WO2010059459A1 - Nouvelles chimies, solutions et systèmes de dispersion pour la décontamination de systèmes chimiques et biologiques - Google Patents

Nouvelles chimies, solutions et systèmes de dispersion pour la décontamination de systèmes chimiques et biologiques Download PDF

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Publication number
WO2010059459A1
WO2010059459A1 PCT/US2009/063840 US2009063840W WO2010059459A1 WO 2010059459 A1 WO2010059459 A1 WO 2010059459A1 US 2009063840 W US2009063840 W US 2009063840W WO 2010059459 A1 WO2010059459 A1 WO 2010059459A1
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Prior art keywords
activator
solution
water
decontamination
peroxide
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PCT/US2009/063840
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English (en)
Inventor
Michael J. Conrad
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Aries Associates, Inc.
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Priority claimed from US12/567,604 external-priority patent/US20100179368A1/en
Application filed by Aries Associates, Inc. filed Critical Aries Associates, Inc.
Priority to EP09828020A priority Critical patent/EP2358643A4/fr
Publication of WO2010059459A1 publication Critical patent/WO2010059459A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/04—Surfactants, used as part of a formulation or alone
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • the present invention relates generally to chemical and biological decontamination solutions and methods of using them.
  • the invention is useful for decontaminating a wide range of compounds and organisms by reducing them to harmless, environmentally safe by-products.
  • the methods, solutions, and formulations of the invention can be used to neutralize organophosphates, mustard agents and other toxic chemicals, bacteria, bacterial spores, fungi, molds and viruses.
  • Communicable pathogens like Influenza A (HlNl), Bacillus anthracis (anthrax), Yersinia ⁇ estis (plague) and Mycobacterium tuberculosis (TB) have the potential to spread quickly across the planet, and to create global pandemics as the result of international travel by air travel, ships and even routine cross border travel on public transit.
  • toxants includes both toxic chemical compounds and biological entities, including, but not limited to, pesticides, blister agents, nerve agents, and biopathogens (e.g., bacteria, bacterial spores, viruses, and toxins). If left without decontamination, toxants can cause death, incapacitation, or permanent harm to humans, animals, or other organisms. Moreover, failure to disinfect to safe levels of communicable pathogens as influenza viruses, bacterial spores and vegetative bacteria can lead to the pandemic spread of infectious diseases.
  • G-class nerve agents like sarin (GB), soman (GD), and tabim (GA), are examples of extremely toxic organophosphate ester derivatives which, when chemically altered, can lose their toxicity, but can also be converted into other undesirable toxic compounds.
  • the G-agents can also be volatile and present vapor hazards.
  • V-dass agents are also organophosphale esters, with VX (S-[2 « (diisopropylamino)ethyl]- Q-ethyl methylphosphonothioate) being the most widely known and deployed.
  • Mustard agents (which are "blister agents"), of which HD (bis-(2-chloroethyl) sulfide or l,r-thiobis(2- chloroethane)) is the most widely known, are not nerve agents or organophosphates, but are CW agents that can be rendered harmless by chemical oxidation under limited circumstances. The stabilities, water solubilities and vapor pressures of these agents can vary. V-agents tend to be persistent on surfaces.
  • BW biological warfare
  • Bacillus anthracis anthrax
  • CBW Yersinia petttis
  • a CBW attack, infectious disease outbreak, or accident can involve either local placement or wide dispersal of the agent or agents so as to affect a population of human individuals. Because of the flexibility with which CBW agents can be deployed, respondents might encounter the agents in a variety of physical states including liquids, aerosols, and vapors.
  • Decontamination includes substantially complete neutralization and/or substantially complete destruction of the chemical warfare or biological warfare agents.
  • technology is desired that would be applicable to a variety of scenarios such as the decontamination of open, semi-enclosed, and enclosed facilities as well as sensitive equipment. Examples of types of facilities where the decontamination formulation may be utilized include a stadium (open), an underground subway station (semi-enclosed), and an airport terminal or office building (enclosed).
  • organophosphatcs including DNA, RNA, phospholipids and many essential cofactors.
  • ⁇ organophosphatcs' * refers to a subset of all organophosphates that act as insecticides or nerve agents by inhibiting the enzyme acetylcholinesterase, which converts acetylcholine to choline and acetate.
  • Acetylcholine is a neurotransmitter found in both the peripheral nervous systems (PNS) and centra] nervous systems (CNS) of many organisms, including humans, which is distinguished by its actions on cholinergic receptors ("cholinergic" actions) at the neuromuscular junction connecting motor nerves to muscles.
  • the parasympathetic nervous system is entirely cholinergic. Neuromuscular junctions, preganglionic neurons of the sympathetic nervous system, the basal forebrain, and brain stem complexes are also cholinergic.
  • the paralytic arrow- poison curare is a naturally occurring nerve agent which acts by blocking transmission at these synapses.
  • Acetylcholinesterase is abundant in the synaptic cleft, and its role in rapidly clearing free acetylcholine from the synapse is essential for proper muscle function.
  • Organophosphate toxants work by inhibiting acetylcholinesterase, leading to excess acetylcholine at the neuromuscular junction which can, in turn, cause paralysis of the muscles needed for breathing and stopping the beating of the heart.
  • Many organophosphates have neurotoxic effects on developing organisms, even at low exposure levels. Their toxicity is not limited to an acute phase, however, and chronic effects have long been noted.
  • organophosphate compounds are also potent pesticides and are classified as weapons of mass destruction by the United Nations according to UN Resolution 687 (passed in April 1991). Their production and stockpiling was outlawed by the Chemical Weapons Convention of 1993. which officially took effect on April 29, 1997.
  • organophosphate has, in recent years, also been used more genetically to describe virtually any organic phosphorus (V)-containing compound, especially when dealing with neurotoxic compounds.
  • V organic phosphorus
  • the nerve agent sarin has the IUPAC name 0-iso ⁇ ropy! methylphosphonofluoridate, and is derived from phosphorous acid (HP(0)(0IJ)2), rather than phosphoric acid (P(OXOHb).
  • P(OXOHb) phosphoric acid
  • compounds that are derivatives of phosphinic acid are used as neurotoxic organophosphatcs.
  • Organophosphate pesticides as well as sarin and the VX nerve agent, irreversibly inactivate acetylcholinesterase, which is essential to nerve function in insects, humans, and many other animals.
  • Organophosphate pesticides affect this enzyme in varied ways, and thus vary in their potential for poisoning. For example, parathion, one of the first organophosphates commercialized, is many times more potent than malathion, an insecticide used in combating the Mediterranean fruit fly (Med-fly) and West Nile Virus-transmitting mosquitoes.
  • organophosphate pesticides degrade rapidly by hydrolysis on exposure to sunlight, air, and soil. However, small amounts of these compounds can still be detected in food and drinking water. The ability to degrade over time has made them an attractive alternative to the persistent organochloride pesticides, such as DDT, aldrin, and dieldrin. Although organophosphates degrade faster than the organochlorides, they have greater acute toxicity, posing risks to people who may be exposed to large amounts of these compounds.
  • organophosphates which have been used as pesticides include parathion, malathion, methyl parathion, chlorpyrifos, diazinon, dichlorvos, phosmet, tetrachlorvinphos, and azinphos methyl.
  • VX is an extremely toxic organophosphate and is so dangerous, even in extremely small volumes, that its only application is in chemical warfare as a nerve agent. VX is also the most toxic of the deployed chemical weapons and is classified as a weapon of mass destruction by the United Nations in UN Resolution 687. Like other organophosphorus nerve agents, VX may be destroyed by reaction with strong n ⁇ clcophiles such as pralidoxirne. The reaction of VX with concentrated aqueous sodium hydroxide results in competing cleavage of P-O and P-S esters, with P-S cleavage dominating.
  • the H-class (known as ''blister agents" or "sulfur mustards") are not organophosphates. Rather, these compounds are a class of cytotoxic, vesicant CBW agents with the ability to form large busters on exposed skin. Vesicants are highly active corrosive materials, even at extremely low concentrations. Compounds of this type comprise the structural element BCH 2 CH 2 X, where B is any leaving group and X is a Lewis base. Such compounds can form cyclic "onium” ions (s ⁇ lfonium, ammoniums, etc.), which are good alkylating agents.
  • blister agents include, but are not limited to, bis(2-chloroethyl) ether, the (2-haloethyl) amines (nitrogen mustards) and sulfur sesquimustard, which has two ⁇ -chloroethyl thioether groups (C1H 2 C-CH 2 - S-) connected by an ethylene (-Cl ⁇ CI'b-) group.
  • These compounds have a similar ability to alkylate DNA, but their physical properties, e.g. , melting point, can vary considerably. Some of these compounds have melting points well below the freezing point of water.
  • mustard gas bis-(2-chloroethyl) sulfide or l,r-thiobis(2-chloroethane)
  • HD a colorless, odorless, viscous liquid
  • HD is a liquid at room temperature and has melting point of 14 °C (57 °F).
  • vesicant agents can be quite deadly as they have a high solubility in lipids (e.g., fatty tissues). Symptoms of exposure to mustard gas include conjunctivitis, blindness, cough, edema of the eyelids, and erythema or necrosis of the skin. When inhaled, this can severely and irreparably damage the respiratory tract. In addition, mustard gas is also a carcinogen. Vesicants have other uses besides chemical warfare, however, the vesicating properties of these compounds are an undesirable/unwanted side effect. For example, some chemotherapy drugs are mild vesicants, as are a variety of industrially useful chemical intermediates.
  • biopathogen encompasses CBW agents that are infectious biological agents which can cause disease or illness to a host. These biopathogens include, but are not limited to, bacteria, bacterial spores, viruses, molds, fungi, and their toxins. Pathogenic bacteria can cause infectious diseases; the most common bacterial disease is tuberculosis, which is caused by the bacterium Mycobacterium tuberculosis. Mycobacterium is a genus of Actinobacteria, which includes many pathogens known to cause serious diseases in mammals, including tuberculosis and leprosy.
  • Pathogenic bacteria also contribute to other globally important diseases, such as pneumonia, which can be caused by bacteria such as Streptococcus and Pseudomonas, and foodborne illnesses, which can be caused by bacteria such as Shigella, Campylobacter, and Salmonella. Pathogenic bacteria also cause infections such as tetanus, typhoid fever, diphtheria, syphilis and leprosy.
  • Pathogenic viruses arc mainly those of the families of: ⁇ denoviridae, Picornavin ' dae, Herpesviridae, Hepadnaviridae, Flavivindae, Retrovi ⁇ dae, Orthomyxoviridae, Paramyxoviridae, Papovaviridae, Rhabdoviridae, Togaviridae.
  • Some notable pathogenic viruses cause smallpox, influenza, mumps, measles, chickenpox, and rubella. ( ⁇ M)20j I ⁇ e threat from biological toxants can be even more serious than the chemical warfare threat.
  • biological toxants can be usefully distinguished as spore forming bacteria which can exist in a vegetative state (e.g., Bacillus anthracis which causes anthrax), bacteria which are vegetative but non-sporulating (e.g., Yersinia pestis the cause of plague.
  • Vibrio cholerae the cause of cholera non-lipid and small viruses (e.g., polio viruses), rungi (e.g., Trichophyton spp.), lipid and medium size viruses (e.g., retroviruses like HIV, Hepatitis B viruses), and bacterial toxins (e.g., botulism, ricin).
  • bacterial spores are recognized to be the most difficult microorganism to kill. Prions are infectious agents composed of protein which propagate by transmitting in a mis-folded protein state, and are not generally considered biological warfare agents. Bacterial spores are highly resistant structures formed by certain gram-positive bacteria usually in response to stressevS in their environment.
  • the most important spore- formers are members of the genera Bacillus (e.g., Bacillus anthracis) and Clostridium (e.g., Clostridium difficile). Spores are considerably more complex than vegetative cells.
  • the outer surface of a spore consists of the spore coat that is typically made up of a dense layer of insoluble proteins usually containing a large number of disulfide bonds.
  • the cortex consists of peptidoglycan, a polymer primarily made up of highly crosslinked N-acetylglucosamiiie and N-acetylmuramic acid.
  • the spore core contains normal (vegetative) cell structures such as ribosomcs and a nucleoid.
  • Antiseptics and disinfectants are used extensively in hospitals and other health care settings for a variety of topical and hard-surface applications to deal with biological toxants. In particular, they are an essential part of infection control practices and aid in the prevention of nosocomial infections.
  • sterilants and disinfectants that can be used to address decontamination of one or more biological pathogens, as shown in Table 1.
  • Table 1 Mechanisms of antibacterial actions of disinfectants and sterilants
  • Biocide is a general term describing a chemical agent, usually broad spectrum, that inactivates microorganisms. Because biocides range in antimicrobial activity, other terms are more specific, including “-static,” referring to agents which inhibit growth (e.g., bacteriostatic, fungistatic, and sporistatic) and “ « cidaK” referring to agents which kill the target organism (e.g., sporicidal, virucidal, and bactericidal). Disinfectants are generally products or biocides that are used on inanimate objects or surfaces. Disinfectants can be sporostatic but are not necessarily sporicidal. Sterilization refers to a physical or chemical process that completely destroys or removes all microbial life, including spores.
  • Organophosphate compounds and other chemical toxants generally have low solubilities in water.
  • the redox reagents that can be used to neutralize toxants e.g., most reactive oxygen species and their dry sources
  • toxants e.g., most reactive oxygen species and their dry sources
  • Previous decontami wo different types of compounds extensively.
  • Current decontamination solutions developed for military use are incapable of dissolving or hydrolyzing significant amounts of organophosphales, nitrogen mustards, or sulfur mustards, and these current decontamination solutions freeze at approximately 32 °F.
  • single decontamination chemical solutions have been unable to decontaminate both chemical and biological toxants using the same formulation.
  • a decontamination formulation is usually a solution, which refers to a homogeneous mixture composed of two or more substances. Io such a mixture, a solute is dissolved in another substance, known as a solvent
  • a solvent refers to a liquid or gas that dissolves a solid, liquid, or gaseous solute, resulting in a solution.
  • the most common solvent is water. Most other commonly-used solvents are organic (carbon-containing) chemicals. These solvents typically have high melting points, low boiling points, evaporate easily, and have limited if any solubility in water.
  • ⁇ typical decontamination formulation is a mixture of two or more substances in a liquid solution, one of which can be an oxidizing agent In such a mixture, the oxidizing agent is the solute and is dissolved in the solvent.
  • solvent-based, decontamination formulations must dissolve and then oxidize, hydrolyze, or otherwise neutralize CW or BW agents, reducing them to non-toxic chemical by-products.
  • Reactions involved in detoxification of chemical agents are typically hydrolyzing and oxidizing reactions involving reagents which convert the toxant molecules to harmless byproducts.
  • Decontamination of biological agents is more complex and is focused on reducing or eliminating the abilities of bacteria, bacterial spores, or viruses to infect a host organism.
  • Various chemical reactions have been used to decontaminate chermcai and biological warfare agents.
  • hypochlorite ion which was usually derived from sodium or calcium hypochlorite (NaClC) and Ca(ClO) 2 )) o ⁇ a hydroxyl radical (OH) (derived from hydrogen peroxide or its dry source, sodium peroxide (NajQ.)).
  • CK hypochlorite ion
  • dry hydrogen peroxide sources e.g., sodium pcrcarbonate or urea peroxide, also known as carbamide peroxide
  • hypochlorites arc also very strong oxidizing agents.
  • M258 skin kit which consists of two packets: Packet ⁇ contains a towelette prewetted with phenol, ethanol, sodium hydroxide, ammonia, and water and Packet iJ contains a towelette impregnated with chloramine-B and a sealed glass ampoule filled with zinc chloride solution. The ampoule in packet II is broken and the toweiette is wetted with the solution immediately prior to use.
  • M291 kit which is a solid sorbent system (Yang, 1995). The kit is used to wipe liquid agent from the skin and is composed of non- woven fiber pads filled with a resin mixture. The resin is made of a sorptive materia!
  • sorptive resin based on styrene/divinylben2ene and a high surface area carbonized macroreticular styrene/divinylbenzene resin, cation-exchange sites (sulfonic acid groups), and anion-exchange sites (tetraalkylanimonium hydroxide groups).
  • the sorptive resin can absorb liquid agents and the reactive resins are intended to promote hydrolysis of the reactions.
  • hypochlorite solutions have been developed for decontamination of BW agents including 2-6% aqueous sodium hypochlorite solution (household bleach); a 7% aqueous slurry or solid calcium hypochlorite (HTO); 7 to 70 percent aqueous slurries of calcium hypochlorite and calcium oxide (supertropical bleach, STB); a solid mixture of calcium hypochlorite and magnesium oxide, a 0.5% aqueous calcium hypochlorite buffered with sodium dihydrogen phosphate and detergent, and a 0.5% aqueous calcium hypochlorite buffered with sodium.
  • 2-6% aqueous sodium hypochlorite solution household bleach
  • HTO 7% aqueous slurry or solid calcium hypochlorite
  • STB supertropical bleach
  • spores are highly resistant to many common physical and chemical agents, a few antibacterial agents are also sporicidal.
