WO 2015/076840 Al 28 May 2015 (28.05.2015) P O P C T
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(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2015/076840 Al 28 May 2015 (28.05.2015) P O P C T (51) International Patent Classification: (74) Agent: OREMLAND, Lawrence R.; Lawrence R. Orem- A61K 33/34 (2006.01) land, P.C., 5055 E. Broadway Blvd., suite C-214, Tucson, AZ 8571 1 (US). (21) International Application Number: PCT/US20 13/07 1669 (81) Designated States (unless otherwise indicated, for every kind of national protection available): AE, AG, AL, AM, (22) International Filing Date: AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, 25 November 2013 (25.1 1.2013) BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, (25) Filing Language: English DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, (26) Publication Language: English KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, (63) Related by continuation (CON) or continuation-in-part MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, (CIP) to earlier applications: OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, US 13/480,367 (CIP) SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, Filed on 24 May 2012 (24.05.2012) TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, US 61/51 9,523 (CIP) zw. Filed on 24 May 201 1 (24.05.201 1) (84) Designated States (unless otherwise indicated, for every US 61/582,322 (CIP) kind of regional protection available): ARIPO (BW, GH, Filed on 3 1 December 201 1 (3 1.12.201 1) GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ, (71) Applicant: AGIENIC, INC. [US/US]; 4541 E. Fort Low UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ, ell Road, Tucson, AZ 85712 (US). TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, ΓΓ, LT, LU, LV, (72) Inventors: AGRAWAL, Anoop; 441 1 N. Camino Sumo, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM, Tucson, AZ 85718 (US). KRASNOW, Nicholas, R.; 2930 TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, N. Tucson Boulevard, Tucson, AZ 85716 (US). CRONIN, KM, ML, MR, NE, SN, TD, TG). John P.; 4545 North Osage Drive, Tucson, AZ 85718 (US). ADAMS, Lori L.; 10950 N. La Canada Drive, Apt Published: 26-202, Tucson, AZ 85737 (US). AKARSU, Murat; — with international search report (Art. 21(3)) Meltem Mah. Ant-belde Sitesi 1., Blok No: 8 07030, Anta — with information concerning one or more priority claims lya (TR). REESER, Ryan, J.; 8001 East Ocotillo Drive, considered void (Rule 26bis.2(d)) Tucson, AZ 85750 (US). LOPEZ-TONAZZI, Juan Car¬ los; 6400 Montrose Dr, Tucson, AZ 85741 (US). UHL- MANN, Donald R.; 5309 East Mission Hills Drive, Tuc son, AZ 85718 (US). © (54) Title: ANTIMICROBIAL COMPOSITIONS FOR USE IN PRODUCTS FOR PETROLEUM EXTRACTION, PERSONAL 0 0 CARE, WOUND CARE AND OTHER APPLICATIONS © (57) Abstract: Compositions having antimicrobial activity contain surface functionalized particles comprising an inorganic copper salt which has low water solubility. These types of inorganic salts may also be introduced in porous particles to yield antimicrobial compositions. The compositions may optionally comprise additional antimicrobial agents, salts with high water solubility, organic o acids, salts of organic acids and their esters. The compositions may be added to various fluids used in the petroleum extraction in dustry, or used as coatings on components used in this industry. These antimicrobial, materials may be used for reducing both anaer obic and aerobic bacteria and are also useful for reducing corrosion of ferrous components caused by anaerobic bacteria. Although such compositions may be used for any antimicrobial application, and some of the other important uses of these compositions are in wound care, personal care and waste processing,. ANTIMICROBIAL COMPOSITIONS FOR USE IN PRODUCTS FOR PETROLEUM EXTRACTION, PERSONAL CARE, WOUND CARE AND OTHER APPLICATIONS CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of co-pending U.S. Application Serial No. 13/480,367, filed May 24, 2012, which application in turn claims priority to U.S. Provisional Patent Application Ser. No. 61/519,523, filed 5/24/201 1, US Provisional Patent Application ser. No. 61/582,322 filed 12/31/201 1; a continuation-in-part of US Application Serial number 13/685,379 filed on 11/26/2012 which is a continuation in part of U.S. Application Serial No. 13/480,367; and is related to and claims priority from US Provisional Patent Application serial numbers 61800122 filed on 3/15/2013; 61/820,561 filed on May 7, 2013, and 61/881,318 filed on Sept 23, 2013. The contents of all of the foregoing applications are incorporated herein by reference in their entirety. FIELD OF THE INVENTION The invention relates to antimicrobial compositions comprising surface functionalized particles of low water solubility inorganic copper salts, or such copper salts or silver salts infused into