WO2008156636A1 - Revêtements antimicrobiens destinés à la conversion de spores en leur forme bactérienne végétative pour une décontamination - Google Patents

Revêtements antimicrobiens destinés à la conversion de spores en leur forme bactérienne végétative pour une décontamination Download PDF

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WO2008156636A1
WO2008156636A1 PCT/US2008/007338 US2008007338W WO2008156636A1 WO 2008156636 A1 WO2008156636 A1 WO 2008156636A1 US 2008007338 W US2008007338 W US 2008007338W WO 2008156636 A1 WO2008156636 A1 WO 2008156636A1
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polymer coating
halamine
heterocyclic
groups
coating
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PCT/US2008/007338
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Steven N. Kaganove
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Michigan Molecular Institute
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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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds

Definitions

  • the present invention relates to antimicrobial coatings for conversion of spores into their bacterial vegative form for decontamination. These antimicrobial surface coatings are effective in killing both vegetative microorganisms and microbiological spores.
  • the ability to form an impervious spore is the key to survival for certain species of bacteria including Bacillus and Clostridium, as well as several other microorganisms. Vegetative bacteria form a metabolically dormant spore in response to environmental stresses, such as nutrient deprivation. The result of spore formation is a highly resistant cell than can endure a variety of environmental stresses, including heat, pressure, radiation, and toxic chemicals. Bacillus and Clostridium are the causative agents for a variety of maladies including anthrax, tetanus, botulism and gas gangrene. Consequently, reliable and versatile treatments for the disinfection of these bacteria and also their spores are needed.
  • US Patent 6,812,298 teaches hyperbranched polyureas, polyurethanes, polyamidoamines, polyamides, and polyesters. Their use as a component in the present invention is not disclosed.
  • Published US 2005/0136522 describes surfaces for protection from toxins but not biocidal materials or germinants.
  • biocidal product that has a broad spectrum of antimicrobial activity, that has the biocidal entity bound to a substrate to avoid leaching, that has a useful longer shelf life, and that could be regenerated with simple chemical agents.
  • the present invention provides antimicrobial coatings that convert bacterial spores into their more vulnerable vegetative form, where they are subsequently deactivated or killed. More specifically, this invention provides an antimicrobial surface polymer coating capable of killing or deactivating bacterial spores which comprises:
  • hyperbranched polymers having (a) at least one heterocyclic N- halamine terminal group, or (b) at least one quaternary ammonium terminal group, or (c) a mixture comprising at least one each of quaternary ammonium and heterocyclic N-halamine terminal groups; or
  • polyamidoamine dendrimers having at least one heterocyclic N- halamine terminal group, or (3) linear PEI with hydantoin and quaternary ammonium groups at each repeat unit.
  • These polymer coatings may optimally be crosslinked and/or grafted to surfaces for increased durability and/or may form the top layer of a polyelectrolyte multilayer (PEM).
  • PEM polyelectrolyte multilayer
  • Any chemical that induces activation and/or germination of bacterial endospores can be utilized.
  • Non-nutrient germinants such as calcium (I + ) dipicolinate, and dodecylamine are also preferred.
  • Sodium taurocholate is preferred for the germination of C. difficile. Mixtures of some or all of the preceding germinants are envisioned.
  • the coating of the present invention is applied to a surface before it is exposed to spores or bacteria of the types desired or intended to be killed by use of this coating.
  • the methods for applying the solution are anything that permits the coating to be applied and dried to the substrate, such as a solution of the polymer in a polar organic solvent or water, and then dipping the substrate into the solution one or more times, spraying the solution onto the substrate, spin coating the solution onto the substrate, or wiping the solution onto the substrate.
  • Figure 1 illustrates the use of PAMAM dendrimers or hyperbranched polyamide polymers (HBP) as biocidal coatings applied to surfaces for the purpose of decontaminating bacterial spores, and which have at least one each of N-chlorohydantoin and alkyl quaternary ammonium terminal groups.
  • HBP hyperbranched polyamide polymers
  • Figure 2 illustrates the use of both (a) PAMAM dendrimers or hyperbranched polymers, which contain internal "cargo space” and (b) PEM, which readily accommodates charged ions and small molecules within available interstitial sites in formation of the antimicrobial coating of this invention.
