(12) United States Patent (10) Patent No.: US 9.422,609 B2 Teichberg (45) Date of Patent: Aug
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USOO9422609B2 (12) United States Patent (10) Patent No.: US 9.422,609 B2 Teichberg (45) Date of Patent: Aug. 23, 2016 (54) METHODS, COMPOSITIONS AND DEVICES (58) Field of Classification Search FOR MANTAINING CHEMICAL BALANCE CPC ........................ C02F 1/725; C12Y 305/01005 OF CHLORINATED WATER USPC ........................... 210/754; 435/195, 227 231 See application file for complete search history. (75) Inventor: Vivian I. Teichberg, Savyon (IL) (56) References Cited (73) Assignees: Mia Levite, Savyon (IL); Yaar Teichberg, Savyon (IL); Nof Lyle U.S. PATENT DOCUMENTS Teichberg, Savyon (IL) 4,793,935 A * 12/1988 Stillman ............... CO2F 1.5236 21Of727 (*) Notice: Subject to any disclaimer, the term of this 6,673,582 B2 * 1/2004 McTavish ..................... 435/122 patent is extended or adjusted under 35 U.S.C. 154(b) by 1044 days. (Continued) (21) Appl. No.: 12/225.18O FOREIGN PATENT DOCUMENTS y x- - - 9 AU 41971 5, 1979 (22) PCT Filed: Mar. 14, 2007 GB 2025919 1, 1980 (86). PCT No.: PCT/L2007/OOO336 (Continued) S 371 (c)(1) OTHER PUBLICATIONS (2), (4) Date: Sep. 16, 2008 Examiner's Report Dated Oct. 6, 2010 From the Australian Govern (87) PCT Pub. No.: WO2007/107.981 ment, IP Australia Re. Application No. 2007228391. (Continued) PCT Pub. Date: Sep. 27, 2007 (65) Prior Publication Data Primary Examiner — Peter Keyworth (74) Attorney, Agent, or Firm — Browdy and Neimark, US 201OfO270228A1 Oct. 28, 2010 PLLC Related U.S. Application Data (57) ABSTRACT (60) Provisional application No. 60/783,028, filed on Mar. A composition-of-matter for use in water treatment, com 17, 2006. posed of a water-insoluble matrix and one or more amidohy drolase, such as cyanuric acid amidohydrolase, incorporated (51) Int. Cl. in or on the matrix, is disclosed. Also disclosed are devices CI2N 9/78 (2006.01) containing same and methods utilizing same for water treat CO2F I/72 (2006.01) ment. The water treatment is effected by an enzymatically (Continued) catalyzed reduction of the concentration of an amide-contain (52) U.S. Cl. ing compound. Such as cyanuric acid, found in chlorinated CPC ... CI2W 30.5/0.005 (2013.01): BOI 20/285 water of Swimming polls, Spas and other similar structures. (2013.01); B01J 20/321 (2013.01); 14 Claims, 11 Drawing Sheets (Continued) (7 of 11 Drawing Sheet(s) Filed in Color) US 9,422.609 B2 Page 2 (51) Int. Cl. FOREIGN PATENT DOCUMENTS CO2F 3/34 (2006.01) f JP 06-086997 3, 1994 CI2N 9/80 (2006.01) RU 1178079 4f1994 CI2N 9/86 (2006.01) WO WO 2007/107.981 9, 2007 CI2N II/00 (2006.01) OTHER PUBLICATIONS BOI 20/32 (2006.01) BOI 20/28 (2006.01) International Preliminary Report on Patentability Dated Dec. 11, 2008 From the International Bureau of WIPO Re. Application No. CO2F IOI/34 (2006.01) PCT/IL2007 OOO336. CO2F IOI/38 (2006.01) International Search Report and the Written Opinion Dated Jul. 8, CO2F IO3/42 (2006.01) 2008 From the International Searching Authority Re. Application No. PCT, ILO7 OO336. A61 K38/00 (2006.01) Communication Pursuant to Rules 70(2) and 70a(2) EPC Dated Jan. (52) U.S. Cl. 13, 2012 From the European Patent Office Re. Application No. CPC .......... B01.J20/3204 (2013.01); B01J 20/3212 O7713356.9. Supplementary European Search Report and the European Search (2013.01); B01J 20/3219 (2013.01); B01.J Opinion Dated Dec. 27, 2011 From the European Patent Office Re. 20/3274 (2013.01); C02F I/725 (2013.01); Application No. 07713356.9. C02F 3/342 (2013.01); CI2N 9/80 (2013.01); Kaplunetal. Database WPI, Week 199507, XP002665268, AN 1995 CI2N 9/86 (2013.01); CI2N II/00 (2013.01); O49825. CI2Y305/01084 (2013.01); C12Y305/02015 Kawachi et al. Database WPI, Week 1994.17, XP002665267, AN (2013.01); A61 K38/00 (2013.01); CO2F 1994-140646. Stamper et al. “Ring-Cleaving Cyanuric Acid Amidohydrolase 2101/34 (2013.01); C02F 2101/38 (2013.01); Activity in the Atrazine-Mineralizing Ralstonia Basilensis M91-3”, C02F 2103/42 (2013.01); C02F2301/046 Database Compendex Online), XP002665270, Database Accession (2013.01); C02F2303/18 (2013.01) No. E2006049659007, Nov. 2005. Abstract. Wackett et al. “Biodegradable of Atrazine and Related S-Triazine (56) References Cited Compounds: From Enzymes to Field Studies'. Database BIOSIS U.S. PATENT DOCUMENTS Online, XP0026665269, Database Accession No. PREV200200181423, Jan. 2002. Abstract. 7,238,287 B2 * 7/2007 Kulperger ..................... 210,632 Office Action Dated Oct. 28, 2014 From the Israel Patent Office Re. 2002/004.5236 A1 4/2002 Wackett et al. Application No. 1941.06 and Its Translation Into English. 2003/0098270 A1* 5/2003 Thompson ................ 210.283 Requisition by the Examiner Dated Feb. 12, 2015 From the Canadian 2006/0024808 A1 2/2006 Darzins et al. ................ 