CN1893827B - 包括第二抗微生物剂的柠檬酸二氢银组合物 - Google Patents
包括第二抗微生物剂的柠檬酸二氢银组合物 Download PDFInfo
- Publication number
- CN1893827B CN1893827B CN200480024459XA CN200480024459A CN1893827B CN 1893827 B CN1893827 B CN 1893827B CN 200480024459X A CN200480024459X A CN 200480024459XA CN 200480024459 A CN200480024459 A CN 200480024459A CN 1893827 B CN1893827 B CN 1893827B
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- composition
- antimicrobial
- dihydrogen citrate
- silver dihydrogen
- silver
- Prior art date
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- A—HUMAN NECESSITIES
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- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
- A01N31/02—Acyclic compounds
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- A—HUMAN NECESSITIES
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- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
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- A—HUMAN NECESSITIES
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- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A—HUMAN NECESSITIES
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- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
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- C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
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Landscapes
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Oncology (AREA)
- Communicable Diseases (AREA)
- Epidemiology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
提供了一种包括柠檬酸二氢银、与一种第二抗微生物化合物的组合物。所述第二抗微生物化合物可以是季铵、氧化剂或卤素类,例如氯、溴或碘。使用所述抗微生物组合物的方法,提供了优越的抗微生物效果。
Description
技术领域
本发明涉及抗微生物组合物及其使用方法。具体而言,本发明涉及包括季铵、一种氧化剂或一种卤素化合物的柠檬酸二氢银组合物,以及使用所述组合物将抗微生物效果赋予多种基质的方法。
背景技术
众多抗微生物化合物已被公知。杀灭或防止微生物扩散的化合物已用于各种目的和众多产品中,以延长产品的贮存期限,并将抗微生物的有益特性赋予最终使用者、其拥有物及其所处环境。某些可提及的抗微生物化合物包括季铵化合物、氧化剂和卤素化合物。