  • Figure 2 shows a schematic representation of a biocidal PEM composed of alternating layers of (a) PDADMAC; (b) PSS; (c) hyperbranched polymer top layer containing at least one each of N-chlorohydantoin and alkyl quaternary ammonium terminal groups; and (d) small molecule germinants adsorbed within interstitial sites of the PEM, and also within the "cargo space" of the hyperbranched polymer.
  • Figure 3 shows a schematic representation of a biocidal PEM composed of alternating layers of (a) PDADMAC; (b) PSS; (c) linear PEI top layer with pendant N- chlorohydantoin and alkyl quaternary ammonium groups; and (d) small molecule germinants adsorbed within interstitial sites of the PEM.
  • Figure 4 illustrates the use of both (a) PEM, which readily accommodate charged ions and small molecules within available interstitial sites with (b) dendritic polymers,
  • FIG. 4 shows a schematic representation of a spore- killing PEM composed of alternating layers of (a) PDADMAC; (b) PSS; (c) PAMAM dendrimer layer near top; (d) linear PEI top layer with pendant N-chlorohydantoin and alkyl quaternary ammonium groups; and (e) small molecule germinants adsorbed within the interstitial sites of the PEM, and within the PAMAM dendrimer layer "cargo space".
  • AFGK means a combination of L-asparagine, D-fructose, D-glucose, and K + ions
  • CaDPA means calcium (I + ) dipicolinate
  • DMF means dimethylformamide
  • DMSO means dimethylsulfoxide
  • HBP means hyperbranched polymer, and can be a polyamide, a polyurea, a polyurethane, a polyethyleneimine or a polyamidoamine
  • NMP means l-methyl-2-pyrrolidinone
  • PAA means poly(acrylic acid)
  • PAH means poly(allyl amine hydrochloride)
  • PAMAM dendrimer means poly(amidoamine) dendrimer
  • PDADMAC means poly(diallyldimethylammonium chloride)
  • PEI poly(ethyleneimine) in its linear or branched form unless specified as a dendrimer
  • PEM means polyelectrolyte multilayers
  • PSS means poly(sodium 4-styrenesulfonate)
  • QACs means quaternary ammonium compounds
  • Room temperature means ambient temperature, about 20 to about 25 0 C
  • the present invention provides versatile coatings containing strongly biocidal chemical entities that convey broad spectrum antimicrobial activity against mold, viruses, bacteria and bacterial spores.
  • the coatings are preferably polymers, and the biocidal entities are chemically grafted to or encapsulated within these polymers so that they cannot leach out over time, and are resistant to repeated wear and tear. Some biocidal entities may be repeatedly regenerated by treatment with commercial cleaning products that contain bleach. These features will convey extended operational lifetimes.
  • the present invention provides for the incorporation of chemical entities that on contact trigger the germination of bacterial spores into vegetative bacteria, which are then more easily killed by the biocidal entities.
  • the amount of incorporated "germinants” is optimized through the use polymer architectures that have a large carrying capacity for these small molecule "guests”.
  • the present invention provides a series of structurally related, potent antimicrobial coatings that can be applied to a variety of common porous and nonporous surfaces, including metal, glass, plastic, fabrics, and fibers; thereby conveying protection to useful items such as clothing, equipment, and air filtration systems.
  • Particular focus is on formulations that can be applied to the fibers of typical air filters for the protection of HVAC systems, thereby providing an effective means of making buildings resistant to attack from biological warfare agents.
  • These coatings can be used on articles typically found in hospitals or long-term care facilities such as bed rails, tray tables and bathroom fixtures in order to prevent the spread of hospital-acquired infections, such as Clostridium difficile, which is also a preferred use.
  • the present invention incorporates a combination of two biocidal chemistries with a cocktail of one or more small molecules that are known to initiate germination of B. subtilis, B. anthracis, or Clostridium difficile spores. It has long been known that germinated spores are more susceptible to biocidal chemistries than dormant spores, and hence, the spore killing efficiency of the coatings is strongly enhanced by the incorporation of germinants.