  • many powerful bactericides may only be inhibitory to spore germination or outgrowth (i.e., sporistatic), rather than sporicidal.
  • sporicidal reagents include, but are not limited to, glutaraSdehyde, formaldehyde, iodine and chlorine oxyacids compounds, peroxy acids, and ethylene oxide. In general, all of these sporicidal compounds are considered to be toxic in and of themselves, so they do not present a widely useful solution to combat biological warfare terrorism.
  • a well known decontamination agent is DF-200, also known as Sandia Foam.
  • DF-200 will freeze at temperatures below 32 °F, and is ineffective below 40 °F.
  • DF-200 is known to take in excess of 30 minutes to neutralize a significant amount of a contaminating substance.
  • DF-200 cannot be used as an aerosol decontaminant, and is not effective against mustards and VX in standard decontaminant tests. Although once identified as the decontaminant of choice by the U.S. Army, in June, 2008, DF-200 was abandoned as a deconlaminant.
  • decontamination agents for chemical and biological warfare agents include DeconGreen, GD- 5/C ASCAD, vaporous hydrogen peroxide (VHP), and titanium oxide (TiOj).
  • VHP vaporous hydrogen peroxide
  • TiOj titanium oxide
  • the compounds that have been developed for use in detoxification of CW and BW agents have been deployed in a variety of ways (e.g., liquids, foams, fogs and aerosols, or as vapor).
  • Stable aqueous foams have been used in various applications including tire fighting and law enforcement applications (such as prison riot containment).
  • Such foams however, have typically been made using anionic surfactants and anionic or non-ionic polymers. These foams, unfortunately, have not been effective in the chemical decomposition and neutralization of most chemical and biological weapons (CBW) agents.
  • a depioyable decontaminant should also be effective at low ratios of decontaminant/toxant, be easy to clean up, be environmentally friendly, non toxic, nonflammable, provide excellent material compatibility, and be biodegradable. Finally, a depioyable decontaminant should be easy to apply either by direct application or as an aerosol spray.
  • the present invention addresses, among other advantages, the neod for a fully integrated decontamination system that (i) dissolves or solubilizcs threat loads of both chemical and biological loxants on surfaces or in aerosol clouds; (ii) provides sufficient concentrations of effective oxidizers to reduce all toxants to safe by-products; (i ⁇ ) comprises solutions that do not freeze or boil over the temperature range -25 °F ⁇ T > +125 °F, are fully depioyable, and which rapidly reduce chemical or biological toxants to aerosol concentrations or surface densities significantly less than the levels established as safe for otherwise unprotected humans.
  • the invention relates to organic/aqueous liquid solutions userul for neutralizing amphipathic chemical toxants. including but not limited to organophosphates, sulfur mustards and toxic industrial compounds, and also, biopathogens, using a single decontamination solution.
  • the invention reduces, or neutralizes, toxants to harmless biodegradable by-products via perhydrolysis.
  • the invention also includes methods of activating components of the organic/aqueous mixtures to provide reactive oxygen species that are perhydrolyzed to generate the oxidizers, which reduce the toxants to harmless biodegradable by-products.
  • the invention relates to the organic/aqueous liquids useful for neutralizing or killing biological toxants.
  • ''neutralization refers to mitigation, detoxification, hydrolysis, reduction to harmless by-products, decontamination, denaturization, or other destruction of toxants that will meet, and if possible, exceed the United States government and military guidelines for decontamination of chemical and biological warfare agents.
  • Certain embodiments of the present invention comprise systems and methods for enhancing nucleophilic substitutions to of toxants, including, but not limited to, organophosphate esters, including pesticides and nerve agents; blister (also known as sulfur and nitrogen mustard) agents; bacteria and bacterial spores; and viruses.
  • the organic/aqueous solutions of the invention can be used to create CHW decontaminant formulations by dissolving a reactive oxygen species or its dry source in sufficient amounts to perhydrolyze the amount of a toxant thai has been dissolved.
  • the reactive oxygen species can be dissolved in its reactive slate. Alternatively, the reactive oxygen species can be inactive when dissolved, or it can be part of another compound when dissolved.
  • the inactive reactive oxygen species can be chemically generated when mixed with other chemicals (“activators") prior to use of the decontaminant to neutralize toxants.
  • activators can also be dry or they can be liquid.
  • Other embodiments include, but are not limited to, surface active components, including but not limited to conventional surfactants and block co-polymers in organic/aqueous mixtures. Surface active components are useful as co-solutes to increase the solubility of the activating components in the organic/aqueous liquid mixtures.
  • Another aspect of the present invention are methods of increasing the solubility of the activating components in the organic/aqueous liquid mixtures. Surface active components also reduce the surface tension of the decontaminant formulations, enabling their use in aerosol and fogging applications. Reducing the surface tension of the formulation by use of block co-polymers as surface active agents also makes it possible to aerosolize the decontaminant as a non-Newtonian fluid, which has low viscosity under dynamic shear and forms microemulsions.
  • each molecule of the reactive oxygen species telraacetylethylenediamine is perhydrolyzed at the appropriate pH by activators such as hydroperoxide anions to generate 2 moles of peroxyacetic acid, which, in turn, form percarboxylate anions and/or singlet oxygen.
  • activators such as hydroperoxide anions to generate 2 moles of peroxyacetic acid, which, in turn, form percarboxylate anions and/or singlet oxygen.
  • hydroperoxide anions which perhydrolzye the reactive oxygen specie are produced by the chain propagation reaction to generate percarboxylate anions and singlet oxygens:
  • the desired percarboxylate anions and singlet oxygens cannot be generated from either hydrogen peroxide alone or from sodium hypochlorite alone.
  • these are generated through the generation of peroxyacetic acid and the subsequent generation of percarboxylate and singlet oxygen oxidizers, as a result of the perhydrolysis of TAED.
  • these compounds react with organophosphates, mustards, bacteria, spores, and viruses via different reaction pathways and mechanisms from those generated by activation of hydrogen peroxide or sodium hypochlorite. These different reaction pathways can be exploited to increasse the efficacy of the decontamination solutions of the invention and avoid the creation of hazardous by-products.
  • the invention relates to a system for decontaminating chemical and biological agents comprising a polar organic amphipathic solvent; an activator; and a reactive oxygen species; whereupon mixing, the amounts of the polar organic amphipathic solvent, the activator and the reactive oxygen species are sufficient to maintain a pH of less than or equal to about 8.5 and to produce an amount of singlet oxygen molecules or percarboxylate anions to decontaminate a threat load of toxant.
  • the pH can he maintained at less than or equal to about 8.0.
  • the invention is active against all agents as pH values between about 7.0 to about 10.5; the buffer capacity is more effective at pl ⁇ values between about 8.0 to about 9.0. However, for maximum active life, the preferred embodiment is maintained a pH values from about 8.0 to about 8.5.
  • the pH can further be maintained at a pH of about 8.5.
  • the decontaminant formulation or the component mixtures from which it is prepared, can comprise a dry activator and at least one liquid component containing one or more reactive oxygen species or their dry sources.
  • the decontaminant formulation, or the component mixtures from which it is prepared can comprise a liquid activator and at least one liquid component containing one or more reactive oxygen species or their dry sources.
  • the activator can be a known activator of the reactive oxygen species, including hydrogen peroxide or its dry source, which are known activators of reactive oxygen species such as tctraacetylethylenediamine (TAED), sodium nonanoyloxybenzenesulfonate (NOBS), or any of the related fatty acid type anionic surfactant activators. This includes, but is not limited to, decanoic acid, 2-[((4-sulfophenoxy)carbonyl]oxy]ethyl ester (DECOBS).
  • the chemical activator in a liquid or dry form, can be any of a number of peroxide or persulfate sources which activate organic peroxyacids, such as peroxycarboxylic acids or compounds which generate and then activate peroxycarboxylic acids.
  • These compounds can be formed from liquid or dry sources, including, but not limited to, tetraacetylethyicnediamine (TAED) or tetraacetylymethylenediarnine (TAMD,) peracids chosen from the in ⁇ doperacids with the general structure:
  • ITie activator can also be a diperacid represented by the general structure H ⁇ 3 -(C ⁇ -l ⁇ p -COsH wherein p is any number between 2 and 10, such as diperoxydodecanedioic acid (DPDDA), any peroxyacid sources selected from compounds having the general formula
  • DPDDA diperoxydodecanedioic acid
  • TAED has the chemical formula
  • hydrogen peroxide from any source including but. not limited to persalts such as sodium perborate, sodium percarbonate, calcium peroxide, magnesium peroxide, zinc peroxide, thioure dioxide, urea hydrogen peroxide (carbamide peroxide, urea peroxide, and percarbamide), or
  • persulfate sources such as potassium monopersulfate.
  • chemical activation entails reaction of hydrogen peroxide from any sources with TAED to release two moles of peroxyacetic acid (also known as "peracetic acid”) per mole of TAED.
  • peroxyacetic acid also known as "peracetic acid”
  • Hydrogen peroxide is an inefficient reactive oxygen species in a decontaminant by itself, whereas the peroxycarboxylic acids are
  • the at least one liquid activator can be selected from peroxides, hydroxyl radicals, hydroxy! ions, hydroperoxide anions, superoxides, persalts, persulfates, and peroxyacetic acid.
  • the decontamination mixture can be prepared using two liquid activators.
  • a first liquid activator comprises hydrogen peroxide.
  • the decontamination mixture can include a surface active compound that is a block co-poiymer, which will impart better aerosolization capabilities to the decontamination solution.
  • the block co-polymer may be an ethylene oxide and propylene oxide di- or tri-block co-poiymer.
  • the block co-polymer may be an ethylene oxide and propylene oxide co-polymer that terminates in primary hydro ⁇ * yJ groups.
  • the invention also relates to a system for decontaminating chemical and biological agents comprising at least a water-soluble polar organic amphipathic solvent; art activator thai provides a buffering system to establish and maintain a pH of about 8.0 to about 8.5; and a reactive oxygen species (ROS). Upon mixing these three components with water, a single-phase, aqueous organic solution is formed. The solution produces and maintains a sufficient amount of singlet oxygen molecules and/or percarboxylate anions to decontaminate a threat load of toxant.
  • a water-soluble polar organic amphipathic solvent art activator thai provides a buffering system to establish and maintain a pH of about 8.0 to about 8.5
  • ROS reactive oxygen species
  • the pi I can be maintained at less than or equal to about 8.0.
  • the invention is active against all agents as pH values between about 7.0 to about 10.5; the buffer capacity is more effective at p ⁇ l values between about 8.0 to about 9.0.
  • the preferred embodiment is maintained a pH values from about 8.0 to about 8.5.
  • the pH can further be maintained at a pH of about 8.5.
  • the invention also relates to a method of decontaminating, or neutralizing, a chemical or biological toxant, the method comprising mixing a water-soluble polar organic amphipathic solvent, an activator that provides a buffering system to establish and maintain a pH of about 8.0 to about 8.5, and a reactive oxygen species with water to form a single-phase aqueous, which can be transparent, decontamination mixture; and physically associating the decontamination mixture with the toxant, wherein the solution produces and maintains a sufficient amount of singlet oxygen molecules or percarboxylate anions, thereby decontaminating a threat load of toxant.
  • the p ⁇ i can be maintained at less than or equal to about 8.0,
  • the invention is active against all agents as pH values between about 7.0 to about 10.5; the buffer capacity' is more effective at pH values between about 8.0 to about 9.0.
  • the preferred embodiment is maintained a pB values from about 8.0 to about 8.5.
  • the pH can further be maintained at a pH of about 8.5.
  • the invention also relates to a method of decontaminating, or neutralizing, a chemical or biological toxant, further comprising testing for the presence of the toxant; and repeating tho steps of mixing the water-soluble polar organic aniphipathic solvent, the activator that provides a buffering system to establish and maintain a pH of about 8.0 to about 8.5 » and the reactive oxygen species with water to form a single-phase aqueous decontamination solution; and physically associating the decontamination solution with the toxant until the level of the toxant is reduced by at least 99.4%, wherein the solution produces and maintains a sufficient amount of singlet oxygen molecules or percarboxyiate anions, thereby decontaminating a threat load of toxant.
  • the decontamination solution can be transparent.
  • the invention further relates to a method of decontaminating a toxant, which method comprises providing an organic/aqueous solution comprising at least two polar amphipathic solvents which can be water-soluble and selected from the groups consisting of the solvents identified above and in Table 2 below, wherein the volume fraction of water in the solution ranges from about 25% to about 75%, and the final pH of the solution is less than or equal to about 8.5; providing at least one chemical activator that provides a buffering system to establish and maintain a pH of about 8.0 to about 8.5; providing at least one reactive oxygen species; mixing the solution, the activator, and at least one reactive oxygen species or its source to form a decontamination mixture; and physically associating the decontamination mixture with the toxant.
  • an organic/aqueous solution comprising at least two polar amphipathic solvents which can be water-soluble and selected from the groups consisting of the solvents identified above and in Table 2 below, wherein the volume fraction of water in the solution ranges from about 25% to about 75%, and
  • the decontamination mixture can be physically associated with the toxant by dispersing the decontamination mixtures as an aerosol.
  • the pH can be maintained at less than or equal to about 8.0.
  • the invention is active against all agents as pH values between about 7.0 to about 10.5; the buffer capacity is more effective at pH values between about 8.0 to about 9.0.
  • the preferred embodiment is maintained a p ⁇ l values from about 8.0 to about 8.5.
  • the pH can further be maintained at a pH of about 8.5.
  • the decontamination mixture prepared and used by the method of the invention can be an organic/aqueous solution comprising at least two polar amphipathic solvents which can be water-soluble and selected from the groups consisting of the solvents listed in Table 2.
  • Solvents can include, but are not limited to, nitriles, ketones, aldehydes, amides, furans, alkanols and polyols.
  • the volume fraction of water in the solution ranges from about 25% to about 75%, and the final pH of the solution is less than or equal to about 8.5.
  • Exemplary solvents include the isomers of butanediol and any of the linear or branched-chain alcohols.
  • the linear or branched-chain alcohols can have from 1 to 15 carbons.
  • the solvents can be mixed with activators or percarboxylic acids or their sources prior to use in decontaminating toxants.
  • the activators can be dry activators and liquid activators.
  • the pH can be maintained at less than or equal to about 8.0.
  • the invention is active against all agents as pH values between about 7.0 to about 10.5; the buffer capacity is more effective at pH values between about 8.0 to about 9.0. However, for maximum active life, the preferred embodiment is maintained a pH values from about 8.0 to about 8.5.
  • the pH can further be maintained at a pH of about 8.5.
  • the dry activator can be tetraaeetylethylenediamine (TAED) or sodium nonanoyloxybenzene-sulfonate (NOBS) or any of the persalts.
  • the at least one activator can be selected from peroxides, hydroxyl radicals, hydroxyl ions, super oxides, or their dry sources.
  • the decontamination mixture can be prepared using at least one liquid activator or one peroxygeii source prior to activation for use as a decontaminant.
  • a first liquid activator can comprise acetic acid and hydrogen peroxide.
  • a second liquid activator comprises a solution of a persalt or a buffering salt such as sodium perearbonate.
  • the chemical activation of the decontamination mixture can be regulated by using the buffering capacity of the persah to regulate the pH of the decontaminant during chemical activation, This will maximize the generation of the reactive oxygen species from their sources.
  • sodium percarbonate cart be used to buffer pH of the formulation during perhydrolysis of TAED to generate peroxyacetic acid.
  • buffer capacity refers to the amount of an acid or base that can be added to a volume of a buffer solution before its pH changes significantly. Water is subject to self-ionization but has no buffer capacity so that generation of peroxycarboxylic acid in an unbuffered formulation rapidly ceases after the initial perhydrolysis.
  • the primary oxidizer can be the hydroni ⁇ m ion, MOO-, which is produced when hydrogen peroxide is used as the reactive oxygen species in alkaline formulations. Addition of NaOH alone to an unbuffered formulation causes offgassing of the peroxide activator, again stopping the perhydrolysis prematurely.
  • the buffer capacity is a quantitative measure of the resistance of the decontaminant solution to pi I change on addition of hydroxide or H+ ions and can be defined as follows;
  • AT W is the self-ionization constant of water and CA is the analytical concentration of the acid, equal to [HA] f (A " j.
  • AV[H* " ] becomes significant at pH greater than about 1 1.5 and the second term becomes significant at pH less than about 2. Both these terms are properties of water and are independent of the weak acid. Considering the third term, it follows that:
  • Buffer capacity is directly proportional to the analytical concentration of the acid. [G063] ]n the preferred embodiment of the present invention, the pKa, buffer and the
  • buffer capacity are selected from the acids and conjugate bases which have a pKa of 8.5 ⁇ 1 and which have the buffer capacity to enable generation of sufficient perhydrolysis of TAED or other peroxyearb ⁇ xylic acid sources to produce sufficient oxidizers to neutralize a full threat load of chemical agent.
