific information on semicarbazone indoxacarb 4.6 Fast using plant growth regulators, due to the nature of agricultural metaflumizone S.1 Fast maintenance, plant growth regulation is not a predictable phthalic acid diamides flubendiamide 4.2 Fast organophosphates chlorpyrifos S.O Fast Science. As used herein, the phrase “plant growth regulator malathion 2.7 Intermediate 65 includes products designed to reduce or retard the growth rate diazinon 3.3 Intermediate of the plant, improve its color and general condition, increase plant branching for enhanced cutting production, or enhance US 9,028,856 B2 25 26 flower initiation or synchronize flowering. As used herein the onates and cyclohexanediones, non-translocated or contact phrase “plant growth regulator” includes a turf growth regu herbicides, including cell membrane destroyers, bipyridyli lator. ums, biphenyl ethers, or nitrophenyl ethers, upwardly mobile The phrase “plant growth regulator” includes: antiauxins, only herbicides, also known as apoplastically translocated, Such as clofibric acid or 2,3,5-tri-iodobenzoic acid; auxins, including photosynthetic inhibitors. Such as triazines, uracils, Such as 4-CPA (4-chlorophenoxyacetic acid), 2,4-D ((2,4- phenylureas, or nitriles. dichlorophenoxy)acetic acid), 2,4-DB (4-(2,4-dichlorophe Examples of acid amide-based herbicides include Stam noxy)butyric acid), 2,4-DEP (tris(2-(2,4-dichlorophenoxy) (3',4'-dichloropropionanilide, DCPA) and Alachlor ethylphosphate), dichlorprop ((RS)-2-(2,4- (2-chloro-2',6'-diethyl-N-(methoxymethyl)-acetanilide). dichlorophenoxy)propionic acid), fenoprop ((RS)-2-(2,4,5- 10 Examples of urea-based herbicides include DCMU (3-(3,4- trichlorophenoxy)propionic acid), IAA (indol-3-ylacetic dichlorophenyl)-1,1-dimethylurea) and rinuron (3-(3,4- acid or B-indoleacetic acid), IBA (4-indol-3-ylbutyric acid), dichlorophenyl)-1-methoxy-1-methylurea). Examples of naphthaleneacetamide, C.-naphthaleneacetic acid, 1-naph sulfonyl urea-based herbicides include benzene sulfonamide thol, naphthoxyacetic acid, potassium naphthenate, sodium (sold under the tradename penoXSulam), thifensulfuromethyl naphthenate, or 2,4,5-T ((2,4,5-trichlorophenoxy)acetic 15 (methyl-3-(4-methoxy-6-methyl-1,3,5-triazin-2-ylcarbam acid); cytokinins, such as 2iP (N'-(3-methylbut-2-enyl)ad oylsulfamoyl)-2-tanoate) and flazesulfuron (1-(4.6- enine or N-(3-methylbut-2-enyl)-1H-purin-6-amine), benzy dimethoxy pyrimidin-2-yl)-3-(3-trifluoromethyl-2- ladenine, kinetin, or Zeatin; defoliants such as calcium cyana pyridylsulfonyl)urea). Examples of dipyridyl-based mide, dimethipin, endothal, ethephon, merphos, metoXuron, herbicides include paraquat dichloride (1,1'-dimethyl-4,4'- pentachlorophenol, thidiaZuron, or tribufos; ethylene inhibi bipyridinium dichloride) and diguat dibromide (6,7-dihy tors. Such as aviglycine or 1-methylcyclopropene; ethylene drodipyride 1,2-a:2', 1'c-pyrazinediium dibromide). One releasers such as ACC (1-aminocyclopropanecarboxylic example of a diazine-based herbicide includes bromacil acid), etacelasil, ethephon, or glyoxime; gibberellins such as (5-bromo-3-sec-butyl-6-methyluracil). Examples of S-triaz gibberellins, gibberellin inhibitors such as trinexapac-ethyl, ine-based herbicides include gesatop (2-chloro-4,6-bis(ethy or gibberellic acid; growth inhibitors such as abscisic acid, 25 lamino)-1,3,5-triazine) and simetryn (2,4-bis(ethylamino)-6- ancymidol, butralin, carbaryl, chlorphonium, chlorpropham, methylthio-1,3,5-triazine). An example of nitrile-based dikegulac, flumetralin, fluoridamid, fosamine, glyphosine, herbicides includes DBN (2,6-dichlorobenzonitrile). isopyrimol, jasmonic acid, maleic hydrazide, mepiduat, Examples of dinitroaniline-based herbicides include triflura piproctanyl, prohydrojasmon, propham, or 2,3,5-tri-iodoben lin (C.O.C.-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine). Zoic acid; morphactins such as chlorfluren, chlorflurenol, 30 Examples of carbamate-based herbicides include thioben dichlorflurenol, or flurenol; growth retardants such as chlo carb (S-p-chlorobenzyl diethylthiocarbamate) and MCC rmeduat, daminozide, flurprimidol, mefluidide, paclobutra (methyl-3,4-dichlorocarbenylate). NIP (2,4-dichlorophenyl Zol, tetcyclacis, or uniconazole; growth stimulators such as p-nitro-phenyl ether) is an example of diphenyl ether-based brassinolide, forchlorfenuron, or hymexazol; and further herbicides. PCP (sodium pentachlorophenoxide) is an includes a variety of unclassified plant growth regulators such 35 example of a phenol-based herbicide. MDBA (3,6-dichloro as benzofluor, buminafos, carvone, ciobutide, clofencet, 2-methoxybenzoic acid dimethylamine salt) is an example of cloxyfonac, cyanamide, cyclanilide, cycloheximide, cypro a benzoic acid-based herbicide. Examples of phenoxy-based Sulfamide, epocholeone, ethychloZate, ethylene, fenridazon, herbicides include 2,4-D sodium salt (sodium 2,4-dichlo heptopargil, holoSulf, inabenfide, karetazan, lead arsenate, rophenoxyacetate), 2,4-D Esters, and mapica (4-chloro-o- methasulfocarb, prohexadione, pydanon, sintofen, triapen 40 toluyl)oxyaceto-o-chloroanilide. Examples of organic phos thenol, or trinexapac. phorus-based herbicides include Glyphosate (N- Specific embodiments of the present invention include MH (phosphonomethyl)glycinate, bialaphos (Sodium salt of L-2- (maleic hydrazide), ethephon (2-chloroethylphosphonic amino-4-(hydroxy(methyl)phosphinoyl-butylyl-alanyl-N- acid), Folex (S.S.S. tributyl phosphorothioate, Dropp (thidi alanine), and glufosinate (ammonium DL-homoalanin-4-yl aZuron), Pix (mepiduat chloride), and trinexapac-ethyl (sold 45 (methyl)phosphinate). TCA sodium salt (sodium under tradenames Primo or Primo Maxx). trichloronate) is an example of an aliphatic group-based her Any defoliating compound that is effective at defoliating a bicides. Hydrogen peroxide is another herbicide. desired plant can be used. Specific embodiments of defoliat In one embodiment, the herbicide used as the pesticide in ing agents include paraquat, diduat, endothall, chlorates, the composition of the present invention is a dipyridyl-based ethephon, tributylyphosphorthoate, cacodylic acid and its 50 herbicide or an organic phosphorus-based herbicides. In a sodium salt, MSMA, diuron, dimethipin, monocarbamide, further embodiment, the herbicide is an organic phosphorus carfentraZone, cyclanalide, and thidiaZuron. based herbicides. In a still further embodiment, the herbicide Herbicides is bialaphos, glufosinate, or glyphosate. Any herbicide that causes the desired result can be used. Acaricides Herbicides are generally broken down into broad categories, 55 Any suitable acaracide can be used. Examples of Suitable including pre-plant herbicides, burndown herbicides, and acaricides include Sumiito (2-tert-butyl-5-(4-tert-butylben post-emergence herbicides. Those of skill in the art appreci Zylthio)-4-chloropyridazine-3-(2H)-one), acricid (2,4-dini ate the appropriate use of Such compounds. tro-6-sec-butylphenyldimethylacrylate), chloromite (isopro There are several classes of post-emergent herbicides. pyl 4,4-dichlorobenzylate), Akar (ethyl 4,4'- These include: downwardly mobile herbicides, otherwise 60 dichlorobenzilate), kelthane (2.2.2trichloro-1,1-bis(p- referred to as symplastically translocated, namely leaf to chlorophenyl)-ethanol), citrazon (benzoic 3-chloro-N- growing points such as auxin growth regulators, including ethoxy-2,6-dimethoxybenzimidic anhydride), omite (2-(p- phenoxy derivatives, benzoic acid derivatives, picolinic acid tert-butylphenoxy)cyclohexyl propyn-2-yl Sulfite), osadan derivatives, amino acid inhibitors such as glyphosate, Sulfo (bistris(2-methyl-2-phenylpropyl)tinoxide), hexythiazox sate, Sulfonylureas, imidazolinones, Sulfonanalides, pigment 65 (trans-5-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2- inhibitors, grass meristem destroyers, otherwise known as oXothiazol-idine-3-carboxamide), and amitraz (N.N-bis(2,4- lipid biosynthesis inhibitors, such as aryloxyphenoxypropi Xylyliminomethyl)methylamine). US 9,028,856 B2 27 28 Disinfectants and Antibacterial Agents TABLE 2-continued Any Suitable disinfectant or antibacterial agent can be used. Examples of Suitable disinfectants/antibacterial agents Classification Representative Compounds include quaternary ammonium salts, captain alcohols, essen Dibenzyl maleate tial oils organic acids, triazines phenols, iodine, halo and nitro Methyl, ethyl, allyl, and benzyl esters of inoleic acid phenols, isothioZolones, terpenes, acridines, esters of para Gamma-linolenic acid hydroxybenzoic acid, aldehydes, aromatic diamidines, bigu Antioxidants, vitamins Ascorbic acid anidines, anionic Surfactants, nonionic Surfactants, betaines, Retinol quinones, quinolines, derivatives of 1.3 dioxane, derivatives Vitamin A 10 Vitamin C of imidazole, and derivatives of hexamine. Vitamin E II. Adjuvants Beta Caroteine Adjuvants useful in the present invention typically fall into Glutathione the general classifications shown below in Table 2. Table 3 Melatonion Ubiquinones sets forth examples of various active ingredients (AIs) and Oric Acid their respective ranges along with those of the adjuvants and 15 Flavenoids (e.g., leucocyanidin, the ratios of AI/adjuvant that were tested. catechin, epicatechin, kaempferol, rutin, quercitin) TABLE 2 Acids benzenepropanoic acid Oleic Classification Representative Compounds Linoleic Palmitic Dibasic esters such as Compound A, which may also be referred Cinnamic Acid Sebacates to as bis (1,2,2,6,6-pentamethyl-4- Alpha linolenic acid piperidinyl) sebacate and methyl Gamma-linolenic acid (1,2,2,6,6-pentamethyl-4-piperidinyl) Omega 3 acids EPA sebacate DHA sebacic acid dibenzyl ester 25 All-cis-7,10,13-hexadecatrienoic acid Other sebecate esters known as hindered ALA amine light stabilizers STD Bis-benzyl esters of carboxylic acids ETE Bis-monosubstituted benzyl esters of ETA dicarboxylic acids DPA Bis-disubstituted benzyl esters of 30 Additional Free Radical buprofen dicarboxylic acids Stabilizers Acetyl salicylic acid Bis-allyl esters of dicarboxylic acids Salicylic acid Bis-monosubstituted allyl esters of Methyl salicylate dicarboxylic acids Tetramethylsilane Bis-disubstituted allyl esters of Trimethylsilane dicarboxylic acids 35 N,N'-di-2-butyl-1,4-phenylenediamine 2,5-di-tert-butyl hydroquinine Dibenzyl carbonate 2.4dimethyl-6-tert-butyl phenol Bis-monosubstituted benzyl carbonates Carprofen Bis-disubstituted benzyl carbonates Naproxen Diallyl carbonate Ketoprofen Bis-monosubstituted allyl carbonates Allyl benzyl ether Bis-disubstituted allyl carboantes 40 Polyphenyl methanes diphenyl methane 2.4.6-Trihydroxyacetophenone triphenyl methane (Gomberg's trityl) 2.4.6-Trihydroxybenzaldehyde triphenyl methyl chloride (tritylchloride) 3,4,5-Trihydroxybenzamide Food grade preservatives BHA, butylated hydroxyanisole Resveratrol BHT, butylated hydroxytoluene Benzotriazole BHQ, butylated hydroxyquinone Surfactants Miranol types TBHQ, tertiary butyl dihydroxyquinone 45 Miritain types Propyl gallate Esters Methyl oleate Methyl linoleate Surprisingly, in Some embodiments, the activity of the Methyl palmitate compositions of the present invention considerably exceeds Ethyl oleate the additive activity of the individual components, namely there is synergism. TABLE 3 Insecticide Adjuvant Class Al Examples Alamount Adjuvant amount Al/Ad Ratio pyrethrums pyrethrins 0.003 g/m sebacates 0.005-0.512 g/m2 1:1.7-1:167 0.006 g/m 0.006-0.512 g/m 1:1-1:83 0.012 g/m· 0.512 g/m 1:42 0.003 g/m acids 0.051-0.512 g/m2 1:17-1:167 pyrethroids deltamethrin O.OOO32% Sebacates 1.00% 1:312S 0.0006 g/m 0.62 g/m· 1:1000 0.012 g/m 1:52 0.48 g/m 0.48 g/m 1:1 0.62 g/m’ 0.62 g/m· 1:1 permethrin 0.24 g/m sebacates 0.48 g/m 1:2 0.31 g/m 0.62 g/m 1:2 0.48 g/m’ 0.48 g/m· 1:1 0.60 g/m? 12:1 US 9,028,856 B2 29 TABLE 3-continued

Insecticide Adjuvant Class Al Examples Alamount Adjuvant amount All Adj Ratio resmethrin 0.31 g/m sebacates 0.62 g/m 1:2 0.62 g/m 1:1 chloronicotinyls imidacloprid 0.31 g/m acids 0.06-3.11 g/m· 5:1-1:10 eSeS 0.06-3.11 g/m 5:1-1:10 preservatives 0.06-3.11 g/m 5:1-1:10 polyphenyl 0.06-3.11 g/m· 5:1-1:2 methanes 0.006 g/m sebacates 3.75 g/m2 1:625 0.062-0.62 g/m2 0.06-3.11 g/m 5:1-1:10 0.022 g/m sebacates 0.002 g/m 10:1 0.004 g/m 5:1 0.011 g/m 2:1 thiamethoxam 0.006 g/m sebacates 0.62 g/m 1:100 0.062 g/m 1:10 0.62 g/m· 1:1 clothianidin 0.062 g/m sebacates 0.62 g/m 1:10 0.31 g/m 1:2 0.62 g/m· 1:1 pyrazoles fipronil 0.00006 g/m sebacates 0.0062-0.62 g/m 1:100-1:10000 0.00062 g/m2 1:10-1:1OOO 0.0062 g/m2 1:1-1:100 ethiprole 0.0062 g/m sebacates 0.0062-0.62 g/m 1:1-1:100 0.062 g/m? 1:10 0.62 g/m 1:1 carbamates bendiocarb 0.0512 g/m· acids 0.512 g/m? 1:10 eSeS preservatives Sebacates 0.0006-0.062 g/m sebacates 0.62 g/m 1:10-1:1000 carbaryl 0.0062-0.062 g/m sebacates 0.62 g/m 1:10-1:100 Botanical oils Rosemary + 0.007-0.75 g/m sebacates 0.006-0.62 g/m2 1:1 peppermint oils peanut oil 0.062 g/m· 0.62 g/m· 1:10