季铵化合物是已显示具有抗细菌特性的阳离子表面活性剂。除抗细菌特性之外,某些季铵化合物还具有除臭、润湿、洗涤、溶解角蛋白及乳化活性。苯扎氯铵(Benzalkonium chloride)是烷基苄基二甲基氯化铵的混合物,被广泛用作临床场合中的抗菌剂。苯扎氯铵还可用作防腐剂,例如在眼用溶液中;这是由于该化合物具有对抗多种细菌的活性,所述细菌包括革兰氏阳性菌和某些革兰氏阴性菌,以及对抗某些病毒和真菌的活性。然而,苯扎氯铵对某些革兰氏阴性菌无效,例如假单胞菌(Pseudomonas)。尽管所述化合物在相对低的浓度时是有益的,但在较高的浓度下会具有刺激性或者甚至具有毒性。而且,季铵化合物还易于在环境中快速消散(dissipate),因此施用于固体表面和其他基质时不易于提供持续的抗微生物效果。
氧化剂,例如过氧化氢,已用作消毒剂。过氧化氢已知可用作消毒剂,为皮肤和伤口消毒以及为供水***消毒。高锰酸钾(KMnO4)是在冷却塔、蒸发冷凝器、洗尘***(air wash system)、冷却喷水器(coolingfountain)及人类饮用水中用作杀细菌剂、杀真菌剂和灭藻剂的氧化剂。高锰酸钾还用于防治养鱼池和观赏性水池中鱼类的外界侵染。单过硫酸盐(例如单过硫酸钾)用作消毒剂,还可用作辅助氧化剂(shockingagent)以用于游泳池和温泉的不定期消毒。用作辅助氧化剂时,单过硫酸盐会氧化并分解氯胺,从而提高游离氯原子的有效浓度或经氯处理过的水中。可提及的其他氧化剂有过氧化苯甲酰和高硼酸钠,它们亦已用作抗微生物化合物。尽管氧化剂是非常有效的消毒剂,但其在环境中易于快速分解,因此不适于提供长期抗微生物效果。
卤素化合物也已用作消毒剂。尽管所述化合物可认为是氧化剂,然而鉴于其特殊性质,故在本申请中将卤素化合物单独分类。最常用的抗微生物卤素化合物是氯和碘。当已知可能接触抗微生物剂的人对氯过敏时,某些情形下也使用溴。
碘是最古老的已知消毒剂之一,用于伤口处理、皮肤消毒和水卫生消毒。碘可以碘酒或碘递体的形式使用。根据USP,碘酒是2%游离碘与2.4%碘化钠的50%乙醇或异丙醇溶液。碘酒可直接用于皮肤消毒和伤口处理,或者用水稀释以用于消毒。
碘递体是包括碘、洗涤剂、润湿剂、加溶剂和其他载体的组合物。碘递体通常包含多至30重量%的碘,其中约70-80%可经稀释后成为可利用的碘。这些物质安全低毒,并且几乎无味。然而,尽管不像碘酒那样刺激,但碘递体用在皮肤上时会起干燥剂的作用,并可导致皮炎。
氯可通过电解含有氯离子的电解质溶剂就地制备。以这种方法制得的氯存在时间较短,却是非常有效的水消毒剂,例如在游泳池、温泉和饮用水***中。氯还可制成液体漂白剂,即次氯酸钠。氯也可制成固体次氯酸盐,这种固态盐通常制成饼状或片状,可直接置于水容器中以获得所需的消毒效果。
溴在比碘窄的范围内用作皮肤消毒剂和伤口处理剂。溴还用作冷却塔、游泳池和温泉中的卫生消毒剂。溶于水时,液溴形成具有消毒效果的次溴酸。具有消毒效果的溴通常以水浓缩液的形式出售给公众。
所有的卤素均具有潜在的刺激性,特别是对眼部、粘膜和裸露的伤口(open wound)。此外,卤素在被吸收时还具有潜在的毒性。因此,通常期望在其最低的有效浓度下使用卤素消毒。
抗微生物金属离子溶液通常用作消毒剂。银溶液已用作冷却塔、游泳池、医院热水***、移动式水***和温泉池中的消毒剂。此外,还已制出银离子溶液用于伤口处理,然而在所建议的方法中使用的银离子并不稳定,且必须在伤口附近产生以将治疗剂量递送至伤口处。
亦已建议将银盐(例如柠檬酸银盐)用作抗微生物粉剂(dustingagent)。然而,这种粉剂必须干燥保存,而且一般不便于使消耗类产品(consumer product)具有防腐性能或者将抗微生物效果递送至最终使用者或最终使用者所处的环境。已发现胶态银具有多种用途,包括:木材防腐剂;食物及饮料容器以及工业加工设备的消毒剂;涂料中的杀细菌剂;合成聚合物膜中的杀生物剂;绷带中的灭菌剂。
美国专利US 6,197,814(全文纳入本申请中)已公开了柠檬酸二氢银和柠檬酸的含水溶液在多种场合中用作消毒剂。这种柠檬酸二氢银和柠檬酸的水溶液通过使电流经过浸在柠檬酸水溶液中的一对银电极而制得。这种柠檬酸二氢银溶液对绝大多数微生物有效,所述微生物包括细菌、病毒和真菌,并且在有效对抗微生物侵染的浓度下于人类环境中无毒。
尽管多种已知的抗微生物化合物具有抗微生物效力,仍然需要一种在更低的抗微生物剂浓度下有效的抗微生物组合物。还需要一种能够提供季铵、氧化剂和卤素化合物优点,并且具有在固体表面和其他基质上的持续的抗微生物效果的抗微生物组合物。本发明满足了上述需求,亦提供了相关优点。
发明内容