  • appropriate selection of the pKa and the buffer capacity enables regulation of perhydrolysis over time, so that the activated "pot-life" of the decontaminant can be prescribed.
  • the term “pot-life"' refers to the time period during which the formulation is optimally active.
  • the decontamination mixture can comprise a block co-polymer, which will impart better solubilization of the reactive oxygen species or its source and improve the aerosolization capabilities of the decontamination solution.
  • the block copolymer can be an ethylene oxide and propylene oxide co-polymer. More specifically, the block co-poiymer can be an ethylene oxide and propylene oxide co-polymer that terminates in primary hydroxyl groups.
  • the method of the invention may be used to decontaminate various toxants.
  • the toxant may be, for example, a phosphoric acid ester, a sulfur mustard, bacteria, bacterial spores, or viruses.
  • the decontamination may be carried out via chemical modification and perhydrolysis of the toxant, on a surface, in an aerosol suspension, or a combination thereof. If applied as an aerosol, the mixture can be dispersed through a nozzle as a microem ⁇ lsion.
  • the total deeomaminanl to toxant volume ratio can range from about 200 to about 0.1.
  • the temperature at which decontamination using the present invention may be carried out has a wide range.
  • the decontamination can be conducted at a temperature of between about -25 °F and about 125 °F.
  • the decontamination can be conducted at a temperature of between about -35 °F and about 140 °F.
  • the method can further comprise testing for the presence of the toxant; and repeating the steps of providing the solution, activator, and at least one reactive oxygen species or source thereof, mixing the solution, activator, and at least one reactive oxygen species, and physically associating the decontamination mixture with the toxant until the level of the toxant present is reduced in concentration by at least two (2) logs from the initial threat load.
  • the decontamination solution may also comprise a surfactant, or block co-polymer, and/or a fluorescent dye.
  • kits or system comprising a solution comprising at least two polar water-soluble organic amphipathie solvents selected from
  • Groups I through IV See Table 2
  • nitriles, ketonCxS, aldehydes, amides, furans, alkanols and polyols wherein the volume fraction of water in the solution ranges from about 25% to about 80% or from about 25% to about 75%, and the pH of the solution is less than or equal to about 8.5; an activator; and at least one liquid reactive oxygen species or source thereof.
  • the polar amphipathie solvents can be water-soluble and can be any of the
  • the activator can be, but is not limited to, hydrogen peroxide or any peroxide or persulfate sources, a peroxycarboxylic acid or any peroxy acid or source thereof.
  • the at least one reactive oxygen species can be a peroxide or a peroxycarboxylic acid, such as peroxyacetic acid or any source thereof. This includes, but is not limited to, the persalts and TAED.
  • the pH can be maintained at less than or equal to about 8.0.
  • the invention is active against all agents as pH values between about 7.0 to about 10.5; the buffer capacity is more effective at pH values between about 8.0 to about 9.0. However, for maximum active life, the preferred embodiment is maintained a pH values from about 8.0 to about 8.5. The pH can further be maintained at a yli of about 8.5.
  • the kit or system may comprise an organic/aqueous solution including at least two polar amphipalhic solvents, which can be water-soluble and selected from Groups I through IV (See Table 2), and at least one activator.
  • One of the activator can be hydrogen peroxide or a source thereof, and a second activator can be any buffering saJt.
  • the system may further comprise a surface active agent and/or a fluorescent dye.
  • the kit or system may further be distinguished by a formulation number such as those given at the bottom of Table 2 above. This number identifies the composition of the organic/aqueous solution that is used in its creation.
  • the kit or system may further comprise a container for mixing the organic/aqueous solution comprising at least two polar amphipathk solvents selected from Groups I through IV (See Table 2), at least one liquid or dry activator and at least one liquid or dry reactive oxygen species or source thereof together into a decontamination mixture; and means for physically associating the decontamination mixture with the toxant.
  • the means for physically associating the decontamination mixture with the toxant comprises at least an aerosolization nozzle, but may include a mixing chamber.
  • the formulation may be packaged in different ways. First, the formulation may be packaged as a four part (quaternary) kit. Second, the formulation may be packaged as a three part (ternary) kits. Finally, in a preferred embodiment of the invention, the formulation is packaged as two part (binary) kit.
  • both the activator and base mix are liquid prior to mixing to form the decontamination solution.
  • both the activator and base mix are liquid prior to mixing to form the decontamination solution.
  • the reactive oxygen species or its source is dissolved in the base mix, and (ii) the activator is part of the chemically activating buffer system.
  • the activating buffer is dissolved in the base mix, and (ii) the reactive oxygen species or its dry source is dissolved in the liquid activator component of the kit.
  • the invention is formulated and packaged as a liquid-dry binary kit.
  • the reactive oxygen species or its source is dissolved in the liquid base mix
  • the activator comprises one or more components of the activating buffer in a dry or ⁇ ndissolved form.
  • the activating buffer is dissolved in the liquid base mix
  • the activator component of the binary kit comprises the reactive oxygen species or its source in a dry or undissolved form.
  • the invention also relates to a system for producing, or for activating and dispersing binary kit formulations for decontamination, neutralization, sterilization, and'or cleaning chcmicai and/or biological toxants comprising a first container for storing the base mix of the binary kit formulation and a second container for storing a corresponding activator in accord with the appropriate one of the binary formulation kits as described above.
  • a first container serves to contain a base mix including at least one water-soluble polar organic amphipathic solvent, water and either (i) a reactive oxygen species (ROS) or its source or (ii) one or more components of the chemically activating buffer system; the second container serves to contain whichever of the ROS or the buffer activator that is not in the first container.
  • the .system comprises at least one container which includes a buffering system to establish and maintain a pH of about 8.0 to about 8.5 and pipes.
  • the system may also comprise at least one valve and/or at least one pump.
  • the solvent, the ROS and the activator may be distributed in concentrated form in which case it may be mixed with water from a water source to form a single-phase aqueous decontamination solution which produces and maintains a sufficient amount of singlet oxygen molecules and/or percarboxylate anions to decontaminate a threat load of toxant over a period of time.
  • a single-phase aqueous decontamination solution which produces and maintains a sufficient amount of singlet oxygen molecules and/or percarboxylate anions to decontaminate a threat load of toxant over a period of time.
  • the decontamination of chemical toxants to a safe level occurs within about 15 minutes.
  • decontamination of biological toxants to a safe level occurs in less than 5 minutes.
  • the first and second containers and the pipes of the system may be transported to a site in need of decontamination.
  • the water source can be a container of water, such as a water drum or a blivet of water, or a hose that can connect to external sources of water.
  • the term blivet is used here to denote an extremely large, flexible container for holding fluids. For example, a blivet can hold upwards of 3,000 gallons of fluid.
  • the system may include at least one valve and the at least one pump both of which are opcrably connected to the system and control flow of the materials through the pipes.
  • live fust and second containers, the water source, the piping, are operably connected, so that the water from the water source is mixed with the base mix, after which die activator is mixed with the base mix and water to activate the decontamination solution prior to use.
  • the activator can be mixed first with the water.
  • the system the invention may further comprise a third container in which the solvent, the ROS and the activator can be mixed with water from the water source, wherein the third container may be used to store the decontamination solution.
  • the invention also relates to a system for activating solutions for decontaminating or disinfecting chemical and biological toxants
  • a system for activating solutions for decontaminating or disinfecting chemical and biological toxants comprising a first container operably connected to a binary base mix inlet and including a binary base mix prepared from at least one water-soluble polar organic amphipathic solvent, a reactive oxygen species (ROS), and water; a second container opcrably connected to an activator inlet and including an activator that provides a buffering system Io establish and maintain a pH of between about 8.0 to about 8.5; a water inlet: and pipes operably connected U) the binary base mix inlet, the activator inlet, and the water inlet.
  • ROS reactive oxygen species
  • the binary base mix and the activator are mixed with water from a water source to form a single-phase aqueous decontamination solution which produces and maintains a sufficient amount of singlet oxygen molecules and/or perearboxylate anions to decontaminate or disinfect a threat load of toxant.
  • the polar organic amphipathic solvent is selected from the group consisting of b ⁇ tanediol, isomers of butanediol, i -hexanol, a linear or branched-chain alcohol with from 1 to 15 carbons, butoxy-alcohol, and combinations thereof.
  • 'l-he activator is a peroxide obtained from a peroxide source selected from the group consisting of a liquid peroxide, hydrogen peroxide, and a dry peroxide source selected from the group consisting of sodium percarbonate, sodium carbonate, sodium perborate, urea peroxide, sodium peroxide, and combinations thereof, wherein the activator is a source of a perhydrolyzmg agent selected from the group consisting of a hydroxy I radical, a hydroxy! ion, and a superoxide; and wherein the activator is chemically activating buffer which, when added to the base mix, establishes and maintains the pH of (he solution at between about 8.0 to about 8.5.
  • a peroxide source selected from the group consisting of a liquid peroxide, hydrogen peroxide, and a dry peroxide source selected from the group consisting of sodium percarbonate, sodium carbonate, sodium perborate, urea peroxide, sodium peroxide, and combinations thereof
  • the activator
  • the reactive oxygen species is selected from the group consisting of tetraaeetylethylenediarninc (TAED) and tetraacetylmethylenediamine (TAN4D).
  • the system can further comprise a block co-polymer, wherein the block copolymer can be a polyethylene oxide and polypropylene oxide co-polymer that is non-ionic or that terminates in primary hydroxy! groups.
  • the block co-polymer can be selected from a group which modifies the teaming, wettability, surface tension, aerosol properties and detcrgency of the final activated formulation. If the bloek-copolymer is employed, it may be added to the base mix.
  • the block co-polymer enables application of the decontamination solution by aeroso ligation and fogging.
  • the system optionally comprises an aerosoH/alion nozzle for physically associating die decontamination solution with the toxant.
  • the invention further relates to a binary system for decontaminating or disinfecting chemical and biological toxants comprising a binary base mix including a water- soluble organic amphipathic solvent, a reactive oxygen species (ROS), and water; and an activator that provides a buffering system to establish and maintain a pK of between about 8.0 to about 8.5.
  • ROS reactive oxygen species
  • a single-phase aqueous decontamination/disinfection solution Upon mixing the base mix and the activator, a single-phase aqueous decontamination/disinfection solution is formed, the solution produces and maintains a sufficient amount of singlet oxygen molecules and/or perearboxylate anions to decontaminate or disinfect a threat load of toxant.
  • the invention further relates to a method of decontaminating, sterilizing, or disinfecting a chemical or biological toxant comprising a) providing a binary base mix including a water-soluble polar organic amphipathic solvent, a reactive oxygen species (ROS), and water; b) mixing the binary base mix and an activator that provides a buffering system to establish and maintain a pH of between about 8.0 to about 8.5 to produce a dewntamination/disinfecting solution: and c) physically associating the decontamination solution with the toxant at a temperature of between about -35 T and about 140 °C.
  • the solution produces and maintains a sufficient amount of singlet oxygen molecules or perearboxylate anions, to decontaminate a threat load of toxant.
  • the method may further comprise testing for the presence of the toxant; and repeating steps a), b). and c) until the level of the toxant is reduced by at least 99.4%, As above, the solution produces and maintains a sufficient amount of singlet oxygen molecules or percarboxylale anions to decontaminate a threat load of toxant.
  • the binary base mix comprises a water-soluble polar organic amphipathie solvent; cither a reactive oxygen species (ROS) or the chemically activating buffer system; and water.
  • the temperature at which the decontamination is conducted at a temperature of between about -35 °C and about 140 °C. More specifically, the temperature can be between about -25 "C and about 125 °C.
  • the ins'cntion further relates to a method as disclosed above, and further comprises testing for the presence of the t ⁇ xant; and repeating the steps of mixing the base mix and the activator to form a single-phase aqueous decontamination solution; and physically associating the decontamination solution with the toxam until the level of the toxant is reduced by at least °-9.4%.
  • the solution produces and maintains a sufficient amount of singlet oxygen molecules and/or pcrcarboxylatc anions, thereby decontaminating and/ or disinfecting a threat load of toxant.
  • the polar organic amphipaihie solvent is selected from the group consisting of butanedi ⁇ l, isomers of butanediol, 1 -hexanol, a linear or branched-ehain alcohol with from 1 to 15 carbons, butoxy-alcohol, and combinations thereof.
  • the activator can be a peroxide obtained from a peroxide source selected from the group consisting of any liquid peroxide, including hydrogen peroxide, and/or dry sources, including but not limited to, sodium pcrcarbonate, sodium carbonate, sodium perborate, urea peroxide, and sodium peroxide, and combinations thereof, wherein the activator is a source of a perhydrolyzing agent selected from the group consisting of a hydroxyl radical, a hydroxy! ion, and a superoxide.
  • Hie activator am include a different buf ⁇ er system that maintains the pH at from between about 8.0 to about 8.5.
  • the reactive oxygen species can be selected from the group consisting of tetraacetylethylcncdiaminc (TAED) and tetiaacetylmethylenediaminc (TAMD).
  • the system can further comprise a block co-polymer, wherein the block copolymer can be a polyethylene oxide and polypropylene oxide co-polymer that terminates in primary hydroxy! groups or that is non-ionic.
  • the block oo-polymer can be selected from a group which modifies the foaming, wettability, surface tension, aerosol properties and detergency of the final activated formulation.
  • the system can also include an aerosolization nozzle for physically associating the decontamination solution with the toxant.
  • Figure 2 depicts a flow chart disclosing the activation and use of the invention.
  • Figure 3 depicts the rate of perhydrolysis of TAED by H 2 O 2 in unbuffered water as a function of pH.
  • Figure 4 depicts the pKa of acetic acid in a dioxane/water solution
  • Figures 5A-5C depict graphs relating to melting and boiling points of various compounds.
  • Figure 5 A shows a comparison between the boiling points of water and other small molecules with similar molecular .structures. There is a steady increase in boiling point in the series ClIu CcIU, S1H4, and SnHL). The boiling point of H ⁇ C), however, is anomalously large because of the strong hydrogen bonds between water molecules.
  • Figure 5 B shows a comparison of melting points.
  • Figure 5C relates to melting point depression behavior for various solutions.
  • Figures 6A-6B depict examples of the physical behavior of pseudoplastic non-
  • Figure 7 depicts a comparison of the effects of shear on the viscosity of fluids.
  • FIG 8A shows the pse ⁇ d ⁇ plastic behavior of carboxymethyl cellulose (CMC).
  • Figure 8B shows a relative viscosity profile of various CMCs.
  • Figure 9 shows that viscoeiastic behavior can differ with temperature.
  • Figure 10 depicts a schematic of how droplet size is determined
  • Figure 11 shows different nozzles which can be used to aerosolize non-Newtonian fluids.
  • Figure ! 2 depicts a standard curve for the detection by absorbance of light at 257 nm by the organophosphate ester dipheny! phosphorochloridate (DPCP), a G agent chemical simulant.
  • DPCP organophosphate ester dipheny! phosphorochloridate
  • Figure 13 depicts a quaternary configuration of a kit of the invention.
  • Figure 14 depicts a binary configuration of a kit of the invention.
  • Figure 15 illustrates the components in one embodiment of a binary decontamitiant activator system.
  • Figure 16 illustrates one potential system for preparing the binary base mix for use in the decontamination techniques and systems discussed herein.
  • Figure 17 depicts a process for manufacturing the binary base mix for use in the decontamination techniques and systems discussed herein.
  • fOOl 15 ⁇ Figure 18 illustrates one potential system for preparing the binary activator for use in the decontamination techniques and systems discussed herein.
  • Figure 19 depicts a process tor manufacturing the binary activator for use in the decontamination techniques and systems discussed herein.
  • the invention is based upon several axioms of die inventor's general model of chemical and/or biological decontamination.
  • the decontamination formulation should be able to sufficiently dissolve lull chemical threat loads (Sec Table 4, below) in an isotropic homogenous solution.
  • the decontamination formulations should preferably be able to dissoK'e sufficient amounts of one or more reactive oxygen species or their sources in the isotropic solution, where the reactive oxygen species can react with the dissolved toxant to reduce a chemical of biological threat toad to a substantially harmless level.
  • the volume ratio for neutralizing threat loads generally determines the reaction rate and logistical footprint and should preferably be less than 50:3 decontarninant to t ⁇ xant.
  • the decomaininant should be a low viscosity fluid, at least under dynamic shear, which is both fluid and effective against a chemical or biological agent over a temperature range from about -25 "F to about 125 °F.
  • the deconlaminatU should preferably remain in contact with the toxant long enough to substantially complete perhydrolysis by, for example, having a sufficiently high viscosity on a surface.
  • an effective decontamination solution for chemical agents should preferably be able to reduce chemical agents to one or more harmless by-products.
  • a deployable chemical and biological decontarainant should preferably meet and, if possible, exceed CF.R49, DOT and DoD transport requirements, NlOSH and EPA BSHO requirements, DOD material compatibility requirements, and all needs for ease of transport and storage, ease and safety of use, ease of clean-up, safe disposal, material compatibility and biodegradability.