  • Nutrient germinants include amino acids, such as those from the group consisting of L- alanine, glycine, L-valine, L-leucine, L-isoleucine, L-praline, L-serine, L-threonine, L- methionine, L-cysteine, L-tyrosine, L-phenylalanine, L-tryptophan, L-asparagine, L- glutamine, L-aspartic acid, L-glutamic acid, L-lysine, L-arginine and L-histidine, as well as other known nutrient germinants such as glucose, taurine, inosine, or AFGK, which is a combination of L-asparagine, D-fructose, D-glucose, and K + ions.
  • amino acids such as those from the group consisting of L- alanine, glycine, L-valine, L-leucine, L-isoleucine
  • a particularly active formulation for germination is the combination of L-alanine and inosine.
  • Non-nutrient germinants include calcium (2 * ) dipicolinate (CaDPA), surfactants (in particular dodecylamine) and treatment at high pressure.
  • CaDPA calcium (2 * ) dipicolinate
  • surfactants in particular dodecylamine
  • Sodium taurocholate is the preferred germinant for C. difficile.
  • the preferred germinants are CaDPA and L-alanine/inosine combination respectively.
  • the biocidal chemical entities to be tested will include quaternary ammonium compounds (QACs) [Domagk, G., Deut. Med. Wienschr. 6_i, 829 (1935); Isquith, A. J. et al, Appl. Microbiol. 24, 859-863 (1972)] and N-halamines [Sun, G. et al, J. Chem. Educ. 82, 60-64 (2005)], which are both known for their antimicrobial activity.
  • QACs quaternary ammonium compounds
  • N-halamines Sun, G. et al, J. Chem. Educ. 82, 60-64 (2005)
  • heterocyclic N-halamine terminal group moieties are selected from the following structures:
  • Ri, R 2 , R 3 and R 4 are independently selected from a Ci -C 4 alkyl, aryl, or hydroxymethyl group; and wherein X is Cl or Br.
  • biocidal functional groups In order to fabricate these biocidal functional groups into robust coatings, they are grafted onto linear and highly branched "dendritic" polymers, as either pendant groups on the former, or as peripheral end-groups on the latter.
  • polymer-based QACs In addition to the clear advantage of durability, polymer-based QACs have also been shown to exhibit enhanced antimicrobial activity over their small molecule counterparts. Both chemistries are expected to function as contact biocides because these active functional groups should stay bound to the polymer surfaces and not leach out.
  • Optional chemical grafting of the polymers to surfaces may also be expected to improve coating durability.
  • a particularly convenient method of synthesizing durable crosslinkable dendritic polymers from commercially available precursors is through attachment of hydrolysable alkoxysilane functionality to their terminal groups.
  • a key technical challenge is to provide "carrying space” for the small molecule germinants and to be able to deliver them to the surface of spores that land on the polymer coated surface.
  • This result is accomplished through the use of polymer architectures that have inherently large carrying capacities, including: (a) dendritic and/or hyperbranched polymers (HBP), which contain internal "cargo space”; (b) PEM, which readily accommodates charged ions and small molecules within available interstitial sites; or (c) a combination of both architectures.
  • Figure 1 illustrates a biocidal coating composed solely of a PAMAM dendrimer or hyperbranched polymer with N-chlorohydantoin and alkyl quaternary ammonium terminal groups, and small molecule germinants are encapsulated within its "cargo space”.
  • Figure 2 illustrates a similar PAMAM dendrimer or hyperbranched polymer (HBP), but which is deposited as the top layer of a PEM. Small molecule germinants are encapsulated both within the "cargo space" of the hyperbranched polymer top layer and within available interstitial sites of the PEM below it.
  • HBP hyperbranched polymer
  • Figure 3 illustrates a biocidal PEM similar to Figure 2, but its top layer is linear PEI with pendant N-chlorohydantoin and alkyl quaternary ammonium groups, and small molecule germinants are only encapsulated with the interstitial sites of the PEM.
  • FIG 4 is composed of a PEM and linear PEI with pendant N-chlorohydantoin and alkyl quaternary ammonium groups as a top layer.
  • PEM PEM
  • linear PEI polyethylene glycol
  • N-chlorohydantoin and alkyl quaternary ammonium groups one constituent of the PEM
  • a dendritic polymer which functions as one or more of the positively charged layers.