porous particles, their preparation, combinations of these copper-based particles with other antimicrobial materials, application of the compositions and methods of preparation. BACKGROUND OF THE INVENTION The antimicrobial effect of various metals and their salts has been known for centuries. Its germicidal effects increased its value in utensils and as jewelry. The exact process of silver's germicidal effect is still not entirely understood, although theories exist. One of these is the "oligodynamic effect," which qualitatively explains the effect on some microorganisms, but cannot explain antiviral effects. Silver is widely used in topical gels and impregnated into bandages because of its wide-spectrum antimicrobial activity. The oligodynamic effect is demonstrated by other metals, specifically gold, silver, copper, zinc, and bismuth. Copper is one such metal. Copper has long been used as a biostatic surface to line the bottoms of ships to protect against barnacles and mussels. It was originally used in pure form, but has since been superseded by brass and other alloys due to their lower cost and higher durability. Bacteria will not grow on a copper surface because it is biostatic. Copper alloys have become important netting materials in the aquaculture industry for the fact that they are antimicrobial and prevent biofouling and have strong structural and corrosion-resistant properties in marine environments. Organic compounds of copper are useful for preventing fouling of ships' hulls. Copper alloy touch surfaces have recently been investigated as antimicrobial surfaces in hospitals for decreasing transmission of nosocomial infections. Numerous scientific investigations have focused on the role of the metal form of copper, and have concluded that multiple mechanisms may be possible for copper's antimicrobial effect, including increased production of reactive oxidation species such as singlet oxygen and hydroxide radicals, covalent binding of copper metal to reactive sites in enzymes and co-factors, interference with lipid bilayer transport proteins, and interaction of copper ions with moieties of microorganisms analogous to what have been proposed for silver ions. SUMMARY OF THE INVENTION The inventors associated with this patent have made the surprising discovery that antimicrobial compositions comprising particles comprising certain low water solubility copper salts have much greater efficacy against a broad range of aerobic and anaerobic microbes, including bacteria, viruses, molds and fungi, than similar silver-based antimicrobial particles. In particular, it has been discovered that particles of copper salts including the copper halide and specifically copper iodide ("Cul"), when formulated in accordance with the teachings herein, is surprisingly effective as a broad-spectrum, fast- acting antimicrobial agent. The particles of these salts are surface functionalized. In a further embodiment, high water solubility salts may be added to the compositions comprising the inventive particles. In a particularly preferred embodiment, the high water solubility salts comprise at least one halide salt with a room temperature water solubility of greater than lg/liter. In yet another embodiment, organic acids, salts of organic acids, and esters of organic acids may be used as functionalization agents for the particles or as additives to the antimicrobial compositions. In yet another embodiment, the antimicrobial compositions of this invention may be used to manufacture solid or liquid products with antimicrobial properties. In a further embodiment, the functionlization agents preferably have a molecular weight of at least 60. In yet another embodiment, the antimicrobial compositions are used in the petroleum extraction industry, personal care products and wound management. Another embodiment of the present invention is the use of the above antimicrobial compositions is to kill anaerobic as well as aerobic bacteria. In yet another surprising discovery, the preparation of the inventive particles using wet grinding processes enhances their economic viability and provides several other benefits. Such processes may be used to produce functionalized particles of other low water solubility salts and compounds such as silver halides. In a further embodiment, one may deposit the copper salts of low water solubility or silver halides in porous particles, wherein such porous particles are used as additives to various carriers (liquids or solids) or products to impart antimicrobial properties to these. These and other features of the present invention will become apparent from the following detailed description and the accompanying drawings BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a plot of Optical Density (OD, Y-axis) against P. aeruginosa growth and/or inhibition by copper iodide particles and Ag-Cul mixed metal halides, and a control.