  • a deployable chemical and biological decontaminant should meet, and if possible, exceed the United States Government and Military guidelines for decontamination of chemical and biological warfare agents. Sec Tables 3 and 4 below. Specifically, the Joint Program Executive Office (JPHO) for chemical and biological defense has listed the following guidelines for VX, GD, and HD (nerve agents) and biological agents, such as Anthrax. Table 3 - Reduction of Toxant
  • an organic/aqueous solution comprises at least one polar amphipathic organic solvent, which can be water-soluble and selected from one or more of the groups consisting of solvents given in Table 2, including: Group ⁇ solvents, which comprise nitriles or other polar aprotic solvents that contain no oxygen; Group U solvents, which comprise alkanols or other polar, monoprotic solvents that contain one -OH moiety; Group HI solvents, which comprise aldehydes, ketones, ethers, or other polar, aprotic solvents that contain oxygen but cannot donate a proton; and Group JV polyprotic solvents and solutes, which comprise polyols, and/or solvents designated hybrids because they share properties of several groups, such as 2-butoxyethanol.
  • Group ⁇ solvents which comprise nitriles or other polar aprotic solvents that contain no oxygen
  • Group U solvents which comprise alkanols or other polar, monoprotic solvents that contain one -OH moiety
  • organic/aqueous solutions can preferably range from about 25% to about 80% or from about 25% to about 75% and the final solution pH can preferably have a value less than or equal to about 8.5.
  • organic/aqueous solutions further comprise at least one reactive oxygen species or at least one oxidizing agent.
  • Suitable reactive oxygen species include, but are not limited to, peroxides and peroxyearboxylic acids; suitable oxidizers include but are not limited to hydroxyl radicals, hydroxyl ions, hydronium ions, hydroperoxide anions, superoxides, o/one.
  • the pH can be maintained at less than or equal to about 8.0.
  • the invention is active against all agents as pH values between about 7.0 to about 10.5: the buffer capacity is more effective at pH values between about 8.0 to about 9.0.
  • the preferred embodiment is maintained a pH values from about 8.0 to about 8.5.
  • the pH can further be maintained at a ptt of about 8.5.
  • the method of the invention contains a series of steps. These steps include providing a solution comprising least one water-soluble polar organic amphipathic solvent providing at least one dry or liquid activator and a reactive oxygen species; mixing the solution, the dry activator, the one liquid activator, and the reactive oxygen species to form a decontamination mixture; and physically associating the decontamination mixture with the toxant.
  • Each solvent can be a polar aprotic solvent, a polar-protic solvent, or combinations thereof. More specifically, the polar organic amphipathic solvent can be a nitrile.
  • the volume fraction of water in the solution can range from about 25% to about
  • the p ⁇ i of the solution is less than or equal to about 8.5.
  • the pH can be maintained at less than or equal to about 8.0.
  • the invention is active against all agents as pli values between about 7.0 to about 30.5: the buffer capacity is more effective at pH values between about 8.0 Io about 9.0. However, for maximum active life, the preferred embodiment is maintained a pH values from about 8.0 to about 8.5. " fTie ph.
  • the invention relates to a system for decontaminating chemical and biological agents comprising a polar organic amphipathic solvent; an activator; and a reactive oxygen species; whereupon mixing, the amounts of the water-soluble polar organic amphipathie solvent, the activator and the reactive oxygen species are sufficient to maintain a pH of less than or equal to about 8.5 and to produce an amount of singlet oxygen molecules or pcrcarboxylate anions to decontaminate a threat load of toxant.
  • the pli can be maintained at less than or equal to about 8.0
  • the invention is active against all agents as pli values between about 7.0 to about 10.5; the butter capacity is more effective at pli values between about 8.0 to about 9.0.
  • the preferred embodiment is maintained a pH values from about 8.0 to about 8.5.
  • the pH can further be maintained at a pH of about 8.5.
  • nitrile refers to any molecule or organic compound or solvent that contains a -C ⁇ N functional group in which the carbon atom and the nitrogen atom are triple bonded together.
  • m ' triles include, but are not limited to acetonitrile and rose nitrile.
  • cyano- is used in chemical nomenclature to indicate the presence of a nitrilc group in a molecule.
  • alkanol refers to any organic compound or solvent containing a single -OH group in its chemical structure.
  • alkanois include, hut are not limited to, .straight chain alcohols, such as methanol, ethanol. propan ⁇ l. isopropanol, butanol and hexanol.
  • polyoP refers to any organic solvent or solute containing at least two -OH groups in its chemical structure. In polymer chemistry, polyols are compounds with multiple hydroxyl functional groups available for organic reactions.
  • the lertn "poiyol” includes, but is not limited to: (i) diols (eg,, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, and any of the isomers of propanediol, butanediol or pentanediol); (ii) triols, which are organic compounds containing three hydroxyl groups (c. ( g., the trihydric alcohol 1.2,3-pro ⁇ ane-triol, CHj(OH)CH(OH)CH ,>(0H).
  • diols eg, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, and any of the isomers of propanediol, butanediol or pentanediol
  • triols which are organic compounds containing three hydroxyl groups (c. ( g., the trihydric alcohol 1.2,3-pro ⁇ ane-triol,
  • polystyrene resin examples include any organic compound having more than two -OH groups (e.g., polyethylene glycol, polypropylene glycol, and polyftetramethyiene ether) glycol and the sugar polyols.
  • -OH groups e.g., polyethylene glycol, polypropylene glycol, and polyftetramethyiene ether
  • polymeric polyols are as rcactants to make other polymers.
  • polymeric polyols can be reacted with isocyanates to make polyurethanes, which use consumes most polyether polyols.
  • Common polyether diols are polyethylene glycol, polypropylene glycol, and poJy(tetramethylene ether) glycol.
  • the preferred polyols of the present invention are low molecular weight diols and triols based on simple carbon chains, and the polyols known collectively as polyoxyethylene-polyoxypropyiene block co-polymers.
  • the solvents used for toxant hydrolysis can be polar, aprotic and/or polar, protic solvents, or a combination thereof, or polar, protic solvents individually, 'flic use of these solvents can promote certain types of nuelcophilic attack and thereby enhance the oxidation and hydrolysis or perhydrolysis of phosphate ester and blister agents, as well as of phospholipids, proteins, and DNA or RNA.
  • hydrolysis or pcrhydrolysis of toxants can be enhanced by using reactive oxygen species, including, but not limited to hydrogen peroxide and pcroxyaceric acid.
  • reactive oxygen species including, but not limited to hydrogen peroxide and pcroxyaceric acid.
  • a peroxide is a compound containing an oxygen-oxygen single bond
  • pcroxy acids also known as peroxyacids and peracids
  • Peroxides and peroxy acid have the general structures:
  • Peroxides tend to decompose easily and can sometimes initiate explosive reactions. Pcroxy acids are generally not very stable in solution and decompose to ordinary oxyacids and oxygen.
  • dry sources of the peroxides and separately, dry sources of the peroxy acids, such as TAED, are stable when dissolved in the organic/aqueous solutions of the invention, and require activation for maximum efficacy and speed against chemical and biological agents, including, but not limited to, aromatic hydrocarbons, mustards, environmental mutagens, organophosphatc pesticides, nerve agents and bacteria.
  • Hydrogen peroxide decontaminates chemical warfare agents (CWAs) more efficiently in alkaline solutions that generate HOO-.
  • CWAs chemical warfare agents
  • the alkaline perhydrolysis process is considerably faster than analogous alkaline hydrolysis or neutral oxidation processes. This is attributed to an increased nucleophilicity of HOO- due to the presence of a lone pair of electrons on the oxygen atom adjacent to the nucleophilie centre. This phenomenon is referred to as the ' ⁇ -efiecf. Although not fully understood, u-effects are historically considered not to occur in the absence of solvent. However, the observed chemistry of modified vaporous hydrogen peroxide (rnVHP) is analogous to the alkaline pcrhydrolysis chemistry observed in solution.
  • rnVHP modified vaporous hydrogen peroxide
  • Pcroxy-oxidizers including but not limited to, peroxycarboxylic acids such as peroxyacetie acid, and dry sources thereof, can dissolve in the isotropic organic/aqueous solutions of the polar amphipathie organic components of the present inventions.
  • these compounds can generate oxidizing agents which (i) overcome the limitations of m VHP; and (ii) accelerate the hydrolysis of phosphate esters, mustards, as well as the phospholipids, proteins and oligonucleotides of bacteria, spores and viruses.
  • a molecule of the reactive oxygen species tetraacelylethylenedi amine ( ' 3'AED) is perhydroiyzed at the appropriate pH by activators such as hydroperoxide anions, and will generate 2 moles of peroxyacelic acid, which, in turn, form percarboxylate anions and/or singlet oxygen.
  • activators such as hydroperoxide anions
  • peroxyacelic acid which, in turn, form percarboxylate anions and/or singlet oxygen.
  • hydroperoxide anions which pcrhydrolzye the reactive oxygen species, arc produced by the chain propagation reaction to generate percarboxylate anions and singlet oxygens:
  • the desired percarboxylate anions and singlet oxygens cannot he generated from either hydrogen peroxide alone and cannot be generated using sodium hypochlorite, but only from the generation of peroxyacetic acid and its oxidizers from TAED. Moreover, these compounds react with organophosphates, mustards, bacteria, spores, and viruses via very different reaction pathways and mechanisms from those generated by activation of hydrogen peroxide or sodium hypochlorite. These different reaction pathways can be exploited to increase the efficacy of the decontamination solutions of the invention and to avoid the creation of hazardous by-products.
  • the reactive oxygen species In order to be most effective in a decontaminunt made from the organic/aqueous solutions of the present invention, the reactive oxygen species .should be able to dissolve in sufficient amounts to achieve stoichiometric hydrolysis and/or pcrhydrolysis of the toxants.
  • reactive oxygen species (“ROS 1 ') refers to peroxides or peioxyaeids, whereas the term “oxidizers” refers to reactive oxygen which may be hi the form of hydroxyl radicals (from peroxides) or peroxycarboxylic anions and singlet oxygen (from peroxy acids).
  • reactive oxygen species include, but are not limited to, hydrogen peroxide, hypochlorite ion, and peroxyacetic acid (PAA). These compounds require some type of activation process during which one or more molecules arc split to generate the oxidizing agents.
  • oxidizing agents include- but arc not limited to, hydroxyl radicals, or peroxyacetic anions and singlet oxygens, which may go on to participate in farther chemical reactions with toxants.
  • radical or “free radical” refers to a cluster of atoms, one of which contains an unpaired electron in its outermost shell of electrons.
  • hydroxyl describes a molecule consisting of an oxygen atom and a hydrogen atom joined by a eovalcnt bond.
  • the neutral form is known as a hydroxyl radical and the singly-charged hydroxyl anion is called hydroxide.
  • Hydroxyl radicals are an unstable configuration, and such radicals generally quickly react with other molecules or other radicals to achieve the stable configuration of four pairs of electrons in their outermost shell (or one pair for hydrogen).
  • inventions are organic/aqueous solutions comprising one or more reactive oxygen species, further comprising one or more chemical activators to generate the oxidizers).
  • the pcroxyearboxylic acids require activation to generate the peroxy anions or singlet oxygen atoms which are the actual oxidizers of the toxants.
  • Methods of activation include, but are not limited to: (0 changing the pH of the solution by adding an alkaline base such as sodium hydroxide to die decontamination mixture; (U) changing the pH by employing buffering systems that both elicit and regulate activation of the perhydroiyzers; (iii) employing catalysts (e.g., NaI, Fe+- ⁇ , transition metals, and lanthanides): (iv) o/onolysis: (v) exposure to ultraviolet light; and/or (vi) use of organic precursor compounds.
  • alkaline base such as sodium hydroxide
  • buffering systems that both elicit and regulate activation of the perhydroiyzers
  • catalysts e.g., NaI, Fe+- ⁇ , transition metals, and lanthanides
  • organic activator compounds are the persalts which, in the present invention, is used in the organic/aqueous solutions as a dry source of hydrogen peroxide, which under appropriate conditions of pH, can quickly pcrhydroly/e TAED to generate peroxyacetic acid, as shown above.
  • organic activators e.g., sodium pcrsulfale. sodium perborate, sodium percarbonate and' or urea peroxide
  • Such a "quasi-steady state equilibrium" effectively lengthens the active pot life of a deeontaminant. yet eliminates the outgassing of Uie peroxide activators, which is another novel aspect of the present invention.
  • Additional embodiments of the invention comprise organic/aqueous solutions comprising one or more oxidizing agents, an activator to generate the oxidizer, surfactants, and co-polymers, the ability of the dcc ⁇ ntaminants to remain effective at extreme temperatures, and the use of block co-polymers to create non-Newtonian dccontaminants that can be aerosolized as mieroernulsions and fogs.
  • Yet other embodiments of the invention comprise organic/aqueous solutions comprising one or more reactive oxygen species, a buffering activator to generate the reactive oxygen species and the oxidizer as part of a quasi-steady state equilibrium process, extending the effective life of the deeontaminant from minutes to hours and even days.
  • the components of the system can be mixed into a container immediately prior to use.
  • the base mix contains the polar organic amphipathie solvent.
  • Other components include at least one reactive ox>gcn species and at least one activator.
  • the activator can include liquid and/or dry activators, and provides buffering capacity.
  • the base mix can further include a second buffer, a block co-polymer and a reactive oxygen species, depending upon the final configuration of the system.
  • Figure 2 shows the method of the invention.
  • the solvent, the activator and the reactive oxygen species are mixed.
  • the solution is applied immediately to a toxant by physical associate. W desired, the level of remaining toxant can be determined, and if the toxant is not sufficiently decontaminated (i.e., greater than about 99.4% is removed or neutralized), the steps can be repeated.
  • the activator can comprise more than one activator, and can be liquid or dry, or a combination thereof.
  • One method of activating the decontaminant formulations of the present invention is to generate the peroxy-oxidants using peroxides as activators which generate peroxycarboxy ⁇ e acids from their dry or dissolved sources.
  • peroxides as activators which generate peroxycarboxy ⁇ e acids from their dry or dissolved sources.
  • Such a system can be based on the use of tctraacety! ethylenedi amine (TAED) or tetraacetylmethyienediaminc (TAMD) as the pcroxyaccde acid source.
  • the activator in such a system can be based upon the use of dry hydrogen peroxide sources, such as urea peroxide, sodium perborate, or sodium percarbonate, which can serve as a buffering agent in an appropriate buffer system to create the quasi-steady state equilibrium of the present invention.
  • Activators provide buffering action for the system.
  • the buffering action of the activators can also be due to carbonate compounds.
  • the function of a buffering agent is generally to drive an acidic or basic solution to a certain pH and then, through the buffering capacity of the solution, prevent a change in the pH.
  • Figure 3 shows the rate of perhydrolysis of TAEiD by H 2 O> in unbuffered water as a function of pJT.
  • the organic/aqueous solutions, the reactive oxygen species and their sources, and the activators are part of a carefully balanced buffer solution which establishes a quasi-steady state equilibrium between the generation of pemxy acids and the buffering acid and its conjugate base.
  • the buffer capacity of a decontaminant formulation is established by the concentrations of an acid and its conjugate base to create a buffer solution which will resist a change in pli as the pcroxycarboxylic acids are generated from their sources.
  • the buffering capacity of the decontaminant vSystem should be selected from those butter solutions which have the midpoint of their titration curves at the optimum of the percarboxylie acid activation curve.
  • One novel discovery that made the present invention possible was the discovery that the isomers of some solvents materially affect the buffering capacity of some buffer systems.
  • the isomers include isomers of butanediol and linear or branehed-chain alcohols, including but not limited to, linear or branched alcohols with from 1 Io at least ! 5 carbon atoms. Use o? these isomers is discussed further below.
  • sodium carbonate is used to generate a bicarbonate buffer system in select organic/aqueous solutions comprising certain solvents from Groups II and 3V ⁇ Sec Table 2), where the rate at which hydrogen peroxide is released from one or more peroxide sources is used to modulate the perhydrolysis of peroxyacetic acid from TAED, thereby creating the quasi-steady state equilibrium of the decontaminants of the present invention.
  • This polarity creates a dipole - dipole bond, or hydrogen bond, between water molecules. More generally, a hydrogen bond is a type of "dipole-dipole bond.”
  • the term "dipole-dipole bond” relates to any solvent which has a large dipoic moment, such as the strong dipole of a water molecule, which can enter into dipole-dipole bonds with such polar aprotic solvents as nitriies.
  • ⁇ cetonitrilc for example, has a very strong dipole moment that can readily enter into dipole-dipoie bonds with water molecules.
  • acetonitrile is soluble in water in ail proportions.
  • a polar-protic solvent is a solvent thai has a hydrogen atom bound to an oxygen as in a hydroxyl group or a nitrogen as in an amine group, or, more generally, any molecular solvent which can donate an H * or proton.
  • polar, protic solvents include: • solvents display hydrogen bonding
  • solvents are able to stabilize ami dissolve ions: o cations by unshared (rat electron pairs o anions by hydrogen bonding
  • Examples of polar, protic solvents arc water, methanol, ethanol, formic acid, butancdiol and perearboxylie acids.
