U.S. patent application number 15/272208 was filed with the patent office on 2017-03-16 for method and formulation for neutralizing toxic chemicals and materials.
The applicant listed for this patent is Emergent Protective Products Canada ULC. Invention is credited to Timothy G. Henry, Barbara B. Price.
Application Number | 20170072239 15/272208 |
Document ID | / |
Family ID | 40512136 |
Filed Date | 2017-03-16 |
United States Patent
Application |
20170072239 |
Kind Code |
A1 |
Henry; Timothy G. ; et
al. |
March 16, 2017 |
Method and Formulation for Neutralizing Toxic Chemicals and
Materials
Abstract
The present invention is directed to a formulation and
associated method for neutralizing one or more toxic chemical
and/or materials including toxic industrial chemicals and toxic
industrial materials, such as irritants, heavy metals, radioactive
metals, acids and acid irritants, pesticides, and various
agricultural chemicals, (collectively referred to as toxic
chemical, materials, or simply toxins) as well as decontaminating
surfaces that have come into contact with these agents. As a
result, the formulation of the present invention can be used for
neutralizing a broad spectrum of toxic chemicals and materials. In
one embodiment, the active ingredient comprises 2,3, butanedione
monoxime (also known as diacetyl monoxime (DAM)), and alkali salts
thereof such as potassium 2,3-butanedione monoxime (KBDO). The
formulation also typically includes a carrier in which the active
ingredient is dispersed. In one embodiment, the carrier comprises
polyethylene glycol (PEG); monomethoxypolyethylene glycol (mPEG);
and combinations and derivatives thereof.
Inventors: |
Henry; Timothy G.;
(Princeton, NJ) ; Price; Barbara B.; (Kane'ohe,
HI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Emergent Protective Products Canada ULC |
Montreal |
|
CA |
|
|
Family ID: |
40512136 |
Appl. No.: |
15/272208 |
Filed: |
September 21, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13920416 |
Jun 18, 2013 |
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15272208 |
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13284465 |
Oct 28, 2011 |
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13920416 |
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12840625 |
Jul 21, 2010 |
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13284465 |
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12017749 |
Jan 22, 2008 |
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12840625 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A62D 3/33 20130101; A62D
2101/26 20130101; A61P 39/04 20180101; A62D 2101/45 20130101; A62D
2101/49 20130101; A62D 3/36 20130101; A61P 39/02 20180101; A62D
2101/04 20130101; A62D 2101/28 20130101; A62D 2101/47 20130101;
A61Q 17/00 20130101; A61K 8/40 20130101; A61P 17/00 20180101; A62D
2101/43 20130101; A62D 2101/02 20130101; A62D 2101/22 20130101;
A62D 3/30 20130101; A62D 2101/24 20130101 |
International
Class: |
A62D 3/33 20060101
A62D003/33; A62D 3/30 20060101 A62D003/30; A62D 3/36 20060101
A62D003/36 |
Claims
1. A method for neutralizing a broad spectrum of toxic industrial
chemicals and materials, the method comprising the steps of
applying a composition having an active ingredient to a toxic
industrial chemical or material to thereby neutralize said toxic
industrial chemical or and material, wherein the active ingredient
comprises one or more of 2,3-butanedione monoxime, an alkali salt
thereof, and an alkaline earth salt thereof, or a derivative
thereof, wherein the toxic industrial chemical or material is
selected from one or more of 1,1'-bi(ethylene oxide),
acrylonitriles, allyl alcohols, allyl chlorides, methyl mercaptan,
sulfuric acid (H.sub.2SO.sub.4), hydrochloric acid (HCl),
hydrofluoric acid (HF), perchloric acid (HClO.sub.4), hydrobromic
acid (HBr), hydroiodic acid (HI), nitric acid (HNO.sub.3), nitrous
acid (HNO.sub.2), acetic acid, hydrogen selenide, hydrogen sulfide
(H.sub.2S), acid byproducts of nitrogen dioxide (NO.sub.2),
phosphoric acids, acetic anhydride, maleic anhydride, mixed
anhydrides, fluoroacetic acid, chloroacetic acid, and
hydrazine.
2. (canceled)
3. The method of claim 1, wherein the toxic industrial chemical or
material is selected from the group consisting of 1,1'-bi(ethylene
oxide), acrylonitriles, allyl alcohols, allyl chlorides, and methyl
mercaptan.
