US 20020025490A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2002/0025490 A1 Shchegolikhin et al. (43) Pub. Date: Feb. 28, 2002 (54) RAMAN-ACTIVE TAGGANTS AND THEIR Related U.S. Application Data RECOGNITION (63) Non-provisional of provisional application No. (76) Inventors: Alexander Nikitovich Shchegolikhin, 60/196,876, filed on Apr. 12, 2000. Moscow (RU); Olgal Leonidovna Lazareva, Moscow (RU); Valery Publication Classification Pavlovich Melnikov, Moscow (RU); Vassili Yu Ozeretski, Moscow (RU); (51) Int. Cl. ................................................... G11B 7124 Lyle David Small, Peyton, CO (US) (52) U.S. Cl. ......... 430/270.15; 430/270.11; 430/270.14; 430/945; 283/90 Correspondence Address: (57) ABSTRACT Law Office of Dale B. Halling, LLC An organic or organoelement, linear or branched, mono Suite 311 meric or polymeric composition of matter having a Raman 24 S. Weber Street active component in the form of particles. The particles Colorado Springs, CO 80903 (US) having a maximum dimension of 50 um. The Raman-active compound is applied to a Substrate. When the Raman-active compound is exposed to a laser light wavelength which is (21) Appl. No.: 09/833,218 batochromically well beyond a spectral region of maximum absorbance of Said Raman-active compound, Raman Scat (22) Filed: Apr. 11, 2001 tering can be detected. Research Nd:YAG, 30 mW 950-nm LED pointer, <3 mW 670-nm red pointer, <3 mW 32OO 3OO 3OOO 29OO 28OO 2700 26 OO 25OO 2400 Arbitrary Yl Wavenumber (cm-1) Patent Application Publication Feb. 28, 2002 Sheet 1 of 33 US 2002/0025490 A1 HC=C-O)-NO. (16) i : -T- Cu C=C-O) (26) N 2400 2200 2000 1800 1600 l1400 1200 1000 800 600 400 Raman Shift, cm FIG. 1(A) Patent Application Publication Feb. 28, 2002 Sheet 2 of 33 US 2002/0025490 A1 2400 2200 2OOO 1800 1600 1400 12CO 1000 Raman Shift, cm FIG. 1 (B) Patent Application Publication Feb. 28, 2002 Sheet 3 of 33 US 2002/0025490 A1 N-CSC-C=C-CH-OH (97) (109) 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 Raman Shift, cm FIG. 1(C) Patent Application Publication Feb. 28, 2002 Sheet 4 of 33 US 2002/0025490 A1 N (114) O Nl (112)1 (O)-CH=CH-CH=CH-CH=-3-o-CH-CH,O N (116) 2200 2000 1800 1600 1400 1200 1000 Raman Shift, cm FIG. 1 (D) Patent Application Publication Feb. 28, 2002 Sheets of 33 US 2002/0025490 A1 3000 2600 2200 1800 1400 1000 600 2OO Raman Shift, cm FIG. 1 (E) GsH, Si C3H7. In 1600 1400 1200 1000 800 600 400 Raman Shift, cm FIG.1(F) Patent Application Publication Feb. 28, 2002. Sheet 6 of 33 US 2002/0025490 A1 Fullerene C60 2400 2000 1600 200 800 400 Raman Shift, cm FIG.1(G) Polyacetylene, cf. 8 & 8 M OU J O to to B O Oh s pp.r t - re r- orm s --- ----- 2400 2000 1600 200 800 400 Raman Shift, cm FIG.1(H) Patent Application Publication Feb. 28, 2002 Sheet 7 of 33 US 2002/0025490 A1 2400 2000 1600 - rm Raman Shift, cm FIG.1(I) Patent Application Publication Feb. 28, 2002 Sheet 10 of 33 US 2002/0025490 A1 1) (32) (Occ O-ce-O-os, O-cis-O-can-C)NO2 (33) (34) O-O-O-(35) (O-et-O-HOO(36) (O-et-O-a-O-O (O-et-O-cha-DCN (O)-c=c-O)-c(39) H-N-(O)N (O)-C=C(O)-c(40) H-N-O)-CH, C C O-os-O-ce-O-e(41) O-cis-O-et-O-is(42) B (43) (44) O H N-C-O-C-C-C-C-O-o--N-(CH2N--O-O-No.(45) H O FIG. 2(b) Patent Application Publication Feb. 28, 2002 Sheet 12 of 33 US 2002/0025490 A1 O-O-O-O-O.(58) O-O-O-O-O. (O-clic-O--O-clic-O) (60) (O-o-O-clic-O--O-clic-O-O-O. (O-O-cac-O-O-c-e-O-O.) (62) FIG.3(b) Patent Application Publication Feb. 28, 2002 Sheet 13 of 33 US 2002/0025490 A1 F F F F O F F (67) F F O2N NO (68) (O-clic-O-5-O-cc-OO HC=C-O-C=CH HN2 NH2 (69) (70) 1 N NH O-O-O-O.