  • a polar aprotic solvent shares ion-dissolving power with protic solvents, but lacks an acidic hydrogen. These solvents generally have high dielectric constants and high polarity.
  • Examples of polar, aprotic solvents are acetonJtrile, dimethyl formamtde, methylene chloride, dimethyl sulfoxide, and dioxane.
  • Polar- protic solvents are favorable for SNI nudeophilic reactions, while polar aprotic solvents are favorable for S. ⁇ 2 nudeophilic reactions.
  • S N 2 reaction the addition of a nueJeophile and the elimination of a leaving group take place simultaneously.
  • S, ⁇ 2 reactions can occur when the central carbon atom is easily accessible to the nucleophiJe.
  • Ss-1 reaction involves two steps. SN I reactions tend to be important when the central carbon atom of the substrate is surrounded by bulky groups, because such groups interfere sterically with the SN2 reaction and a highly substituted carbon forms a stable carbocation.
  • organic/aqueous solutions of the present invention comprise one or more organic solvents selected from four (4) separate groups consisting of:
  • Polar aprotic solvents that do not contain oxygen but have large dipole moments, such as nitriles. haloalkanes. and amides;
  • polyo.s • polar, polyproHc solvents (collectively, "polyo.s") that contain two or more -OH moieties, and have large dipole moments, such as die diols, rriols and higher order polyols.
  • Hybrid solvents that have the properties of two or more groups are included within the scope of the present invention.
  • exemplary hybrid solvents include 2-butoxyethanol, eya ⁇ oearboxylic acids, butanoic acid, and ethyl acetate.
  • present invention are further restricted to solvent mixtures wherein the volume fraction of water in the solution ranges from about 25% to about 75%, and the final pH of the solution is less than or equal to about 8.5.
  • the pH can be maintained at less than or equal to about 8.0.
  • the invention is active against all agents as pH values between about 7.0 (o about 10.5; the buffer capacity is more effective at pH values between about 8.0 to about 9.0.
  • the preferred embodiment is maintained a pH values from about 8.0 to about 8.5.
  • the pH can further be maintained at a pH of about 8.5.
  • Exemplary solutions include the alkanediol/water solutions, comprising one of the isomers of propanediol, butanediol, or pentanediol, and solutions made from linear monoprotie alkanols, such as cthanol or butanol or a hybrid of two solvent types such as 2-butoxyethanol.
  • the linear or branehed-chai ⁇ monoprotie alkanols can have from 1 to at least 15 carbons. Additional properties of the organic/aqueous solutions of the present invention should preferably include:
  • Decontamination solutions of die present invention may be effectively deployed in neutralizing loxants over a temperature range of between about -25 V 'F and about 140 °F.
  • the decontamination solutions may be deployed and dispersed as aerosolized sprays over the range of temperatures of between about -25 °F and about 140 °F.
  • Other embodiments within the scope of the invention include decontaminants with improved hydrolytic activity at about -25 1 T, but which do not rapidly evaporate at temperatures as high as about 125 T. Rapid evaporation would limit the effectiveness of the decontamination solution and thus should be avoided, if possible.
  • the solutions may also be applied directly to a surface by pouring or otherwise applying the solution to the surface.
  • the working temperature range for decontamination can be adjusted by selection of the type and relative amounts of polar amphipathic solvents in organic/aqueous solutions according to the total amount of pcroxy- oxidanl can vary according to the embodiments of the invention.
  • One skilled in the art having the present specification as their guide would know that the solutions made using polyprotic acids, such as the Group [V solvents, will have an entirely different buffering capacity as compared to solutions which comprise monoprotic solvents from Group II. Similarly, it will be
  • a solvent with a high donor number making it a strong Lewis base
  • a solvent with a high dielectric constant making it a good solvent for ionic species.
  • fOOHSj Dimtheylsullbxide (DMSO) has a lower dielectric constant than water, is less polar, dissolves non-polar, hydrophobic substances more readily, and has a measurable ⁇ ' ⁇ range of about I to 30.
  • ⁇ cetonitrile is less basic than DMSO.
  • acids are generally weaker and bases are generally stronger in this solvent.
  • HClO.' is - 1 and HCiU 4 is a strong acid.
  • organic acids like the percarboxylic acids.
  • inductive effect and mesomeric effects affect the pK * values.
  • a simple example is provided by the effect of replacing the hydrogen atoms in acetic acid by the more electronegative chlorine atom.
  • the electron-withdrawing effect of the subse uent makes ionization easier, so successive pK ⁇ values decrease in the series 4.7, 2.8, 1.3, and 0.7 when 0, 1 , 2 or 3 chlorine atoms are present.
  • Hie Hamniett equation provides a general expression for the effect of substituents:
  • K n is the dissociation constant of a substituted compound
  • K ⁇ ° is the dissociation constant when the subslituent is hydrogen
  • p is a property of the unsubstituted compound
  • ⁇ has a particular value for each substituent.
  • a plot of log K a against ⁇ is a straight line with intercept log A' a ° and slope p. This is an example of a linear free energy relationship as log K u is proportional to the standard fee energy change.
  • Hammett originally formulated the relationship with data from benzoic acid with different substituents in the ortho- and para- positions: some numerical values are in Hammctt equation. This and other studies allowed substituents to be ordered according to their electron-withdrawing or electron-releasing power.
  • One aspect of the present invention is the use of mixed solvents to create dccontaminant formulations which can dissolve threat loads of amphipathie compounds like the nerve or mustard agents and their respective simulants that have limited solubility in water. It is a common practice (in the pharmaceutical industry, for example) to determine pA ' a values in solvent mixture such as water/dioxane or water/oefanol, in which the compound is more soluble.
  • the pX a value rises steeply with increasing percentage of 1 ,4- dioxane, a GROtH* IH solvent with two hydrogen bond acceptors, as the dielectric constant of the mixture is decreasing.
  • a pA' ⁇ value obtained in a mixed solvent cannot be used directly for aqueous solutions, because when the solvent is in its standard state, its activity is defined as one.
  • the standard state of wate ⁇ dioxane 9: 1 is precisely that solvent mixture with no added solutes.
  • the total amount of pcroxy-oxidant used can vary according to the embodiments of the invention.
  • the total decontaminant to toxant ratio can range from about HX) to about 0.1.
  • the solutions of the invention can be used for hydroly/ing a substrate in an organic/aqueous solution by providing both the toxant and the oxidizers with an isotropic solution in which to react.
  • toxant hydrolyses can be conducted from between about -35 °F and 140 °F.
  • substrate hydrolysis reactions are conducted between about -25 ⁇ F and about 125 °F.
  • the total decontaminant to toxant ratio by volume can range from about 100 to about 0.1.
  • Biopathogens used for biological warfare, s ⁇ ch as bacterial ceils, bacterial spores, viruses, and other biopathogens have certain structural features that must be considered. The organization and structure of phospholipids and proteins in ceil membranes, spore coats and viral capsids can be readily disrupted and hydrolyzed by the organic/aqueous solutions and reactive oxygen species of the invention. These solutions can destroy the integrity of the membranes, spore coats, and viral capsids, exposing the proteins and nucleic acids within the pathogen.
  • Suitable polar aprotic solvents include, but are not limited to, those of Groups 1 through IV. These include nitrilcs, ketones, dimethyl sulfoxide, and tctruhydrofuran.
  • Suitable polar-protic solvents include, but are not limited to, alcohols and polyois (e.g., diols, triols and certain complex sugars such as fructose).
  • the volume fraction of water in the composition may range from about 25% to about 75%.
  • the final solution pH has a value less than or equal to about 8.5 but is determined by the buffering capacity of the buffer system.
  • a solution, such as the solutions of the invention contains both acid and its salt, and has a titration curve, which has a mid-point at which a certain pH can be maintained. In order to maintain the pl i of a solution, a buffer that has a mid-point at the desired pH would be selected.
  • Additional embodiments of the invention provide methods of decontaminating toxants, which include phosphoric acid esters, sulfur mustards, bacteria, bacteria! spores and viruses.
  • the pH can be maintained at less than or equal to aboui 8.0.
  • the invention is active against all agents as pH values between about 7.U to about 10.5; the buffet' capacity Ls more effective at pH values between about 8.0 to about 9.0.
  • the preferred embodiment is maintained a pH values from about 8.0 to about 8.5.
  • the pH can further be maintained at a pH of about 8.5.
  • decontamination solutions may be deployed over a temperature range of between about -35 C F to about 140 °F.
  • the decontamination solutions of the invention may be deployed at a temperature of between about -25 °F to about 125 °F.
  • the working temperature range can be adjusted by varying the type and relative amounts of polar amphipathic solvents in the aqueous organic solutions.
  • the total amount of peroxy- ⁇ xidaot can vary according to embodiments of the invention.
  • the total decontaminant (and hence oxidant) to toxant ratio can range from about KK) to about 0.1 by volume. Because of the potential for corrosion, the nozzle, if employed, should preferably be made of stainless steal or a thermoplastic material.
  • One embodiment of the invention encompasses isotropic organic/aqueous solutions comprising at least two polar amphipathic organic solvents, which can be water-soluble and selected from tha four distinct solvent groups as set forth in Table 2. Examples of these solutions include but are not limited to those given in Tables 6A-6D helow. According to certain aspects of the invention, methods of decontaminating toxants may use a decontamination solution comprising an organic/aqueous solution containing at least two polar amphipathic organic solvents.
  • J(M)124 J Another embodiment of the invention encompasses organic/aqueous solutions comprising at least two polar amphipathie organic solvents, which may be water-soluble and which may further comprise at least one fully dissolved reactive oxygen species, or at least one oxidizers and an activator.
  • Suitable oxidizers, or activators include, but arc not limited to, hydroxy! radicals, hydroperoxide anions, superoxides, hydroni ⁇ m ions, peroxyacetic anions, and singlet oxygen.
  • amphiphile-' and "amphipath” describe chemical compounds possessing both hydrophilic and hydrophobic properties.
  • the hydrophobic group is typically a large hydrocarbon moiety, such as a long chain of the form CMj(CHj) n , wilh n •> 4.
  • the hydrophilic group can fail into one of the several categories.
  • the hydrophilic group can be a charged group, which can be anionic or cationic.
  • Anionic groups are positively charged, and can be carboxylates, sulfates, sulfonates and phosphates, Phosphate esters can be part of an atnphipathic compounds and contain a charged functionality as in phospholipid compounds and nerve agents.
  • Cationic groups have a negative charge, and are exemplified by amines.
  • hydrophilic groups can be polar, uncharged groups.
  • polar, uncharged groups include alcohols with large R groups, such as diacyl glycerol (DAG) and oKgoethylencglycols with long alkyl chains.
  • amphophilic species have several hydrophobic parts, several hydrophilic parts, and/or several of both. Proteins and some block co-polymers are examples of such compounds. ' ⁇ * he hydrophobic regions of these compounds are usually of hydrocarbon nature. The hydrophilic regions are generally represented by either ionic or uncharged polar functional groups. As a result of having both hydrophobic and hydrophilic structural regions, some amphophilic compounds may dissolve in water, and to some extent in non-polar organic solvents. The organic/aqueous solutions of the present invention, when placed in an immiscible triphasic system consisting of aqueous and hydrophobic solvent, will partition the two phases.
  • methods arc provided for decontaminating toxants which include orgarsoph ⁇ sphate esters, sulfur and nitrogen mustards, bacteria, bacterial spores, and viruses.
  • examples of the four different Groups of polar organic solvents of the present invention are listed in Tables 6A-6D below.
  • Tables 6A- ⁇ D include examples and properties of some solvents used in the organic /aqueous solutions and the deeontaminants of the present invention as well as some unsuitable solvents.
  • the melting point C'M.Pt." and the boiling point (“B.Pt.”) are the temperatures at which an undiluted compound undergoes its solki-to-Hquid and its liquid-to-vapor phase transitions, respectively.
  • the principal organic component is considered the "solvent.” whereas the water and other components are all considered the “solutes.”
  • the boiling point and the freezing point of an organic/aqueous solution are two colligative properties that are impacted by the deviation of die solution from ideality (/. ⁇ *., properties that depend on the number of particles, not the mass of the particles, which include, but are not limited to, lowering of vapor pressure, elevation of boiling point, depression ⁇ f freezing point, and osmotic pressure).
  • polar solvent refers to solvents with large iHpole moments and high dielectric constants; those with low dipolc moments and small dielectric constants are classified as non-polar ("apolar").
  • apolar non-polar
  • solvents that are miscible with water are polar, while those that arc not are non-polar, as well as solvents lacking the ability to form dipole ••• dipole bonds, of which hydrogen bonds are a subset.
  • polar-protie solvent refers to a solvent able to donate a hydrogen bond between Us oxygen and another molecule as between a hydroxy, group or a nitrogen, such as found an amine group, and the oxygen in a Group ill solvent.
  • polar-protic solvents include water. (VC12 alkanols ( ⁇ '.#., cthanol), diois, and polyols, acetic acid, formic acid, hydrogen fluoride, and ammonia. More generally, any molecular solvent which contains dissociable H ' , such as hydrogen fluoride, can be considered to be a "protic" solvent. Hie molecules of such solvents can donate an J-T (proton).
  • PoSar-protic solvents are favorable for SN I nucleophilic reactions.
  • Examples of compounds that arc hydrogen acceptors but not donors arc dimethyl sulfoxide, diniethylf ⁇ rmamide, and dioxane.
  • Examples of hydrogen bond donor compounds include 2-butoxyethanol and ethyl acetate, which have oxygens that are both hydrogen bond acceptors, but only one of which is a donor.
  • aprotic means solvents that cannot donate a hydrogen atom.
  • One important characteristic of a protic solvent is that it displays hydrogen bonding, both as an acceptor and a donor. This term includes any solvent that has a similar ion-dissolving power as protic solvents, but lacks an acidic hydrogen.
  • solvents generally have high dielectric constants and high polarity, and can either act as a hydrogen bond acceptor or enter into strong dipolc-dipole bonds that need not involve a hydrogen atom bound to an oxygen.
  • Polar aprotic solvents are favorable for $N2 nucleophilic reactions.
  • dielectric constant refers to the relative static permittivity, or static relative permittivity, of a material under given conditions.
  • Fhc dielectric constant is a measure of the extent to which a material concentrates electrostatic lines of flux. It is the ratio of the amount of stored electrical energy when a potential is applied, relative to the permittivity of a vacuum.
  • the relative static permittivity is the same as die relative permittivity evaluated ibr a frequency of zero.
  • the strength of the hydrogen bonds formed by solvent isomers having the same chemical composition is significantly impacted by the number and positions of the hydrogen bond donor and acceptor atoms.
  • the present invention is intended for use in commerce, which means it must be safe to transport on commercial trucks, trains, and airplanes.
  • the Hash point of a compound is one indication of how easily a compound or a solution may burn, or the minimum temperature at which a liquid gives off vapor within a test vessel in sufficient concentration to form an ignitable mixture with air near the surface of the liquid. Chemicals with higher flash points have lower vapor pressures and arc less hazardous than chemicals with lower flash points. ⁇ ht flash point of a chemical or a solution is the lowest temperature at which it will evaporate enough fluid to form a combustible concentration of gas, and thus is an indication of how easily a chemical may burn.
  • the Code of Federal Regulations 49 C.F.R.
  • ⁇ 173: 120 identifies ranges of flash points of materials that are characterized as "flammable,” “combustible.” and “non-combustible” compounds. Non-combustible compounds are typically safer than combustible and flammable compounds.
  • a flammable liquid has a flash point of not more than 60 °C (140 °F); a combustible liquid has a flash point above 60 °C ( 140 °F) and below 93 °C (200 0 F). That said, as an example, decontaminants made using the isomers of butanediol are considered safe for all forms of transport without special handling.
  • the invention relates to methods of decontaminating toxants using a decontaminant comprising an organic/aqueous solution containing at least one polar solvent, which formulation is distinguished by a flash point in organic aqueous solution > 140 °F.
  • a decontaminant comprising an organic/aqueous solution containing at least one polar solvent, which formulation is distinguished by a flash point in organic aqueous solution > 140 °F.
  • This allows for the creation of decontaminants with low vapor pressures and high flash points that are safe to ship, store, and use ovar the temperature range of 125 °F to -25 °F.
  • the impact of hydrogen bonding on the flash point of a deeontami riant is important in selecting the aqueous/organic mixtures of the present invention.
  • Table 8 shows that two butanedioi isomers and a branched propanediol, all of which have the same molecular composition, C4H10O 2 , and which differ only in the separations of their hydroxy! groups, nonetheless have significantly different flash points. Those differences notwithstanding, in terms of flammability and transportation safety, all three diols are acceptable solvents for a deployable deeontaminant; whereas among the monoprotic solvents of Table 6B, there are no high Hash point alcohol solvents. Table $ - Structure and Flash Point of Butanediol and Propanediol Compounds
  • FIG. 5A-5C the boiling point and melting points of water are uniquely elevated relative to other compounds that can form hydrogen bonds.