In one embodiment, the activity of the composition of the 35 adjuvant component. Furthermore, certain embodiments present invention provides a hastened effect compared to the comprise between about 0.05% and about 60% of the pesti pesticide, alone. cide component and between about 0.0025% and about 60% In one embodiment, the compositions allows for a lesser of the adjuvant component. Still further, certain embodiments amount of pesticide needed to result in an equivalent effect. comprise between about 0.1% and about 50% of the pesticide As will be demonstrated herein, the amount of adjuvant is an 40 component and between about 0.005% and about 50% of the amount effective to decrease the amount of active ingredient adjuvant component. required to achieve a comparable kill rate by at least around Thus, active ingredients may be used in varying amounts, 10%, at least around 20%, or at least around 30% or more. including as little as about 0.001%. As hereinabove In still another embodiment, the residual activity of the described, the ratio of pesticide: adjuvant provides a syner composition of the present invention exceeds the total of the 45 gistic kill rate and will vary from about 0.01:1 to about 1:100. residual activity of the individual components. III. Other Formulation Components As discussed herein, the pesticide component may also The formulations can also include additional components. comprise one or more fungicidally, acaricidally, or insecti The compositions of the present invention can be formu cidally active components, which also may be admixed. lated as Solutions, emulsions, wettable powders, Suspensions, The weight ratios of the components of the composition 50 powders, dusts, pastes, soluble powders, granules, Suspen may be varied within a relatively wide range. Sion-emulsion concentrates, natural and synthetic materials In general, the combinations according to the invention impregnated with pesticide, and microencapsulations in include a pesticide and an adjuvant, wherein the composition polymeric materials. provides a synergistic kill rate. In one embodiment, the pes These formulations are produced using known techniques ticide is present in a parts ratio as compared to adjuvant in an 55 in the art. One example includes mixing the components with amount of about 0.01 part of pesticide to up to about 100 parts extenders, that is, liquid solvents and/or Solid carriers, option of adjuvant. In another embodiment, the pesticide is an insec ally with the use of surfactants, that is, emulsifiers and/or ticide and is presentina parts ratio compared to adjuvant in an dispersants, and/or foam formers. If the extender used is amount of about 0.01 parts insecticide to up to 100 parts of water, it is also possible, for example, to use organic solvents adjuvant. Without implicit limitation, specific embodiments 60 as cosolvents. The following are examples of liquid solvents: include 0.01:1, 0.1:1, 1:1, 1:5, 1:10, 1:20, 1:50, and 1:100. aromatics such as Xylene, toluene or alkylnaphthalenes, chlo The formulations generally comprise between about rinated aromatics or chlorinated aliphatic hydrocarbons such 0.001% and about 80% by weight of a pesticide component as chlorobenzenes, chloroethylenes or methylene chloride, and between about 0.00005% and about 80% by weight of an aliphatic hydrocarbons such as cyclohexane or paraffins, for adjuvant component; and more specifically between about 65 example mineral oil fractions, mineral and vegetable oils, 0.01% and about 70% by weight of the pesticide component alcohols such as butanol or glycol and their ethers and esters, and between about 0.0005% and about 70% by weight of the ketones such as acetone, methyl ethylketone, methyl isobutyl US 9,028,856 B2 31 32 ketone or cyclohexanone, strongly polar solvents such as above 30°C., preferably above 45° C. can be replaced in part dimethyl-formamide and dimethyl sulphoxide, or else water. by organochemical solvents of high or medium Volatility, Solid carriers include, for example, ammonium salts and provided that the solvent mixture also has an evaporation ground natural minerals such as kaolins, clays, talc, chalk, number of above 35 and a flash point of above 30°C., pref quartz, attapulgite, montmorillonite or diatomaceous earth, erably above 45°C., and that the mixture is soluble or emul and ground synthetic materials such as highly-disperse silica, sifiable in this solvent mixture. alumina and silicates; Suitable Solid carriers for granules are: In one embodiment, some of the organochemical Solventor for example crushed and fractionated natural rocks Such as Solvent mixture is replaced by an aliphatic polar orga calcite, marble, pumice, Sepiolite and dolomite, or else Syn nochemical solvent or solvent mixture. Aliphatic orga thetic granules of inorganic and organic meals, and granules 10 of organic material Such as sawdust, coconut shells, maize nochemical solvents which contain hydroxyl or ester or ether cobs and tobacco stalks; Suitable emulsifiers and/or foam groups may be used. Such as, for example, glycol ethers, formers are: for example nonionic and anionic emulsifiers esters, or the like. Such as polyoxyethylene fatty acid esters, polyoxyethylene Organochemical binders used for the purposes of the fatty alcohol ethers, for example alkylaryl polyglycol ethers, 15 present invention are the synthetic resins or binding drying alkylsulphonates, alkyl Sulphates, arylsulphonates, or else oils which are known in the art and which can be diluted in protein hydrolysates; Suitable dispersants are: for example water or dissolved or dispersed or emulsified in the orga lignin-Sulphite waste liquors and methylcellulose. nochemical solvents employed, in particular binders com Tackifiers such as carboxymethylcellulose and natural and prising, an acrylate resin, a vinyl resin, for example polyvinyl synthetic polymers in the form of powders, granules or lati acetate, polyester resin, polycondensation or polyaddition ces, such as gum arabic, polyvinyl alcohol and polyvinyl resin, polyurethane resin, alkyd resin or modified alkyd resin, acetate, or else natural phospholipids such as cephalins and phenol resin, hydrocarbon resin Such as indene? coumarone lecithins and synthetic phospholipids can be used in the for resin, silicone resin, drying vegetable or drying oils or physi mulations. Other additives can be mineral and vegetable oils. cally drying binders based on a natural or synthetic resin. The compositions may include one or more colorants, such 25 The synthetic resin employed as binder can be employed in as inorganic pigments, for example iron oxide, titanium oxide the form of an emulsion, dispersion or Solution. Bitumen or and Prussian Blue, and organic colorants such alizarin colo bituminous Substances may also be used as binders, in rants, azo colorants and metal phthalocyanine colorants, and amounts of up to 10% by weight. In addition, colorants, trace nutrients such as salts of iron, manganese, boron, cop pigments, water repellants, odour-masking agents, and per, cobalt, molybdenum and zinc. 30 inhibitors or anticorrosive agents and the like, all of which are The compositions may be composed of mixtures of pesti known perse, can be employed. cides, such as insecticides, attractants, sterilants, bacteri In accordance with the invention, the composition or the cides, acaricides, nematicides, fungicides, growth-regulating concentrate preferably comprises, as organochemical bind substances, or herbicides. The insecticides include, for ers, at least one alkyd resin or modified alkyd resin and/or a example, phosphates, carbamates, carboxylates, chlorinated 35 drying vegetable oil. hydrocarbons, phenylureas and Substances produced by Some or all of the abovementioned binder can be replaced microorganisms. Mixtures with other known active com by a fixative (mixture) or plasticizer (mixture). These addi pounds such as herbicides or with fertilizers and growth regu tives are intended to prevent volatilization of the active com lators are also possible. pounds, and also crystallization or precipitation. A suitable solvent or diluent is an organochemical Solvent 40 The plasticizers, for use as a plasticizer and not as an or solvent mixture or an oily or oil-type organochemical adjuvantas herein described, are from the chemical classes of solvent or solvent mixture of low volatility or a polar orga the phthalic esters, such as dibutyl phthalate, dioctyl phtha nochemical Solvent or solvent mixture or water and, if appro late or benzylbutyl phthalate, phosphoric esters such as tribu priate, an emulsifier or wetter. tyl phosphate, adipicesters such as di-(2-ethylhexyl)-adipate, Organochemical solvents which are preferably employed 45 Stearates such as butyl Stearate or amyl Stearate, oleates Such are oily or oil-type solvents with an evaporation number of as butyl oleate, glycerol ethers or higher-molecular-weight above 35 and a flash point of above 30°C., preferably above glycol ethers, glycerol esters and p-toluenesulphonic esters. 45° C. Such oily and oil-type solvents which are insoluble in Fixatives are based chemically on polyvinyl alkyl ethers water and of low volatility and which are used are suitable Such as, for example, polyvinyl methyl ether, or ketones Such mineral oils or their aromatic fractions or mineral-oil-con 50 as benzophenone and ethylenebenzophenone. taining solvent mixtures, preferably white spirit, petroleum Other suitable solvents or diluents are, in particular, water, and/or alkylbenzene. Representative solvents include if appropriate as a mixture with one or more of the above acetone, chloroform, ethanol, ethyl acetate, n-hexane, metha mentioned organochemical Solvents or diluents, emulsifiers nol, methylene chloride, toluene, and Xylene. and dispersants. Mineral oils with a boiling range of 170 to 220°C., white 55 In addition to the pesticides, other agents can benefit from spirit with a boiling range of 170 to 220°C., spindle oil with the enhanced penetration into the plant or insect cuticle. a boiling range of 250 to 350° C., petroleum and aromatics Examples include transfection agents and DNA desired to be with a boiling range of 160 to 280°C., oil of terpentine, and transfected into the plant, wood treatment chemicals, and the like are advantageously used. disinfectants and antibacterial agents. In one embodiment, the solvent may be a liquid aliphatic 60 There are numerous known transfection agents, any of hydrocarbons with a boiling range of about 180° C. to about which can be used in the compositions described herein. The 210° C., high-boiling mixtures of aromatic and aliphatic transfection agents are used in combination with genetic hydrocarbons with a boiling range of about 180° C. to about material to be transfected into a cell, and optionally, an appro 220° C., spindle oil, or monochloronaphthalene, Such as priate vector, for example, an adenoviral vector. The genetic C-monochloronaphthalene. 65 material can be any genetic material capable of effecting a The organic oily or oil-type solvents of low volatility and desired alteration in the plant genetic code, and can be in the with an evaporation number of above 35 and a flash point of form of a plasmid. The genetic material is preferably DNA. US 9,028,856 B2 33 34 Any wood treatment chemical capable of inhibiting cophaea maderae, Blattella germanica; from the order of the destruction of wood by termites, fungus, mold and the like Dernaptera, for example, Forficula auricularia; from the can be used. Examples of suitable wood treatment chemicals order of the Isoptera, for example, Reticulitermes spp.; from include CCA, polyethylene glycol, fungicides, termiticides, the order of the Phthiraptera, for example, Pediculus humanus and known fungicides. corporis, Haematopinus spp., Linognathus spp., Tri The compositions of the present invention may include one chodectes spp., Damalinia spp.; from the order of the Thys or more attractant. Attractants are inertingredients that entice anoptera, for example, Hercinothrips femoralis, Thrips a pest. Such as an insect to approach the bait, to touch the bait, tabaci, Thrips palmi, Frankliniella occidentalis; from the to consume the bait, and/or to return to the bait. Inert ingre order of the Heteroptera, for example, Eurygaster spp., Dys dients that are able to achieve these goals belong to the group 10 of food attractants and non-food attractants. dercus intermedius, Piesma quadrata, Cimex lectularius, The following may be mentioned by way of example as Rhodnius prolixus, Triatoma spp.; from the order of the food attractants: water, cereal powders such as wheat powder, Homoptera, for example, Aleurodes brassicae, Bemisia maize powder, malts, powder, rice powder, rice bran and the tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevico like, starches such as potato starch, maize starch, and the like, 15 ryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Sugars such as Sucrose, maltose, arabinose, galactose, lactose, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera Sorbitose, glucose, fructose, Sorbitol, corn syrup, maple vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., syrup, coca cola syrup, invert Sugars (Invertix), molasses, Phorodon humuli, Rhopalosiphum padi, Empoasca spp., honey and the like, and glycerol and the like. Proteins such as Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, meat, meat extracts, meat flavours and milk powder, fish Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, meal, fish extracts or fish flavour, sea food, sea food extracts Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., or seafood flavour, yeast, yeast extract and yeast, flavour and Psylla spp.; from the order of the Lepidoptera, for example, the like. Fruits such as apple, apricot, banana, blackberry, Pectinophora gossypiella, Bupalus piniarius, Cheinatobia cherry, currant, gooseberry, grapefruit, raspberry, strawberry brumata, Lithocolletis blancardella, Hyponomeuta padella, (pure, syrup or extract). Fats and oils such as Vegetable oils 25 Plutella xylostella, Malacosoma neustria, Euproctis chrysor from e.g. corn, olive, caraway, peanut, Sesame oil, soybean, rhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnis sunflower, animal derived fats and fish derived oils and the tis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insu like. These baiting Substances can be used alone or as a lana, Heliothis spp., Mamestra brassicae, Panolis flammea, mixture of two or more in any ratio. Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, The following may be mentioned by way of example as 30 Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kueh non-food attractants: alcohols such as benzyl alcohol, niella, Galleria mellonella, Tineola bisselliella, Tinea pel butanol, decanol, ethanol, glycerin, hexanol and isobutanol: lionella, Hofmannophila pseudospretella, Cacoecia podana, pheromones such as (Z)-9-Tricosene (also known as musca Capua reticulana, Choristoneura filmiferana, Clysia ambig lure), a product referred to under the trade name LEJ 179, uella, Homona magnanima, Tortrix viridana, Cnaphalocerus which is a mixture of n-butyric acid, muscalure, and at least 35 spp., Oulema oryzae; from the order of the Coleoptera, for one fatty acid component. Attractants which further may be example, Anobium punctatum, Rhizopertha dominica, mentioned by way of example are fatty acids such as caprylic Bruchidius Obtectus, Acanthoscelides Obtectus, Hylotrupes acid, caproic acid, capric acid, lauric acid, oleic acid and the bajulus, Agelastica alni, Leptinotarsa decemlineata, Phae like, higher alcohols such as octyl alcohol, dodecyl alcohol, don cochleariae, Diabrotica spp., Psylliodes chrysocephala, oleyl alcohol and the like, and natural and artificial flavours 40 Epillachna varivestis, Atomaria spp., Oryzaephilus Surina such as onion flavour, milk flavour, butter flavour, cheese mensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sul flavour, and the like. These attractants can be used alone or as catus, Cosmopolites Sordidus, Ceuthorrhynchus assimilis, a mixture of two or more in any ratio. Preferred non-food Hypera postica, Dernestes spp., Trogoderma spp., Anthrenus attractants are alcohol, pheromones, and flavours. spp., Attagenus spp., Lyctus spp., Melligethes aeneus, Ptinus IV. Pests That Can be Treated 45 spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., The compositions of the present invention are suitable for Tenebrio molitor; Agriotes spp., Conoderus spp., Melolontha controlling pests, preferably arthropods, nematodes, and melolontha, Amphimallon solstitialis, Costelytra zealandica, arachnids, in particular insects and arachnids found in agri Lissorhoptrus Oryzophilus; from the order of the culture, in animal health, inforests, in the protection of stored Hymenoptera, for example, Diprion spp., Hoplocampa spp., products, in homes and businesses, in materials, and in the 50 Lasius spp., Monomorium pharaonis, Vespa spp.; from the hygiene sector. order of the Diptera, for example, Aedes spp., Anopheles spp., The compositions of the present invention are believed to Culex spp., Drosophila melanogaster; Musca spp., Fannia be active against normally sensitive and resistant species, and spp., Caliphora erythrocephala, Lucilia spp., Chrysomyia against all or individual developmental stages. The present spp., Cuterebra spp., Gastrophilus spp., Hippobosca spp., invention is useful against the following pests: from the order 55 Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., of the Isopoda, for example, Oniscus asellus, Armadillidium Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., vulgare, Porcellio scaber; from the order of the Diplopoda, Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula for example, Blaniulus guttulatus; from the order of the paludosa, Hvlemyia spp., Liriomyza spp.; from the order of Chilopoda, for example, Geophilus carpophagus, Scutigera the Siphonaptera, for example, Xenopsylla cheopis, Cerato spp.; from the order of the Symphyla, for example, Scutiger 60 phyllus spp.; and from the class of the Arachnida, for ella immaculate; from the order of the Thysanura, for example, Scorpio maurus, Latrodectus mactans, Acarus Siro, example, Lepisma saccharina; from the order of the Collem Argas spp., Ornithodoros spp., Dermanyssus gallinae, Erio bola, for example, Onychiurus armatus; from the order of the phyes ribis, Phylocoptruta oleivora, Boophilus spp., Rhipi Orthoptera, for example, Acheta domesticus, Gryllotalpa cephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Locusta migratoria migratorioides, Melanoplus spp., 65 spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarson Schistocerca gregaria; from the order of the Blattaria, for emus spp., Bryobia praetiosa, Panonychus spp., Tetranychus example, Blatta Orientalis, Periplaneta americana, Leu spp., Hemitarisonemus spp., Brevipalpus spp. US 9,028,856 B2 35 36 Plant-parasitic nematodes include, for example, Pratylen and Ischnocerina, for example, Trimenopon spp., Menopon chus spp., Radopholus similis, Dity lenchus dipsaci, Tvlen spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepi chulus semipenetrans, Heterodera spp., Globodera spp., kentron spp., Damalina spp., Trichodectes spp., Felicola spp.; Meloidogyne spp., Aphelenchoides spp., Longidorus spp., from the order Diptera and the suborders Nematocerina and Xiphinema spp., Trichodorus spp., Bursaphelenchus spp. Brachycerina, for example, Aedes spp., Anopheles spp., When treating a building for pest infestation, particularly Culex spp., Simulium spp., Eusimulium spp., Phlebotomus by treating non-porous Surfaces within or around the build spp., Lutzomyia spp., Culicoides spp., Chrysops spp., ing, representative pests include: from the order of the Scor Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota pionidea, for example, Buthus Occitanus. From the order of spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea the Acarina, for example, Argas persicus, Argas reflexus, 10 spp., Stomoxys spp., Haematobia spp., Morelia spp., Fannia Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesti spp., Glossina spp., Caliphora spp., Lucilia spp., Chry cus, Ornithodorus moubat, Rhipicephalus sanguineus, Trom somyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus bicula alfreddugesi, Neutrombicula autumnalis, Der spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., matophagoides pteronissimus, Dermatophagoides forinae; Lipoptena spp., Mellophagus spp.; from the order of the from the order of the Araneae, for example, Aviculariidae, 15 Siphonapterida, for example, Pulex spp., Ctenocephalides Araneidae: from the order of the Opiliones, for example, spp., Xenopsylla spp., Ceratophyllus spp.; from the order of Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, the Heteropterida, for example, Cimex spp., Triatoma spp., Opiliones phalangium; from the order of the Isopoda, for Rhodnius spp., Panstrongylus spp.; from the order of the example, Oniscus asellus, Porcellio scaber; from the order of Blattarida, for example, Blatta Orientalis, Periplaneta ameri the Diplopoda, for example, Blaniulus guttulatus, Polydes cana, Blattelagermanica, Supella spp.; from the Subclass of mus spp. From the order of the Chilopoda, for example, the Acaria (Acarida) and the order of the Meta- and Mesos Geophilus spp.; from the order of the Zygentoma, for tigmata, for example, Argas spp., Ornithodorus spp., Otobius example, Ctenolepisma spp., Lepisma saccharina, Lepis spp., Ixodes spp., Amblyomma spp., Boophilus spp., Derma modes inquilinus; from the order of the Blattaria, for example, centor spp., Haemophysalis spp., Hyalomma spp., Rhipi Blatta Orientalies, Blattella germanica, Blattella asahinai, 25 cephalus spp., Dermanyssus spp., Raillietia spp., Pneu Leucophaea maderae, Panchlora spp., Parcoblatta spp., monyssus spp., Sternostoma spp., Varroa spp.; and from the Periplaneta australasiae, Periplaneta americana, Periplan order of the Actinedida (Prostigmata) and Acaridida (AStig eta brunnea, Periplaneta fuliginosa, Supella longipalpa. mata), for example, Acarapis spp., Cheyletiella spp., Orni From the order of the Saltatoria, for example, Acheta domes thochevletia spp., Myobia spp., Psorergates spp., Demodex ticus; from the order of the Dermaptera, for example, For 30 spp., Trombicula spp., Listrophorus spp., Acarus spp., ficula auricularia; from the order of the Isoptera, for example, Trophagus spp., Caloglyphus spp., Hypodectes spp., Pteroli Kalotermes spp., Reticulitermes spp.; from the order of the chus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Psocoptera, for example, Lepinatus spp., Liposcelis spp.; Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cyto from the order of the Coleptera, for example, Anthrenus spp., dites spp., Laminosioptes spp. Attagenus spp., Dermestes spp., Latheticus Oryzae, Necrobia 35 The compositions described herein are also suitable for spp., Ptinus spp., Rhizopertha dominica, Sitophilus grana controlling arthropods which attack agricultural livestock rius, Sitophilus Oryzae, Sitophilus zeanais, Stegobium pan Such as, for example, cattle, sheep, goats, horses, pigs, don iceum; from the order of the Diptera, for example, Aedes keys, camels, buffaloes, rabbits, chickens, turkeys, ducks, aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles geese, honeybees, other domestic animals such as, for spp., Caliphora erythrocephala, Chrysozona pluvialis, 40 example, dogs, cats, birds, fish, hamsters, guinea pigs, rats, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, and mice. By controlling these arthropods, cases of death and Drosophila spp., Fannia canicularis, Musca domestica, Phle reductions in productivity, including for meat, milk, wool, botomus spp., Sarcophaga Camaria, Simulium spp., Stomoxy's hides, eggs, honey, and the like, could be diminished, so that calcitrans, Tipula paludosa; from the order of the Lepi more economical and simpler animal husbandry is possible doptera, for example, Achroia grisella, Galleria mellonella, 45 by the use of the active compound combinations according to Plodia interpunctella, Tinea cloacella, Tinea pellionella, the invention. Tineola bisselliella; from the order of the Siphonaptera, for When used for cattle, poultry, domestic animals and the example, Ctenocephalides canis, Ctenocephalides felis, like, the active compound combinations can be applied as Pulex irritans, Tunga penetrans, Xenopsylla cheopis; from formulations (for example powders, emulsions, flowables) the order of the Hymenoptera, for example, Camponotus 50 comprising the active compounds, either directly or after herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbra dilution, or they may be used as a chemical dip. tus, Monomorium pharaonis, Paravespula spp., Tetramorium Moreover, the compositions described herein show a caespitum; from the order of the Anoplura, for example, potent insecticidal action against insects which destroy indus Pediculus humanus capitis, Pediculus humanus corporis, trial materials. The following insects may be mentioned by Phthirus pubis; and from the order of the Heteroptera, for 55 way of example and with preference, but not by way of example, Cimex hemipterus, Cimex lectularius, Rhodinus limitation: Beetles Such as Hylotrupes bajulus, Chlorophorus prolixus, Triatoma infestans. pilosis, Anobium punctatum, Xestobium rufo villosum, Ptili The compositions described herein are not only active nus pecticonis, Dendrobium pertinex, Emobius mollis, Prio against plant pests, hygiene pests, stored-product pests, and bium carpini, Lyctus brunneus, Lyctus africanus, Lyctus pla household pests, but also, in the Veterinary medicine sector, 60 nicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon againstanimal parasites, including ectoparasites. Such as hard aequale, Minthes rugicollis, Xvleborus spec. Tryptodendron ticks, soft ticks, mange mites, harvest mites, flies, including spec. Apate monachus, Bostrychus capucins, Heterobostry stinging and licking, parasitizing fly larvae, lice, hair lice, bird chus brunneus, Sinoxylon spec., Dinoderus minutus; Der lice, and fleas. These parasites include: from the order of the mapterans such as Sirex juvencus, Urocerus gigas, Urocerus Anoplurida, for example, Haematopinus spp., Linognathus 65 gigas taignus, Urocerus augur, Termites Such as Kalotermes spp., Pediculus spp., Phtirus spp., Solenopotes spp.; from the flavicollis, Cryptoternes brevis, Heterotermes indicola, Reti order of the Mallophagida and the suborders Amblycerina culitermes flavipes, Reticulitermes Santonensis, Reticuliter US 9,028,856 B2 37 38 mes lucifiugus, Mastotermes darwiniensis, Zootermopsis liquid evaporators, gel and membrane evaporators, propeller nevadensis, Coptotermes formosanus; and Bristle-tails such driven evaporators, energy-free, or passive, evaporation sys as Lepisma saccharina. Particularly, representative insects to tems, moth papers, moth bags and moth gels, as granules or be combated or controlled by the compositions described dusts, in baits for spreading or in bait stations. herein include Order Isoptera, Mastotermitidae, Kalotermiti The plants and parts of plants can be treated with the dae such as Kalotermes spp., Cryptotermes spp. etc., Termop compositions directly or by action on their environment, sidae such as Zootermopsis spp. etc., Rhinotermitidae such as habitat or storage area according to customary treatment Reticulitermes spp. Heterotermes spp., Coptotermes spp. methods, for example by dipping, spraying, evaporating, etc., Termitidae such as Amitermes spp., Nasutitermes spp., atomizing, broadcasting, brushing-on and, immersion, spray Acanthotermes spp., Mikrotermes spp. etc., Order 10 ing, evaporation, fogging, scattering, painting on and, in the Coleoptera, Lyctidae such as Lyctus brunneus etc., Bostry case of propagation material, in particular in the case of seeds, chidae such as Bostrychus capucinus, Dinoderus minutus furthermore by one- or multi-layer coating. A particularly etc.. Anobiidae such as Anobium punctatum, Xyletinus pelta preferred method of application is to apply the compositions tus, Xestobium rufo villosum, Ptilinus pectinicomis etc., Cer to the roots, either directly or though administration to the ambycidae Such as Hylotrupes bajulus, Hesperophanus 15 soil. In this manner, uptake of the active agricultural chemi cinereus, Stromatium filvum, Chlorophorus pilosus etc., cals is significantly faster than if no free radical stabilizers Oedemeridae, Serropulpidae, Curculionidae, Seolytida, and/or plasticizers are used. Platypodidae, Order Hymenoptera, Siricidae such as Sirex As already mentioned above, it is possible to treat all plants spp., Urocerus spp., or Formicidae such as Camponotus spp., and their parts according to the invention. In a preferred In the above Isopterous insects, especially, there may be embodiment, wild plant species and plant cultivars, or those mentioned as examples of termites in Japan: Deucotermes obtained by conventional biological breeding methods. Such speratus, Coptotermes formosanus, Glyptotermes fircus, as crossing or protoplast fusion, and parts thereof, are treated. Glyptotermes satsumensis, Glyptotermes nakajimai, Glypto In a further preferred embodiment, transgenic plants, and termes Kodanai, Incisitermes minor, Neotermes koshunen plant cultivars obtained by genetic engineering, if appropriate sis, Cryptotermes domesticus, Hodotermopsis japonica, Reti 25 in combination with conventional methods, and parts thereof culitermes miyatakei, Odontotermes formosanus, are treated. Nasutitermes takasagoensis, Capritermes initobei, and the The treatment results in Synergistic effects: namely one or like. more of (i) enabling one to use reduced application rates; (ii) V. Application of Pesticide/Adjuvant Combinations widening of the activity spectrum; (iii) an increase in the The combinations of pesticides and adjuvants described 30 activity of the Substances and compositions which can be herein can be administered in a similar manner to how pesti used; (iv) better plant growth; (v) increased tolerance to high cides are commonly administered, to plants, to locations or low temperatures; (vi) increased tolerance to drought or to where insects are likely to be found, and in aerosol applica water or soil salt content; (vii) increased flowering perfor tions. mance; (viii) easier harvesting; (ix) accelerated maturation; As one example, traps are well known in the art for con 35 (X) higher harvestyields; (xi) better quality; (xii) higher nutri trolling pest populations. They typically include a chemical tional value of the harvested products; (xiii) better storage that attracts a desired insect, for example, a pheremone or stability; and (xiv) better processability of the harvested prod other insect attractant, and also typically includean pesticide. ucts. Also, the active compounds in the compositions can Traps are well known for use in controlling populations of show increased residual activity. burrowing insects, flying insects, or crawling insects, for 40 Exemplary crop plants include cereals (wheat, rice), maize, example, roaches, ants, Japanese beetles, termites, mosqui Soya beans, potatoes, cotton, tobacco, oilseed rape, and also toes, and many other insects. The traps may further include a fruit plants (apples, pears, citrus fruits, and grapes), and par permeabilizer to enhance the ability of the insecticide to ticular emphasis is given to maize, soya beans, potatoes, control the insects. cotton, tobacco, and oilseed rape. VI. Use of the Compositions to Treat a Crop Locus 45 VII. Use of the Compositions for Pest Infestation According to the invention, it is possible to treat all plants The active compound combinations are also suitable for and parts of plants. Plants are to be understood here as mean controlling pests, in particular insects, arachnids and mites, ing all plants and plant populations such as desired and undes which are found in enclosed spaces such as, for example, ired wild plants or crop plants, including naturally occurring dwellings, factory halls, offices, vehicle cabins, and the like. crop plants. Crop plants can be plants which can be obtained 50 They can be employed in domestic insecticide products for by conventional breeding and optimization methods or by controlling these pests. They are active against sensitive and biotechnological and genetic engineering methods or combi resistant species and against all developmental stages. nations of these methods, including the transgenic plants and The compositions can be used as aerosols, pressure-free including the plant cultivars which can or cannot be protected spray products, for example pump and atomizer sprays, auto by plant breeders certificates. Parts of plants are to be under 55 matic fogging Systems, foggers, foams, gels, evaporator prod stood as meaning all above-ground and below-ground parts ucts with evaporator tablets made of cellulose or polymer, and organs of plants, such as shoot, leaf flower and root, liquid evaporators, gel and membrane evaporators, propeller examples which may be mentioned being leaves, needles, driven evaporators, energy-free, or passive, evaporation sys stems, trunks, flowers, fruit-bodies, fruits and seeds and also tems, moth papers, moth bags and moth gels, as granules or roots, tubers and rhizomes. Parts of plants also include har 60 dusts, in baits for spreading or in bait stations. Vested plants and vegetative and generative propagation Ideally, the compositions are applied to non-porous Sur material, for example seedlings, tubers, rhizomes, cuttings faces, so that the active compounds remain present at the and seeds. Surface. The compositions are extremely effective against The compositions can be used as aerosols, pressureless insects that drag portions of their bodies along a surface, in spray products, for example pump and atomizer sprays, auto 65 particular, crawling insects. matic fogging Systems, foggers, foams, gels, evaporator prod In one embodiment, the compositions are applied to non ucts with evaporator tablets made of cellulose or polymer, porous tile (i.e., glazed tile). As shown in various working US 9,028,856 B2 39 40 examples below, the compositions typically show enhanced enes and methylene chloride, aliphatic or alicyclic hydrocar efficacy when applied to glazed versus unglazed tiles. bons, such as cyclohexane or paraffins, for example, mineral The compositions can also be used in spray applications, or oil fractions, alcohols, such as butanol or glycol as well as applied to screens or other places where flying insects are their ethers and esters, ketones, such as acetone, methyl ethyl prone to land, in order to provide effective control of flying ketone, methyl isobutyl ketone or cyclohexanone, or strongly insects. The components of a conventional aerosol spray for polar solvents, such as dimethylformamide and dimethylsul mulation can be used with the combinations of active agents foxide, as well as water. and adjuvants described herein. By liquefied gaseous diluents or carriers are meant liquids The material which is to be protected from insect attack is which are gaseous at normal temperature and under normal very especially preferably wood and timber products. Wood 10 pressure, for example, aerosol propellants, such as haloge and timber products which can be protected by the composi nated hydrocarbons as well as butane, propane, nitrogen and tion according to the invention, or mixtures comprising it, are carbon dioxide. to be understood as meaning, for example: Construction tim As solid diluents there may be used ground natural miner ber, wooden beams, railway sleepers, bridge components, als, such as kaolins, clays, talc, chalk, quartz, attapulgite, jetties, vehicles made of wood, boxes, pallets, containers, 15 montmorillonite or diatomaceus earth, and ground synthetic telephone poles, wood lagging, windows and doors made of minerals, such as highly-dispersed silicic acid, alumina and wood, plywood, chipboardjoinery, or timber products which silicates. quite generally are used in house construction or building AS Solid carriers for granules there may be used crushed joinery. and fractionated natural rocks such as calcite, marble, pum The active compound combinations can be used as such, in ice, Sepiolite and dolomite, as well as synthetic granules of the form of concentrates or generally customary formulations inorganic and organic meals, and granules of organic material Such as powders, granules, Solutions, Suspensions, emulsions Such as sawdust, coconut shells, maize cobs and tobacco or pastes. The compound combinations can be applied to the stalks. materials by spraying, dipping, or other means. AS emulsifying and/or foam-forming agents there may be The above-mentioned formulations can be prepared in a 25 used nonionic and ionic emulsifiers. Such as polyoxyethyl manner known to those of skill in the art, for example, by ene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, mixing a pesticide with an effective amount of an adjuvant, for example, alkylaryl polyglycol ethers, alkylsulfonates, along with at least one solvent or diluent, emulsifier, dispers alkylsulfates, arylsulfonates as well as albumin hydrolysis ant, binder, or fixative, water repellant, if desired, desiccants, products. Dispersing agents include, for example, lignin and, if desired colorants and pigments and other processing 30 Sulfite waste liquors and methyl cellulose. auxiliaries. Adhesives such as carboxymethyl cellulose and natural Particularly effective timber protection is achieved by and synthetic polymers, (such as gum arabic, polyvinyl alco industrial-scale impregnating processes, for example the hol and polyvinyl acetate) can be used in the formulations in vacuum, double-vacuum or pressure processes. the form of powders, granules or emulsifiable concentrations. In one embodiment, the invention relates to the use of 35 It is possible to use colorants such as inorganic pigments, combinations of pesticidal compounds and adjuvants to com for example, iron oxide, titanium oxide and Prussian Blue, bat insects, for example, termites, that are known to destroy and organic dyestuffs, such as alizarin dyestuffs, azo dye technical materials, such as wood. In some embodiments, stuffs or metal phthalo-cyanine dyestuffs, and trace elements, depending on the pesticidal compounds, or the addition of Such as salts of iron, manganese, boron, copper, cobalt, other compounds, the technical materials can be protected not 40 molybdenum and zinc. only against insects, but also against fungi, bacteria, and In order to protect the above-mentioned materials against algae. In some embodiments, the compositions are also useful fungi, bacteria and algae, they can be treated with composi for treating soil to protect technical materials against termite tions may further contain at least one biological active fungi infestations. cide, bactericide, or algizide. Different pests are known to infest technical materials, so 45 Exemplary fungicides include compounds and biological that due to serious damage is caused. This produces undesir Substances, including trihalosulfenyl-Compounds such as able effects on the living environment and cultural assets N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenyl-sul principally made of these materials have posed a social prob furic acid diamide (Dichlofluanide), N-dichlorofluorometh lem, urgently requiring effective controlling of the pests. ylthio-N',N'-dimethyl-N-p-toluylsulphamide (Tolylflu Termites are known as important examples of these pests. 50 anide), N-trichloromethylthiophthalimide (Folpet), The active compounds can be prepared into the customary N-dichlorofluoromethylthiophthalimide (Fluorfolpet), and formulations, such as Solutions, emulsions, Suspensions, the like, iodine-compounds Such as 3-iodo-2-propynyl-butyl powders, foams, pastes, granules, aerosols, natural and Syn carbamate (IPBC), 3-iodo-2-propynyl-hexylcarbamate, thetic materials impregnated with active compounds, and 3-iodo-2-propynyl-cyclohexylcarbamate, 3-iodo-2-propy micro-capsules. 55 nyl-phenylcarbamate, diiodimethyl-p-tolylsulphone (Amical These formulations may be produced in a known manner, 48), and the like, phenols such as ortho-phenylphenol, tribro for example, by mixing the active compounds with extenders, mophenol, tetrachlorophenol, pentachlorophenol, and the that is to say liquid or liquefied gaseous or Solid diluents or like, azole-compounds such as 1-(4-chlorophenoxy)-3.3- carriers, optionally with the use of Surface-active agents, that dimethyl-1-(1H-1.2.4 triazol-1-yl)-2-butanone (Triadime is to say emulsifying agents, dispersing agents, and/or foam 60 fon), beta-(4-chlorophenoxy)-alpha-(1,1 dimethyl-ethyl)- forming agents. In the case of using water as an extender, 1H-1.2.4 triazole-1-ethanol (Triadimenol), +/-alpha2-(4- organic solvents can, for example, also be used as auxiliary chlorophenyl)ethylalpha-(1,1-dimethylethyl)-1H-1,2,4- Solvents. triazole-1-ethanol (Tebuconazole), 1-2(2,4-dichlorophenyl) As liquid diluents or carriers can be mentioned, for 4-propyl-1,3-dioxolan-2-ylmethyl)-1H-1,2,4-triazole example, aromatic hydrocarbons, such as Xylene, toluene and 65 (Propiconazol), 1-2(2,4-dichlorophenyl)-1,3-dioxolan-2-yl alkyl naphthalenes, chlorinated aromatic or chlorinated ali methyl)-1H-1,2,4-triazole (AZaconazol), (RS)-2(2,4-dichlo phatic hydrocarbons, such as chlorobenzenes, chloroethyl rophenyl)-1-(1H-1.2.4 triazol-2-yl)-2-ol (Hexaconazol), US 9,028,856 B2 41 42 1-N-propyl-N-2-(2,4,6-trichlorophenoxy)ethylcarbam EXAMPLES oylimidazol (ProchloraZ), and the like, tin compounds such as tributyl tin octoate, tributyl tin oleate, bistributyl tin oxide, As will be appreciated by those skilled in the art, the tributyl tin naphthenate, tributyl tin phosphate, tributyl tin following examples are representative of the present inven benzoate, and the like, thiocyanate Compounds such as meth tion. All formulations herein described may be further opti ylenebisthiocyanate (MBT), 2-thiocyanomethylthioben mized, as all such further development should be considered Zothiazole (TCMTB), and the like, quarternary ammonium within the scope of the present invention. compounds such as benzyl-dimethyl-tetradecylammonium The pesticidal action of the compositions described herein chloride, benzyl-dimethyl-dodecylammoniumchloride, and can be seen from the examples which follow. While the indi the like: Benzimidazole compounds such as 2-(2-Furyl)-1H 10 vidual active compounds may show weaknesses in their benzimidazole (Fuberidazole), Methylbenzimidazol-2-yl action as an individual agent, the combination shows a syn carbamate (BCM), 2-(41-thiazolyl)benzimidazole (Thia ergistic action, namely that which exceeds a simple sum of bendazole), Methyl(1-butylcarbamoyl)-2-benzimidazole actions. carbamate (Benomy1), Isothiazolinone compounds Such as Given that many of the adjuvants, preferably free radical N-Methylisothiazolin-3-one. 5-Chloro-N-methylisothiazo 15 stabilizers, have no pesticidal properties of their own, any lin-3-one, 4,5-Dichloro-N-octylisothiazolin-3-one, N-Octyl increase in activity of the pesticide when combined with the isothiazolin-3-one, Morpholine compounds such as C14 free radical stabilizer is due to synergy with the free radical C11-4-Alkyl-2,6-dimethylmorpholine (Tridemorph), stabilizer. Pyridine compounds Such as 1-Hydroxy-2-pyridine-thione The action for a combination of two compounds can be and Sodium Iron, Manganese or Zinc-Salt thereof, Tetra calculated as follows, using the formula of S. R. Colby, Weeds chloro-4-methyl sulphonyl pyridine, N-Cyclohexyldiazini 15 (1967), 20-22, herein incorporated by reference: umdioxy compounds such as Tris-(N-cyclohexyldiazinium dioxy)aluminium, Bis-(N-cyclohexyldiaziniumdioxy) E-XY (X times Y 100 copper, Naphthenate compounds such as Zinc naphthenate, where Quinoline compounds Such as the copper salt of 8-hydroxy 25 X is efficacy, expressed as % of the untreated control, when quinoline, Nitriles such as 1,2,3,5-Tetrachloro-4,6-cy employing a first compound at an application rate of mg/ha anobenzene, Boric compounds such as boric acid, borax, or in a concentration of m ppm, borates, Ureas such as N'(3,4-dichlorophenyl)-N,N-dimethy Y is efficacy, expressed as % of the untreated control, when lurea, Furane derivatives such as FurmecycloX. employing a second compound at an application rate of m These fungicidally-effective substances are added to the 30 g/ha or in a concentration of m ppm, and composition to protect against wood-discoloring fungi such E is efficacy, expressed as % of the untreated control, when as Ascomycetes (Caratocystis minor), Deuteromycetes (As employing a combination of the first and second com pergillus niger, Aureobasidium pullulans, Dactyleum fitsari pounds at application rates of mand ng/ha or in a concen oides, Penicillium Variabile, Sclerophoma pithyophila, tration of m and n ppm. Scopularia phycomyces, Trichoderma viride, Trichoderma 35 If the actual pesticidal kill rate exceeds the calculated liguorum), Zygomycetes (Mucor spinosus), and/or wood value, the action of the combination is synergistic. destroying fungi such as Ascomycets (Chetonium alba In this case, the actually observed insecticidal kill rate arenulum, Chaetonium globosum, Humicola grisea, Petriella should exceed the value calculated using the above formula setifera, Trichurus spiralis), Basidiomycetes (Coniophera for the expected insecticidal kill rate (E). puteana, Coriolus versicolor, Donbiopora expansa, Glenos 40 In this test, for example, the following compositions pora graphii, Gloeophyllum abietinum, Gloeophyllum ado including a combination of pesticide and adjuvant as ratum, Gloeophyllum protactum, Gloeophyllum trabeum, described herein exhibit a synergistically enhanced activity Gloeophyllum sepiarium, Lentinus cyathioformes, Lentinus compared to the active compounds applied individually. edodes, Lentinus lepideus, Lentinus squavrolosus, Paxillus The examples that follow demonstrate the use of various panuoides, Pleurofits Ostreatus, Poria placenta, Poria mon 45 adjuvants, some of which are free radical stabilizers and some ticola, Poria vailantii, Poria vaporia, Serpula himantoides, of which are UV absorbers, or both, including various organic Serpula lacrymans, Tvromyces palustris), and Deutero acids, esters, preservatives (BHA, BHT), polyphenyl meth mycetes (Cladosporium herbarum). anes, and sebacates Such as Compound A, which may also be Generally the compositions also will include at least one referred to as bis(1.2.2.6,6-pentamethyl-4-piperidinyl)seba additional diluent, emulsifier, melting agent, organic binding 50 cate and methyl(1.2.2.6,6-pentamethyl-4-piperidinyl)seba agent, auxiliary Solvents, processing additives, fixatives, cate, with insecticides such as imidacloprid, deltamethrin, plasticizers, UV-stabilizers or stability enhancers, dyes (wa thiamethoxam, resmethrin, permethrin, fipronil, Ethiprole, ter Soluble, water insoluble), color pigments, siccatives, cor bendiocarb, various cyfluthrins, and pyrethrins and pyre rosion inhibitors, antisettlement agents, additional insecti throids, against insects and arachnids such as the bait averse/ cides (such as insecticidal carbamates, organophosphorus 55 resistant German cockroach (T-164 Strain), the susceptible compounds, halogenated hydrocarbons, pyrethroides etc.), German cockroach (Monheim Strain), the Argentine ant, the anti-skinning agents and the like. The above-mentioned addi odorous house ant, the red imported fireant (RIFA), the Aedes tional ingredients and their use are described, for example, in aegypti Mosquito, the Culex quinquefasciatus mosquito, and EP 370 665 A, DE 3531 257 A, DE 3414 244 A. various spiders. The compositions can be provided as ready for use prod 60 In the examples that follow, one or more standard method ucts or as concentrates, which have to be diluted prior to use. ology was used. One of these standard methods is described The compositions can be applied by means of brushing, below. spraying, dipping, double vacuum and the like as known in Determination of the Efficacy of Formulations on Surfaces the art. The compositions can be prepared by any technique The surfaces were treated as follows: known in the art. 65 A flat fan nozzle (type SS 8003-E) in a spray cabin was The present invention will be better understood with refer moved automatically over a defined area where the solutions ence to the following non-limiting examples. were sprayed very evenly onto the surfaces. The formulation US 9,028,856 B2 43 44 was mixed with water to give a concentration which corre Example 2 sponded to the desired quantity of a.i./m. A defined quantity of this solution was sprayed onto the area (nominal 350 liter/ Evaluation of the Synergy of Organic Acids with ha=0.77 ml per surface). Imidacloprid Against Bait Averse/Resistant German All Surfaces were provided with talcum-coated glass rings Cockroach (T-164 Strain) (diameter 9.5 cm, height 5.5 cm) one day later. The test insects were anesthetized with CO 20 individuals The objective of this study was to investigate the Synergis were placed onto the treated Surfaces and the glass ring was tic effect of imidacloprid in combination with organic acids covered with wire gauze ring. on efficacy against bait averse/resistant German cockroach Knockdown was determined after 15 and 30, 1, 2, 4 and 6 10 (T-164 strain). hours, mortality after 1 day exposure. MATERIALS AND METHODS: Solutions of imidaclo Each test consisted of at least one replicate and any addi prid at 0.5% AI were prepared with and without benzenepro tional replicates are noted. panoic acid (benzenepropanoic acid) (a)0.1, 1.0 and 5.0% in acetone. Treatments were applied using a micropipette to Example 1 15 dispense 1 ml of test solution evenly on a 6"x6" glazed tile. Actual coverage was about 5"x5" (or 161 cm) for easy han Evaluation of the Synergy of Organic Acids with dling. Treatments were allowed to dry overnight. Five male Imidacloprid Against the Argentine Ant Germancockroaches were placed within a Fluon-coated PVC ring (p7.6 cmxH 5.1 cm) under continuous exposure. A small vial cap filled with a cotton ball soaked in water was added as The objective of this study was to investigate the Synergis a drinking Source after 3 hours. Treatments were replicated a tic effect of imidacloprid in combination with organic acids minimum of three times. Evaluations for knockdown/mortal on efficacy against the Argentine ant, Linepithema humile. ity were made at various intervals and at 24 hours after expo MATERIALS AND METHODS: Solutions of imidaclo SUC. prid at 0.5% active ingredient (hereinafter AI) were pre 25 RESULTS: Table 5 and FIG. 2: Summary of imidacloprid/ pared with and without benzenepropanoic acid (benzenepro benzenepropanoic acid synergy study against German cock panoic acid) (a)0.1, 1.0 and 5.0% in acetone. Treatments were roach (T-164 strain) applied using a micropipette to dispense 1 ml of test Solution evenly on a 6"x6" glazed tile. Actual coverage was about 5"x5" (or 161 cm) for easy handling. Treatments were 30 Average % Knockdown & allowed to dry overnight. Ten Argentine ant workers were Mortality after placed within a fluon or talc-coated PVC ring (cp7.6 cmxH5.1 Rate 15 30 1 2 24 cm) under continuous exposure. A Small vial filled with a Treatment (g/m) min min hir hir hir cotton ball soaked in water was added as a drinking Source 35 UTC O O O O O O after 3 hours. Treatments were replicated a minimum of three imidacloprid (0.5%) O.31 O O 7 27 27 times. Evaluations forant knockdown/mortality were made at imidacloprid (0.5%) + 0.31 + 3.11 93 1OO 100 100 100 benzenepropanoic various intervals and at 24 hours after exposure. acid (5%) RESULTS: A summary of imidacloprid/benzenepropanoic imidacloprid (0.5%) + O31 - 0.62 13 33 67 100 8O acid synergy study against the Argentine ant is shown, Table 40 benzenepropanoic 4 and FIG. 1 acid (1%) imidacloprid (0.5%) + O31 - 0.06 7 7 33 47 33 benzenepropanoic acid (0.1%) Average % Knockdown & benzenepropanoic O +3.11 O O O O 2O Mortality after acid (5%) 45 benzenepropanoic O + 0.62 O O O O O Rate 30 1 3 7 24 acid (1%) Treatment (g/m) min hr hr hr hr benzenepropanoic O -- 0.06 O O O O 13 acid (0.1%) UTC O O O O O O imidacloprid (0.5%) O.31 O O O O 2O imidacloprid (0.5%) + 0.31 + 3.11 O 7 7O 97 100 50 benzenepropanoic acid (5%) SUMMARY: A synergistic effect was seen with the three imidacloprid (0.5%) + O.31 - O.62 O O O 3 27 rates of benzenepropanoic acid with imidacloprid against benzenepropanoic acid (1%) German cockroaches (T-164 strain). Some recovery was imidacloprid (0.5%) + O.31 - OO6 O O O 3 7 observed at 24 hours. Benzenepropanoic acid alone was benzenepropanoic acid (0.1%) slightly to not toxic to the German cockroach. Benzenepropanoic acid (5%) O +3.11 O O O 7 7 55 Benzenepropanoic acid (1%) O + 0.62 O O O O 3 Benzenepropanoic acid (0.1%) O -- 0.06 O O O O O Example 3 Evaluation of the Synergy of Organic Acids with SUMMARY: A synergistic effect was seen with the two Imidacloprid Against Bait Averse/Resistant German high rates (1 & 5%) of benzenepropanoic acid with imidaclo 60 Cockroach (T-164 Strain) prid against the Argentine ants. Benzenepropanoic acid alone at all rates tested was not toxic to the Argentine ants. The The objective of this study was to investigate the Synergis results are illustrated in FIG.1, both imidacloprid and the free tic effect of imidacloprid in combination with organic acids radical stabilizer benzenepropanoic acid showed a relatively on efficacy against bait averse/resistant German cockroach low mortality against the Argentine ant at a concentration of 65 (T-164 strain). 5%, whereas the combination of the two showed relatively MATERIALS AND METHODS: Solutions of imidaclo high mortality. prid at 0.5% AI were prepared with and without Oleic acid US 9,028,856 B2 45 46 (a)0.1, 1.0 and 5.0% in acetone. Treatments were applied RESULTS: Table 7 and FIG. 4: Summary of imidacloprid/ using a micropipette to dispense 1 ml of test solution evenly Oleic acid synergy study against the Argentine ant: on a 6"x6" glazed tile. Actual coverage was about 5"x5" (or 161 cm) for easy handling. Treatments were allowed to dry overnight. Five male German cockroaches were placed 5 Average % Knockdown & within a Fluon-coated PVC ring (cp7.6 cmxH 5.1 cm) under Mortality after continuous exposure. A small vial cap filled with a cotton ball Rate 30 1 3 7 24 soaked in water was added as a drinking source after 3 hours. Treatment (g/m) min hir hir hir hir Treatments were replicated a minimum of three times. Evalu UTC O O O O O O ations for knockdown/mortality were made at various inter 10 imidacloprid (0.5%) O.31 O 3 3 3 43 imidacloprid (0.5%) + 0.31 + 3.11 100 100 100 100 100 vals and at 24 hours after exposure. Oleic acid (5%) RESULTS: Table 6 and FIG. 3: Summary of imidacloprid/ imidacloprid (0.5%) + 0.31 + 0.62 50 93 100 100 100 Oleic acid (1%) Oleic acid synergy study against German cockroach (T-164 imidacloprid (0.5%) + O31 - 0.06 O O O O 90 strain) 15 Oleic acid (0.1%) Oleic acid (5%) O +3.11 93 100 100 100 100 Oleic acid (1%) O + 0.62 14 50 82 1 OO 100 Oleic acid (0.1%) O -- 0.06 O O O O O Average % Knockdown & Mortality after SUMMARY: A synergistic effect was seen with the three rates of Oleic acid with imidacloprid against the Argentine Rate 15 30 1 2 24 ants. Oleic acid alone at the high rates (1 & 5%) was toxic to Treatment (g/m) min min hir hir hir the Argentine ants, but not at the low rate (0.1%). UTC O O O O O O Example 5 imidacloprid (0.5%) O.31 13 44 50 50 25 imidacloprid (0.5%) + 0.31 + 3.11 88 1OO 100 100 100 Evaluation of the Synergy of Esters with Oleic Acid (5%) Imidacloprid Against the Argentine Ant imidacloprid (0.5%) + 0.31 + 0.62 47 80 100 100 100 The objective of this study was to investigate the Synergis Oleic Acid (1%) 30 tic effect of imidacloprid in combination with esters on effi imidacloprid (0.5%) + 0.31 + 0.06 7 7 13 27 67 cacy against the Argentine ant, Linepithema humile. Oleic Acid (0.1%) MATERIALS AND METHODS: Oleic Acid (5%) O + 3.11 O O 44 94 94 Solutions of imidacloprid at 0.5% AI were prepared with and without methyl oleate (a)0.1, 1.0 and 5.0% in acetone. Oleic Acid (1%) O + 0.62 O O O O 7 Treatments were applied using a micropipette to dispense 1 Oleic Acid (0.1%) O -- 0.06 O O O O O 35 ml of test solution evenly on a 6"x6" glazed tile. Actual coverage was about 5"x5" (or 161 cm) for easy handling. Treatments were allowed to dry overnight. Ten Argentine ant SUMMARY: A synergistic effect was seen with the three workers were placed within a fluon or talc-coated PVC ring rates of Oleic acid with imidacloprid against German cock (p7.6 cmxH 5.1 cm) under continuous exposure. A Small vial roaches (T-164 strain). Oleic acid alone was toxic to German 40 filled with a cotton ball soaked in water was added as a cockroaches at the high rate (5%), but not toxic at the two low drinking source after 3 hours. Treatments were replicated a rates. minimum of three times. Evaluations for ant knockdown/ mortality were made at various intervals and at 24 hours after exposure. Example 4 45 RESULTS: Table 8 and FIG. 5: Summary of imidacloprid/ Methyl Oleate synergy study against the Argentine ant: Evaluation of the Synergy of Organic Acids with Imidacloprid Against the Argentine Ant Average % Knockdown & 50 Mortality after The objective of this study was to investigate the Synergis Rate 15 30 1 4 24 tic effect of imidacloprid in combination with organic acids Treatment (gfm) min min hir hir hir on efficacy against the Argentine ant, Linepithema humile. UTC O O O O O 3 MATERIALS AND METHODS: Solutions of imidaclo imidacloprid (0.5%) O.31 O O O 7 10 55 imidacloprid (0.5%) + 0.31 + 3.11 53 90 100 100 100 prid at 0.5% AI were prepared with and without Oleic acid Methyl Oleate (5%) (a)0.1, 1.0, and 5.0% in acetone. Treatments were applied imidacloprid (0.5%) + 0.31 + 0.62 O O O 17 43 using a micropipette to dispense 1 ml of test solution evenly Methyl Oleate (1%) imidacloprid (0.5%) + 0.31 + 0.06 O O O 13 47 on a 6"x6" glazed tile. Actual coverage was about 5"x5" (or Methyl Oleate (0.1%) 161 cm) for easy handling. Treatments were allowed to dry 60 Methyl Oleate (5%) O +3.11 3 3 67 100 100 overnight. Ten Argentine ant workers were placed within a Methyl Oleate (1%) O + 0.62 O 3 3 55 65 fluon or talc-coated PVC ring (p7.6 cmxH 5.1 cm) under Methyl Oleate (0.1%) O -- 0.06 O O O 13 13 continuous exposure. A small vial filled with a cotton ball soaked in water was added as a drinking source after 3 hours. SUMMARY: A synergistic effect was seen with the three Treatments were replicated a minimum of three times. Evalu 65 rates of methyl oleate with imidacloprid tested against the ations for ant knockdown/mortality were made at various Argentine ants. Methyl oleate alone was toxic to the Argen intervals and at 24 hours after exposure. tine ants. US 9,028,856 B2 47 48 Example 6 after 3 hours. Treatments were replicated a minimum of three times. Evaluations forant knockdown/mortality were made at Evaluation of the Synergy of Esters with various intervals and at 24 hours after exposure. Imidacloprid Against Bait Averse/Resistant German RESULTS: Table 10 and FIG. 7: Summary of imidaclo Cockroach (T-164 Strain) prid/Methyl Linoleate synergy study against the Argentine The objective of this study was to investigate the Synergis ant: tic effect of imidacloprid in combination with esters on effi cacy against bait averse/resistant German cockroach (T-164 Average % Knockdown & strain). 10 Mortality after MATERIALS AND METHODS: Solutions of imidaclo prid at 0.5% AI were prepared with and without methyl oleate Rate 15 30 1 4 24 (a)0.1, 1.0 and 5.0% in acetone. Treatments were applied Treatment (g/m) min min hr hr hir using a micropipette to dispense 1 ml of test solution evenly UTC O O O O O 3 on a 6"x6" glazed tile. Actual coverage was about 5"x5" (or 15 imidacloprid (0.5%) O.31 O O O O 70 imidacloprid (0.5%) + O31 - 3.11 43 77 97 100 100 161 cm) for easy handling. Treatments were allowed to dry Methyl Linoleate (5%) overnight. Five male German cockroaches were placed imidacloprid (0.5%) + O31 - 0.62 7 7 17 37 90 within a Fluon-coated PVC ring (cp7.6 cmxH 5.1 cm) under Methyl Linoleate (1%) continuous exposure. A small vial cap filled with a cotton ball imidacloprid (0.5%) + O31 - 0.06 3 3 3 3 63 Methyl Linoleate (0.1%) soaked in water was added as a drinking source after 3 hours. Methyl Linoleate (5%) O + 3.11 7 7 20 67 97 Treatments were replicated a minimum of three times. Evalu Methyl Linoleate (1%) O + 0.62 O O O 7 2O ations for knockdown/mortality were made at various inter Methyl Linoleate (0.1%) O -- 0.06 O O O O 3 vals and at 24 hours after exposure. RESULTS: Table 9 and FIG. 6: Summary of imidacloprid/ Methyl Oleate synergy study against German cockroach 25 SUMMARY: A synergistic effect was seen with the two high rates (1 & 5%) of methyl linoleate with imidacloprid (T-164 strain) against the Argentine ants. Methyl linoleate alone at high rates (1 & 5%) was toxic to the Argentine ants. Average % Knockdown & Mortality after 30 Example 8 Rate 15 30 1 2 24 Treatment (g/m) min min hir hir hir Evaluation of the Synergy of Esters with UTC O O O O O O Imidacloprid Against Bait Averse/Resistant German imidacloprid (0.5%) O.31 O 7 13 27 40 imidacloprid (0.5%) + 0.31 + 3.11 88 1OO 100 100 100 35 Cockroach (T-164 Strain) Methyl Oleate (5%) imidacloprid (0.5%) + O31 - 0.62 O 93 100 100 100 Methyl Oleate (1%) The objective of this study was to investigate the Synergis imidacloprid (0.5%) + O31 - 0.06 O 2O 47 60 73 tic effect of imidacloprid in combination with esters on effi Methyl Oleate (0.1%) cacy against bait averse/resistant German cockroach (T-164 Methyl Oleate (5%) O + 3.11 7 13 87 100 100 40 strain). Methyl Oleate (1%) O + 0.62 O O 7 40 87 Methyl Oleate (0.1%) O -- 0.06 O O O 7 13 MATERIALS AND METHODS: Solutions of imidaclo prid at 0.5% AI were prepared with and without methyl linoleate (a)0.1, 1.0 and 5.0% in acetone. Treatments were SUMMARY: A synergistic effect was seen with the three applied using a micropipette to dispense 1 ml of test Solution rates of methyl oleate with imidacloprid against the insecti 45 evenly on a 6"x6" glazed tile. Actual coverage was about cide-resistant German cockroaches (T-164 strain). Methyl 5"x5" (or 161 cm) for easy handling. Treatments were oleate at the higher rates (1 & 5%) showed delayed toxic allowed to dry overnight. Five male German cockroaches effect to the German cockroach. were placed within a Fluon-coated PVC ring (cp7.6 cmxH 5.1 Example 7 50 cm) under continuous exposure. A Small vial cap filled with a cotton ball soaked in water was added as a drinking Source after 3 hours. Treatments were replicated a minimum of three Evaluation of Synergy of Esters with Imidacloprid times. Evaluations for knockdown/mortality were made at Against the Argentine Ant various intervals and at 24 hours after exposure. The objective of this study was to investigate the Synergis 55 RESULTS: Table 11 and FIG. 8: Summary of imidaclo tic effect of imidacloprid in combination with esters on effi prid/Methyl Linoleate synergy study against German cock cacy against the Argentine ant, Linepithema humile. roach (T-164 strain) MATERIALS AND METHODS: Solutions of imidaclo prid at 0.5% AI were prepared with and without methyl linoleate (a)0.1, 1.0 and 5.0% in acetone. Treatments were 60 Average % Knockdown & applied using a micropipette to dispense 1 ml of test Solution Mortality after evenly on a 6"x6" glazed tile. Actual coverage was about Rate 15 30 1 2 24 5"x5" (or 161 cm) for easy handling. Treatments were Treatment (gfm) min min hir hir hir allowed to dry overnight. Ten Argentine ant workers were UTC O O O O O 2O placed within a fluon or talc-coated PVC ring (cp7.6 cmxH5.1 65 imidacloprid (0.5%) O.31 O O 40 47 47 cm) under continuous exposure. A Small vial filled with a imidacloprid (0.5%) + 0.31 + 3.11 67 1OO 100 100 100 cotton ball soaked in water was added as a drinking Source US 9,028,856 B2 49 50 -continued Example 10 Average % Knockdown & Evaluation of the Synergy of Esters with Mortality after Imidacloprid Against Bait Averse/Resistant German Rate 15 30 1 2 24 Cockroach (T-164 Strain) Treatment (g/m) min min hir hir hir The objective of this study was to investigate the Synergis Methyl Linoleate (5%) tic effect of imidacloprid in combination with esters on effi imidacloprid (0.5%) + 0.31 + 0.62 13 69 81 94 100 cacy against bait averse/resistant German cockroach (T-164 Methyl Linoleate (1%) imidacloprid (0.5%) + 0.31 + 0.06 O 2O 47 53 8O 10 strain). Methyl Linoleate MATERIALS AND METHODS: Solutions of imidaclo (0.1%) prid at 0.5% AI were prepared with and without methyl Methyl Linoleate (5%) O + 3.11 O 2O 6O 1 OO 100 palmitate (a)0.1, 1.0 and 5.0% in acetone. Treatments were Methyl Linoleate (1%) O + 0.62 O O O 2O 53 applied using a micropipette to dispense 1 ml of test Solution Methyl Linoleate O -- 0.06 O O O O 2O evenly on a 6"x6" glazed tile. Actual coverage was about (0.1%) 15 5"x5" (or 161 cm) for easy handling. Treatments were allowed to dry overnight. Five male German cockroaches SUMMARY: A synergistic effect was seen with the three were placed within a Fluon-coated PVC ring (cp7.6 cmxH 5.1 rates of methyl linoleate with imidacloprid against German cm) under continuous exposure. A Small vial cap filled with a cotton ball soaked in water was added as a drinking Source cockroaches (T-164 strain). Methyllinoleate alone was toxic after 3 hours. Treatments were replicated a minimum of three to the German cockroach. times. Evaluations for knockdown/mortality were made at various intervals and at 24 hours after exposure. Example 9 RESULTS: Table 13 and FIG. 10: Summary of imidaclo prid/Methyl Palmitate synergy study against German cock Evaluation of the Synergy of Esters with 25 roach (T-164 strain) Imidacloprid Against the Argentine Ant