本发明主要(of matter)提供了抗微生物组合物。所述组合物包括柠檬酸二氢银、柠檬酸和一种第二抗微生物剂。所述第二抗微生物剂选自季铵化合物、氧化剂和卤素化合物。
本发明还提供了赋予基质抗微生物效果的方法。所述方法包括将抗微生物组合物施用于基质。所述抗微生物组合物包括柠檬酸二氢银、柠檬酸和一种选自季铵化合物、氧化剂和卤素化合物的物质。
具体实施方式
本申请中所述的发明提供一种具有抗微生物活性的组合物,所述微生物例如细菌、病毒和真菌。所述组合物包括柠檬酸二氢银、柠檬酸和一种选自季铵化合物、氧化剂和卤素化合物的物质。本发明还提供使用上述组合物的抗微生物方法。
本申请中,术语“柠檬酸二氢银”是指具有化学式AgC6H7O7的分子。其化学结构如式I表示:
及其位置异构体,例如其中Ag+离子在3-羧酸基团处而不是在图示的1-羧酸基团处。本领域普通技术人员将领会式I化合物是盐。因此,柠檬酸二氢银将以离解状态存在于溶液中。
本发明提供了包括作为第一抗微生物剂的柠檬酸二氢银、柠檬酸和一种第二抗微生物剂的组合物。所述第二抗微生物剂有利地选自季铵化合物、氧化剂和卤素化合物。此外(in combination),由于银离子(Ag+)与第二抗微生物剂的结合(combined)抗微生物活性,柠檬酸二氢银、柠檬酸和第二抗微生物剂还能够产生改进的抗微生物效果。在某些实施方案中,由于柠檬酸二氢银和第二抗微生物剂的结合,组合物提供了即时的抗微生物效果;并且,即使第二抗微生物剂发生分解,由于柠檬酸二氢银在被处理基质上的持久的抗微生物效果,组合物还提供了持续的抗微生物效果。在上述实施方案中,柠檬酸二氢银在干燥时形成了能够提供长期抗微生物效果的结晶残余物。例如,当被施用于基质时,例如表面或物品时,一种柠檬酸二氢银、柠檬酸和季铵化合物的组合物提供了对抗广谱微生物,包括假单胞菌的即时抗微生物效果,同时还提供了持续的抗微生物效果。作为另一个实例,当被施用于基质时,由于柠檬酸二氢银与氧化剂的结合,一种柠檬酸二氢银、柠檬酸和氧化剂的组合物提供了即时的抗微生物活性,同时还提供了长期抗微生物有益特性。
在其他实施方案中,柠檬酸二氢银和第二抗微生物剂的结合能够产生协同的效应。本申请所定义的术语“协同的”,是指两种或两种以上试剂的结合效果优于这两种试剂单独使用时能够达到的效果。一般而言,对于特定的有机体而言,其含义是指,当满足下式时,两种活性试剂A和B的结合是协同的:
EC50(A+B)<EC50(A)+EC50(B)
其中EC50指使有机体活性测量值有效降低50%的浓度。A和B表示两种抗细菌剂,EC50(A+B)是A与B结合的EC50,EC50(A)是单独使用A的EC50,EC50(B)是单独使用B的EC50。有机体活性既可以是有机体增殖(proliferation),也可以是有机体活力(vitality)。例如,当所需的抗微生物效果是抑制细菌效果时,EC50是试剂使有机体细胞***率降低50%时的浓度测量值。当抗微生物效果是杀细菌效果时,EC50是使活的有机体数量降低50%时的试剂浓度。例如,一种包括柠檬酸二氢银、柠檬酸和卤素化合物的组合物所需要的柠檬酸二氢银和一种卤素化合物的浓度,要少于其各自单独用作抗细菌剂、抗真菌剂或抗病毒剂时所必需的浓度的一半。
本发明提供了包括季铵化合物的柠檬酸二氢银组合物。季铵化合物可由式II或III表示:
其中R1、R2、R3和R4各自独立地为有机基团,n为整数,Xn-为带n个负电荷的阴离子(抗衡离子(counter-ion))。
上式II和III中合适的有机基团包括烷基、链烯基、炔基、具有至少一个取代基的烷基、具有至少一个取代基的链烯基、及具有至少一个取代基的炔基。
在式II和III中,烷基指任选有支链的、完全饱和的C1-C30烃基。链烯基指任选有支链的、部分或完全不饱和的C2-C30烃基,其中每个不饱和链为一个碳-碳双键。炔基指任选有支链的、完全或部分不饱和的C2-C30烃基,其中至少一个不饱和链是碳-碳叁键。适合的烷基包括甲基、乙基、异丙基、正丙基、正丁基、叔丁基、仲丁基,以及任选有支链的戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基(triskaidecyl)、十八烷基、二十烷基(C20)等。适合的链烯基包括:乙烯基、1-丙烯基、2-丙烯基、3-丙烯基、1-丁烯-4-基、2-丁烯-4-基,以及任选有支链的戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一烯基、十二烯基、十三烷基、十八烯基、5,8,11,14-二十四烯基、9,12-十八二烯基、9,12,15-十八三烯基等。适合的炔基包括:乙炔基、1-丙炔基、3-丙炔基、2-丁炔-1-基等。