  • Figure 5A depicts the boiling temperature of various compound, as compared to the molecular weight.
  • curve of Figure 5B the melting points of molecules that are structurally related to water, which otherwise difler primarily in their molecular masses, shows that the melting points of the series can be predicted from the molecular mass.
  • the sole exception is water, which has a melting point approximately 100 C C higher than would have been predicted from molecular mass alone.
  • the lower curve compares the corresponding structural analogs in which the central atom is drawn from compounds that do not significantly form hydrogen bonds.
  • ⁇ T - kt-m from Raouh's Law
  • i !!! total moles of ions after solution/moles of solute before solution.
  • the properties of a non-ideal solution are not generally the simple sum of the properties of the component pure liquids. As such, the solubility of a component is not guaranteed over the entire composition range.
  • the vapor pressure above a solution will be smaller than would be calculated using Rao ⁇ it's law. This in turn would mean a higher flash point and boiling point. Conversely, if the unlike-molccule interactions arc more repulsive, then the vapor pressure would be greater than for the corresponding idea! solution. In addition, the flash point and boiling point would be lower.
  • the organic/aqueous formulations of the present invention can be non-ideal solutions, in which the strong hydrogen bonds of the water traction are replaced by interactions with the organic solvents. This usually results in changes in the coUigativc properties, including but not limited to, the boiling and freezing points, vapor pressure, and flash point.
  • methods of decontaminating toxants use a decontamination solution comprising an aqueous/organic solution containing at least two polar amphipathtc organic solvents (at least one aprotic and one protie solvent in combination or at least two protie solvents in combination).
  • the solvents are distinguished by having cither: (i) strong dipolc moments but contain no oxygen atom; (ii) by their capacities to act as hydrogen bond acceptors; or (iii) by the extent to which they can act as both hydrogen bond donors and acceptors.
  • Suitable polar amphipathtc solvents are included in the four groups discussed above and shown in Table 2, with examples given in Tables 6A-6D. j00l40j According to certain aspects of the invention, methods of decontaminating toxants use a decontamination solution comprising an organic-aqueous solution containing at least two water-soluble polar amphipathic organic solvents, in which the melting point of the solution is lowered compared to the melting point of water.
  • the organic solvents selected for use in decontaminants should have a melting point in the neat, or undiluted, solution that is lower that the melting point of water, and in fact ⁇ should have a melting point lower than -25° F.
  • the boiling point of the organic solvent in the neat solvent should be sufficiently elevated to allow for decontaminanl solutions that are in liquid form over the range of about 125 °F to about -25 °F. See Figures 5A- 5C.
  • Deccmtaminant solutions can be prepared comprising an organic/aqueous solution containing at least one polar amphipathie organie solvent and water in which the melting point of the solution is lowered compared to the melting point of water.
  • the boiling point remains sufficiently elevated enabling the creation of tiecontammant solutions that remain lluid and do not freeze or boil over the temperature range of about 125 ⁇ F to about -25 °F. Methods of using such decontamination solutions are encompassed by the invention.
  • methods of decontaminating toxants use a decontamination .solution comprising an organic-aqueous solution containing at least two polar amphipathic organic solvents that are dissolved in water as a homogeneous, single-phase solution that remains liquid over the temperature range of about -25 °F to about 125 C F.
  • methods of decontaminating toxants use a decontamination solution comprising an organic/aqueous solution containing at least two water-soluble polar amphipathic organic solvents that are dissolved in water as a homogeneous, single-phase isotropic solution, which is capable of dissolving at least one threat load of a toxant in a homogeneous, isotropic solution, and which remains liquid over the range of about -25 °F to about 125 S F.
  • a decontamination solution comprising at) organic'aqueous solution containing at least two water -soluble polar amphipathic organic solvents that are dissolved in water as a homogeneous, isotropic solution, which solution: (i) is capable of dissolving at least one threat load of a toxant in a homogeneous isotropic solution; (ii) is also capable of dissolving reactive oxygen species or their dry sources in sufficient quantities and concentrations to rapidly hydrolyze or otherwise neutralize threat loads of toxants in small volume ratios of decontaminant solution to toxant; and (iii) remains liquid over the temperature range of about -25 °F to 125 °F.
  • a decontamination solution comprising an organic/aqueous solution containing at least two water-soluble polar amphipathic organic solvents (at least one aprotic and one protic solvent in combination or at least two protic solvents in combination) and at least one polyol block copolymer that are dissolved as a homogeneous, isotropic solution, which solution: (i) is capable of dissolving at least one threat load of a toxant in a homogeneous isotropic solution; (U) is also capable of dissolving reactive oxygen species or their dry sources in sufficient concentrations to rapidly hydrolyze or otherwise neutralize full threat loads of toxants in small volume ratios of decontaminant solution to toxant; (iii) can be sprayed in high volumes without change of composition; and (iv) can be applied by spraying onto contaminated surfaces where it dissolves toxants to achieve the hydrolysis of dissolved toxants to by-products.
  • This spraying comprising an organic/aqueous solution containing at least two water-soluble
  • the invention relates to solutions in which the solute is dissolved.
  • the solution tonus Hq ⁇ id-in-liquid particles which arc not miceliar in nature.
  • the solutions of the invention are completely soluble, isotropic solutions that only form liquid-in- liquid microemujsions that are particulate, when sheared in a nozzle.
  • these decontaminant formulations can be aerosolized to produce a liquid- in-liquid microemulsion (e.g., a microcolloidal system, which has decontaminant and microemulsion components) instead of a homogeneous, single-phase solution.
  • a liquid- in-liquid microemulsion e.g., a microcolloidal system, which has decontaminant and microemulsion components
  • the liquid-in-liquid microemulsion can also be a non-Newtonian fluid possessing desirable properties as both an aerosol and a surface decontammant.
  • Organophosphates can be hydro.yzed when they are dissolved in an aqueous/organic solution comprising polar-protjc and/or polar aprotic amphipathic organic solvents, if sufficient molar equivalents of the appropriate activated oxidizers) are also dissolved in the formulation.
  • solvents are identified in Table 2. including but are not limited to: alkanols, polyols, polar-protic solvents, and polar aprotic amphipathic solvents (e.g., alkanols and nitriles).
  • the term ''surface active agents includes the more common term “surfactants” and refers to one or more wetting agents that lower the surface tension of a liquid, allowing easier spreading, and lowering the interfacia! tension between two liquids.
  • Surfactants are usually organic compounds that arc amphophilic, meaning they contain both hydrophobic groups (their tl tails") and hydrophilic groups ⁇ their ''heads ' ").
  • Block co-polymers have alternating "blocks” that are hydrophilic or hydrophobic and have a more complex surface behavior in which the hydrophobic blocks of the polymer can be solubilized in polar solvents. Whereas the apolar blocks are positioned at an interface, such as an air water interface.
  • both conventional surfactants and the block co-p ⁇ lymers can be soluble in both organic solvents and water. Both types of compounds reduce the surface tension of water by adsorbing at the liquid- gas interface. Both types of compounds also reduce the interfacial tension between oil and water by adsorbing at the liquid-liquid interface. Many surfactants and many block co-poiymers can also form aggregates in a bulk solution. Examples of such aggregates are vesicles, micelles, and the mieroemulsions of the present invention, all of which are quite different from one another. The concentration at which surfactants begin to form micelles is known as the critical micelle concentration ("CMC").
  • CMC critical micelle concentration
  • Surfactant's are also often classified into four primary groups based upon charge: anionic, cationic, non-ionic, and *wi tier ionic, or dual charge.
  • the preferred surfactants arc alkanols and the preferred block co-polymers are poly( ethylene oxide) and polypropylene oxide), e.g. * poloxamers or poloxammcs.
  • the preferred colloidal form once aerosolized is a non-Newtonian fluid that is also a liquid-in-liquid microemulsion that conforms to the axioms of the general model of decontaminant formulation set forth in this patent application.
  • co-polymer refers to polymers that are derived from two or more monomelic units, albeit each unit may have a large molecular weight.
  • Block co-polymcrs are comprised of two or more homopolymcr subuwits that can be linked by covalent bonds. The union of the homopolymcr subunits may require an intermediate non-repeating sub ⁇ nit, which is known as a junction block.
  • Block co-polymcrs with two or three distinct blocks arc called diblock co-polymers and triblock co-polymers, respectively.
  • Block co-polymcrs can "mierophase separate” to form periodic nanostructures, also called “micropaiticlcs” or * “microsomes", that are contained within a liquid-in-liquid microemulsion. Because of the microfmc structure of the microparticles in such a mieroemulsion, a microscope or fluorescent label is required to detect ami examine tlic structure of the micropartieies. jOO 151
  • Microphasc separation refers to a property of solutions when mixing substances such as oil and water, which are normally immiscible. Due to incompatibility between the blocks of an amphiparhic block co-polymer, one would expect the compounds to undergo a similar phase separation in the present invention. However, because the blocks are covalently bonded to each other, they cannot dcmix macroscopically, as do water and oil. In microphasc separation * the blocks of the polymers form micrometer-sized structures. Depending on the relative lengths of each block of the polymer, several types of morphologies can be obtained. 1 « the present invention, the blocks can form niicron-si/.cd particles.
  • polymeric mixtures are far less miseible than mixtures of small molecule materials. Miseible materials usually form a solution because of an increase in entropy and free energy associated with increasing the amount of volume available Io each component.
  • polymeric molecules are much larger and hence generally have much higher specific volumes than small molecules, the number of molecules involved in a polymeric mixture are far less than the number in a small molecule mixture of equal volume.
  • the energetics of mixing are comparable on a per volume basis for polymeric and small molecule mixtures. This tendvS to increase the free energy of mixing for polymer solutions and thus make solvation less favorable. Thus, concentrated solutions of polymers are less likely than those of small molecules.
  • the properties of the polymer can be characterized by the interaction between the solvent and the polymer, in a suitable solvent, the polymer appears swollen and occupies a large volume.
  • intermolecular forces between the solvent mid monomer subunits dominate over intramolecular interactions.
  • intramolecular forces dominate and the chain can contract.
  • theta solvent also called the Flory condition
  • Some block co-polymers include poloxamers. Poloxamcns are nonionie triblock co-polymers composed of a central hydrophobic chain of polyoxypropylene (poly( propylene oxide)) flanked by two hydrophilie chains of polyoxyethylcne (polyethylene oxide)). Poioxamers include, but are not limited to. the Plutonic* block co-polymers ⁇ e.g., Pluronic* F127, Pluronic"' Fl 88, Pluronic" 68, and Pluronic* Fl 25).
  • the Pluronic block co-polymers are ethylene oxide and propylene oxide co-polymers. More specifically, the block co-polymer may be an ethylene oxide and propylene oxide co-polymer that terminates in primary hydroxyl groups, one example of which is Pluronic* F 127.
  • the block co-polymers can have different ranges of molecular weights. Because of their amphophilic structure, the polymers have surfactant-like properties that make them useful in industrial and pharmaceutical applications. Among other things, they can be used to increase the water solubility of hydrophobic, oily substances, such as organophosphale esters, pesticides, and nerve agents. These compounds can also increase the miscibility of two substances with different hydrophobicitics through the formation of micr ⁇ emulsions.
  • these polymers can also be employed in pharmaceutical applications as model systems tor slow release drug delivery applications or, as in the present invention, to enhance the solubility of ainphipathic toxaiHs and polar reactive oxygen species or their sources in a single isotropic phase.
  • the triblock eo-polymers used in aqueous organic decontamination solutions capable of forming inicroem ⁇ isions are hydrophilic non-ionic tri block co-polymers consisting of a central hydrophobic block of polypropylene glycol flanked by two hydrophilic blocks of polyethylene glycol.
  • the approximate lengths of the two PEG blocks are KM) repeat units white the approximate length of the propylene glycol block is 65 repeat units (see Table 2).
  • the molecular weights of the various triblock co-polymers vary with the number of blocks.
  • other such block co-polymers can be made to carry a permanent charge enabling the formation of particles in the microexnulsions of the present invention which carry a net positive or negative charge, as desired.
  • the preferred forms of the co-polymers used in the present invention are the polymers synthesized from the simple alkene et'hcne, called polyethylene ⁇ . These compounds retain the -ene suffix, even though the double bond is removed during the polymerization process.
  • the co-polymers of the invention which can be simple ⁇ i- or tri- block copolymers, generally can have alternating hydrophobic and hydrophilic regions. If the block copolymer has a dipole moment, certain regions of the molecule will gather at the interface between two phases of a biphasic solution. The surface tension will also be reduced, which helps solubilize longer chain alcohols.
  • Polymers containing amide or carbonyl groups can form hydrogen bonds between adjacent chains because the partially positively charged hydrogen atoms in N-M groups of one chain are strongly attracted to the partially negatively charged oxygen atoms in C Q groups on another. These strong hydrogen bonds can result in the high tensile strength and melting point of polymers containing urethane or urea linkages. Ethene, however, has no permanent dipole. The attractive forces between polyethylene chains arise from weak van der Waals force*?. Molecules such as these can be thought of as being surrounded by a cloud of negative elections.
  • Fluorescent dyes can be used to detect one or more toxants both before and after treatment with the decontaminating solution, to analyze the mixing, reaction and neutralization of aenvsolized toxant in real time, and to analyze the area or volume coverage, extent of loxant neutralization, and elimination of toxant threat during surface decontamination.
  • FIG. 1 Other embodiments of the invention relate to methods of using optoelectronic hardware and software, combined with fluorescent dyes, to regulate the operation and use of the decontamination solution and the dispersal system.
  • such hardware and software can be used to detect one or more toxants both before and after treatment with the decontaminating solution, to analyze the mixing, reaction and neutralization of aerosolized toxant in real time, and to analyze the area or volume coverage, extent of toxant neutralization, and elimination of toxant threat during surface decontamination.
  • toxant decontamination can be detected using chromatographic methods including to High Performance Liquid Chromatography (IiPLC) and Gas
  • GC * Chromatography
  • detectors that employ various detectors, such as absorbance detectors, flame ionization detectors, electron capture detectors, mass spectroscopic detectors, and fluorescence detectors.
  • the solutions of the invention may be applied directly to a desired surface to be decontaminated or sprayed as an aerosol.
  • certain solution parameters should be followed.
  • the flow rate, or capacity of a fluid through a nozzle is affected by a number of factors including pressure, specific gravity, and viscosity of the fluid.
  • the specific gravity, or density, of a liquid represents the ratio of a mass of given volume of liquid to the mass of the same volume of water, as shown by the following equation:
  • Unidirectional fluid flow such as through a pipe or nozzle is generally modeled as comprised of layers of fluid flowing past one another.
  • the viscosity of a liquid is a measure of the resistance to flow
  • hi fluid dynamics Couette flow refers to the laminar flow of a viscous fluid in the space between two parallel plates, one of which is moving relative to the other. The flow is driven by virtue of viscous drag force acting on the fluid and the applied pressure gradient parallel to the plates.
  • shear occurs whenever the fluid is physically moved or distributed (e.g., pouring, spreading, spraying, or mixing). Specifically, shear will occur when a fluid is moved through a nozzle in an atomizing spray head, such as an ultrasonic no/7.le. Highly viscous fluids require more force to move than less viscous materials.
  • In a viscosity model, two parallel planes of fluid of equal area "A" are separated by a distance "dx" and are moving in the same direction, but at different velocities "Vl " and *'V2.”
  • viscosity In a Newtonian fluid, the force required to maintain this difference in speed is proportional to the difference in speed through the liquid, or the velocity gradient.
  • the "velocity gradient” is a measure of the change in speed at which the intermediate layers move with respect to each other, ft describes the shearing the liquid experiences and is called “shear rate.” This is symbolized as * ⁇ _r and its unit of measure is called the “reciprocal second" (sec- 1 ).
  • F/ ⁇ indicates the force per unit area required to produce the shearing action. It is referred to as ''shear stress” and is symbolized by “F' with units of measurement in "dynes per square centimeter” (dynes/cm 2 ). Using these simplified terms, viscosity may be defined mathematically by:
  • Pscudoplastic non-Newtonian fluids include paints, emulsions, and dispersions of many types.
  • a common household example of a strongly shear thinning fluid is styling gel.
  • Styling gels are aqueous/organic fluids that are primarily composed of water and a vinyl acetate/vinyl pyrrol idone co-polymer (PVlVPA).
  • pseudoplastic fluids whose viscosities decrease with increased shear include molten lava, ketchup, whipped cream, biood, and nail polish. It is also a common property of polymer solutions and the aqueous-Organic solutions of the present invention in which block co-polymers are dissolved.
  • the shear rate is varied, the shear stress does not vary in the same proportion, or even necessarily in the same direction.
  • the viscosity of such fluids thus changes as the shear rate is varied, as shown in Figure 7.
  • the experimental parameters of the viscosity model all have an effect on the measured viscosity of a non-Newtonian fluid, which is called the "apparent viscosity" of the fluid.
  • non-Newtonian refers to a fluid whose flow properties are not described by a single constant value of viscosity.