The objective of this study was to investigate the Synergis Average % Knockdown & tic effect of imidacloprid in combination with esters on effi Mortality after cacy against the Argentine ant, Linepithema humile. 30 Rate 30 1 2 4 24 MATERIALS AND METHODS: Solutions of imidaclo Treatment (g/m) min hir hr hr hir prid at 0.5% AI were prepared with and without methyl UTC O O O O O O palmitate (a 0.1, 1.0 and 5.0% in acetone. Treatments were imidacloprid (0.5%) O.31 O O O O 47 applied using a micropipette to dispense 1 ml of test Solution imidacloprid (0.5%) + 0.31 + 3.11 2O 73 80 80 73 35 Methyl Palmitate (5%) evenly on a 6"x6" glazed tile. Actual coverage was about imidacloprid (0.5%) + O31 - 0.62 O 40 40 40 47 5"x5" (or 161 cm) for easy handling. Treatments were Methyl Palmitate (1%) allowed to dry overnight. Ten Argentine ant workers were imidacloprid (0.5%) + O31 - 0.06 O O O 27 60 placed within a fluon or talc-coated PVC ring (cp7.6 cmxH5.1 Methyl Palmitate (0.1%) Methyl Palmitate (5%) O + 3.11 O O O O O cm) under continuous exposure. A Small vial filled with a Methyl Palmitate (1%) O + 0.62 O O O O O cotton ball soaked in water was added as a drinking Source 40 after 3 hours. Treatments were replicated a minimum of three Methyl Palmitate (0.1%) O -- 0.06 O O O O O times. Evaluations forant knockdown/mortality were made at SUMMARY: A synergistic effect was seen with the three various intervals and at 24 hours after exposure. rates of methyl palmitate with imidacloprid against German RESULTS: Table 12 and FIG. 9: Summary of imidaclo cockroaches (T-164 strain). Methyl palmitate alone was not prid/Methyl Palmitate synergy study against the Argentine 45 toxic to the German cockroach. ant: Example 11 Average % Knockdown & Mortality after 50 Evaluation of the Synergy of Preservatives with Rate 30 1 3 7 24 Imidacloprid Against the Argentine Ant Treatment (g/m) min hir hr hr hir