  • Small molecule germinants are encapsulated within available charged interstitial sites of the PEM, and also within the cargo space of the dendritic polymer layers. The amount of small molecule guests that could be accommodated within the coatings should be controllable based on the selected thickness of the PEMs, and the size/generation of the dendritic polymers.
  • PEMs are becoming increasingly popular in current polymer and materials science research because they are relatively easy to fabricate, and they are comprised of charged polymers that are usually commercially available and relatively inexpensive. Their thickness is precisely controllable through rational manipulation of a variety of parameters including the number of deposited layers, concentration of coating solutions, time of immersion, polymer molecular weight, and the concentration of added salts, if present. When two weakly ionized polyelectrolytes such as PAA and PAH are used, the thickness can also be controlled by precise adjustment of the coating solution pH for the deposition of each layer. In addition to this property, high porosity can be introduced through brief immersion of PAA/PAH multilayers in low pH solutions, which is described in US Published Patent 2006/0029634 and the references mentioned therein.
  • the antimicrobial polymers described herein can be used as topmost layers on porous PAA/PAH multilayers, and can also be chemically grafted to these layers provided that at least a small number primary or secondary amine functional groups are available for reaction with underlying PAA layers.
  • the underlying porous structure provides additional cargo space for small molecule germinants.
  • Hyperbranched polymers as described in US Patent 6,812,298 can be used with QACs and heterocyclic N-halamine end-groups in this invention.
  • the synthesis of linear polymers with pendant QACs or dendrimers with QAC end- groups has been reported the literature [e.g., Ikeda, T et al, Makromol. Chem. 184, 869 (1984); Chen, C. Z., et al, Biomacromolecules X, 473-480 (2000)].
  • the synthesis of crosslinked polymers containing both pendant QACs and N-halamines (hydantoins) has also been reported [see Liang, J. et al, Biomaterials 27, 2495-2501 (2006)].
  • the number of surface groups present as terminal groups will depend upon the polymer used and the generation of the dendrimer. At least one heterocyclic N-halamine terminal group and/or quaternary ammonium group must be present in the polymer. To obtain better efficacy it is desirable that more of these groups are present as terminal groups; preferably these terminal groups are of a number of groups sufficient to occupy from about 20% to about 100% of the terminal groups; and more preferably these terminal groups are of a number of groups sufficient to occupy from about 50% to about 100% of the terminal groups. Preparation of the antimicrobial coating.
  • the polymer coating is made from a polymer having the terminal groups on its surface and possible encapsulated small molecule germinants by dissolving, suspending or emulsifying the polymer with a suitable solvent such as water or a polar organic solvent, including but not limited to methanol, ethanol, DMSO and DMF. This is preferably done at room temperature, although the need for temperatures slightly above room temperature may be necessary.
  • the liquid is then applied to the substrate by dipping the object into the liquid (such as cloth, glass slides, objects) where one or more coats of the polymer coating of this invention is applied, or sprayed on the object, or wiped on the object, or spin coated on the object, or any other means that applies the liquid to the desired site. Upon drying (using air, heat, etc.) the antimicrobial coating is formed.
  • the Figures provided illustrate the present coating as formed.
  • the antimicrobial coating has as one of its purposes that spores are made subject to easier destruction by causing them to change from their spore form to their vegetative form. Thus when spores come into contact with the present polymer coating they are more easily killed or render harmless.
  • These polymer coatings are useful in a variety of settings for hazard reduction caused by such spores, such as i) in hospitals, for example to coat bed handrails, call buttons, disposable gowns, instruments, bedpans, and other surfaces that require a longer spore clearance than is usually available from a disinfectant, ii) in air systems, for example by coating the filters and/or conduits to remove spores from the air stream of an HVAC system, iii) in water systems, for example for by coating pipes as outlets from water supplies, or filters, or iv) any place that can be coated for longer treatment to eliminate spores and reduce the hazard from such spores.
  • the substrate that is coated can be sterilized to spores or bacteria prior to using the present polymer coating for additional longer sterilization. This polymer coating is not intended for use in diagnostic applications or assays.