  • the relation between the shear stress and the strain rate is linear, the constant, of proportionality being the coefficient of viscosity.
  • the relationship between the shear stress and the strain rate is nonlinear and can be time-dependent. Therefore, a constant coefficient of viscosity cannot be defined.
  • a ratio between shear stress and rate of strain (or shear-dependent viscosity) can be defined, this concept being more useful for fluids without time-dependent behavior.
  • There are several types of non-Newtonian flow behavior, which are characterized by the way a fluid's viscosity changes in response to variations in shear rate.
  • the most common types of non-Newtonian fluid are those of greatest interest as potential deeontaminant solutions of the present invention.
  • Fluids of this type that can be used for coating and adhering to, or being retained on, surfaces are known as pseudoplastic non-Newtonian fluids. These fluids are also easily aerosolized.
  • thixotropie A subcaiegory of non-Newtonian fluids is known as "thixotropie" fluids.
  • a thlxotropic, non-Newtonian fluid undergoes a decrease in viscosity with time, when subjected to constant shear.
  • Modem alkyd and latex paint varieties arc often thixotr ⁇ pie and will not am off the painter's brush, but will still spread easily and evenly, since the gel-like paint "liquefies-' when brushed out.
  • Other examples of thixotropic fluids whose viscosity decreases with time include, but are not limited to, paint, yogurt, milk, carboxymethyl cellulose, glues, starch, and block co-polymers.
  • non-Newtonian fluids In contrast to the Newtonian fluid dynamics of the simple monomeric diols such as the preferred isomers of butancdiol.
  • polyols such as block co-polymers can be used in organic aqueous solutions to form non-Newtonian fluids. These fluids are mildly viscous when static, but have low viscosity under shear.
  • Non-Newtonian flow can be envisioned by thinking of any fluid as a mixture of molecules with different shapes and sizes. As they pass by each other, as happens during flow, the size, shape, and interactions of the molecules (e.g., hydrogen bonding) will determine how much force is required to move them. At each specific rate of shear, the alignment of the molecules may be different and more or less force may be required to maintain motion.
  • the polyols used to form non-Newtonian fluids are polymers comprised of many monomeric diols.
  • preferred polymeric diols arc the polyethylene glycols (PECJs), the polypropylene glycols (PPGs). random co-polymers and polyalkylene glycols (PAGs), and block co-polymers.
  • PECJs polyethylene glycols
  • PPGs polypropylene glycols
  • PAGs polyalkylene glycols
  • block co-polymers As a general rule, the polymer names are designated by one or more capital letters that represent the oxide used to make the polymer. For example. E represents ethylene oxide (EO). and P is propylene oxide (PO).
  • the name indicates that both oxides are used, as is the case in the block co-polymers of polyethylene oxide, polypropylene oxide (PEO-PPO).
  • a number following the letters of the name indicate the approximate molecular weight.
  • the viscosities of certain monomcric diols are not satisfactory for use in creating aerosol dccoantaminants.
  • An example is monomelic ethylene glycol, which is a Newtonian fluid most temperatures and is too viscous for aerosolization.
  • the polyethylene block co-polymcrs of the present invention have low viscosities even at low temperatures.
  • Monomcric ethylene glycol is representative of all of the ethylene glycols.
  • the viscosity is highly non linear with rcspccl to its mole fraction when mixed with water to form, one of the aqueous/organic solutions of the present invention, becoming highly viscous at low water fractions.
  • aqueous/organic solutions freeze at temperatures below 40 ⁇ F, and the water fraction is below 40 % by volume, rendering them useless as chemical agent decontamination solutions under extreme weather conditions.
  • many simple monomelic diols cannot be used at higher concentrations to create solutions that can be aerosolized or sprayed for use in decontamination. Instead, they can only be used in localized surface applications.
  • Carboxymethylcellulose is actually a family of cellulose derivatives with carboxymethyl groups (-CHs-COOJi) bound to some of the hydroxy! groups of the glucopyranose monomers that make up the cellulose backbone.
  • Most CMCs dissolve rapidly in cold water and are mainly used for controlling viscosity without gelling (CMC, at typical concentrations, docs not gel even in the presence of calcium ions). As its viscosity drops during heating, it may be used to improve the volume yield during baking by encouraging gas bubble formation. Its control of viscosity allows use as thickener, phase and emulsion stabilizer (for example, with milk ca.scin), and suspending agent.
  • FIG. 8A shows the pseudoplastie behavior of the thixotropic fluid, carboxymethyl cellulose (CMC).
  • CMC carboxymethyl cellulose
  • Figure SB shows a relative viscosity profile of various earboxymethyleelluloses.
  • Figure 9 relates to the change in viscosity of cellulose solutions due to temperature changes.
  • the Avicer" RC/CL (microorystalline cellulose) dispersible celluloses are used in pharmaceutical suspensions, emulsions, nasal sprays, and creams.
  • the wide range of thixotropies. viscosities, gel strengths, and dispersion characteristics of this product line provide unparalleled suspension stability and functional versatility.
  • These polymers are non-Newtonian in solution, however, we have found that their use in decontarninants is largely restricted to topical applications, rather than in sprays, aerosols and fogs.
  • Another one of the novel discoveries of the present invention is that many polymers form non-Newtonian fluids that are useful in modifying the fluid dynamics of liquids and aerosols.
  • the block co-polymers of the present invention form Hquid-in-liquid microemulsions that are used in creating decontaminanls that can be used as aerosols or togs.
  • Another embodiment of the present invention relates to methods of aerosolizing decontamination solutions by dispersing the solution;? through a nozzic.
  • Shear can be induced by air pressure moving fluids through tubing and nozzles. 'Hie air pressure used in moving the decontaminanl solutions of the present invention through tubing, the tubing itself, and the geometry and operation of the aerosolizing or spray nozzle, all generate shear.
  • Droplet formation, or atomization begins when a liquid is forced through a hydraulic nozzle under pressure so that the liquid forms a thin sheet that subsequently breaks up into droplets. Each nozzle produces a range of droplet sizes, known as the droplet spectra or drop-size distribution. Droplet size is measured in microns ⁇ m).
  • Droplet size is both a consequence of the formulation and a determinant of surface coverage at the target surface. Small droplets arc more subject to off target drift than larger droplets. Increasing the velocity of the droplet will make it less susceptible to drift. Small drops are more likely to be retained by surfaces titan large drops, it has been found in agricultural spraying that very few. if any droplets larger than 200 microns are retained by plant leaves which are difficult to wet. The drops will bounce off the leaf surface, and be deposited on the ground.
  • Figure 10 shows how the number and size of droplets are determined during aerosolization.
  • FIG. 1 Several of the nozzles used in evaluating the aerosol and fogging properties of the present invention are shown in Figure 1 1.
  • Changing the diameter of a pipe will create both hack pressure and internal friction, if the objective is to push the same volume of fluid through a smaller diameter.
  • TVshaped joints, valves and other common assemblies also can increase shear. Further, the more distance a solution has to travel, the more shear it encounters.
  • the geometry of the nozzle and the turbulence at the nozzle head ail can induce shear. Ail of these factors can change the sizes of the microparticles at die nozzle head.
  • die formulations of the present invention are aerosolized is a iiquid-in-Hquid rnieroemulsion, which is a non-Newtonian fluid, as described above.
  • Conversion of the organic/aqueo ⁇ s solutions of the present invention to block copolymer microcmuisions facilitates dispersal of the decontamination solutions using a range of high performance nozzles including, but not limited to, ultrasonic nozzles.
  • an additional aspect of the present invention are, collectively, methods of converting organic-'aqucous mixtures of the invention to pseitdoplastic non-Newtonian solutions for use with a range of high performance nozzles including, but not limited to, ultrasonic nozzles.
  • Surface active components of the organic/aqueous mixtures are also useful for forming microemulsion fogs that enhance aerosol decontamination by increasing (i) the rates of toxant hydrolysis, (ii) the acroso! persistence of the decontaminating solution when dispersed through high performance nozzles; and (iii) the area covered per unit volume of deeontaminant.
  • the surfactant components can also form niicrocmulsion sprays that enhance surface decontamination when dispersed through high performance nozzles. In this case, the surface active components form a thin film that holds the decontamination solution on the surface to be decontaminated.
  • embodiments of the present invention include methods of forming microemulsion fogs or sprays when dispersed through high performance nozzles.
  • One embodiment of the present invention are decontamination solutions with minimum viscosity at the dispersion nozzle, but optimum viscosity for diffusion and retention on the target surface Such formulations produce medium sized droplets with no change in droplet si/e with speed, pressure, flow fluctuations, and temperature.
  • droplet diameters derived using the same assessment method must be used.
  • Figure 10 shows how droplet sue is determined. Viscosity and surface tension arc the two main factors that influence droplet sue.
  • methods of decontaminating toxants can use a decontamination solution comprising an aqueous/organic solution providing certain capabilities.
  • the solution can rapidly dissolve full threat loads of toxaiHs in a homogeneous, isotropic solution; can rapidly dissolve reactive oxygen species or their dry sources in sufficient concentrations to rapidly and completely hydrolyze or otherwise neutralise full threat; can rapidly dissolve loads of toxants in small volume ratios of decontaminant solution to toxant; and can remain a low viscosity liquid with a low vapor pressure from about 125 °F to about -25 °F.
  • the solution can also improve the reaction kinetics of decontamination; can minimize the volume ratio of decontamination solution/toxant for greater efficacy; can utilize surfactant/block co-polymer synergies to create non-Newtonian solutions; and can minimize damage to sensitive equipment (e.g., electronics and specialized materials).
  • the solution should also have a sufficiently low vapor pressure and high flash point, to ensure easy and safe shipping, storage, and use. In addition, ease of cleanup and disposal of the solution and the toxant by-products is desirable, as are environmental safety and biodegradability.
  • Another aspect of the invention relates to systems comprising the decontaminants of the instant invention.
  • One system configuration for any of the polyol based formulations can comprise four parts: the base mix, at least one liquid activator (which may be two liquid activators), and a dry activator.
  • This format is known as a quaternary system ( Figure 13).
  • Alternative system configurations can comprise three parts (a ternary kit) or two pans (a binary kit).
  • the latter vsystcm would include a base solution which contains all of the components except either (i) the reactive oxygen species or its source, or (ii) the liquid activator or de ⁇ activator or source thereof.
  • the binary system configuration of the present invention ( Figure 14) has the peroxy acid sources) dissolved in their stable unactivated states in the base mix, amt the activator source, in either its stable liquid or dry source, would be contained in a separate container.
  • the system components can be routinely supplied in two, three, or four containers, depending upon the system configuration.
  • the components can be mixed on an as- needed basis in the required volumes.
  • the base mix can be shipped fully diluted with water, or, in the case of the high Hash point polyol based formulations, shipped without the water traction.
  • Certain embodiments of the invention comprise mixed components as a solution ready for deployment.
  • Other embodiments include hardware for dispersal of decontamination solutions as either an aerosol fog or as a spray for surface applications.
  • Other embodiments of the invention use the solutions as fogs or sprays to hydroly/c chemical toxants,
  • Example 1 The melting point of a solution of 9% isopropyl alcohol PA, *)%
  • H>O 2 , and 82% H 2 O by volume can be determined.
  • CHJ-CH(OH J )-OH does not dissociate appreciably and forms an ideal solution. 2 moles of hydrogen peroxide are disproportionate
  • H 2 O 2 -> 2 H 2 O t Ch so die solute is CH A -CH(CHJ)-OH.
  • Example 3 The amount of NaCl that must be added to 1.00 L of H 2 O to decrease the freezing point to -2O°C can be calculated: where NaCl(S) -» Na+ (aq) + Cl- (aq) i » • 2 and i kf » ⁇ 2( 1.86 °C kg mol '1 ). Therefore, 5.376 mol x 58.44 g / mot * 314. l7g NaCl must be added to 1 kg (1 L) of H 1 O.
  • Example 4 The amount of NaO ⁇ must be added to i .00 L of H 2 O to decrease the freezing point to -20°C can also be cakulated.
  • the salts CsCh, RbCIh, KO 2 , and Na 2 O 2 were prepared by the direct reaction of Oi with the respective alkali metal.
  • the C)-O bond distance in NaOj is 1.33 K vs. 1.23 A in O 2 and 1.49 A in O: .
  • the overall trend corresponds to a reduction in the bond order from 2 (O 2 ), to 1.5 ( O 1 - ), to 1 (Oj ' ).
  • the alkali salts of sodium are orange-yellow in color and quite stable, provided they are kept dry. Upon dissolution of these salts in water, however, the dissolved decomposes extremely rapidly:
  • Example 5 This example relates to the ultraviolet absorbance spectra of diphenyl phospboroehloridate (DPC 1 P) and establishing a standard curve for detecting and quantitating hydrolysis of an organophosphate ester, diphenyl ehlorophosphatc, which is a stimulant for G-class Nerve Agents.
  • DPC 1 P diphenyl phospboroehloridate
  • DPCP has two six-carbon aromatic phenyl rings attached to a single phosphorous atom through an ether bond.
  • One objective of this example is to establish a standard curve for the detection of diphenyl chlorophosphate.
  • the detection technologies evaluated in this example include absorbance spectroscopy using cuvette sampling; reversed phase MPLC with an absorbance detector: HPLC/Mass Spectroscopy; gas chromatography with a flame ionization detector; and solid phase .sampling with HPLC.
  • Example 6 This example relates to the generation of a standard curve for the detection ⁇ f the organophosphate ester DPPC, which structure and characteristics are given above. The following equations are useful for the determination of hydrolysis of a biological or chemical warfare agents.
  • Example 7 This exainple relates to the hydrolysis of an organophosphate ester by reactive oxygen species in an organic/aqueous solution of the present invention. 'Hie following diagram shows the results of the hydrolysis of an organophosphate ester by a reactive oxygen species in an organicaqueous .solution as described herein.
  • Example 8 The following dccontaminant formulation is uxi anotlier example of the invention in the quaternary kit configuration.
  • the formulation has been used a ⁇ s the reference standard or "baseline” formulation for decontamination efficacy and stability ⁇ aka “Shelf Life") against which all other decontaminant formulations and kit configurations have been compared:
  • Example 9 The following dee ⁇ ntamina ⁇ t formulation is another example of the invention in the binary kit configuration.
  • a second aspect of the reference standard formulations is that they contain a molar excess of hydrogen peroxide relative to die molar amount of 'IAED. Under such conditions, the amount and rate of perhydrolysis are not regulated by buffering capacity of the solution.
  • the reference standards were established for the purpose of creating formulations with optimum: (i) rates of perhydrolyj ⁇ s of the percarboxyiic acid sources; (ii) stocihiometries of activator and reactive species for maximum activated life (pot Hie); and (iii) optimum efficacy against known threat loads of toxants. Establishing such reference standards against which the efficacy of other formulations could be compared was an important invention.
  • the method of chemical activation is not a simple pH adjustment with a base, but instead is an activation by a buffering system in which the buffering capacity is used to establish the quasi-steady state equilibrium of reactive species production as described above.
  • ⁇ second aspect of the preferred embodiment of the invention is that the stoichiometry of the activator and reactive oxygen species is optimized to provide the greatest rate and efficacy in reducing threat loads of chemical or biological toxants.
  • the kit configuration is binary. It is yet a fourth aspect of the preferred embodiment of the invention that such a kit would have a small logistical footprint.
  • a fifth aspect of the preferred embodiment of the invention is that it can be readily aerosolized as a spray.
  • a sixth aspect of the preferred embodiment of the invention is a formulation that is easy and safe to ship, store, use, and cleanup.
  • a preferred embodiment of the invention is that the formulation is environmentally safe to use and has excellent materials compatibility.
  • Example 10 The invention also relates to a quaternary kit 1300 comprising a kit container 1310 for the components to prepare a chemical or biological deeontaminant solution.
  • the kit container 1310 can be, but is not limited to, a suitcase, a box, or a bucket-type kit container.
  • the kit container 1310 can be opaque or transparent. If transparent, an end user is able to determine if the kit 1300 contains the exact components desired.
  • the kit can comprise at least at least one polar organic aanphipathic solvent Base Mix 1320, at least one dry or liquid activators or sources thereof. 1330 and 1340, and at least one liquid or dry reactive oxygen species, 1350.
  • the solvent can be a polar aprotic solvent, a polar-protic solvent, or combinations thereof. Further, the solvent can be a nitrilc, a ketone, an aldehyde, a carboxyiic acid, an amide, a furan, an aikanol or a polyol.
  • the volume fraction of water in decontaminant solution can range from about 25% to about 80% or from about 25% to about 75%, and the pH of the solution can be less than or equal to about 8.5.
  • the polar amphipathic solvents can be butanedioi, an isomer of butancdiol, l-hcxanol, a linear or branched-chain alcohol with 1 to 15 carbons, an n-aJcohol, a butoxy-aleohol, or a combination thereof.
  • the active oxygen species can be tetraacetylethylenediamine (TAED) or tetraacetylmethyienediamine (TAMD).
  • the pH can be maintained at less than or equal to about 8.0.