UTC O O O O O O The objective of this study was to investigate the Synergis imidacloprid (0.5%) O.31 O O O O 2O tic effect of imidacloprid in combination with common food imidacloprid (0.5%) + 0.31 +3.11 O 7 7O 97 100 55 preservatives on efficacy against the Argentine ant, Linepi Methyl Palmitate (5%) thema humile. imidacloprid (0.5%) + O31 - 0.62 O O O 3 27 Methyl Palmitate (1%) MATERIALS AND METHODS: Solutions of imidaclo imidacloprid (0.5%) + O31 - 0.06 O O O 3 7 prid at 0.5% AI were prepared with and without butylated Methyl Palmitate (0.1%) hydroxyanisole (BHA) (a)0.1, 1.0 and 5.0% in acetone. Treat Methyl Palmitate (5%) O +3.11 O O O 7 7 60 Methyl Palmitate (1%) O + 0.62 O O O O 3 ments were applied using a micropipette to dispense 1 ml of Methyl Palmitate (0.1%) O -- 0.06 O O O O O test solution evenly on a 6"x6" glazed tile. Actual coverage was about 5"x5" (or 161 cm) for easy handling. Treatments SUMMARY: A synergistic effect was seen with the two were allowed to dry overnight. Ten Argentine ant workers high rates (1 & 5%) of methyl palmitate with imidacloprid 65 were placed within a fluon or talc-coated PVC ring (cp7.6 against the Argentine ants. Methyl palmitate alone at all rates cmxH 5.1 cm) under continuous exposure. A small vial filled tested was not toxic to the Argentine ants. with a cotton ball soaked in water was added as a drinking US 9,028,856 B2 51 52 Source after 3 hours. Treatments were replicated a minimum RESULTS: Table 15 and FIG. 12: Summary of imidaclo of three times. Evaluations forant knockdown/mortality were prid/BHA synergy study against German cockroach (T-164 made at various intervals and at 24 hours after exposure. strain) RESULTS: Table 14 and FIG. 11: Summary of imidaclo prid/BHA synergy study against the Argentine ant: 5 Average % Knockdown & Mortality after