  • Example 1 Preparation of linear PEI with pendant hydantoin functional groups, and quaternary ammonium functionality attached to most, or all, of the repeat units
  • Hydantoin is attached to the PEI backbone (Oxazogen) as shown in Scheme 1 below, using the known reaction of 3-hydroxymethyl-5,5-dimethylhydantoin with secondary amines. 3-Hydroxymethyl-5,5-dimethylhydantoin is found to react with PEI to a high degree of conversion. Quaternary ammonium functionality is generated in a subsequent step by exhaustive alkylation of the resulting tertiary amine with 1-bromohexane.
  • Example 2 Preparation of G4 PAMAM dendrimer with 100% 5,5-dimethylhydantoin functionalized end-groups
  • the potassium salt of 5,5-dimethylhydantoin was prepared according to procedures outlined in US Patents 4,412,078 and 6,969,769.
  • the G4 PAMAM dendrimer (Dendritech) was lyophilized under high vacuum overnight in a round-bottomed flask equipped with a magnetic stirring bar, and then weighed (1.696 g; 0.1192 mmol; 7.628 mmol Of-NH 2 groups).
  • the flask was covered with a rubber septum, and anhydrous NMP (25 mL) was added to the flask via syringe through the septum.
  • the rubber septum was replaced with a pressure-equalized addition funnel.
  • the hydantoin- PAMAM derivative was purified by ultrafiltration in water (Millipore YMl; MWCO 1000) in six passes. The water was removed by rotary evaporation, and the dendrimer was lyophilized under high vacuum overnight, yielding a brown, glassy solid (2.668 g; 0.0994 mmol; 83% yield)and its spectra are as follows:
  • Example 3 Preparation of G4 PAMAM dendrimer with approximately 50% 5,5- dimethylhydantoin functionalized end-groups and 50% quaternary ammonium functionalized end-groups
  • the potassium salt of 5,5-dimethylhydantoin was prepared according to procedures outlined in US Patents 4,412,078 and 6,969,769.
  • the ethanol was removed by rotary evaporation, and the solid potassium salt was dried under vacuum at 60 0 C for 2 days.
  • the flask was covered with a rubber septum, and anhydrous NMP (5 mL) was added to the flask via syringe through the septum. This solution was stored at room temperature for several days for subsequent reaction with the dendrimer.
  • the G4 PAMAM dendrimer (Dendritech) was lyophilized under high vacuum overnight in a round-bottomed flask equipped with a magnetic stir bar, and then weighed (0.85 g; 0.060 mmol; 3.8 mmol Of-NH 2 groups).
  • N,N-dimethyldecylamine (0.36g; 1.9 mmol) was dissolved in anhydrous NMP (5 mL), combined with the potassium salt of 5,5-dimethylhydantoin in NMP, then transferred to the pressure-equalized addition funnel, and then added dropwise to the stirred reaction mixture over 1 hour.
  • the reaction mixture was stirred for an additional 1 hour at room temperature, and then slowly heated up to 80 0 C and stirred for 72 hours. After the first 2 hours of stirring at 80 0 C, additional N,N-dimethyldecylamine (1.50 g; 8.09 mmol) was added to the reaction mixture.
  • the hydantoin-PAMAM derivative was purified by ultrafiltration in methanol (Millipore YMl; MWCO 1000) in six passes. The methanol was removed by rotary evaporation, and the dendrimer was lyophilized under high vacuum overnight, yielding a brown, glassy solid (1.407 g) and its spectra are as follows:
  • Polyelectrolyte multilayers were formed on I"x3" (2.54 cm x 7.62 cm) cleaned glass or quartz slides, QCM resonators, and silicon substrates by sequential immersion in respective aqueous polyelectrolyte solutions. After treatment with each polyelectrolyte solution (preferably 20 min at 1 mM), the substrates were immersed for 30 sec in deionized water, and then rinsed in a fresh stream of deionized water. Substrates were first modified with a "priming layer" of branched polyethyleneimine (BPEI) followed by deposition of alternating layers of PSS and PAH to make a BPEI/(PSS/PAH) n assembly. After assembly of the multilayered structures, coated substrates were immersed in
  • each germinant including calcium dipicolinate (Ca-DPA), inosine, dodecylamine, alanine, and sodium taurocholate.