上述烷基、链烯基和炔基的取代基包括:环烷基(饱和或部分不饱和的)、芳基、杂环基(饱和或部分不饱和的)、杂芳基、氟、氯、溴、碘、羟基、巯基、硝基等。环烷基包括饱和环烷基,例如环丙基、环丁基、环戊基、环己基、环戊基、环辛基等。芳基包括:苯基、萘基、蒽基等。杂环基包括:吡咯烷基、哌啶基、哌嗪基、吗啉代、硫代吗啉代(thiomorpholino)等。杂芳基包括吡啶基、硫苯基、呋喃基、噻唑基、嘧啶基等。
本发明提供了包括柠檬酸二氢银和柠檬酸与特定的式II和II的季铵化合物结合的组合物,其中R1、R2、R3和R4各自为甲基、乙基、异丙基、正丙基、正丁基、叔丁基、仲丁基、C4-C20烷基,或具有取代基的下述基团之一:甲基、乙基、异丙基、正丙基、正丁基、叔丁基、仲丁基或C4-C20烷基,其中所述取代基为芳基,特别是苯基。可提及的特别有益的R1、R2、R3和R4为甲基、乙基、异丙基、正丙基、十二烷基、十八烷基、二十烷基、苄基、苯乙基等。
本发明提供了包括柠檬酸二氢银、柠檬酸和一种式II或III的季铵化合物的特定组合物,其中抗衡离子为具有-1、-2或-3电荷的阴离子。适合的抗衡离子包括:氯离子、溴离子、碘离子、亚硝酸根、硝酸根、亚硫酸氢根、硫酸氢根、亚硫酸根、硫酸根、磷酸根、磷酸氢根、磷酸二氢根、氢氧根等。
本发明提供了包括柠檬酸二氢银、柠檬酸和一种特定季铵化合物的特定组合物,所述季铵化合物的实例有:四丁基溴化铵、四丁基硫酸氢铵、四丁基氟化铵、四丁基氯化铵、四乙基溴化铵、四乙基氯化铵、四乙基碘化铵、四丙基溴化铵、四丙基碘化铵、四甲基氯化铵、四甲基溴化铵、四甲基碘化铵、四甲基氢氧化铵、四辛基溴化铵、四辛基氯化铵、四辛基碘化铵、四辛基氢氧化铵、苄基三乙基氯化铵、苄基三丁基氯化铵、苄基三甲基氯化铵、苄基三甲基二氯碘化铵、苄基三甲基溴化铵、丁基三乙基溴化铵、甲基三辛基氯化铵、甲基三辛酰基(capryl)氯化铵、甲基三丁基氯化铵、十四烷基三甲基溴化铵、十六烷基三甲基溴化铵(cetrimide)、十六烷基三甲基溴化铵、十二烷基三甲基氯化铵、苯基三甲基氯化铵、苯扎氯铵、四丁基高氯酸铵、四丁基对甲苯磺酸铵、四乙基对甲苯磺酸铵、十六烷基三甲基对甲苯磺酸铵、四乙基甲苯磺酸铵、四丁基甲苯磺酸铵、十六烷基三甲基甲苯磺酸铵、十六烷基氯化吡啶鎓、十六烷基溴化吡啶鎓、十二烷基氯化吡啶鎓及十二烷基溴化吡啶鎓。
依据组合物的预期用途,本发明提供了多种浓度的包括柠檬酸二氢银、柠檬酸和一种季铵化合物的组合物。例如,本发明提供了包括至少约0.5ppm柠檬酸二氢银和至少约50ppm季铵化合物的组合物。
本发明还提供了包括柠檬酸二氢银、柠檬酸、一种季铵化合物和一种分散剂的组合物。适合的分散剂一般为表面活性剂,例如十二烷基硫酸钠或Octoxynol(聚乙二醇十八烷基醚)。所述组合物包括约0.01%(重量/重量)以上的分散剂。
本发明提供了包括柠檬酸二氢银、柠檬酸和一种或多种氧化剂结合的组合物。可提及的氧化剂有过氧化物,例如过氧化氢和过氧化苯甲酰;高锰酸盐,例如高锰酸钾;过硫酸盐,例如单过硫酸钾。
依据组合物的预期用途,本发明提供了多种浓度的包括柠檬酸二氢银、柠檬酸和一种氧化剂的组合物。例如,本发明提供了包括至少约0.5ppm柠檬酸二氢银和至少约50ppm氧化剂的组合物。
本发明还提供了包括柠檬酸二氢银、柠檬酸、一种氧化剂和一种分散剂的组合物。适合的分散剂一般为表面活性剂,例如十二烷基硫酸钠或Octoxynol。所述组合物包括约0.01%(重量/重量)以上的分散剂。
本发明提供了包括柠檬酸二氢银、柠檬酸和一种或多种卤素化合物结合的组合物。可提及的卤素化合物有碘(I2)、溴(Br2)、氯(Cl2)、次氯酸钠、次氯酸钙等。用碘作成分时,可将其以碘酒或碘递体的形式加入。用溴作成分时,可将其以液溴或稀释溶液的形式加入。用氯作成分时,可将其以Cl2气的形式鼓泡通入溶液,或者可将其以液体或固体次氯酸盐化合物的形式加入。
依据组合物的预期用途,本发明提供了多种浓度的包括柠檬酸二氢银、柠檬酸和一种卤素化合物的组合物。例如,本发明提供了包括至少约0.1ppm柠檬酸二氢银和至少约2ppm卤素化合物的组合物。
本发明还提供了包括柠檬酸二氢银、柠檬酸、一种卤素化合物和一种分散剂的组合物。适合的分散剂一般为表面活性剂,例如十二烷基硫酸钠或Octoxynol。所述组合物包括约0.01%以上的分散剂。