Rate 30 1 2 4 24 Average % Knockdown & Treatment (g/m) min hir hir hir hir Mortality after 10 UTC O O O O O O imidacloprid (0.5%) O.31 7 7 7 2O 67 Rate 30 1 2 4 24 imidacloprid (0.5%) + 0.31 + 3.11 93 1OO 100 100 100 Treatment (g/m) min hir hr hr hir BHA (5%) imidacloprid (0.5%) + 0.31 + 0.62 0 13 20 20 40 15 BHA (1%) UTC O O O O O 63 imidacloprid (0.5%) + 0.31 + 0.06 0 7 13 20 40 BHA (0.1%) imidacloprid (0.5%) O.31 O O O O 30 Butylated hydroxy- O +3.11 O O 2O 2O 73 imidacloprid (0.5%) + 0.31 +3.11 O O O 12 64 anisole (BHA) (5%) BHA (5%) Butylated hydroxy- O + 0.62 O O O O O anisole (BHA) (1%) imidacloprid (0.5%) + O31 - 0.62 O O O 7 47 Butylated hydroxy- O -- 0.06 O O O O 2O BHA (1%) anisole (BHA) (0.1%) imidacloprid (0.5%) + O31 - 0.06 O O O 10 S2 BHA (0.1%) SUMMARY: A synergistic effect was seen with the high Butylated hydroxyanisole O +3.11 O O O 19 74 25 rate (5%) of BHA with imidacloprid against German cock (BHA) (5%) roaches (T-164 strain). BHA at the high rate (5%) was toxic to Butylated hydroxyanisole O + 0.62 O O O 3 40 the German cockroach, but not at its lower rates (1.0 and (BHA) (1%) 0.1%) tested. Butylated hydroxyanisole O -- 0.06 O O O 10 37 30 Example 13 (BHA) (0.1%) Evaluation of the Synergy of Preservatives with Imidacloprid Against the Argentine Ant SUMMARY: No synergistic effect was seen with the three rates of BHA with imidacloprid tested against the Argentine 35 The objective of this study was to investigate the Synergis ants. BHA alone showed delayed toxicity to the Argentine tic effect of imidacloprid in combination with common food ants. Due to the unusual high mortality in UTC, the trial will preservatives on efficacy against the Argentine ant, Linepi be repeated. thema humile. MATERIALS AND METHODS: Solutions of imidaclo Example 12 40 prid at 0.5% AI were prepared with and without butylated hydroxytoluene (BHT) (a)0.1, 1.0 and 5.0% in acetone. Treat ments were applied using a micropipette to dispense 1 ml of Evaluation of the Synergy of Preservatives with test solution evenly on a 6"x6" glazed tile. Actual coverage Imidacloprid Against Bait Averse/Resistant German was about 5"x5" (or 161 cm) for easy handling. Treatments Cockroach (T-164 Strain) 45 were allowed to dry overnight. Ten Argentine ant workers were placed within a fluon or talc-coated PVC ring (cp7.6 The objective of this study was to investigate the Synergis cmxH 5.1 cm) under continuous exposure. A small vial filled tic effect of imidacloprid in combination with common food with a cotton ball soaked in water was added as a drinking preservatives on efficacy against baitaverse/resistant German 50 Source after 3 hours. Treatments were replicated a minimum cockroach (T-164 strain). of three times. Evaluations forant knockdown/mortality were made at various intervals and at 24 hours after exposure. MATERIALS AND METHODS: Solutions of imidaclo RESULTS: Table 16 and FIG. 13: Summary of imidaclo prid at 0.5% AI were prepared with and without butylated prid/BHT Synergy study against the Argentine ant: hydroxyanisole (BHA) (a)0.1, 1.0 and 5.0% in acetone. Treat ments were applied using a micropipette to dispense 1 ml of 55 test solution evenly on a 6"x6" glazed tile. Actual coverage Average % Knockdown & was about 5"x5" (or 161 cm) for easy handling. Treatments Mortality after were allowed to dry overnight. Five male German cock Rate 30 1 2 18 24 roaches were placed within a Fluon-coated PVC ring (cp7.6 60 Treatment (g/m) min hr hr hr hr cmxH 5.1 cm) under continuous exposure. A Small vial cap UTC O O O O O O imidacloprid (0.5%) O.31 O 14 14 17 21 filled with a cotton ball soaked in water was added as a imidacloprid (0.5%) + 0.31 +3.11 13 17 20 90 100 drinking source after 3 hours. Treatments were replicated a BHT (5%) minimum of three times. Evaluations for knockdown/mortal imidacloprid (0.5%) + O31 - 0.62 11 11 14 29 39 65 BHT (1%) ity were made at various intervals and at 24 hours after expo imidacloprid (0.5%) + O31 - 0.06 7 10 13 55 58 SUC. US 9,028,856 B2 54 -continued showed antagonistic effect. All BHT rates tested were not toxic to the German cockroach strain. Average % Knockdown & Mortality after Example 15 Rate 30 1 2 18 24 Evaluation of the Synergy of Preservatives with Treatment (g/m) min hr hr hr hr Imidacloprid Against Bait Averse/Resistant German BHT (0.1%) Cockroach (T-164 Strain) Butylated hydroxytoluene O +3.11 7 7 7 83 (BHT) (5%) The objective of this study was to investigate the Synergis Butylated hydroxytoluene O + 0.62 3 3 3 3 3 10 (BHT) (1%) tic effect of imidacloprid in combination with common food Butylated hydroxytoluene O -- 0.06 7 10 preservatives on efficacy against baitaverse/resistant German (BHT) (0.1%) cockroach (T-164 strain). MATERIALS AND METHODS: Solutions of imidaclo prid at 0.5% AI were prepared with and without tertiary butyl SUMMARY: A synergistic effect was seen with the three 15 dihydroxyquinone (TBHQ) (a)0.1, 1.0 and 5.0% in acetone. rates of BHT with imidacloprid tested against the Argentine Treatments were applied using a micropipette to dispense 1 ants. BHT alone was toxic to the Argentine ants. ml of test solution evenly on a 6"x6" glazed tile. Actual coverage was about 5"x5" (or 161 cm) for easy handling. Example 14 Treatments were allowed to dry overnight. Five male German cockroaches were placed within a Fluon-coated PVC ring Evaluation of the Synergy of Preservatives with (p7.6 cmxH 5.1 cm) under continuous exposure. A Small vial Imidacloprid Against Bait Averse/Resistant German cap filled with a cotton ball soaked in water was added as a drinking source after 3 hours. Treatments were replicated a Cockroach (T-164 Strain) minimum of three times. Evaluations for knockdown/mortal 25 ity were made at various intervals and at 24 hours after expo The objective of this study was to investigate the Synergis SUC. tic effect of imidacloprid in combination with common food RESULTS: Table 18 and FIG. 15: Summary of imidaclo preservatives on efficacy against baitaverse/resistant German prid/TBHQ synergy study against German cockroach (T-164 cockroach (T-164 strain). strain) MATERIALS AND METHODS: Solutions of imidaclo prid at 0.5% AI were prepared with and without butylated 30 hydroxytoluene (BHT) (a)0.1, 1.0 and 5.0% in acetone. Treat Average % Knockdown & ments were applied using a micropipette to dispense 1 ml of Mortality after test solution evenly on a 6"x6" glazed tile. Actual coverage was about 5"x5" (or 161 cm) for easy handling. Treatments Rate 30 1 2 4 24 were allowed to dry overnight. Five male German cock 35 Treatment (g/m) min hir hir hr hir roaches were placed within a Fluon-coated PVC ring (cp7.6 UTC O O O O O O imidacloprid (0.5%) O.31 O O 33 47 47 cmxH 5.1 cm) under continuous exposure. A Small vial cap imidacloprid (0.5%) + 0.31 + 3.11 O 7 7 13 20 filled with a cotton ball soaked in water was added as a TBHQ (5%) drinking source after 3 hours. Treatments were replicated a imidacloprid (0.5%) + O31 - 0.62 O O 7 13 2.7 minimum of three times. Evaluations for knockdown/mortal 40 TBHQ (1%) imidacloprid (0.5%) + O31 - 0.06 O O 14 21 36 ity were made at various intervals and at 24 hours after expo TBHQ (0.1%) SUC. TBHQ (5%) O + 3.11 O 7 7 7 47 RESULTS: Table 17 and FIG. 14: Summary of imidaclo TBHQ (1%) O + 0.62 O O O O 40 prid/BHT Synergy study against German cockroach (T-164 TBHQ (0.1%) O -- 0.06 O O O 7 7 strain) 45 SUMMARY: Synergistic effect was seen with the three rates of TBHQ with imidacloprid against German cock Average % Knockdown & Rate Mortality after roaches (T-164 strain). TBHQ at the higher rates (1 & 5%) 50 showed delayed toxic effect to the German cockroach. Treatment (g/m) 30 min 1 hr 5 hr 24 hr