  • the invention is active against all agents a* pH values between about 7.0 to about 10.5; the buffer capacity is more effective at pU values between about 8.0 to about 9.0. However, for maximum active life, the preferred embodiment is maintained a pH values from about 8.0 to about 8.5.
  • the pH can further be maintained at a pH of about 8.5.
  • the at least one liquid or dry activator 1330, 1340 of the quaternary kit can comprise any peroxide or persulfate which is the source in the decontaminant solution of hydroxyl radicals, hydroxy! ions, super oxides, or other oxidizers, which pcrhydrolyzc the reactive oxygen species source.
  • the at least one reactive oxygen species 1350 can comprise peroxvaeetic acid or its source, a first activator 3330 that is a hydrogen peroxide activator and a second activator 1340 that comprises a buffer system, which includes, but is not limited to. carbonate or sodium hydroxide based buffer systems.
  • the kit of the invention can further comprise a block co-polymer, which would be pre-mixed with the base mix solvent 1320.
  • the block co-polymer can be ethylene oxide and propylene oxide co-polymer that terminates in primary hydroxy! groups.
  • the quaternary kit can also comprise a container 1360 for mixing the solution, the at least one solvent 1320, at least one dry or liquid activator or source thereof 1330, 1340, and at least one reactive oxygen species 1350, which can be combined together into a decontamination mixture, along with means for physically associating the decontamination mixture with the toxant.
  • the quarternary kit 1310 can use a wide variety of materials to store the components of the system, such as vessels made of, but not limited to, rneiai. clear glass, colored glass or plastic.
  • the means for physically associating the decontamination mixture with the toxant can comprise an applicator 1380 including, but not limited to, an aerosolization nozzle.
  • the kit container 1310 can comprise a handle 1370 for carrying the kit container with components.
  • Hie kit container 1310 can also comprise wheels for ease of transport (not shown). Further, the kit can comprise instructions for use 1390.
  • Example 11 The invention also relates to a binary kit 1400 comprising a kit container 1410 for the components to prepare a chemical or biological de-contaminant solution.
  • the kit container 1410 can be. but is not limited to, a suitcase, a box, or a bucket-type kit container.
  • the kit container 1410 can be, but is not limited to. a suitcase, a box. or a bucket-type kit container.
  • the kit container 14S0 can be opaque or transparent. If transparent, art end user is able to determine if the kit 1400 contains the exact components desired.
  • the kit is not limited to, a suitcase, a box, or a bucket-type kit container.
  • 14(K) can comprise: (i) a liquid Base Mix 1420, comprising at least at Ieasl one polar organic amphipathic solvent and a reactive oxygen species or ils source, and (ii) at least one dry or liquid activator or source thereof 1430,
  • the solvent(s) can be a polar aprotic solvent, a polar- protic solvent, or combinations thereof.
  • the solvenl(s) can be a nitrile, a ketone, an aldehyde, a carboxylie acid, an amide, a ftirans. an alkanol, or a polyoi.
  • the volume .Taction of water in decontaminant solution can range from about 25% to about 75%, and the pH of the solution can less than or equal to about 8.5.
  • the polar amphipathic solvents can be butanediol, an isomer of butanediol, a linear or branchcd-chain alcohol with i to 15 carbons, an n-alcohol. a buioxy-aleohoi, other polyols, or a combination thereof.
  • the active oxygen species can be tetraacctylethylenediamine (TAED) or tetraacetyhnethylenediamine (TAMD).
  • the at least one reactive oxygen species can comprise pcroxyacetie acid or its source.
  • the pH can be maintained at less than or equal to about 8.0.
  • the invention is active against all agents as pH values between about 7.0 to about 10.5; the buffer capacity is more effective at pH values between about 8.0 to about 9.0.
  • the preferred embodiment is maintained a pH values from about 8,0 to about 8.5.
  • the pH can further be maintained at a pH of about 8.5.
  • the least one liquid or dry activator 1430 of the binary kit can comprise any peroxide or source thereof which is the source in the decontaminant solution of hydroxy! radicals, hydroxyl ions, super oxides, and which pcrhydrolyze the reactive oxygen species source.
  • the binary kit can comprise a first activator 1430 (e.g., a hydrogen peroxide activator) and a second activator 1440 ⁇ eg,, a carbonate or sodium hydroxide based buffer system).
  • the kit of the invention can l ⁇ rther comprise a block co-polymer, which would be prc- mixed witli the Base Mix 1420. wherein the block co-polymer can be an ethylene oxide arid propylene oxide co-polymer that terminates in primary hydroxy] groups.
  • ' l"hc binary kit 1410 can use a wide variety of materials to store the components of the system, such as vessels made of, but not limited to, metal clear glass, colored glass, or plastic.
  • the binary kit can also comprise a mixing container 1440 or an automated system for simultaneous mixing and activation of the Base Mix 1420 containing at least one reactive ⁇ xygen species with the at least one dry' or liquid activator or source thereof 1430, which can be combined to create a decontamination mixture, along with means for physically associating the decontamination mixture with the toxant.
  • the means tor physically associating the decontamination mixture with the toxant can comprise an applicator 1480 including, but not limited to, an aerosoli/ation nozzle.
  • the kit container 1410 can comprise a handle 1450 for carrying the kit container with components. Further, the kit can comprise instructions for use
  • Example 12 ⁇ top view illustration of a system 15(K) for storing, transporting and dispersing the decontamination ami/or disinfection solutions easily and conveniently at sites that have been contaminated by chemical and/or biological agents or toxants is shown in Fig. 15.
  • System 1500 may be transported in or on the bed of a truck, airplane, tank, jeep or other military or governmental vehicle, or brought in via skid rails. Alternatively, the system may be permanently deployed in high risk areas.
  • This system 1500 may include frame 1501.
  • the frame 1501 houses a container including & binary base mix 1510, a container including an activator 1515, and a water inlet 1506.
  • the system 1500 further comprises a mixing pump 1535, a blender 1540, a system of pipes 152Oa, 152Ob, 352Oc, 152Od, 1520e, 1520f, 152Og, a system control panel or box 1555, a generator 1560, and an air compressor 1565.
  • the frame 1501 comprises inlets 151 1 and 1516.
  • the binary base mix container 1510 and the activator container 1515 are operably connected to the inlets 151 1 and 1516, respectively, via collars 1507, 1517, respectively.
  • Collars 1512, 1517 are standard pipe couplings that can either be permanent or quick release couplings.
  • outlet 1545 is an aerosolization nozzle system.
  • outlet 1545 can be a spigot (not shown).
  • the system 1500 optionally comprises a water container 1505 and/or an activated solution container 1550,
  • the activated solution container 1550 has an outlet (not shown), which can be a spigot or can be coupled to an aerosolization or fogging system (not shown).
  • system 1500 optionally includes a heater 1525 by which the water can be kept in the desired liquid state.
  • Each component of the system can be made from a wide variety of materials, including but not limited to, metals, plastics, and tempered glass.
  • the system of pipes 1520a, 1520b, 1520c, 1520d, 1520e, 1520f, ! 520g enable the materials Io flow through the system 15(X) and provide areas where the binary base mix, the activator and water arc mixed. Flow of these materials is controlled by valves 152Oa, 153Ob. 153Oc, 153Od, 153Oe, which are located along pipes 1520b, 1520c. 1520e, 1520f, ! 520g. respectively.
  • System i 500 includes a source of water 3505.
  • the water may be dcionized water, distilled water, or any other purified water.
  • system 1500 includes a hose (not shown) for connection, via water inlet 1506, with an external source of water.
  • Collar 1507 provides the point of attachment.
  • Collar 1507 is a standard pipe coupling that can either be a permanent or quick release coupling.
  • the water from the water source 1505 flows through pipe 1520b.
  • the water from the water source 1505 flows through pipe 1520b.
  • the activator container 1515 can contain a dried activator or a liquid activator, both of which are be added through pipe 1520a and mixed with the water from pipe 152Ob by the mixing pump 1535.
  • the mixing pump 1535 provides a vacuum which pulls the water and the activator through pipes 1520a. 152Ob. which results in mixing the two components together.
  • the binary base mix also flows into pipe 1520c, and mixes with the water and the activator via the vacuum provided by mixing pump 1535. Mixing of the components occurs immediately.
  • the decontamination solution flows through pipe 1520c, where the shear blender 1540 provides a final mixing of the decontamination solution to either a fully dissolved solution or a permanent suspension.
  • the decontamination solution is sent through the piping 152Oe. either through pipe 1520f to the optional activated solution container 1550, or through pipe 152Og through outlet 1545 for application to the chemical or biological warfare toxant for decontamination.
  • System 1500 also has a system control panel or box 1555, from which the system can be programmed and the decontamination/disinfection solution prepared.
  • 'Hie system conlrol panel 1555 can comprise sensors (not shown) which measure solution parameters, including pH.
  • the system control panel can be operated via buttons or levers.
  • an external computer (not shown) can be networked to system 15(K), for a backup control and/or override system.
  • the connections between the system panel 1555 and the other elements of the system 1500 are not shown to avoid obscuring the invention.
  • the system control panel 1555 controls the flow of the materials through the pipes 1520a, 152Ob, 1520c, 152Od, 1520c 152Of.
  • valve 1520g by opening or closing valves 152Oa, 1530b, 153Oc, 153Od, 153Oe.
  • These valves can be butterfly valves, or any valves that can be opened or closed to various levels to control the flow of materials.
  • the pH should be maintained at between about 8.0 and about 8.5. If the pH goes over about 8.5, the flow of the binary base mix is decreased by closing valve 1530b. If the pH is too low, valve 153Ob can be opened. Alternatively, the flow of water can be increased by opening valve 153Oa if the pH is too high, and closed if the pH drops.
  • System 1500 includes an air compressor 1565, which provide a pressure system for dispersing the activated decontamination/disinfection solution.
  • the air compressor can function in two ways. First, pressure can be applied onto the liquid in cither the optional activated container 1550 or through pipe 1520g to be aerosolized through outlet 1545.
  • the air compressor 1565 controls the application of the decontamination/disinfection solution to the toxant.
  • System 1500 also comprises a generator 1560 to provide power for the system to function.
  • Generator 1560 can be, but is not limited to, a diesel generator, an electric generator, or a natural gas generator.
  • Example 13 A schematic representation of one system 1600 tor preparing the base mix for transport to a site in need of decontamination is shown in Fig. 16.
  • the preparation of the base mix generally takes place in three stages. The first stage involves mixing water from a water source 1605 or a water storage tank 1608 with the polar organic amphipathk solvent from container 1615. The mixture is then stored in a stage 1 pre-base mix holding tank 1625. At the second stage, the block co-polymer and a buffer component are added from containers 1635, 1638. respectively. These components arc mixed in blender 1630 with die stage I pre-base mix and stored in a stage 2 pre-base mix holding tank 1645.
  • Stage 3 mixes the reactive oxygen species (ROS) from container 1660 with the stage 2 pre-base mix in a blender S 655.
  • the final base mix is then sent to a holding tank 1670,
  • the base mix is then sent to a base mix container 1680 and ultimately transported to a site in need of decontamination.
  • ROS reactive oxygen species
  • the water flows from the water source 1605 or a water holding tank 1608. through pipes 1610a, 1610b to a stage 1 pre-base mix holding tank 1625.
  • the amount of water from the water source 1605 or the water holding tank 1608 is controlled by a process metering pump 1609.
  • the polar organic amphipathic solvent flows from a drum or other container 1615 through pipe !61Oc, 161Od, into the stage 1 pre-base mix holding tank 1625.
  • the solvent addition is controlled by the process metering pump 1620.
  • the prc-ba.se mix is sent through pipe 161Oe to a blender 1630.
  • a buffer component for pH maintenance and chemical activation by the buffer system is added from the buffer component container 1638.
  • the buffer component can be, but is not limited to, sodium carbonate, sodium percarbonate, sodium perborate, urea peroxide, sodium peroxide, or combinations thereof.
  • a block co-polymer can be added from the block co-polymer container 1635. While these two components can be added as a powder, they can also be added as pre-dissolvcd liquids.
  • the stage 2 pre-base mix After mixing with the buffer component and. optionally, the block co-polymer, the stage 2 pre-base mix then flows through pipe 16!Of to the stage 2 pre-base mix holding tank 1645.
  • the solution is re-circulated for optimum mixing by a recirculation pump 1640 through pipes 161Og. 161Oh.
  • the reactive oxygen species is added from the ROS container 1635 and mixed with the pre-base mix.
  • 'Hie ROS can be in either liquid or dry form.
  • the ROS is mixed with the pre-base mix in a blender 1655, and then flows through pipe 161 Oj to a base mix holding tank 1670. Additional mixing is provided by shear pump 1675 in pipe 1610k. Alternatively, the positions of the shear pump 1675 and the recirculation pump 1640 can be reversal (not .shown).
  • -Hie base mix then flows through pipe 36101 and into base mix container 1680 for transport to the decontamination site.
  • Flow through the system can be controlled by a series of valves 1650a, 1650b, 1650c, depending upon the stage of mixing, if necessary, base mix can also be dispensed through spigot 1685.
  • the base mix container be dispensed via a pump and pipe system (not shown).
  • Each component of the system can be made from a wide variety of materials, including but not limited to, metals, plasties, and tempered glass.
  • Example 14 One embodiment of a process for preparing the base mix for transport to a decontamination site, as shown in Fig. 17.
  • distilled water 1705 and the polar organic amphipathic solvent 1710 are mixed to form a stage 1 pre-base mix 1715.
  • buffer component 1723 and, optionally, the block co-polymer 1720 arc mixed with the stage 1 pre-basc mix to form a stage 2 pre-base mix 1725.
  • the reactive oxygen species 1730 is added to the stage 2 pre-base mix 1725, in either liquid or dry form 1730 is then added to form a stage 3 base mix 1740.
  • the base mix 1740 is then transferred to the desired number of totes or containers 1745, which can be transported in or on a wide variety of vehicles Io the site requiring decontamination.
  • the first step is generally completed in about one hour.
  • the second step is also completed in about one hour.
  • the third step and transfer to transport containers 1745 takes about 2 hours. Further, production of the base mix can be performed in cycles, so that the process has a continuous flow.
  • Example 15 A schematic representation of one system 1800 for preparing the activator for transport to a site in need of decontamination is shown in Fig. 18.
  • System 1800 comprises a water source 1805 and a peroxide source ! in a container 1815.
  • System 1800 optionally includes peroxide source 2 in container 1825.
  • the water from the water source 1805, the peroxide source 1 are mixed and sent to an activator holding tank.
  • Peroxide source 2 can be added at the same time as peroxide source 1.
  • the mixed activator is then sent to an activator container for transport to the site of decontamination,
  • the water source 1805 is operably connected to the activator holding tank 1835 by pipe 1810a.
  • the flow can be controlled by gravity, siphoning, or a pump (not shown).
  • Peroxide source 1 is drawn from container 1815 through pipe 1810b by a pump 1820, and then the peroxide source Hows through pipe 1810c to the activator holding tank 1835. If peroxide source 2 is used, this is drawn from container 1825 through pipe 181Od by pump 1830. The peroxide source 2 then flows to the activator holding tank. After mixing in the activator holding tank 1835, the activator mix can be pumped by pump 1840 through pipes 18101 * 181Og and into the activator container 1845.
  • the activator can be dispensed if necessary through spigot 1850 or via piping and a pump (not shown).
  • the peroxide source can be, but is not limited to, a hydrogen peroxide solution and/or a peroxyacetic acid solution.
  • Each component of the system can be made from a wide variety of materials, including but not limited to, metals, plastics, and tempered glass.
  • Example 36 One embodiment of a process for preparing the activator mix, For transport to a decontamination site, as shown in Fig. 19.
  • water 1905, the first peroxide source 1910, and the optional second peroxide source 1915 are mixed to form the activator 1920.
  • the activator 1920 is then transferred to the desired number of totes or containers 1925, which can be transported in or on a wide variety of vehicles to the site requiring decontamination.
  • the preparation of the activator mix generally takes about one hour for mixing and about one hour to transfer to the totes 1925 tor transport to the site of decontamination. This process can be run in cycles, an described above for the base mix preparation.

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  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)

Abstract

La présente invention porte de façon générale sur des solutions de décontamination chimique et biologique et sur des procédés pour leur utilisation. L'invention est utile pour décontaminer et/ou désinfecter une large gamme de composés et d'organismes. En particulier, les systèmes, procédés, solutions et formulations selon l'invention peuvent être utilisés pour retirer et/ou neutraliser des organophosphates, des agents moutarde, et d'autres produits chimiques toxiques, des bactéries, des spores de bactérie, des champignons, des moisissures et des virus.
PCT/US2009/063840 2008-11-20 2009-11-10 Nouvelles chimies, solutions et systèmes de dispersion pour la décontamination de systèmes chimiques et biologiques WO2010059459A1 (fr)

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US12/567,604 US20100179368A1 (en) 2008-11-07 2009-09-25 Novel Chemistries, Solutions, and Dispersal Systems for Decontamination of Chemical and Biological Systems
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