一般而言,式I的柠檬酸二氢银可通过将银电极浸入含有柠檬酸的电解质水溶液中而制得。然后将电解势加至电极,由此在溶液中产生银离子。当以此种方式结合时,银离子和柠檬酸生成柠檬酸二氢银,该银盐在柠檬酸水溶液中是稳定的。在本发明的某些实施方案中,电解质包含约5%以上、优选约10%以上的柠檬酸(%重量/体积),更优选20%或更多。然后如本申请另述,使柠檬酸二氢银与其他成分结合。
柠檬酸二氢银、柠檬酸和至少一种选自季铵化合物、氧化剂和卤素化合物的物质的组合物,可通过将柠檬酸二氢银溶液与一种或多种选自季铵化合物、氧化剂、卤素化合物及其结合物的合适成分相结合而制得。在某些实施方案中,将如上所述的柠檬酸二氢银溶液稀释至合适浓度以获得工作溶液,向其中加入合适量的成分并混合。可选将其他抗微生物成分、分散剂或其结合加入至所述工作溶液中。当全部所需成分都加入溶液并与溶液充分结合时,再进一步用水稀释所述溶液以形成最终组合物。本领域普通技术人员可以领会,柠檬酸二氢银和其他成分的加入顺序可按需改变,这并不会影响溶液的效力。
柠檬酸二氢银已显示具有对抗多种有机体的抗微生物活性,所述有机体包括细菌、真菌和病毒。已证实对其具有效力的特定微生物包括:铜绿假单胞菌(Pseudomonas aeruginosa)(尤其是ATCC 15442)、猪霍乱沙门氏菌(Salmonella choleraesuis)(尤其是ATCC 10708)、金黄色葡萄球菌(Staphylococcus aureus)(尤其是ATCC 65328和ATCC 700698)、大肠杆菌(E.coli)(尤其是0157:H7、ATCC 43888和ATCC11229)、单核细胞增生李斯特氏菌(Listeria monocytogenes)(尤其是ATCC 11543和19111)、屎肠球菌(Enterococcus faecium)(尤其是ATCC 6569和ATCC 700221)、1型人免疫缺陷病毒(HIV1)、1型单纯疱疹病毒(HSV1)、2型脊髓灰质炎病毒、流感病毒A、鼻病毒、疮疱丙酸杆菌(Propionibacterium acnes)(尤其是ATCC 6921)、须疮癣菌(Trichophyton mentagrophytes)(尤其是ATCC 9533)。因此,本发明提供了具有对抗广谱微生物活性的组合物,包括对抗细菌,例如以下属:假单胞菌属(Pseudomonas)、沙门氏菌属(Salmonella)、葡萄球菌属(Staphylococcus)、埃希氏菌属(Escherichia)、李斯特氏菌属(Listeria)、肠球菌属(Enterococcus)和丙酸杆菌属(Propionbacterium)。本发明还提供了具有对抗皮肤真菌活性的组合物,例如对抗发癣菌属(Trichophyton)。
季铵化合物已显示具有对抗广谱微生物的抗微生物效果,所述微生物包括革兰氏阳性菌和革兰氏阴性菌,以及对抗某些病毒和真菌。特别地,已发现苯扎氯铵对腮腺炎病毒、轮状病毒、风疹病毒、麻疹病毒和HIV有效。
氧化剂已显示具有广谱抗微生物效果。例如,3%过氧化氢水溶液已用作局部抗菌剂。过氧化氢(3%)也以与5%乙酸(醋酸(vinegar))溶液以结合处理的形式用作表面处理剂,以杀灭沙门氏菌(Salmonella)和其他种类细菌。高锰酸钾(KMnO4)是一种已在冷却塔、蒸发冷凝器、洗尘***、冷却喷水器及人类饮用水中用作杀细菌剂、杀真菌剂和灭藻剂的氧化剂。高锰酸钾还用于抑制养鱼池和观赏性水池中鱼类的外界侵染。单过硫酸盐(例如单过硫酸钾)用作氧化剂,用于游泳池和温泉中的辅助氧化清洁(shocking)。可提及的其他氧化剂还有过氧化苯甲酰和高硼酸钠。过氧化苯甲酰的5%或10%溶液已用作痤疮治疗剂。
卤素化合物也已显示具有广谱抗微生物效果。氯被认为是水处理的首选消毒剂,例如在供水***、冷却塔、游泳池和温泉中。虽然氯通常以约1,000ppm的浓度使用,但是游泳池和温泉中的总氯(totalchlorine)浓度一般为3至5ppm。溴已用作抗菌剂和消毒剂。溴浓度约1,000ppm时,用作抗菌剂有效,约4至6ppm时用于水处理。碘既可用作消毒剂,也可用作抗菌剂。用作抗菌剂时一般浓度为约1至2%。