UTC O O O O O imidacloprid (0.5%) O.31 O 6 19 25 Example 16 imidacloprid (0.5%) + 0.31 +3.11 O O O O BHT (5%) Evaluation of the Synergy of Preservatives with imidacloprid (0.5%) + O31 - 0.62 O O 47 47 55 Imidacloprid Against the Argentine Ant BHT (1%) imidacloprid (0.5%) + O31 - 0.06 O 13 27 27 BHT (0.1%) The objective of this study was to investigate the Synergis Butylated hydroxytoluene O +3.11 O O O 7 tic effect of imidacloprid in combination with common food (BHT) (5%) Butylated hydroxytoluene O + 0.62 O O O 7 60 preservatives on efficacy against the Argentine ant, Linepi (BHT) (1%) thema humile. Butylated hydroxytoluene O -- 0.06 O O O O MATERIALS AND METHODS: Solutions of imidaclo (BHT) (0.1%) prid at 0.5% AI were prepared with and without tertiary butyl dihydroxyquinone (TBHQ) (a)0.1, 1.0 and 5.0% in acetone. SUMMARY: Synergistic effect was seen with the lower 65 Treatments were applied using a micropipette to dispense 1 rates (1 & 0.1%) of BHT with imidacloprid against German ml of test solution evenly on a 6"x6" glazed tile. Actual cockroaches (T-164 strain). BHT at the high rate (5%) coverage was about 5"x5" (or 161 cm) for easy handling. US 9,028,856 B2 55 56 Treatments were allowed to dry overnight. Ten Argentine ant RESULTS: Table 20 and FIG. 17: Summary of imidaclo workers were placed within a fluon or talc-coated PVC ring prid/Diphenyl methane Synergy study against the Argentine (p7.6 cmxH 5.1 cm) under continuous exposure. A Small vial ant: filled with a cotton ball soaked in water was added as a drinking source after 3 hours. Treatments were replicated a Average % Knockdown & minimum of three times. Evaluations for ant knockdown/ Mortality after mortality were made at various intervals and at 24 hours after exposure. Rate 30 1 2 4 24 Treatment (g/m) min hir hir hr hir RESULTS: Table 19 and FIG. 16: Summary of imidaclo 10 prid/TBHQ synergy study against the Argentine ant: UTC O O O O 3 33 imidacloprid (0.5%) O.31 O O O 7 33 imidacloprid (0.5%) + 0.31 + 3.11 O O O 13 33 DPM (5%) Average % Knockdown & imidacloprid (0.5%) + O31 - 0.62 O O O 3 47 DPM (1%) Mortality after 15 imidacloprid (0.5%) + O31 - 0.06 O O O 17 53 DPM (0.1%) Diphenyl methane O + 3.11 O O O O 7 Rate 30 1 4 6 24 (DPM) (5%) Treatment (g/m) min hir hr hr hir Diphenyl methane O + 0.62 O O O O 7 (DPM) (1%) Diphenyl methane O -- 0.06 O O O 13 27 UTC O O O O O O (DPM) (0.1%) imidacloprid (0.5%) O.31 O O O 7 28 imidacloprid (0.5%) + 0.31 +3.11 O O O 22 100 SUMMARY: No synergistic effect was seen with the three TBHQ (5%) rates of diphenyl methane with imidacloprid tested against 25 the Argentine ants. Diphenyl methane alone was not toxic to imidacloprid (0.5%) + O31 - 0.62 O O O 23 100 the Argentine ants. TBHQ (1%) imidacloprid (0.5%) + O31 - 0.06 O O O O 38 Example 18 TBHQ (0.1%) 30 Evaluation of the Synergy of Polyphenyl Methanes TBHQ (5%) O +3.11 O O 10 23 100 with Imidacloprid Against Bait Averse/Resistant TBHQ (1%) O + 0.62 O O O 10 100 German Cockroach (T-164 Strain) TBHQ (0.1%) O -- 0.06 O O O 7 11 The objective of this study was to investigate the Synergis 35 tic effect of imidacloprid in combination with polyphenyl SUMMARY: A synergistic effect was seen with the two methanes on efficacy against bait averse/resistant German high rates (1 & 5%) of TBHQ with imidacloprid tested cockroach (T-164 strain). against the Argentine ants. However, the effect may be MATERIALS AND METHODS: Solutions of imidaclo directly contributed by the toxic effect of TBHQ to the Argen prid at 0.5% AI were prepared with and without diphenyl tine ants. 40 methane (DPM) (a)0.1, 1.0 and 5.0% in acetone. Treatments were applied using a micropipette to dispense 1 ml of test solution evenly on a 6"x6" glazed tile. Actual coverage was about 5"x5" (or 161 cm) for easy handling. Treatments were Example 17 allowed to dry overnight. Five male German cockroaches 45 were placed within a Fluon-coated PVC ring (cp7.6 cmxH 5.1 cm) under continuous exposure. A Small vial cap filled with a Evaluation of Synergy of Polyphenyl Methanes with cotton ball soaked in water was added as a drinking Source Imidacloprid Against the Argentine Ant after 3 hours. Treatments were replicated a minimum of three times. Evaluations for knockdown/mortality were made at The objective of this study was to investigate the Synergis 50 various intervals and at 24 hours after exposure. tic effect of imidacloprid in combination with polyphenyl RESULTS: Table 21 and FIG. 18: Summary of imidaclo methanes on efficacy against the Argentine ant, Linepithema prid/Diphenyl methane synergy study against German cock humile. roach (T-164 strain) MATERIALS AND METHODS: Solutions of imidaclo 55 prid at 0.5% AI were prepared with and without diphenyl Average % Knockdown & methane (a)0.1, 1.0 and 5.0% in acetone. Treatments were Mortality after applied using a micropipette to dispense 1 ml of test Solution Rate 30 1 2 3 24 evenly on a 6"x6" glazed tile. Actual coverage was about Treatment (g/m) min hir hir hr hir 5"x5" (or 161 cm) for easy handling. Treatments were 60 UTC O O O O O 6 allowed to dry overnight. Ten Argentine ant workers were imidacloprid (0.5%) O.31 O O 7 7 33 placed within a fluon or talc-coated PVC ring (cp7.6 cmxH5.1 imidacloprid (0.5%) + 0.31 + 3.11 O 11 21 21 26 cm) under continuous exposure. A Small vial filled with a DPM (5%) imidacloprid (0.5%) + O31 - 0.62 O O O 7 33 cotton ball soaked in water was added as a drinking Source DPM (1%) after 3 hours. Treatments were replicated a minimum of three 65 imidacloprid (0.5%) + O31 - 0.06 O O O O 27 times. Evaluations forant knockdown/mortality were made at DPM (0.1%) various intervals and at 24 hours after exposure. US 9,028,856 B2 58 -continued Example 20 Average % Knockdown & Evaluation of Synergy of Polyphenyl Methanes with Mortality after Imidacloprid Against Bait Averse/Resistant German Rate 30 1 2 3 24 Cockroach (T-164 Strain) Treatment (g/m) min hir hir hr hir The objective of this study was to investigate the Synergis Diphenyl methane O +3.11 O O O O 20 (DPM) (5%) tic effect of imidacloprid in combination with polyphenyl Diphenyl methane O + 0.62 O O O O 6 methanes on efficacy against bait averse/resistant German (DPM) (1%) 10 cockroach (T-164 strain). Diphenyl methane O -- 0.06 O O O O 8 MATERIALS AND METHODS: Solutions of imidaclo (DPM) (0.1%) prid at 0.5% AI were prepared with and without tritylchloride (a)0.1, 1.0 and 5.0% in acetone. Treatments were applied SUMMARY: No synergistic effect was seen with all rates using a micropipette to dispense 1 ml of test solution evenly on a 6"x6" glazed tile. Actual coverage was about 5"x5" (or of diphenyl methane with imidacloprid against German cock 161 cm) for easy handling. Treatments were allowed to dry roaches (T-164 strain). Diphenyl methane alone was not toxic overnight. Five male German cockroaches were placed to German cockroaches. within a Fluon-coated PVC ring (cp7.6 cmxH 5.1 cm) under continuous exposure. A small vial cap filled with a cotton ball Example 19 soaked in water was added as a drinking Source after 3 hours. Treatments were replicated a minimum of three times. Evalu ations for knockdown/mortality were made at various inter Evaluation of the Synergy of Polyphenyl Methanes vals and at 24 hours after exposure. with Imidacloprid Against the Argentine Ant RESULTS: Table 23 and FIG. 20: Summary of imidaclo 25 prid/Tritylchloride synergy study against German cockroach The objective of this study was to investigate the Synergis (T-164 strain) tic effect of imidacloprid in combination with polyphenyl methanes on efficacy against the Argentine ant, Linepithema humile. Average % Knockdown & 30 Mortality after MATERIALS AND METHODS: Solutions of imidaclo Rate 30 1 2 3 24 prid at 0.5% AI were prepared with and without tritylchloride Treatment (g/m) min hir hir hr hir (a)0.1, 1.0 and 5.0% in acetone. Treatments were applied using a micropipette to dispense 1 ml of test solution evenly UTC O O O O O O imidacloprid (0.5%) O.31 O O O 7 20 on a 6"x6" glazed tile. Actual coverage was about 5"x5" (or 35 imidacloprid (0.5%) + 0.31 + 3.11 O O O O O 161 cm) for easy handling. Treatments were allowed to dry Tritylchloride (5%) imidacloprid (0.5%) + O31 - 0.62 O O O O 19 overnight. Ten Argentine ant workers were placed within a Tritylchloride (1%) fluon or talc-coated PVC ring (p7.6 cmxH 5.1 cm) under imidacloprid (0.5%) + O31 - 0.06 O O O O 31 continuous exposure. A small vial filled with a cotton ball Tritylchloride (0.1%) soaked in water was added as a drinking source after 3 hours. 40 Tritylchloride (5%) O + 3.11 O O O O O Treatments were replicated a minimum of three times. Evalu Tritylchloride (1%) O + 0.62 O O O O O ations for ant knockdown/mortality were made at various Tritylchloride (0.1%) O -- 0.06 O O O O O intervals and at 24 hours after exposure. SUMMARY: No synergistic effect was seen with all rates RESULTS: Table 22 and FIG. 19: Summary of imidaclo 45 of tritylchloride with imidacloprid against the insecticide prid/tritylchloride synergy study against the Argentine ant: resistant German cockroaches (T-164 strain). Tritylchloride alone was not toxic to the resistant German cockroach strain. Average % Knockdown & Mortality after Example 21 50 Rate 30 1 2 S 24 Evaluation of the Synergy of Sebacates with Treatment (g/m) min hir hir hr hir Imidacloprid Against Bait Averse/Resistant German UTC O O O O O 10 Cockroach (T-164 Strain) imidacloprid (0.5%) O.31 O O O 4 SO imidacloprid (0.5%) + 0.31 +3.11 O O O O 24 55 The objective of this study was to investigate the Synergis Tritylchloride (5%) imidacloprid (0.5%) + O31 - 0.62 O O O 13 81 tic effect of imidacloprid in combination with sebacates on Tritylchloride (1%) efficacy against bait averse/resistant German cockroach imidacloprid (0.5%) + O31 - 0.06 O O O 7 72 (T-164 strain). Tritylchloride (0.1%) MATERIALS AND METHODS: Solutions of imidaclo Tritylchloride (5%) O +3.11 O O O O O 60 prid at 0.5% AI were prepared with and without dibutyl seba Tritylchloride (1%) O + 0.62 O O O O O cate (DBS) (a)0.1, 1.0 and 5.0% in acetone. Treatments were Tritylchloride (0.1%) O -- 0.06 O O O O 7 applied using a micropipette to dispense 1 ml of test Solution evenly on a 6"x6" glazed tile. Actual coverage was about SUMMARY: A synergistic effect was seen with the two 5"x5" (or 161 cm) for easy handling. Treatments were lower rates of tritylchloride with imidacloprid tested against 65 allowed to dry overnight. Five male German cockroaches the Argentine ants. Tritylchloride alone was not toxic to the were placed within a Fluon-coated PVC ring (cp7.6 cmxH 5.1 Argentine ants. cm) under continuous exposure. A Small vial cap filled with a US 9,028,856 B2 59 60 cotton ball soaked in water was added as a drinking Source RESULTS: Table 25 and FIG. 22: Summary of imidaclo after 3 hours. Treatments were replicated a minimum of three prid/Dibutyl Sebacate synergy study against the Argentine times. Evaluations for knockdown/mortality were made at ant: various intervals and at 24 hours after exposure. RESULTS: Table 24 and FIG. 21: Summary of imidaclo Average % Knockdown & prid/Dibutyl Sebacate synergy study against German cock Mortality after roach (T-164 strain) Rate 30 1 2 4 24 Treatment (gfm) min hir hir hir hir 10 UTC O O O O 3 26 Average % Knockdown & imidacloprid (0.5%) O.31 O O O O 55 Mortality after imidacloprid (0.5%) + 0.31 + 3.11 100 100 100 100 100 DBS (5%) imidacloprid (0.5%) + 0.31 + 0.62 O O O 47 81 Rate 30 45 1 2 24 DBS (1%) Treatment (g/m) min min hir hir hir 15 imidacloprid (0.5%) + O31 - 0.06 O O O 7 S4 DBS (0.1%) UTC O O O O O O DBS (5%) O +3.11 S3 100 100 100 100 DBS (1%) O + 0.62 O O O 77 100 imidacloprid (0.5%) O.31 O O O O 2O DBS (0.1%) O -- 0.06 O O O 9 44 imidacloprid (0.5%) + 0.31 + 3.11 100 100 100 100 100 DBS (5%) SUMMARY: No synergistic effect was seen with the three imidacloprid (0.5%) + 0.31 + 0.62 93 100 100 100 100 rates of DBS with imidacloprid tested against the Argentine DBS (1%) ants. DBS alone was toxic to the Argentine ants, and the lower imidacloprid (0.5%) + 0.31 + 0.06 21 43 57 57 43 rates (0.1 & 1.0%) of DBS showed delayed toxicity. DBS (0.1%) 25 Example 23 DBS (5%) O + 3.11 O O 6 13 100 DBS (1%) O + 0.62 O O O O 7 Evaluation of the Synergy of Combination of DBS (0.1%) O -- 0.06 O O O O O Compound A & Compound B with Deltamethrin Against Aedes aegypti Mosquito 30 SUMMARY: A synergistic effect was seen with all rates of The objective of this study was to investigate the Synergis tic effect of deltamethrin in combination with the adjuvant on DBS with imidacloprid against the German cockroaches efficacy against Aedes aegypti mosquito. (T-164 strain). Some recovery was observed at the lowest rate MATERIALS AND METHODS: Aqueous solutions of of DBS (a)0.1% with imidacloprid at 24 hours. DBS alone 35 1% deltamethrin with and without an adjuvant composition, was not toxic to German cockroaches, except at its highest which is sold under the tradename Suspend RSC. The adju rate (5%) tested. vant is a combination of Compound A at 1% and Compound B at 0.5%. Pre-cut fiberglass screen (5"x5", or 161.3 cm) were dipped in each treatment Solution and excessive Solution 40 was allowed to drain completely (see FIG. 23 a). Weight of the solution coated on the screen was then determined. The treated screen was then allowed to air-dry overnight. USDA Example 22 Petri Dish Method was used as initial screening protocol (see FIG. 23 b). Twenty, 4-6 day old female Aedes aegypti were exposed to treated window screen for 3 minutes and then Evaluation of the Synergy of Sebacates with 45 moved onto a clean untreated white paper index card. Treat Imidacloprid Against the Argentine Ant ments were replicated a minimum of three times. Mosquito knockdown was evaluated at 3 minute intervals for the first 15 The objective of this study was to investigate the Synergis minutes and then at 5 minute intervals for the remainder of an tic effect of imidacloprid in combination with sebacates on hour. A small cotton ball with Sucrose solution was added on efficacy against the Argentine ant, Linepithema humile. 50 the screen top of the Petridish as a drinking source. Mortality was evaluated at 24 hours after exposure. MATERIALS AND METHODS: Solutions of imidaclo RESULTS: Table 26 and FIGS. 23a, 23b, and 23c: Sum prid at 0.5% AI were prepared with and without dibutyl seba mary of deltamethrin/adjuvant synergy study against Aedes aegypti mosquito cate (DBS) (a)0.1, 1.0 and 5.0% in acetone. Treatments were 55 applied using a micropipette to dispense 1 ml of test Solution evenly on a 6"x6" glazed tile. Actual coverage was about Average % Knockdown & 5"x5" (or 161 cm) for easy handling. Treatments were Mortality after allowed to dry overnight. Ten Argentine ant workers were 60 Rate 3 9 15 30 60 24 placed within a fluon or talc-coated PVC ring (cp7.6 cmxH5.1 Treatment (g/m) min min min min min hir cm) under continuous exposure. A Small vial filled with a UTC O O O O O O O deltamethrin (1%) O.48 O O O 27 84 100 cotton ball soaked in water was added as a drinking Source deltamethrin (1%) + O.48 16 83 1OO 100 100 100 adjuvant after 3 hours. Treatments were replicated a minimum of three 65 times. Evaluations forant knockdown/mortality were made at adjuvant O O O O 1 3 10 various intervals and at 24 hours after exposure. US 9,028,856 B2 61 62 SUMMARY: Synergy between deltamethrin and adjuvant Five male German cockroaches were placed within a Fluon was observed at 3 minutes after exposure against A. aegypti. coated PVC ring (cp7.6 cmxH5.1 cm) under continuous expo Deltamethrin in combination with adjuvant provides 100% sure. A small vial cap filled with a cotton ball soaked in water mosquito knockdown within 15 minutes after exposure. Del was added as drinking source after 3 hours. Treatments were tamethrin alone provides good knockdown with 100% mor replicated a minimum of three times. Evaluations for cock tality at 24 hours after exposure. roach knockdown/mortality were made at various intervals Example 24 for 1 hour and at 24 hours after exposure. RESULTS: Table 28 and FIG. 25: Summary of delta Evaluation of the Synergy of Combination of methrin/adjuvant synergy study against bait averse German Compound A & Compound B with Deltamethrin 10 Against Argentine Ant cockroach (IHOP strain) The objective of this study was to investigate the Synergis tic effect of deltamethrin in combination with the adjuvant on Average % Mortality after efficacy against Argentine ant, Linepithema humile. 15 MATERIALS AND METHODS: Aqueous solutions of Treatment Rate (g/m) 10 min 30 min 60 min 24 hr deltamethrin at 1% AI were formulated with and without adjuvant. The adjuvant is a combination of Compound A at 1% and Compound B at 0.5%. Treatments were applied using UTC O O O O a micropipette to dispense 1 ml of test solution on 6"x6" deltamethrin (1%) O.62 2O 93 1OO 100 glazed tile. Actual coverage was about 5"x5" (or 161 cm) for deltamethrin (1%) + O.62 2O 87 93 100 easy handling. Treatments were allowed to dry overnight. Ten adjuvant Argentine ant workers were placed within a fluon or talc adjuvant O O O O coated PVC ring (p7.6 cmxH5.1 cm) under continuous expo Sure. Treatments were replicated a minimum of three times. Evaluations for ant knockdown/mortality were made at vari 25 ous intervals for 30 minutes after exposure. SUMMARY: Synergy between deltamethrin at 1% AI and RESULTS: Table 27 and FIG. 24: Summary of delta adjuvant was not seen against bait averse/resistant German methrin/adjuvant synergy study against Argentine ant cockroaches (IHOP). A lower rate of deltamethrin in combi nation with adjuvant may produce a positive response. 30 Average 90 Mortality after Treatment Rate (g/m) 10 min 15 min 20 min 30 min Example 26 UTC O O O O deltamethrin (1%) O.62 9 33 67 82 35 deltamethrin (1%) + O.62 47 94 1OO 100 adjuvant Evaluation of the Synergy of Combination of adjuvant O O 22 56 Compound A & Compound B with Deltamethrin Against Culex quinquefasciatus Mosquito SUMMARY: A synergistic response was observed for del 40 tamethrin and adjuvant against Argentine ant, the evaluations The objective of this study was to investigate the Synergis were terminated at 30 minutes. High mortality in the adjuvant tic effect of deltamethrin in combination with adjuvant on treatment may be due to the Sticky nature of the adjuvant efficacy against Culex quinquefasciatus mosquito. ingredients on glazed tile. deltamethrin was formulated in MATERIALS AND METHODS: Aqueous solutions of water instead of acetone to treat the tiles. As a result, when the 45 adjuvant composition dried, a sticky residue was present on 1% deltamethrin with and without adjuvant were prepared the Surface of the glazed tile, causing some of the ants to get using product sold under the tradename Suspend(RSC. The stuck and die. adjuvant is a combination of Compound A at 1% and Com Example 25 50 pound B at 0.5%. Pre-cut fiberglass screen (5"x5", or 161.3 cm) were dipped in each treatment solution and excessive Evaluation of the Synergy of Combination of solution was allowed to drain completely. Weight of the solu Compound A & Compound B Synergy Deltamethrin tion coated on the screen was then determined. The treated Against Bait Averse/Resistant German Cockroach screen was then allowed to air-dry overnight. USDA Petri (IHOP Strain) 55 Dish Method was used as initial screening protocol. Twenty, The objective of this study was to investigate the Synergis 4-6 day old female Culex quinquefasciatus were exposed to tic effect of deltamethrin in combination with adjuvant on treated window screen for 3 minutes and then moved onto a efficacy against bait averse/resistant German cockroach clean untreated white paper index card. Treatments were rep (IHOP strain), Blattella germanica. 60 MATERIALS AND METHODS: Aqueous solutions of licated a minimum of three times. Mosquito knockdown was deltamethrin at 1% AI were prepared with and without adju evaluated at 3 minute intervals for the first 15 minutes and vant. The adjuvant is a combination of Compound A at 1% then at 5 minute intervals for the remainder of an hour. A and Compound B at 0.5%. Treatments were applied using a Small cotton ball soaked in Sucrose solution was added on the micropipette to dispense 1 ml of treatment solution on 6"x6" 65 glazed tile. Actual coverage was about 5"x5" (or 161 cm) for screen top of the petri-dish as a drinking source. Mortality easy handling. Treatments were allowed to dry overnight. was evaluated at 24 hours after exposure. US 9,028,856 B2 63 64 RESULTS: Table 29 and FIG. 26: Summary of delta MATERIALS AND METHODS: Aqueous solutions of methrin/adjuvant synergy study against Culex quinquefascia deltamethrin at 1% AI were formulated with and without tliS mosquito adjuvant. The adjuvant is a combination of Compound A at 1% and Compound B at 0.5%. Treatments were applied using a micropipette to dispense 1 ml of treatment solution on 6"x6" Average % Knockdown & Mortality after glazed tile. Actual coverage was about 5"x5" (or 161 cm) for easy handling. Treatments were allowed to dry overnight. Ten Rate 15 30 45 60 4 24 Red Imported Fire ant workers were placed within a fluon or Treatment (g/m) min min min min hr hr 10 talc-coated PVC ring (cp7.6 cmxH 5.1 cm) under continuous UTC O O O O O O O exposure. Treatments were replicated minimum three times. deltamethrin (1%) O.48 O 2 3 8 S2 86 Evaluations for ant knockdown/mortality were made at vari deltamethrin (1%) + O.48 2 18 28 43 6O 90 adjuvant ous intervals for 60 minutes after exposure. adjuvant O O O O O O RESULTS: Table 31 and FIG. 28: Summary of delta 15 methrin/adjuvant synergy study against RIFA SUMMARY: Synergy between deltamethrin and adjuvant was seen with Culex. Deltamethrin in combination with adju vant increased speed of knockdown of Culex compared to Average % Mortality after deltamethrin alone with overall mortality being similar at 24 Treatment Rate (g/m) 10 min 20 min 40 min 60 min hours. UTC O O O O Example 27 deltamethrin (1%) O.62 37 100 1OO 100 deltamethrin (1%) + O.62 57 100 1OO 100 Evaluation of the Synergy of Combination of adjuvant Compound A & Compound B with Deltamethrin adjuvant O O O O Against Odorous House Ant 25 SUMMARY: Synergy was not seen with deltamethrin at The objective of this study was to investigate the Synergis 1% AI and adjuvant against RIFA. It is believed that a lower tic effect of deltamethrin in combination with adjuvant on rate of deltamethrin in combination with adjuvant will pro efficacy against Tapinoma sessile, Odorous House ant. duce a positive response. MATERIALS AND METHODS: Aqueous solutions of 30 deltamethrin at 1% AI were formulated with and without adjuvant. The adjuvant is a combination of Compound A at Example 29 1% and Compound B at 0.5%. Treatments were applied using a micropipette to dispense 1 ml of test solution on 6"x6" Evaluation of Synergy of Combination of Compound glazed tile (FIG. 27a). Actual coverage was about 5"x5" (or A & Compound B with Deltamethrin Against 161 cm2) for easy handling. Treatments were allowed to dry 35 Susceptible German Cockroach (Monheim Strain) overnight. Ten Odorous House ant workers were placed within a fluon or talc-coated PVC ring (cp7.6 cmxH 5.1 cm) The objective of this study was to investigate the Synergis under continuous exposure. Treatments were replicated mini mum three times. Evaluations for ant knockdown/mortality tic effect of deltamethrin in combination with adjuvant on were made at various intervals for 2 hours after exposure. 40 efficacy against Susceptible/normal German cockroach RESULTS: Table 30 and FIGS. 27a and 27b: Summary of (Monheim), Blattella germanica. deltamethrin/adjuvant synergy study against Odorous House MATERIALS AND METHODS: Aqueous solutions of ant deltamethrin at 1% AI were prepared with and without adju vant. The adjuvant is a combination of Compound A at 1% 45 and Compound B at 0.5%. Treatments were applied using a Average 90 Mortality after micropipette to dispense 1 ml of treatment solution on 6"x6" glazed tile. Actual coverage was about 5"x5" (or 161 cm) for Treatment Rate (g/m) 20 min 60 min 90 min 2hr easy handling. Treatments were allowed to dry overnight. UTC O O O O Five male German cockroaches were placed within a Fluon deltamethrin (1%) O.62 43 8O 90 93 50 coated PVC ring (cp7.6 cmxH5.1 cm) under continuous expo deltamethrin (1%) + O.62 13 45 58 65 adjuvant Sure. Treatments were replicated a minimum of three times. adjuvant 10 21 25 27 Evaluations for cockroach knockdown/mortality were made at various intervals for 20 minutes after exposure. SUMMARY: Evaluations were terminated after 2 hours RESULTS: Table 32 and FIG. 29: Summary of delta 55 methrin/adjuvant synergy study against German cockroach due to the lack of synergy between deltamethrin and adjuvant against Odorous House ants. (Monheim strain) Example 28 Average % Mortality after Evaluation of Synergy of Combination of Compound 60 A & Compound B with Deltamethrin Against Red Treatment Rate (g/m) 4 min 8 min 12 min 20 min Imported Fire Ant (RIFA) UTC O O O O deltamethrin (1%) O.62 27 1OO 100 100 deltamethrin (1%) + O.62 13 1OO 100 100 The objective of this study was to investigate the Synergis adjuvant tic effect of deltamethrin in combination with adjuvant on 65 adjuvant O O O O efficacy against Red Imported Fire ant (RIFA), Solenopsis invicta. US 9,028,856 B2 65 66 SUMMARY: Synergy between deltamethrin at 1% AI and ment solution on 6"x6" glazed tile. Actual coverage was adjuvant was not seen against Susceptible/normal German about 5"x5" (or 161 cm) for easy handling. Treatments were cockroaches (Monheim). A lower rate of deltamethrin in allowed to dry overnight. Ten Argentine ant workers were combination with adjuvant may produce a positive response. placed within a talc-coated PVC ring (cp7.6 cmxH 5.1 cm) under continuous exposure. A Small vial filled with a cotton Example 30 ball soaked in water was added as a drinking source after 3 hours. Treatments were replicated a minimum of three times. Evaluation of Synergy of Combination of Compound Evaluations for ant knockdown/mortality were made at vari A & Compound B Synergy Thiamethoxam Against ous intervals and at 24 hours after exposure. Aedes aegypti Mosquito 10 RESULTS: Table 34 and FIG. 30: Summary of thia The objective of this study was to investigate the Synergis methoxam/adjuvant synergy study against Argentine ant tic effect of thiamethoxam in combination with adjuvant on efficacy against Aedes aegypti mosquitoes. MATERIALS AND METHODS: A Solution of thia 15 Average % Mortality after methoxam at 1, 0.1 and 0.01% AI were prepared with and without adjuvant in acetone. The adjuvant is a combination of Rate 15 6O 1 3 21 Compound A at 1% and Compound B at 0.5%. Treatments were applied using a micropipette to dispense 1 ml of test Treatment (g/m) min min hr hr hir solution evenly on 6"x6" glazed tile. Actual coverage was about 5"x5" (or 161 cm) for easy handling. Treatments were UTC O O O O 25 allowed to dry overnight. USDA Petri Dish Method was used Thiamethoxam (1%) O.62 3 6 22 34 100 as initial screening protocol. Twenty, 4-6 day old female Thiamethoxam (1%) + O.62 O O 73 89 100 Aedes aegypti mosquitoes were exposed to each treatment for adjuvant 3 minutes and then moved to a clean untreated white paper 25 Thiamethoxam (0.1%) O.O6 12 21 36 46 100 index card. Treatments were replicated a minimum of three Thiamethoxam (0.1%) + O.O6 3 21 79 97 100 times. Mosquito knockdown was evaluated at various inter adjuvant vals through 7 hours after exposure. A small cotton ball soaked in Sucrose solution was added on the Screen top of the Thiamethoxam (0.01%) O.OO6 O 3 13 19 100 Thiamethoxam (0.01%) + O.OO6 O O 55 77 100 petri-dish as a drinking source. Mortality was evaluated at 24 30 hours after exposure. adjuvant RESULTS: Table 33 (no figure): Summary of thia adjuvant O O 12 29 88 methoxam/adjuvant synergy study against Aedes aegypti mosquito 35 SUMMARY: All rates of thiamethoxam in combination with adjuvant showed a synergistic effect against Argentine Average % Knockdown & ant for speed of knockdown (FIG. 30). Overallant mortality Rate Mortality after was equivalent against thiamethoxam with or without adju Treatment (g/m) 2 hr 3 hr 7r 24 hr vant. Synergy was still evident even though adjuvant-only 40 UTC O O O O treatment had high ant mortality. Thiamethoxam (1%) O.62 2 2 4 4 Thiamethoxam (1%) + O.62 4 5 5 5 adjuvant Example 32 Thiamethoxam (0.1%) O.O6 O O O O Thiamethoxam (0.1%) + O.O6 O O O 2 adjuvant 45 Evaluation of Synergy of Combination of Compound Thiamethoxam (0.01%) O.OO6 O O O O A & Compound B with Thiamethoxam Against Thiamethoxam (0.01%) + O.OO6 2 6 13 13 adjuvant Odorous House Ant adjuvant 2 2 2 2 50 The objective of this study was to investigate the Synergis SUMMARY: No activity was observed with thia tic effect of thiamethoxam in combination with adjuvant on methoxam and adjuvant against Aedes aegypti mosquito. efficacy against Odorous House ant, Tapinoma sessile. MATERIALS AND METHODS: Solutions of thia Example 31 methoxam at 1, 0.1 and 0.01% AI were prepared with and 55 Evaluation of Synergy of Combination of Compound without adjuvant in acetone. The adjuvant is a combination of A & Compound B with Thiamethoxam Against Compound A at 1% and Compound B at 0.5%. Treatments Argentine Ant were applied using a micropipette to dispense 1 ml of test solution evenly on a 6"x6" glazed tile. Actual coverage was The objective of this study was to investigate the Synergis 60 about 5"x5" (or 161 cm) for easy handling. Treatments were tic effect of thiamethoxam in combination with adjuvant on allowed to dry overnight. Ten odorous house ant workers efficacy against Argentine ant, Linepithema humile. were placed within a talc-coated PVC ring (cp7.6 cmxH 5.1 MATERIALS AND METHODS: Solutions of thia cm) under continuous exposure. A Small vial cap filled with a methoxam at 1, 0.1 and 0.01% AI were prepared with and cotton ball soaked in water was added as a drinking Source without adjuvant in acetone. The adjuvant is a combination of 65 after 3 hours. Treatments were replicated minimum three Compound A at 1% and Compound B at 0.5%. Treatments times. Evaluations forant knockdown/mortality were made at were applied using a micropipette to dispense 1 ml of treat various intervals and at 24 hours after exposure. US 9,028,856 B2 67 68 RESULTS: Table 35 and FIG. 31: Summary of thia -continued methoxam/adjuvant synergy study against Odorous House ant Average % Knockdown & Mortality after