(71) ()C^ (72) O-o-o-o- 74) chie-O--O-c-ch(75) no-C-C-C-O-Si-O-clic-O-9.O (80) FIG. 3 (c) Patent Application Publication Feb. 28, 2002 Sheet 14 of 33 US 2002/0025490 A1 -o-o-o-o: C (83) O-O-O-OO 5.COOH F-O-clic-O--O-o-c-O- e. F-( )-cis-O-O-C c-O-F 5 (85) O O Hoc p=CH O HCEC-Si-CeCH (O)-c=c-Si-C=C-(O) O IO HCsC-Ge-CECH Si (86) (87) HC=d Yo=CH (88) (89) P(Bu), P(Bu) FIG. 3(d) Patent Application Publication Feb. 28, 2002 Sheet 16 of 33 US 2002/0025490 A1 N-CEC-CEC-N (103) (O) Core-O-cis-O-cis-O-os-O-- C C on-O--cBr t-O-cc-clic-cle-O-chi-O-O.(106) Br H O O O H O2N NO2 O O H OSN-C=C-C=C-C=C-C) (108) O2NO-She-clo-c-e-ch-R-C) H (109) O NO2 FIG. 4(b) Patent Application Publication Feb. 28, 2002 Sheet 19 of 33 US 2002/0025490 A1 Fullerene C60 Fullerene C76 33NSS:ES A.S.E. A. AAAAAA y g $3% E3:E. N $2.2%; Tubulene FIG. 7 Patent Application Publication Feb. 28, 2002 Sheet 20 of 33 US 2002/0025490 A1 O) occ Oce, to-3-3NO2 -Ocac, (O-O-O) (130) (O) (O) O-cc-O-cc-Oct. (142) HO)-se-O- -O- se-O-O-O-KO-CF3 (143) FIG. 8(a) Patent Application Publication Feb. 28, 2002 Sheet 21 of 33 US 2002/0025490 A1 pentamer, hexamer, etc. tetramer (144) FIG. 8(b) Patent Application Publication Feb. 28, 2002 Sheet 22 of 33 US 2002/0025490 A1 Q HC-O-S-N-3-O-(CH)n-C=C-C=C-(CH2n-o-3-N-S-C)-CH,O H H O Wherein n = 1, 2, 3, 4, 5, 7, 9 (145) Q Q Br-CH-CH-C-N-C-O-(CH)n-C=C-C=C-(CH2)n-O-C-N-C-CH-CH-Br H H Wherein n = 1, 2, 3, 4, 5, 7, 9 (146) H H Wherein n = any integer > 1 R18-O-C-N-(CH)n-C=C-C= -(CH2n-N-6-O-R19 H H Wherein n = 1, 2, 3 (148) R18 = R19 or R187R19 and, independently of each other, is: an Alkyl, an Aryl, a Heteroaryl, or a substituted Alkyl, a substituted Aryi, a substituted Heteroary, etc. Q CH=CH-3-N-3-O-(CH)n-C=C-C=C-(CH)n-O-3-N-3-CH=CH:H H Wherein n = any integer > 1 (149) HOOC-(CH2)n-CsC-CEC-(CH2)n-COOH (150) Wherein n = an integer from 0 up to 20 HOOC-(CH2)n-C=C-CsC-(CH2)m-CH3 (151) Wherein n and m, independently of each other, are any integer from 1 up to 20 FIG. 9(a) Patent Application Publication Feb. 28, 2002 Sheet 23 of 33 US 2002/0025490 A1 Wherein n = any integer from 1 to 20; m = 2 - 100,000 H H H H six-is-e-cis-cis-e-...----o'-O O p ly O r (156) Wherein n = an integer from 1 to 20; m = 10 - 100,000; P = 1 - 10; q = 500 - 100,000; r = 1 - 10; XF alkylene or arylene, e.g. : hexamethylene, -C)- -O)-CH-O)- etc. ÇH. Z = -CH2-CH2-CH2-CH2-, -CH-CH2-, -CH2-CH2-, -O)- etC. FIG. 9(b) Patent Application Publication Feb. 28, 2002 Sheet 24 of 33 US 2002/0025490 A1 Up-converting phosphor “A” Up-converting phosphor “B” ---------------------------- --- 3200 2800 2400 2000 600 1200 Raman Shift, Cm Note: Exciting Nd:YAG laser having 1064 nm (or 9394 cm) wavelength has been used FIG. 10 Patent Application Publication Feb. 28, 2002 Sheet 25 of 33 US 2002/0025490 A1 Prior art + D of this invention Sub-class D of this invention, neat 250 2000 500 000 500 Raman shift, cm FIG. 11(a) rior art -- J of this invention Sub-class J of this invention, neat 2500 2000 1soo 1000 500 Raman shift, cm FIG. 1 1(b) Patent Application Publication Feb. 28, 2002 Sheet 26 of 33 US 2002/0025490 A1 Sub-class J of this invention, Perkin-Elmer 1720 NIR-FT Ranan 2200 2000 1800 1600 1400 1200 1000 800 60 Raman Shift, cm FIG. 12(a) -The same sample of the sub-class J, portable fiber optic spectrometer of this invention --- 2200 2000 1800 1600 400 1200 1000 800 60 Raman Shift, cm FIG. 12(b) Patent Application Publication Feb. 28, 2002 Sheet 27 of 33 US 2002/0025490 A1 J--D FIG. 13 Patent Application Publication Feb. 28, 2002 Sheet 28 of 33 US 2002/0025490 A1 | || | | | J - |- -- S1 | - 2300 2200 2100 2000 1900 isoo 1700 1600 1500 Raman Shift, cm FIG. 14 Patent Application Publication Feb. 28, 2002 Sheet 29 of 33 US 2002/0025490 A1 -60 Temperature, deg. C 1550 15 OO 1450 Arbitrary Y / Wavenumber (cm-1) FIG.