聚维酮碘(povidone iodine)已显示具有对抗广谱细菌的活性,包括变形菌(Proteus)、葡萄球菌(Staphylococcus)、假单胞菌(Pseudomonas)、链球菌(Streptococcus)、埃希氏菌(Escherichia)、沙门氏菌(Salmonells)、念珠菌(Candida)、沙雷氏菌(Serratia)、Spores-Baccillus;梭菌(Clostridium)、Trichomomonas、肠杆菌(Enterobacter)、克雷伯氏菌(Klebsiella)、梭菌(Clostridium)、志贺氏菌(Shigella)、棒杆菌(Corynebacterium)、双球菌(Diplococcus)、分枝杆菌(Mycobacterium)、芽孢杆菌(Bacillus)、八叠球菌(Sarcina)、发癣菌(Trichophyton)、曲霉(Aspergillus)、小小菌(Mima)、赫尔氏菌(Herella)、爱德华氏菌(Edwardsiella)、柠檬酸杆菌(Citrobacter)、普罗威登斯菌(Providencia)、Acienetobacter、表皮癣菌(Epidermophyton)、小孢子菌(Microsporum)、青霉(Pencillium)和诺卡氏菌(Nocardia)。除对抗广谱细菌的活性之外,还发现聚维酮碘(碘递体)在固定腺病毒、腮腺炎病毒、轮状病毒、脊髓灰质炎病毒、柯萨奇病毒、鼻病毒(rhionvirus)、单纯疱疹病毒、风疹病毒、麻疹病毒、流感病毒和人免疫缺陷病毒(HIV)方面有效。(参见R.Kawana等,Dermatology 195,增刊2,29-35(1997))。
本发明提供了包括柠檬酸二氢银、柠檬酸和一种选自季铵化合物、氧化剂和卤素的第二抗微生物剂的抗微生物组合物的使用方法。本发明还提供了用所述抗微生物组合物处理多种基质以获得抗微生物效果的方法。所述抗微生物效果可以是抗细菌、抗病毒和/或抗真菌效果。所述抗细菌效果可以是杀细菌或抑制细菌。所述抗病毒效果包括固定及破坏病毒体。所述抗真菌效果包括杀真菌和抑制真菌效果。所述方法包括将有效量的处理组合物施用于基质以获得所需抗微生物效果。
一般而言,本申请中的术语“基质”是指需要进行抗微生物处理的任何表面、物品或环境。本发明提供了处理多种表面,包括台面、地面、玻璃表面、金属表面(例如不锈钢、铬及铜表面)、砖瓦表面、混凝土表面、乙烯基地板材料(vinyl flooring)和涂料涂敷的表面。本申请中所用的术语“表面”是指任何表面,包括不同物体的内外表面,包括容器(例如锅炉、水罐、游泳池等)内部、管内部、家具(householdfixture)及家用电器外部、台面、玻璃门窗。本申请中用术语“表面”与整个物品相区别。抗微生物溶液以常规方式施用于表面,例如将溶液倾倒、喷洒或擦拭于表面。将溶液从表面方便地擦去或冲洗掉;然而在某些实施方案中,将溶液留在表面上干燥,由此在表面上得到长效的抗微生物残余物或膜。
本发明提供了处理其他基质的方法,包括处理多种物品,例如织物、金属物品、塑料物品、天然物品及通常由含水清洗溶液处理的其他物品。例如,本发明提供了用包括柠檬酸二氢银、柠檬酸和第二抗微生物剂的抗微生物组合物处理食品的方法。由所述抗微生物组合物处理的食品的实例包括蔬菜和水果。可由所述抗微生物组合物处理的蔬菜包括:块根类(例如胡萝卜类、甜菜类、萝卜类);块茎类(例如马铃薯类、芜菁类、甘薯类及薯蓣类);鳞茎类(例如洋葱类、薤类);球茎类(例如蒜);绿叶植物类(例如菠菜、甘蓝、莴苣及卷心菜);十字花科苗(例如椰菜和花椰菜);以及豆类(例如大豆和落花生)。可由所述抗微生物组合物处理的水果的实例包括:南瓜、甜瓜、苹果、桃、梨、香蕉、番茄、柑桔(例如橙、葡萄柚、橘、桔柚、柠檬和酸橙)、葡萄和橄榄。本发明还提供了将所述抗微生物组合物在食品上喷洒或擦拭以处理食品的方法。作为选择,本发明还提供了将食品浸入抗微生物组合物以获得抗微生物效果的方法。
本发明还提供了用抗微生物的柠檬酸二氢银、柠檬酸和第二抗微生物剂的组合物处理多种物品的方法。例如,可将抗微生物组合物喷洒或擦拭于各种物品上,所述物品包括用于食品服务或食品加工制造的机械零件。抗微生物组合物也可用于清洗玩具以及儿童和婴儿使用的其他物品。抗微生物组合物还可用于清洗织品,例如服装、抹布、床上用品及其他织品。
本发明还提供了用抗微生物组合物处理水的方法。一种所述方法包括提供具有预先选定浓度的柠檬酸二氢银和卤素化合物的抗微生物组合物。适于该组合物的示例性柠檬酸二氢银浓度为约、尤其是约1,000ppm至约5,000ppm;适合的组合物中卤素化合物的示例性的浓度为约2,000至约20,000ppm。然后将一定量的抗微生物组合物加入至水容器中,达到约0.1ppm至约50ppm、尤其是约0.2ppm至约20ppm的柠檬酸二氢银浓度,以及约0.5ppm至约50ppm、尤其是约1至10ppm的卤素化合物浓度。然后使水容器中的水循环,以确保柠檬酸二氢银与卤素化合物完全彻底混合。有益的作法是,在加入抗微生物组合物后,测试柠檬酸二氢银水平和/或卤素化合物水平,以确保柠檬酸二氢银和卤素化合物的抗微生物量在水容器中保持不变。已知的是,例如,氯和溴的化合物在有机体(叶、枝)、生物(细菌、藻类)和可能引入水容器的其他外部物质的存在下会被损耗。因此,如果水容器是浑浊的,或者原本被认为是包含有机体或生物侵染的,则应在加入抗微生物组合物之后定期检测水体,以确保柠檬酸二氢银的浓度维持在上述范围内。