  • Ca-DPA calcium dipicolinate
  • inosine inosine
  • dodecylamine dodecylamine
  • sodium taurocholate sodium taurocholate.
  • Their uptake was monitored by a shift in resonant frequency when QCM resonators were used as the coated substrate.
  • QCM results for the deposition of two and three PSS-PAH bilayers, followed by treatment with Ca-DPA and L-alanine are shown in Tables I-IV below. In each case, frequency shifts ranging from 9-36 Hz indicated successful uptake of small molecule germinants into the fabricated PEM coatings.
  • the strain Bacillus subtilis 168 was used as a model for B. anthracis. Spores were prepared using either modified G or CCY medium as the sporulation broth. After three days incubation, cells were pelleted by centrifiigation at 3200 rpm, 22°C, 15 minutes in a swinging bucket rotor (Rotanta 460R). Culture supernatants were decanted, and pellets resuspended in sterile-filtered deionized water. Water washes were repeated at least six times prior to heat inactivation to kill remaining vegetative cells (65°C for 30 minutes). Approximately 95% or more refractile spores were observed in every spore prep used, and aliquots were stored at -20 0 C until use.
  • a 10 microliter ( ⁇ L) volume of Bacillus spore suspension (approximately 10 5 viable spores) was spotted onto the surface of coated I"x3" (2.54 cm x 7.62 cm) glass slides.
  • each slide was placed in a humidity chamber (Petri plate that contained a wetted filter disk) to prevent dehydration of the spot while the spores incubated for one hour at ambient room temperature ( ⁇ 25°C). After incubation, each spot was collected from the slide in addition to three equivalent volume washes of each spot with sterile deionized water.
  • the collected spots were then split into two volumes: one for total viable cell count, and one for viable spore count.
  • the total viable cell count was performed by plating serial dilutions of the slide- incubated spores onto brain-heart infusion agar (Bio- World). In order to detect germinated spores, the aliquot to evaluate viable spore counts was placed into a water bath heated to 65°C and incubated for 30 minutes prior to dilution and plating. The ratio of viable cells remaining in the heat killed sample to total viable cells was used to calculate the percent Bacillus spores that germinated after one hour incubation on each slide. Table V represents the results of the testing.
  • Example 6 Coating of antimicrobial polymers as thin films on bare substrates, and as top layers on polyelectrolyte multilayers
  • Antimicrobial polymers prepared above in Examples 1-3 are deposited on glass and on quartz slides as thin films by immersion in dilute solution.
  • the antimicrobial polymers of Examples 1 and 3 are also deposited as a top cationic layer on polyelectrolyte multilayers.
  • the hydantoin functional groups are chlorinated by treatment with commercial grade bleach. This may be done either prior to deposition of the polymer on the PEM or after. The amount of chlorine in the coating of selected samples is probed by colorimetric titration.
  • Example 7 Exposure of slides coated with antimicrobial polymers to spores of B. subtilis, B. anthracis, and E. coli to determine antimicrobial and spore killing effectiveness

Abstract

La présente invention concerne un revêtement polymère de surface antimicrobienne susceptible d'éliminer ou de désactiver des spores bactériennes, et qui comprend : (1) des polymères hyperbranchés possédant (a) au moins un groupe terminal hétérocyclique N-halamine, (b) au moins un groupe terminal ammonium quaternaire, ou (c) un mélange comprenant au moins un groupe terminal ammonium quaternaire et un groupe terminal hétérocyclique N-halamine; ou (2) des dendrimères polyamidoamine comprenant au moins un groupe terminal hétérocyclique N-halamine ou (3) un PEI linéaire pourvu de groupes hydantoïne et ammonium quaternaire sur chaque unité de répétition. Le revêtement est utilisé de préférence pour enfermer de toutes petites molécules de germinant. Le substrat à revêtir peut être stérilisé avant d'appliquer le revêtement, mais cela n'est pas nécessaire.