Rate 30 60 90 3 24 Average % Knockdown & Treatment (g/m) min min min hir hir Mortality after Thiamethoxam (0.1%) O.O6 7 73 93 100 100 Rate 15 30 6O 2 20 Thiamethoxam (0.1%) + O.O6 7 87 100 100 100 Treatment (g/m) min min min hr hr adjuvant 10 Thiamethoxam (0.01%) O.OO6 13 67 87 100 100 UTC O O O O O 10 Thiamethoxam (0.01%) + O.OO6 7 53 93 100 100 Thiamethoxam (1%) O.62 O O O 21 65 adjuvant Thiamethoxam (1%) + O.62 O O 7 13 70 adjuvant O O O O O 7 adjuvant Thiamethoxam (0.1%) O.O6 O O O 3 33 Thiamethoxam (0.1%) + O.O6 O 4 11. 32 61 15 SUMMARY: Thiamethoxam at 1% in combination with adjuvant adjuvant showed a synergistic effect against Susceptible Ger Thiamethoxam (0.01%) O.OO6 O O O 9 71 Thiamethoxam (0.01%) + O.OO6 3 9 23 31 60 man cockroach for speed of knockdown (FIG.32). At 3 hours adjuvant after exposure, cockroach knockdown/mortality was similar adjuvant O O O O O 22 with and without adjuvant. The lower rates of thiamethoxam showed no synergy with the adjuvant SUMMARY: Thiamethoxam at 0.1% in combination with Example 34 adjuvant showed an increase in speed of knockdown and efficacy compared to thiamethoxam alone (FIG. 31). No Evaluation of Synergy of Combination of Compound treatment reached 100% control of Odorous House ant. A & Compound B with Resmethrin Against Aedes 25 aegypti Mosquito Example 33 The objective of this study was to investigate the Synergis tic effect of resmethrin in combination with adjuvant on effi cacy against Aedes aegypti mosquitoes. Evaluation of Synergy of Combination of Compound 30 MATERIALS AND METHODS: Solutions of resmethrin A & Compound B with Thiamethoxam Against at 1 and 0.5% AI were prepared with and without adjuvant in Susceptible German Cockroach (Monheim Strain) acetone. The adjuvant is a combination of Compound A at 1% and Compound B at 0.5%. Treatments were applied using a The objective of this study was to investigate the Synergis micropipette to dispense 1 ml of test solution evenly on 6"x6" 35 glazed tile. Actual coverage was about 5"x5" (or 161 cm) for tic effect of thiamethoxam in combination with adjuvant on easy handling. Due to the extremely short half life of res efficacy against Susceptible/normal German cockroach strain methrin exposed to light, treatments were covered with alu (Monheim strain). minum foil and placed in a dark room to dry (2-3 hours). MATERIALS AND METHODS: Solutions of thia USDA Petri Dish Method was used as initial screening pro methoxam at 1.0, 0.1 and 0.01% AI were prepared with and 40 tocol. Twenty, 4-6 day old female Aedes aegypti mosquitoes without adjuvant in acetone. The adjuvant is a combination of were exposed to each treatment for 3 minutes and then moved Compound A at 1% and Compound B at 0.5%. Treatments to a clean untreated white paper index card. Treatments were were applied using a micropipette to dispense 1 ml of test replicated a minimum of three times. Mosquito knockdown solution evenly on a 6"x6" glazed tile. Actual coverage was was evaluated at 3 minute intervals for the first 15 minutes and about 5"x5" (or 161 cm) for easy handling. Treatments were 45 then at 5 minute intervals for the remainder of an hour. A allowed to dry overnight. Five male German cockroaches Small cotton ball soaked in Sucrose solution was added on the were placed within a talc-coated PVC ring (cp7.6 cmxH 5.1 screen top of the petri-dish as a drinking source. Mortality cm) under continuous exposure. A Small vial cap filled with a was evaluated at 24 hours after exposure. cotton ball soaked in water was added as a drinking Source RESULTS: Table 37 and FIG.33: Summary of resmethrin/ after 3 hours. Treatments were replicated a minimum of three 50 adjuvant synergy study against Aedes aegypti mosquito times. Evaluations for knockdown/mortality were made at various intervals and at 24 hours after exposure. Average % Knockdown & RESULTS: Table 36 and FIG. 32: Summary of thia Rate Mortality after methoxam/adjuvant synergy study against German cock 55 Treatment (g/m) 3 min 15 min 30 min 60 min 24 hr roach (Monheim) UTC O O O O 2 Resmethrin (1%) O.62 66 100 100 1OO 1OO Resmethrin (1%) + O.62 26 65 66 71 71 Average % Knockdown & adjuvant Mortality after 60 Resmethrin (0.5%) O.31 O O O O 8 Resmethrin O.31 25 97 100 1OO 1OO Rate 30 60 90 3 24 (0.5%) + adjuvant Treatment (g/m) min min min hir hir UTC O O O O O 7 Thiamethoxam (1%) O.62 13 73 8O 93 100 SUMMARY: Although an antagonistic effect was seen Thiamethoxam (1%) + O.62 60 1OO 100 100 100 65 with resmethrin at 1% in combination with adjuvant, an adjuvant increase in efficacy was seen with resmethrin at 0.5% AI and adjuvant against Aedes aegypti (FIG.33) Resmethrin at 0.5% US 9,028,856 B2 69 70 AI alone did not provide mosquito knockdown; however, the an effective rate range, aqueous solutions of permethrin at addition of adjuvant caused a significant increase in efficacy 1.25, 1.0 and 0.05% AI were prepared with and without to nearly 100% in 15 minutes. adjuvant. The adjuvant is a combination of Compound A at 1% and Compound B at 0.5%. Pre-cut fiberglass screens Example 35 (5"x5" or 161.3 cm) were dipped in each treatment solution allowing excessive solution to drain completely. Weight of Evaluation of Synergy of Combination of Compound the solution coated on the screen was then determined. The A & Compound B with Resmethrin Against Culex treated screen was then allowed to air-dry overnight. USDA quinquefasciatus Mosquito Petri Dish Method was used as initial screening protocol (see 10 photo, right). Twenty, 4-6 day old female Aedes aegypti were The objective of this study was to investigate the Synergis exposed to treated window screen for 3 minutes and then tic effect of Resmethrin in combination with adjuvant on moved to a clean untreated white paper index card. Treat efficacy against Culex quinquefasciatus mosquitoes. ments were replicated a minimum of three times. Mosquito MATERIALS AND METHODS: Solutions of resmethrin 15 knockdown was evaluated at 3 minute intervals for the first 15 at 1 and 0.5% AI were prepared with and without adjuvant in minutes and then at 5 minute intervals for the remainder of an acetone. The adjuvant is a combination of Compound A at 1% and Compound B at 0.5%. Treatments were applied using a hour. A small cotton ball with Sucrose solution was added on micropipette to dispense 1 ml of test solution evenly on 6"x6" the screen top of the petri-dish as a drinking source. Mortality glazed tile. Actual coverage was about 5"x5" (or 161 cm) for was evaluated at 24 hours after exposure. easy handling. Due to the extremely short half life of res RESULTS: Tables 39 and 40 and FIG. 35: Summary of methrin exposed to light, treatments were covered with alu Permethrin without adjuvant against Aedes aegypti mosquito minum foil and placed in a dark room to dry (2-3 hours). USDA Petri Dish Method was used as initial screening pro tocol. Twenty, 4-6 day old female Culex quinquefasciatus Average % Knockdown & mosquitoes were exposed to each treatment for 3 minutes and 25 Mortality after then moved to a clean untreated white paper index card. Treatments were replicated a minimum of three times. Mos Rate 3 9 15 30 60 24 quito knockdown was evaluated at 3 minute intervals for the Treatment (g/m) min min min min min hir first 15 minutes and then at 5 minute intervals for the remain 30 der of an hour. A Small cotton ball soaked in Sucrose solution UTC O O O O O O O was added on the screen top of the petri-dish as a drinking Permethrin (5%) 2.4 75 1OO 100 100 100 100 source after the 2 hour evaluation. Mortality was evaluated at 24 hours after exposure. Permethrin (2.5%) 1.2 56 100 100 100 100 100 RESULTS: Table 38 and FIG. 34: Summary of Res Permethrin (1.75%) O.84 40 95 100 100 100 100 methrin/adjuvant synergy study against Culex quinquefascia 35 Permethrin (1.5%) * 0.72 O O 2 2 3 16 tus mosquito Permethrin O.60 46 71 71 72 79 82 (1.25%) * Permethrin (1.0%) O.48 O 2 2 5 18 34 Average % Knockdown & Permethrin (0.5%) O.24 O O O O O 9 Mortality after 40 Permethrin (0.1%) O.OS O O O O O 5 Rate 3 15 30 6O 2 24 Treatment (g/m) min min min min hr hr Possible error with dilution of Permethrin at 1.5% Al and for 1.25% Al. UTC O O O O O O Table 40 (No Figure): Summary of Permethrin/Adjuvant Resmethrin (1%) O.62 O 2 13 11 2 4 45 Resmethrin (1%) + O.62 O 2 2 2 2 O Study Against Aedes aegypti Mosquito adjuvant Resmethrin (0.5%) O.31 O O O O O O Resmethrin (0.5%) + O.31 2 49 53 55 51 34 adjuvant Average % Knockdown & Mortality after 50 SUMMARY: Although some mosquito recovery occurred Rate 3 9 15 30 60 24 with resmethrin at 0.5% AI and adjuvant, synergy was still Treatment (g/m) min min min min min hir evident (FIG. 34). UTC O O O O O O O Permethrin (1.25%) O.60 O O 2 2 3 7 Permethrin O.60 O 19 31 40 47 50 Example 36 55 (1.25%) + adjuvant Permethrin (1.0%) O.48 2 2 2 4 13 28 Evaluation of Synergy of Combination of Compound Permethrin O.48 O 3 12 44 64 64 A & Compound B with Permethrin Against Aedes (1.0%) + adjuvant aegypti Mosquito Permethrin (0.5%) O.24 O 1 1 O O 6 Permethrin O.24 3 41 8O 95 1OO 100 60 (0.5%) + adjuvant The objective of this study was to investigate the Synergis adjuvant O O O O O O tic effect of permethrin in combination with adjuvant on efficacy against Aedes aegypti mosquito. MATERIALS AND METHODS: Several rates of per SUMMARY: A synergistic effect was seen with per methrin without adjuvant were prepared using product sold 65 methrin and adjuvant at all three rates tested; however, per under the tradename Permanone R 40 to determine an effec methrin at 0.5% AI with adjuvant showed the greatest tive rate against Aedes aegypti mosquitoes. After determining increase in mosquito knockdown and mortality. US 9,028,856 B2 71 72 Example 37 RESULTS: Table 42 and FIG.37: Summary of Permethrin/ adjuvant synergy study against baitaverse Germancockroach Evaluation of Synergy of Combination of Compound (IHOP) A & Compound B with Permethrin Against Argentine Ant Average 90 Mortality after The objective of this study was to investigate the Synergis Treatment Rate (g/m) 10 min 20 min 40 min 60 min tic effect of permethrin in combination with adjuvant on efficacy against Argentine ant, Linepithema humile. UTC O O O O 10 Permethrin (0.5%) O.31 40 87 93 100 MATERIALS AND METHODS: Aqueous solutions of Permethrin (0.5%) + O.31 2O 87 1OO 100 permethrin at 0.5% AI were prepared with and without adju adjuvant vant. The adjuvant is a combination of Compound A at 1% adjuvant O O O O and Compound B at 0.5%. Treatments were applied using a micropipette to dispense 1 ml of treatment solution on 6"x6" glazed tile. Actual coverage was about 5"x5" (or 161 cm) for 15 SUMMARY: Permethrin is very fast acting against a bait easy handling. Treatments were allowed to dry overnight. Ten adverse strain of German cockroaches (IHOP), with or with Argentine ant workers were placed within a fluon or talc out added adjuvant (see FIG. 37). In situations such as this, coated PVC ring (p7.6 cmxH5.1 cm) under continuous expo where the insecticidal agent works very quickly, presumably Sure. Treatments were replicated a minimum of three times. by quickly penetrating the insect cuticle even in the absence Evaluations for ant knockdown/mortality were made at 5 of an adjuvant (permethrin referred to in Table 1 as fast with minute intervals for 20 minutes after exposure. a Log P of 6.1), Synergism may not be observed readily at all RESULTS: Table 41 and FIG. 36: Summary of permethrin/ concentrations. It is believed that by using the adjuvant, in this adjuvant synergy study against Argentine ant case a free radical stabilizer, one can achieve high mortality 25 with lower rates of permethrin, compared to using permethrin alone, against bait averse/resistant German cockroaches. Average 90 Mortality after Treatment Rate (g/m) 5 min 10 min 15 min 20 min Example 39 UTC O O O O 30 Permethrin (0.5%) O.31 58 100 1OO 100 Evaluation of Synergy of Combination of Compound Permethrin (0.5%) + O.31 78 1OO 1OO 100 adjuvant A & Compound B with Permethrin Against Odorous adjuvant O O O O House Ant

35 SUMMARY: Evaluations were terminated at 20 minutes The objective of this study was to investigate the Synergis due to 100% ant mortality. No significant difference was seen tic effect of permethrin in combination with adjuvant on between permethrin alone and permethrin with adjuvant efficacy against Odorous House ant, Tapinoma sessile. (FIG. 36). It is believed that lower rates of permethrin can be MATERIALS AND METHODS: Aqueous solutions of used synergistically with an adjuvant, likely functioning, in 40 permethrin at 0.5% AI were prepared with and without adju this instance, as free radical stabilizers, and this will show vant. The adjuvant is a combination of Compound A at 1% comparable efficacy as higher rates of permethrin in the and Compound B at 0.5%. Treatments were applied using a absence of such free radical stabilizers. micropipette to dispense 1 ml of treatment solution on 6"x6" glazed tile. Actual coverage was about 5"x5" (or 161 cm) for Example 38 45 easy handling. Treatments were allowed to dry overnight. Ten Odorous House ant workers were placed within a fluon or Evaluation of Synergy of Combination of Compound talc-coated PVC ring (cp7.6 cmxH 5.1 cm) under continuous A & Compound B with Permethrin Against Bait exposure. Treatments were replicated minimum three times. Averse/Resistant German Cockroach (IHOP Strain) Evaluations for ant knockdown/mortality were made at 5 50 minute intervals for 60 minutes after exposure. The objective of this study was to investigate the Synergis tic effect of permethrin in combination with adjuvant on RESULTS: Table 43 and FIG.38: Summary of Permethrin/ efficacy against bait averse/resistant German cockroach adjuvant synergy study against Odorous House ant (IHOP strain), Blattella germanica. 55 MATERIALS AND METHODS: Aqueous solutions of Average % Mortality after permethrin at 0.5% AI were prepared with and without adju vant. The adjuvant is a combination of Compound A at 1% Treatment Rate (g/m) 10 min 20 min 30 min 60 min and Compound B at 0.5%. Treatments were applied using a UTC O O O O 60 Permethrin (0.5%) O.31 13 50 93 100 micropipette to dispense 1 ml of treatment solution on 6"x6" Permethrin (0.5%) + O.31 97 100 1OO 100 glazed tile. Actual coverage was about 5"x5" (or 161 cm) for adjuvant easy handling. Treatments were allowed to dry overnight. adjuvant O O O O Five male German cockroaches were placed within a Fluon coated PVC ring (p7.6 cmxH5.1 cm) under continuous expo 65 SUMMARY: Permethrin at 0.5% AI with adjuvant showed sure. Evaluations for cockroach knockdown/mortality were synergy against Odorous House ants (FIG. 38). Evaluations made at various intervals and at 60 minutes after exposure. were terminated after 60 minutes due to 100% ant control. US 9,028,856 B2 73 74 Example 40 and Compound B at 0.5%. Treatments were applied using a micropipette to dispense 1 ml of treatment solution on 6"x6" Evaluation of Synergy of Combination of Compound glazed tile. Actual coverage was about 5"x5" (or 161 cm) for A & Compound B with Permethrin Against Red easy handling. Treatments were allowed to dry overnight. Five male German cockroaches were placed within a Fluon Imported Fire Ant 5 coated PVC ring (cp7.6 cmxH5.1 cm) under continuous expo Sure. Treatments were replicated a minimum of three times. The objective of this study was to investigate the Synergis Evaluations for cockroach knockdown/mortality were made tic effect of permethrin in combination with adjuvant on at 10 minute intervals for 30 minutes and at 4 hours after efficacy against Red Imported Fire ant, Solenopsis invicta. exposure. MATERIALS AND METHODS: Aqueous solutions of 10 RESULTS: Table 45 and FIG.40: Summary of Permethrin/ permethrin at 0.5% AI were prepared with and without adju adjuvant synergy study against bait normal German cock vant. The adjuvant is a combination of Compound A at 1% roach (Monheim) and Compound B at 0.5%. Treatments were applied using a micropipette to dispense 1 ml of treatment solution on 6"x6" glazed tile. Actual coverage was about 5"x5" (or 161 cm) for Average % Mortality after easy handling. Treatments were allowed to dry overnight. Ten Red Imported Fire ant workers were placed within a fluon or Treatment Rate (g/m) 10 min 20 min 30 min 4hr talc-coated PVC ring (cp7.6 cmxH 5.1 cm) under continuous UTC O O O O exposure. Treatments were replicated a minimum of three Permethrin (0.5%) O.31 1OO 100 1OO 100 Permethrin (0.5%) + O.31 1OO 100 1OO 100 times. Evaluations forant knockdown/mortality were made at adjuvant various intervals and at 60 minutes after exposure. adjuvant O O O O RESULTS: Table 44 and FIG.39: Summary of Permethrin/ adjuvant synergy study against RIFA SUMMARY: As shown in FIG. 40, permethrin was effec 25 tive against Susceptible/normal German cockroach Strain Average %. Mortality after (Monheim), even in the absence of the added free radical stabilizers. Although this rate of permethrin appears too high Treatment Rate (g/m) 5 min 15 min 30 min 60 min to show Synergy with adjuvant against a susceptible/normal UTC O 3 3 3 German cockroach strain (Monheim), it is believed that lower Permethrin (0.5%) O.31 43 100 1OO 100 30 rates of permethrin can be used, in combination with an Permethrin (0.5%) + O.31 93 100 1OO 100 adjuvant acting as a free radical stabilizers, than permethrin adjuvant alone, to achieve a comparable mortality rate in a comparable adjuvant 3 3 7 7 amount of time. SUMMARY: Permethrin is active against Red Imported 35 Example 42 Fire ants, even in the absence of an adjuvant that works as a free radical stabilizer. Thus, the synergistic effect is minimal Evaluation of Synergy of Compound A with Fipronil (see FIG. 39). One can see that near 100% mortality was Against Argentine Ant achieved in about 6 minutes when the adjuvant was added, versus about 13 minutes in the absence of the adjuvant. Due to 40 The objective of this study was to investigate the Synergis 100% ant mortality, evaluations were terminated after 60 tic effect of fipronil in combination with Compound A on minutes. It is believed that lower application rates of per efficacy against Argentine ant, Linepithema humile. methrin can be used, when combined with free radical stabi MATERIALS AND METHODS: Solutions of fipronil at lizers, to achieve the same results. 0.01 and 0.001% AI were prepared with and without Com 45 pound A at 1, 0.1, and 0.01% in acetone. Treatments were Example 41 applied using a micropipette to dispense 1 ml of treatment solution on 6"x6" glazed tile. Actual coverage was about Evaluation of Synergy of Combination of Compound 5"x5" (or 161 cm) for easy handling. Treatments were A & Compound B with Permethrin Against allowed to dry overnight. Ten Argentine ant workers were Susceptible German Cockroach (Monheim Strain) 50 placed within a talc-coated PVC ring (cp7.6 cmxH 5.1 cm) under continuous exposure. A Small vial filled with a cotton The objective of this study was to investigate the Synergis ball soaked in water was added as a drinking source after 3 tic effect of permethrin in combination with adjuvant on hours. Treatments were replicated a minimum of three times. efficacy against Susceptible/normal German cockroach Evaluations for ant knockdown/mortality were made at vari (Monheim strain), Blattella germanica. 55 ous intervals and at 24 hours after exposure. MATERIALS AND METHODS: Aqueous solutions of RESULTS: Table 46, Trial 1, see also FIG. 41 permethrin at 0.5% AI were prepared with and without adju Summary of Fipronil/Compound A Synergy study against vant. The adjuvant is a combination of Compound A at 1% Argentine ant