本发明提供了包括柠檬酸二氢银和卤素化合物的抗微生物组合物的使用方法。所述抗微生物组合物如上制成,其中柠檬酸二氢银的量为约1,000ppm至约5,000ppm,卤素化合物的量为约2,000ppm至约20,000ppm。就供水***、饮用水、水池和温泉的处理而言,将一定量的上述组合物加入至水中,达到浓度约0.1至约100ppm的柠檬酸二氢银,以及约0.2至约20ppm的卤素化合物。就表面消毒、食品和非食物物品的处理而言,可将所述组合物稀释制成约0.1至约100ppm柠檬酸二氢银和约0.2至约20ppm卤素化合物的组合物。然后将稀释过的溶液施用于待处理的食品、非食物物品或表面。将溶液施用于物品或表面,将产生即时且长期的抗微生物效果。
本发明还提供了处理固体表面的方法,例如食物制造及食物服务业中接触到的固体表面。一种所述方法采用具有预先选定浓度的柠檬酸二氢银和季铵化合物的抗微生物组合物。适于处理组合物的柠檬酸二氢银浓度为约0.1ppm至约100ppm的柠檬酸二氢银和约0.2ppm至约20ppm的季铵化合物。然后将处理组合物施用于固体表面,例如不锈钢表面。本方法提供了持续的余效保护以避免微生物侵染。当季铵化合物消散时,柠檬酸二氢银仍有留存,以向固体表面以及任何可能与表面接触的物质提供持续的抗微生物有益特性。
本发明提供了处理固体表面的另一种方法,该方法采用了包括柠檬酸二氢银、柠檬酸和氧化剂的抗微生物组合物。所述抗微生物组合物具有预先选定浓度的柠檬酸二氢银和氧化物。适于处理组合物的柠檬酸二氢银浓度为约0.1ppm至约100ppm的柠檬酸二氢银;适合的处理组合物中氧化剂的浓度为约0.2ppm至约20ppm氧化剂。将所述抗微生物组合物施用于固体表面,例如不锈钢表面或台面。该方法提供了持续的余效保护以避免微生物侵染。当氧化剂消散时,柠檬酸二氢银残余物仍有留存,以向固体表面以及任何可能与表面接触的物质提供持续的抗微生物有益特性。
本发明还提供了一种处理基质的方法,例如用包括柠檬酸二氢银、柠檬酸和氯或溴的抗微生物组合物处理食品或非食物物品的方法。适于抗微生物组合物的柠檬酸二氢银浓度为至少约0.1ppm,尤其是至少约0.5ppm。适合的处理组合物中的氯或溴的浓度为至少约0.2ppm,特别是约0.2ppm至约20ppm。将所述处理组合物施用于基质,所述基质可以是固体表面、食品或非食物物品。该方法提供了协同的抗微生物效力。
参考以下示例性和非限制性实施例,可更充分地理解本发明。
实施例
实施例1:柠檬酸二氢银储液的制备
将水引入反渗透装置,经半透膜除去杂质,获得去离子水。将99%纯的无水柠檬酸与上述水混合,获得200加仑的20%(重量/体积)(每加仑水796g柠檬酸)溶液。将上述200加仑的20%柠檬酸径直引入带有正负电极的离子室中,每个电极由200金衡制盎司的999纯银构成。正负电极间相距至少2.0mm,使柠檬酸溶液在两个电极之间通过。使包括有正负导体的离子发生调节器(IGC)电源连接到上述正负电极上。IGC在17伏下施加5安培的电流,每9秒一次脉冲,间隔1分钟改变一次极性。整个过程中通过调节电极间距,以维持5安培-17伏特的输出。电流流动引起离子流在正负电极间流动,在稀释过的柠檬酸溶液中获得游离的银离子。银离子与柠檬酸溶液中的柠檬酸反应生成柠檬酸二氢银溶液。使所述20%的柠檬酸溶液以每分钟50加仑的流量循环经过离子室144小时,直至达到所需的银离子浓度。然后将所得柠檬酸二氢银溶液静置,以使过程中形成的所有固体沉淀下来。所得产品为银离子浓度为2400ppm的柠檬酸二氢银溶液。在本申请下文中,将该溶液称为储液。该储液可在以下实施例中立即使用,或者储存待用。
本领域技术人员应理解的是,多种电极尺寸和/或间距的变化,以及多种峰值电压的变化,以及多种间隔电压极性的时间顺序的变化,均可方便地用于获得用于本发明的柠檬酸二氢银。
实施例2:含有柠檬酸二氢银与季铵化合物、氧化剂
或卤素化合物的组合物的制备
(a)有色香味中间体组合物:在1,000ml的PyrexTM玻璃烧瓶中,
将列于表1的成分以所示比例结合:
表1
成分 | 比例 |
药用级纯水 | 98.882% |