PCT/US2008/007338 2007-06-12 2008-06-12 Revêtements antimicrobiens destinés à la conversion de spores en leur forme bactérienne végétative pour une décontamination WO2008156636A1 (fr)

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WO2011101661A1 (fr) * 2010-02-16 2011-08-25 Insight Health Limited Compositions comprenant un germinat et un agent antimicrobien
EP2850077A1 (fr) * 2012-05-17 2015-03-25 University Of Manitoba Composés biocides et procédés d'utilisation associés
WO2016064559A1 (fr) * 2014-10-21 2016-04-28 Auburn University Compositions fibreuses contenant une n-halamine et utilisations associées
CN105625059A (zh) * 2016-02-29 2016-06-01 苏州纺友新材料有限公司 一种无醛高固色效应的纺织固色剂
WO2016083819A1 (fr) * 2014-11-27 2016-06-02 Aston University Composé destiné au traitement contre clostridium difficile
CN105672007A (zh) * 2016-02-29 2016-06-15 苏州纺友新材料有限公司 一种耐酸碱型无醛固色剂的制备方法
WO2017079841A1 (fr) * 2015-11-13 2017-05-18 Exigence Technologies Inc. Monomères, polymères et formulations de revêtement qui comprennent au moins un précurseur de n-halamine, un centre cationique et un groupe d'incorporation de revêtement
EP2740355B1 (fr) * 2012-10-30 2018-08-01 Baxter International Inc. Couche antimicrobienne contenant de résine d'ammonium quaternaire et procédés de sa régéneration
CN109575704A (zh) * 2018-12-12 2019-04-05 武汉理工大学 纳米多孔强聚电解质薄膜的制备方法
CN110522955A (zh) * 2019-09-27 2019-12-03 淮阴工学院 一种抗菌纳米合成及抗菌涂层的制备方法
WO2020081296A1 (fr) * 2018-10-18 2020-04-23 Milliken & Company Compositions pour l'entretien du linge comprenant des composés de polyéthylèneimine contenant de la n-halamine et des dérivés de ceux-ci
WO2020081299A1 (fr) * 2018-10-18 2020-04-23 Milliken & Company Articles comprenant un substrat textile et des composés de polyéthylèneimine contenant de la n-halamine
WO2020081294A1 (fr) * 2018-10-18 2020-04-23 Milliken & Company Composés de polyéthylène-imine contenant de la n-halamine et dérivés de ceux-ci
WO2020081300A1 (fr) * 2018-10-18 2020-04-23 Milliken & Company Procédé d'élimination des odeurs sur un substrat textile et composés de polyéthylèneimine contenant de la n-halamine
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US11299591B2 (en) 2018-10-18 2022-04-12 Milliken & Company Polyethyleneimine compounds containing N-halamine and derivatives thereof
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JP2017178947A (ja) * 2012-05-17 2017-10-05 ユニヴァーシティー オブ マニトバ 殺生物化合物及びその使用方法
EP2850077A1 (fr) * 2012-05-17 2015-03-25 University Of Manitoba Composés biocides et procédés d'utilisation associés
JP2015523331A (ja) * 2012-05-17 2015-08-13 ユニヴァーシティー オブ マニトバ 殺生物化合物及びその使用方法
EP2850077A4 (fr) * 2012-05-17 2015-08-26 Univ Manitoba Composés biocides et procédés d'utilisation associés
EP3357920A1 (fr) * 2012-05-17 2018-08-08 Exigence Technologies Inc. Composés biocides et procédés d'utilisation associés
EP2740355B1 (fr) * 2012-10-30 2018-08-01 Baxter International Inc. Couche antimicrobienne contenant de résine d'ammonium quaternaire et procédés de sa régéneration
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JP2017536348A (ja) * 2014-10-21 2017-12-07 オーバーン・ユニバーシティＡｕｂｕｒｎ Ｕｎｉｖｅｒｓｉｔｙ Ｎ−ハラミン含有繊維質組成物およびその使用
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CN108884340A (zh) * 2015-11-13 2018-11-23 埃克斯根杰技术公司 单体，聚合物，以及包括至少一种n-卤胺前体、阳离子中心和涂层整合基团的涂层制剂
US10975260B2 (en) 2015-11-13 2021-04-13 University Of Manitoba Monomers, polymers and coating formulations that comprise at least one N-halamine precursor, a cationic center and a coating incorporation group
CN105672007A (zh) * 2016-02-29 2016-06-15 苏州纺友新材料有限公司 一种耐酸碱型无醛固色剂的制备方法
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