Rate Average 90 Mortality after Treatment (g/m) 5 min 15 min 30 min 60 min 2 hr 4 hr 24hr UTC O O O O O O 21 Fipronil (.01%) O.OO62 O O O O O 47 100 Fipronil (.01%) + Compound A O.0062 10 76 1OO 100 1OO 100 100 (1%) US 9,028,856 B2 75 76 -continued Rate Average % Mortality after Treatment (g/m) 5 min 15 min 30 min 60 min 2 hr 4 hr 24 hr Fipronil (.01%) + Compound A 0.0062 O O O O 29 100 100 (0.1%) Fipronil (.01%) + Compound A 0.0062 O O O O O 1 OO 100 (0.01%) Fipronil (.001%) O.OOO62 O O O O O 74 100 Fipronil (.001%) + Compound A 0.00062 10 81 100 100 1OO 100 100 (1%) Fipronil (.001%) + Compound A 0.00062 O O O O O 61 100 (0.1%) Fipronil (.001%) + Compound A 0.00062 O O O O O 93 100 (0.01%) Compound A (1%) O 33 1OO 100 100 1OO 100 100 Compound A (0.01%) O O O O O O O 13

Trial 2, Table 47, see FIG. 41: Summary of Fipronil/Com pound A Synergy study against Argentine ant

Rate Average % Mortality after Treatment (g/m) 5 min 15 min 30 min 60 min 2 hr 4 hr 24 hr UTC O O O O O O 7 Fipronil (.001%) O.OOO62 O O O O O 28 100 Fipronil (.001%) + Compound A (1%) O.OOO62 O 94 100 1OO 1OO 100 100 Fipronil (.001%) + Compound A O.OOO62 O O O O O 3 100 (0.1%) Fipronil (.001%) + Compound A O.OOO62 O O O O O 21 100 (0.01%) Compound A (1%) O O 65 94 1OO 1OO 100 100 Compound A (0.1%) O O O O O O 13 19 Compound A (0.01%) O O O O O O 3 26 Combination (Compound A+ O O O O O 19 52 71 Compound B)

SUMMARY: Although both rates of fipronil in combina- 40 MATERIALS AND METHODS: Solutions of fipronil at tionknockdown with Compound and mortality A (1%) against showed Argentine increased ant, Compound speed of 0.01, 0.001 and 0.0001% AI were prepared with and without A (1%) alone also displayed the same efficacy. A second trial adjuvant in acetone. The adjuvant is a combination of Com was conducted to repeat Fipronil at 0.001% AI in combina- pound A at 1% and Compound B at 0.5%. Treatments were tion with the three rates of Compound A. Compound A (0.1%) 45 applied using a micropipette to dispense 1 ml of test Solution alone and the Combination (Compound A+Compound B) were also added for comparison. The same results were evenly on 6"x6" glazed tile. Actual coverage was about 5"x5" achieved in the second trial as in the first. Argentine ant (or 161 cm) for easy handling. Treatments were allowed to efficacy with fipronil (0.001%) in combination with Com- d ight. USDA Petri Dish Method d as initial pound A (1%) was very similar to Compound A (1%) alone. 50 ry overnight. C1 J1S VOC. WaS USC aS 1118 This data is summarized in FIG. 41. The single adjuvant screening protocol. Twenty, 4-6 day old female Aedes aegypti (Compound A) had significant ant mortality at 24 hours, as mosquitoes were exposed to each treatment for 3 minutes and previously seen with Combination (Compound A and Com pound B, Supra) the Argentine ant; however, Compound A then moved to a clean untreated white paper index card. (1%) alone was more toxic to Argentine ant. The addition of 55 Treatments were replicated a minimum of three times. Mos only Compound A to fipronil appears to increase the speed of quito knockdown was evaluated at various intervals through 6 knockdown, but not to provide a synergistic effect. hours after exposure. A Small cotton ball soaked in Sucrose Example 43 Solution was added on the Screen top of the petri-dish as a 60 - Evaluation of Synergy of Combination of Compound drinkrinking source.. MortalityMortal was evaluatedluated aat 24 hOUIS a ft A & Compound B with Fipronil Against Aedes exposure. aegypti Mosquito The objective of this study was to investigate the Synergis- 65 tic effect offipronil in combination with adjuvant on efficacy RESULTS: Table 48 and FIG. 42: Summary of Fipronil/ against Aedes aegypti mosquitoes. adjuvant synergy study against Aedes aegypti mosquito US 9,028,856 B2 77 78

Average % Knockdown & Mortality after Treatment Rate (g/m) 15 min 30 min 60 min 4hr 6 hr 24hr UTC O O O O O 2 Fipronil (.01%) O.0062 5 6 19 42 56 72 Fipronil (.01%) + O.0062 17 28 41 51 62 91 adjuvant Fipronil (.001%) O.OOO62 O O O O 3 3 Fipronil (.001%) + O.OOO62 4 4 13 7 7 7 adjuvant Fipronil (.0001%) O.OOOO62 O O O 3 3 9 Fipronil (.0001%) + O.OOOO62 O O 2 1 11 22 adjuvant adjuvant O O O O O O

15 SUMMARY: A synergistic effect was seen with fipronil at acting as a free radical stabilizer, as compared to around 25 0.01% AI in combination with adjuvant against Aedes aegypti hours in the absence of the adjuvant. mosquito (see FIG. 42). Example 45 Example 44 Evaluation of Synergy of Combination of Compound Evaluation of Synergy of Combination of Compound A & Compound B with Fipronil Against Culex A & Compound B with Fipronil Against Argentine quinquefasciatus Mosquito Ant 25 The objective of this study was to investigate the Synergis The objective of this study was to investigate the Synergis tic effect offipronil in combination with adjuvant on efficacy tic effect offipronil in combination with adjuvant on efficacy against Culex quinquefasciatus mosquitoes. against Argentine ant, Linepithema humile. MATERIALS AND METHODS: Solutions of Fipronil at MATERIALS AND METHODS: Solutions of fipronil at 30 0.01, 0.001 and 0.0001% AI were prepared with and without 0.01, 0.001 and 0.0001% AI were prepared with and without adjuvant in acetone. The adjuvant is a combination of Com adjuvant in acetone. The adjuvant is a combination of Com pound A at 1% and Compound B at 0.5%. Treatments were pound A at 1% and Compound B at 0.5%. Treatments were applied using a micropipette to dispense 1 ml of test Solution applied using a micropipette to dispense 1 ml of treatment evenly on 6"x6" glazed tile. Actual coverage was about 5"x5" solution on 6"x6" glazed tile. Actual coverage was about 35 (or 161 cm) for easy handling. Treatments were allowed to 5"x5" (or 161 cm) for easy handling. Treatments were dry overnight. USDA Petri Dish Method was used as initial allowed to dry overnight. Ten Argentine ant workers were screening protocol. Twenty, 4-6 day old female Culex mos placed within a fluon or talc-coated PVC ring (cp7.6 cmxH5.1 quitoes were exposed to each treatment for 3 minutes and then cm) under continuous exposure. A Small vial filled with a moved to a clean untreated white paper index card. Treat cotton ball soaked in water was added as a drinking Source 40 ments were replicated a minimum of three times. Mosquito after 3 hours. Treatments were replicated a minimum of three knockdown was evaluated at various intervals through 3 times. Evaluations forant knockdown/mortality were made at hours after exposure. A Small cotton ball soaked in Sucrose various intervals and at 24 hours after exposure. Solution was added on the Screen top of the petri-dish as a RESULTS: Table 49 and FIG. 43: Summary of Fipronil/ 45 drinking source. Mortality was evaluated at 24 hours after adjuvant synergy study against Argentine ant exposure. RESULTS: Table 50 and FIG. 44: Summary of Fipronil/ adjuvant synergy study against Culex quinquefasciatus mos Rate Average 90 Mortality after quito Treatment (g/m) 30 min 60 min 2 hr 3 hr 24hr 50 UTC O O O O 3 Rate Average % Knockdown & Mortality after Fipronil (.01%) O.OO62 O O O O 100 Fipronil (.01%) + O.OO62 9 56 82 1OO 100 Treatment (g/m) 30 min 60 min 2hr 3 hr 24 hr adjuvant Fipronil (.001%) O.OOO62 O O O 3 100 55 UTC O O O O O Fipronil (.001%) + O.OOO62 30 76 91 1OO 100 Fipronil (.01%) O.0062 O O O O 48 adjuvant Fipronil (.01%) + O.0062 O O 2 2 95 Fipronil (.0001%) OOOOO62 O O O O 74 adjuvant Fipronil (.0001%) + 0.000062 O 3 3 9 71 Fipronil (.001%) O.OOO62 O O O O 2 adjuvant Fipronil (.001%) + O.OOO62 O 5 5 4 O adjuvant O O 3 12 73 adjuvant 60 adjuvant O O O O O SUMMARY: In this trial, fipronil at 0.001% AI in combi nation with adjuvant showed a increase in efficacy against SUMMARY: Although no initial synergy was seen with Argentine ant. Synergy was also seen with adjuvant and fipronil and adjuvant, an increase in efficacy was seen with fipronil at 0.01%. The results are summarized in FIG. 43. As 65 fipronil at 0.01% AI in combination with adjuvant at 24 hours shown in FIG. 43, 100% mortality was seen in as little as 4 (FIG.44). Indeed, mortality approaching 100% was observed hours when fipronil is combined with the adjuvant, believed when the free radical stabilizer was combined with fipronil, US 9,028,856 B2 79 80 compared to around 50% mortality in the absence of the adjuvant in acetone. The adjuvant is a combination of Com adjuvant, believed to be acting as a free radical stabilizer. pound A at 1% and Compound B at 0.5%. Treatments were applied using a micropipette to dispense 1 ml of treatment Example 46 solution on 6"x6" glazed tile. Actual coverage was about 5"x5" (or 161 cm) for easy handling. Treatments were Evaluation of Synergy of Combination of Compound allowed to dry overnight. Ten Red Imported Fire ant workers A & Compound B with Fipronil Against Odorous were placed within a talc-coated PVC ring (cp7.6 cmxH 5.1 House Ant cm) under continuous exposure. A Small vial filled with a 10 cotton ball soaked in water was added as a drinking Source The objective of this study was to investigate the Synergis after 3 hours. Treatments were replicated a minimum of three tic effect offipronil in combination with adjuvant on efficacy times. Evaluations forant knockdown/mortality were made at against Odorous House ant, Tapinoma sessile. various intervals and at 24 hours after exposure. MATERIALS AND METHODS: Solutions of Fipronil at RESULTS: Table 52 and FIG. 46: Summary of Fipronil/ 0.01, 0.001 and 0.0001% AI were prepared with and without 15 adjuvant synergy study against Red Imported Fire ant adjuvant in acetone. The adjuvant is a combination of Com pound A at 1% and Compound B at 0.5%. Treatments were applied using a micropipette to dispense 1 ml of treatment Rate Average % Mortality after solution on 6"x6" glazed tile. Actual coverage was about 5"x5" (or 161 cm) for easy handling. Treatments were Treatment (g/m) 30 min 60 min 2 hr 3 hr 24hr allowed to dry overnight. Ten Odorous House ant workers were placed within a talc-coated PVC ring (cp7.6 cmxH 5.1 UTC 11 cm) under continuous exposure. A Small vial filled with a Fipronil (.01%) O.0062 1OO cotton ball soaked in water was added as a drinking Source Fipronil (.01%) + O.0062 38 76 1OO after 3 hours. Treatments were replicated a minimum of three 25 adjuvant times. Evaluations forant knockdown/mortality were made at Fipronil (.001%) O.OOO62 O O O 25 1OO various intervals and at 24 hours after exposure. Fipronil (.001%) + O.OOO62 12 18 82 RESULTS: Table 51 and FIG. 45: Summary of Fipronil/ adjuvant adjuvant synergy study against Odorous House ant 30 Fipronil (.0001%) OOOOO62 3 3 3 6 47 Fipronil (.0001%) + 0.000062 O O O 3 50 Average % Mortality after adjuvant adjuvant O O O 3 65 Treatment Rate (g/m) 30 min 60 min 2hr 24 hr UTC O O O 3 35 Fipronil (.01%) O.0062 O O 6 100 SUMMARY: A synergistic effect was seen with fipronil at Fipronil (.01%) + O.0062 44 79 97 100 0.01% AI in combination with adjuvant against Red Imported adjuvant Fipronil (.001%) O.OOO62 O O O 100 Fireant (see FIG. 46). As shown in FIG. 47, a relatively high Fipronil (.001%) + O.OOO62 39 70 97 100 percentage of mortality (around 80%) was observed in just adjuvant 40 around 3 hours when the adjuvant, believed to be acting as a Fipronil (.0001%) O.OOOO62 O 3 3 S4 Fipronil (.0001%) + O.OOOO62 O 3 3 45 free radical stabilizer, is present, versus a comparable level of adjuvant mortality in around 20 hours in the absence of the adjuvant. adjuvant O O O 50

45 Example 48 SUMMARY: In this trial, fipronil at 0.001% AI in combi nation with adjuvant was the lowest rate that showed the greatest increase in efficacy against Odorous House ant. Syn Evaluation of Synergy of Combination of Compound ergy was also seen with adjuvant and fipronil at 0.01%. A & Compound B with Fipronil Against Susceptible Results are summarized in FIG. 46. As shown in FIG. 45, 50 German Cockroach (Monheim Strain) 100% mortality was observed in around 1 hour in the pres ence of the adjuvant, believed to be acting as a free radical The objective of this study was to investigate the Synergis stabilizer, versus 25 hours in the absence of the adjuvant. This tic effect offipronil in combination with adjuvant on efficacy shows a synergistic effect of the adjuvant. against Susceptible/normal German cockroach Strain (Mon 55 heim strain). Example 47 MATERIALS AND METHODS: Solutions of fipronil at 0.01, 0.001 and 0.0001% AI were prepared with and without Evaluation of Synergy of Combination of Compound adjuvant in acetone. The UV Blocker is a combination of A & Compound B with Fipronil Against Red Compound A at 1% and Compound B at 0.5%. Treatments Imported Fire Ant 60 were applied using a micropipette to dispense 1 ml of test solution evenly on a 6"x6" glazed tile (FIG. 48). Actual cov The objective of this study was to investigate the Synergis erage was about 5"x5" (or 161 cm) for easy handling. Treat tic effect offipronil in combination with adjuvant on efficacy ments were allowed to dry overnight. Five male German against Red Imported Fire ant, Solenopsis invicta. 65 cockroaches were placed within a talc-coated PVC ring (cp7.6 MATERIALS AND METHODS: Solutions of Fipronil at cmxH 5.1 cm) under continuous exposure. A small vial cap 0.01, 0.001 and 0.0001% AI were prepared with and without filled with a cotton ball soaked in water was added as a US 9,028,856 B2 81 82 drinking source after 3 hours. Treatments were replicated a mortality was observed at 25 hours in the presence of the minimum of three times. Evaluations for knockdown/mortal adjuvant, compared to around 40% mortality at 25 hours in ity were made at various intervals and at 24 hours after expo the absence of the adjuvant. SUC. Example 49 RESULTS: Table 53 and FIG. 48: Summary of Fipronil/ Evaluation of Synergy of Compound A with adjuvant synergy study against German cockroach (Mon Ethiprole Against Argentine Ant heim) The objective of this study was to investigate the Synergis 10 tic effect of ethiprole in combination with Compound A on Average % Knockdown & efficacy against Argentine ant, Linepithema humile. Rate Mortality after MATERIALS AND METHODS: Solutions of ethiprole at Treatment (g/m) 60 min 3 hr 5 hr 24 hr 0.01 and 0.001% AI were prepared with and without Com pound A at 1, 0.1, and 0.01% in acetone. Treatments were UTC O O O O 7 15 applied using a micropipette to dispense 1 ml of treatment Fipronil (.01%) O.OO62 O 7 7 1OO solution on 6"x6" glazed tile. Actual coverage was about Fipronil (.01%) + adjuvant O.OO62 O O 33 1OO Fipronil (.001%) O.OOO62 O O O 40 5"x5" (or 161 cm) for easy handling. Treatments were Fipronil (.001%) + adjuvant O.OOO62 O O O 1OO allowed to dry overnight. Ten Argentine ant workers were Fipronil (.0001%) O.OOOO62 O 7 7 7 placed within a talc-coated PVC ring (cp7.6 cmxH 5.1 cm) Fipronil (.0001%) + adjuvant O.OOOO62 O 7 7 13 under continuous exposure. A Small vial filled with a cotton adjuvant O O O O 7 ball soaked in water was added as a drinking source after 3 hours. Treatments were replicated a minimum of three times. Evaluations for ant knockdown/mortality were made at vari SUMMARY: An increase in overall mortality was seen ous intervals and at 24 hours after exposure. with fipronil at 0.001% AI and adjuvant against susceptible RESULTS: Table 54 (no figure): Trial 1: Summary of German cockroach (FIG. 48). As shown in FIG. 48, 100% Ethiprole? Compound A Synergy study against Argentine ant

Average % Mortality after Treatment Rate (g/m) 10 min 30 min 60 min 90 min 2 hr 4 hr 24hr UTC O O O O O O 10 Ethiprole (0.01%) O.OO62 O O O O O 16 100 Ethiprole (0.01%) + O.0062 36 91 1OO 100 1OO 100 100 Compound A (1%) Ethiprole (0.01%) + O.0062 O O 10 42 SS 100 100 Compound A (0.1%) Ethiprole (0.01%) + O.0062 O O O O O 10 81 Compound A (0.01%) Compound A (1%) O 25 91 1OO 100 1OO 100 100 Compound A O O O O O O 17 36 (0.01%)

Table 55 and FIG. 49: Trial 2: Summary of Ethiprole? Compound A Synergy Study Against Argentine Ant

Rate Average % Mortality after

Treatment (g/m) 10 min 30 min 60 min 90 min 2 hr 3 hr 24hr

UTC O O O O O O O Ethiprole (0.01%) O.OOO62 O O O O O 6 72 Ethiprole (0.01%) + Compound A O.OOO62 100 100 1OO 1OO 100 100 100 (1%) Ethiprole (0.01%) + Compound A O.OOO62 O O 24 86 100 100 100 (0.1%) Ethiprole (0.01%) + Compound A O.OOO62 O O O O 4 11 89 (0.01%) Compound A (1%) O 57 100 1OO 1OO 100 100 100 Compound A (0.1%) O O 4 4 12 12 16 16 Compound A (0.01%) O O O O 24 31 62 UVB (Compound A+ Compound B) O O O 13 23 40 SO 83