80%季铵浓缩液 | 0.300% |
Triton X-100TM表面活性剂 | 0.500% |
无毒香味剂 | 0.300% |
无毒颜料 | 0.015% |
(b)无色香味组合物:在1,000ml的PyrexTM玻璃烧瓶中,将列于表2的成分以所示比例结合:
表2
成分 | 比例 |
药用级纯水 | 98.897% |
80%季铵浓缩液 | 0.300% |
Triton X-100TM表面活性剂 | 0.500% |
无毒香味剂 | 0.300% |
(c)有色无味组合物:在1,000ml的PyrexTM玻璃烧瓶中,将列于表3的成分以所示比例结合:
表3
成分 | 比例 |
药用级纯水 | 99.182% |
80%季铵浓缩液 | 0.300% |
Triton X-100TM表面活性剂 | 0.500% |
无毒颜料 | 0.015% |
(a)无色无味组合物:在1,000ml的PyrxTM玻璃烧瓶中,将列于表4的成分以所示比例结合:
表4
成分 | 比例 |
药用级纯水 | 99.197% |
80%季铵浓缩液 | 0.300% |
Triton X-100TM表面活性剂 | 0.500% |
将上述(a)-(b)所得中间体组合物混合约15分钟,然后加入实施例1的0.003%柠檬酸二氢银储液。然后将所有成分再混合1小时。所得组合物(测试溶液(a)-(d))在实施例3中使用。
实施例3:实施例3组合物的抗微生物效果
35℃下大肠杆菌测试株(E.coli PIPSA,德国H.)生长24小时。离心10分钟以采集细胞,并用Butterfield’s磷酸盐缓冲液(BPB pH.7.2)洗涤两次。然后使细胞再悬浮于BPB中以获得约108CFU/ml的细胞悬浮液。(最终测试溶液中的目标种菌水平为约106CFU/ml)
提供两片一组的无孔载玻片共三组。对每组测试载玻片,其中一片用实施例3的测试溶液处理,另一片用实施例3的中间体测试溶液处理。然后用大肠杆菌对各载玻片接种。
接种后,将测试载玻片贮存1和24小时,然后在指定时段铺开,培养24小时。结论“通过”表示无细菌生长。结论“未通过”表示有细菌生长。以下表5中的结果证明,柠檬酸二氢银和季铵化合物的结合具有残余活性,而仅包括季铵化合物的组合物则不具有此特性。
表5
采样间隔/成分 | 1小时 | 24小时 |
柠檬酸二氢银+季铵化合物 | 通过 | 通过 |
通过 | 通过 | |
通过 | 通过 | |
仅季铵化合物 | 通过 | 未通过 |
通过 | 未通过 | |
通过 | 未通过 |
由上述实施例可以看出,本发明在抗微生物方法领域具有显著优势。本发明提供了具有广谱抗微生物特性的抗微生物组合物和方法。此外,本发明还提供了具有协同抗微生物特性的组合物和方法。而且,本发明也提供了施用于基质时具有持续的抗微生物特性的抗微生物组合物。
尽管本发明依据某些示例性的实施方案进行了表述,但本领域普通技术人员可以领会,也可在本发明上述总体描述的范围内实现其他实施方案。
Claims (17)
1.一种组合物,包括柠檬酸二氢银(SDC)、柠檬酸和选自季铵化合物、氧化剂和卤素化合物的一种第二抗微生物剂,其中SDC/柠檬酸使所述组合物具有比仅含第二抗微生物剂作为抗微生物剂的组合物更长的持续的有效使用期。
2.权利要求1的组合物,其中所述第二抗微生物剂为季铵化合物。
3.权利要求1的组合物,其中所述第二抗微生物剂为氧化剂。
4.权利要求3的组合物,其中所述氧化剂选自过氧化氢、单过硫酸钾和高锰酸钾。
5.权利要求1的组合物,其中所述第二抗微生物剂为卤素化合物。
6.权利要求5的组合物,其中所述卤素化合物为氯、次氯酸盐、溴或碘。
7.权利要求1的组合物,还包括一种分散剂。
8.权利要求7的组合物,其中所述分散剂为洗涤剂。
9.权利要求8的组合物,其中所述洗涤剂为十二烷基硫酸钠或Octoxynol。
10.使用权利要求1的组合物的方法,包括将所述组合物施用于基质,从而获得抗微生物效果。
11.权利要求10的方法,其中所述基质为固体表面。
12.权利要求10的方法,其中所述基质为织物。
13.权利要求10的方法,其中所述基质为物品。
14.权利要求10的方法,其中所述抗微生物效果为杀细菌效果。
15.权利要求10的方法,其中所述抗微生物效果为抑制细菌效果。
16.权利要求10的方法,其中所述抗微生物效果为杀病毒效果。
17.权利要求10的方法,其中所述抗微生物效果为杀真菌效果。
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