435,195 Intellectual Property Office Re. Application No. 2,645,147. 2006/0289344 A1* 12/2006 Queirel ............ ... 210,167.1 2007/009576.0 A1* 5, 2007 Girvan et al. ................. 210,696 * cited by examiner U.S. Patent Aug. 23, 2016 Sheet 2 of 11 US 9,422,609 B2 U.S. Patent Aug. 23, 2016 Sheet 4 of 11 US 9,422,609 B2 U.S. Patent Aug. 23, 2016 Sheet 5 of 11 US 9,422,609 B2 U.S. Patent Aug. 23, 2016 Sheet 6 of 11 US 9,422,609 B2 ººº,-sis^peue»od: ros:uznanooaunuoneuluosueur ;-----------------------------------------------------------------------------,••••••••••••••••••••••••••••••••••••••••••••••••••••••••••----------------------~--~~~~--~~~~••••* U.S. Patent Aug. 23, 2016 Sheet 7 of 11 US 9,422,609 B2 **~upanoudeuna eueuqueumeoeu,dn»eeuqoneseuozuequumqueuneauu,N Å™_\{}å U.S. Patent Aug. 23, 2016 Sheet 8 of 11 US 9,422,609 B2 U.S. Patent Aug. 23, 2016 Sheet 9 of 11 US 9,422,609 B2 ::::38 3828.8 U.S. Patent Aug. 23, 2016 Sheet 10 of 11 US 9,422,609 B2 09? 04·614 (uudd)gaun?g |071 AAoe eu/Zue pezieu joN U.S. Patent Aug. 23, 2016 Sheet 11 of 11 US 9,422,609 B2 s a Y: wax to: & six re: s 38 is: ww X 8S e.8 US 9,422,609 B2 1. 2 METHODS, COMPOSITIONS AND DEVICES The mechanism of the biocidic action exerted by free FOR MAINTAINING CHEMICAL BALANCE chlorine-producing agents, such as sodium hypochlorite and OF CHLORINATED WATER hypochlorous acid, is not fully understood. It is assumed that free chlorine is responsible for the oxidation reactions with RELATED APPLICATIONS the cytoplasm of microorganisms (e.g., bacteria, vegetative bacteria, algae, spore, virus, or fungus), after diffusion This application is a National Phase Application of PCT through the cell walls. Hypochlorous acid penetrates the cell Application No. PCT/IL2007/000336 having International walls readily due to its size, structure and neutrality, which Filing Date of Mar. 14, 2007, which claims the benefit of U.S. are similar to that of water. Once present in the cell, chlorine Provisional Patent Application No. 60/783,028, filed on Mar. 10 disturbs the production of ATP (adenosine triphosphate), an 17, 2006. The contents of the above Applications are all essential compound for the respiration of microorganisms, incorporated herein by reference. as well as the structure and thus activity of polynucleic acids, which are essential for all cell functions and repro FIELD AND BACKGROUND OF THE duction. 15 INVENTION Direct use of chlorine gas and/or HOCl is limited due to their high reactivity and aggressiveness as oxidizing agents. The present invention relates to methods, compositions Hence, the use of compounds that are capable of releasing and devices for chemical balancing of chlorinated water, and HOCl and thus act as indirect oxidizing agents is preferred. more particularly, to methods compositions and devices of Chemical compounds which release a halogen disinfec modulating the level of amide-containing chemicals such as tant agent when coming in contact with water, primarily free cyanuric acid in chlorinated water of Swimming pools, spas chlorine donor biocides, are the major and most commonly and similar water reservoirs. used sanitizers in Swimming pools. These sanitizers ensure Artificial swimming pools are known to have been built by that the water in the Swimming pool remains clean and safe for the swimmers throughout the day. However, hypochlo the ancient Greeks and Romans who used them for athletic 25 rous acid is highly unstable, and readily decomposes into training in the palestras as well as for nautical games and inactive breakdown products, such as hydrochloric acid, military exercises. Roman emperors had private Swimming water and oxygen, via UV radiation driven photochemical pools in which fish also were kept, whence the Latin word for reactions upon exposure to direct Sun light, and/or upon pool, piscina. In modern days, open air Swimming pools exposure to moderate and high temperatures. During the represent a major worldwide attraction for children and adults 30 Summer, which is the peak season for Swimming pools, up all over the world as a recreational pastime, as providing the to 90% of the total active chlorine species are lost in a sunny means for one of the most beneficial forms of exercise and as day over two to three hours. In order to control these effects serving one of the major national and Olympic sports. The and preserve the effectiveness of the chlorine, agents aimed evergrowing number of Swimming pools is estimated to be in at stabilizing the chlorine are often added to the water. excess of 20 millions pools worldwide. Preserving the water 35 The most commonly used and effective chlorine stabilizer quality of these pools is a major health and aesthetic concern is cyanuric acid, also known by its tautomer's name, S-tri and the Source of an industry and business of several hundreds azinetrione or isocyanuric acid (see, Scheme 2 below).