4. (canceled)
5. The method of claim 1, wherein the toxic industrial chemical or
material is selected from the group consisting of sulfuric acid
(H.sub.2SO.sub.4), hydrochloric acid (HCl), hydrofluoric acid (HF),
perchloric acid (HClO.sub.4), hydrobromic acid (HBr), hydroiodic
acid (HI), nitric acid (HNO.sub.3), nitrous acid (HNO.sub.2),
acetic acid, hydrogen selenide, hydrogen sulfide (H.sub.2S), acid
byproducts of nitrogen dioxide (NO.sub.2), phosphoric acids, acetic
anhydride maleic anhydride, mixed anhydrides, fluoroacetic acid,
and chloroacetic acid.
6. The method of claim 1, wherein the active ingredient is
dispersed in a carrier that is selected from the group consisting
of polyethylene glycol, monomethoxypolyethylene glycol, and
polyethylene glycol ether.
7. The method of claim 1, wherein the toxic industrial chemical or
material is hydrazine.
8. The method of claim 1, wherein the composition containing the
active ingredient is applied in an amount ranging from about 1:1 to
20:1 based on the amount of toxic industrial chemical or
material.
9. (canceled)
10. The method of claim 1, wherein the step of neutralizing said
toxic industrial chemical or material comprise sequestering said
toxic industrial chemical or material.
11-15. (canceled)
16. A method of neutralizing a broad spectrum of pesticides, the
method comprising: reacting a composition having an active
ingredient with a pesticide to thereby neutralize said pesticide,
wherein the active ingredient comprises one or more of
2,3-butanedione monoxime, an alkali salt thereof, and an alkaline
earth salt thereof, and wherein the pesticide is selected from the
group consisting of carbamates, organochlorine, and pyrethroids,
wherein the carbamate is selected from the group consisting of
2-methyl-2-(methylthio)propionaldehyde O-methylcarbamoyloxime,
2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate,
3-hydroxycarbofuran, ethyl N-[2-(4-phenoxyphenoxy)ethyl]carbamate,
ethienocarb, aldicarb sulfone, aldicarb sulfoxide, butylate,
S-ethyl dipropylthiocarbamate, methiocarb, methomyl, molinate,
oxamyl, pebulate, propham, propoxur, thiobencarb, triallate, and
2-(1-methylpropyl)phenyl N-methylcarbamate.
17. The method of claim 16, wherein the pesticide includes a
carbamate selected from the group consisting of
2-methyl-2-(methylthio)propionaldehyde O-methylcarbamoyloxime,
2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate,
3-hydroxycarbofuran; ethyl N-[2-(4-phenoxyphenoxy)ethyl]carbamate,
ethienocarb, aldicarb sulfone, aldicarb sulfoxide, butylate,
S-ethyl dipropylthiocarbamate, methiocarb, methomyl, molinate,
oxamyl, pebulate, propham, propoxur, thiobencarb, triallate, and
2-(1-methylpropyl)phenyl N-methylcarbamate.
18. The method of claim 16, wherein the composition is applied to
the skin of a person in need thereof.
19. The method of claim 16, wherein the composition is a cream, a
gel, or a lotion.
20. The method of claim 16, wherein the active ingredient is
dispersed in a carrier and wherein the method further comprises
reacting the carrier with the pesticide to thereby sequester the
pesticide.
21. The method of claim 16, wherein the active ingredient is
2,3-butanedione monoxime or an alkali salt thereof, or a
combination thereof.
22. The method of claim 21, wherein the active ingredient comprises
potassium 2,3-butanedione monoxime.
23. The method of claim 16, wherein the composition further
comprises a carrier in which the active ingredient is
dispersed.
24. The method of claim 23, wherein the active ingredient is
dispersed in a carrier that is selected from the group consisting
of polyethylene glycol, monomethoxypolyethylene glycol, and
polyethylene glycol ether.
25. The method of claim 16, wherein the composition containing the
active ingredient is applied in an amount ranging from about 1:1 to
20:1 based on the amount of the pesticide.
26. The method of claim 16, wherein the composition is for use in
1) protecting a skin surface prior to or after exposure to the
pesticide, or 2) decontaminating a surface after exposure to the
pesticide.
27. The method of claim 1, wherein the active ingredient is
2,3-butanedione monoxime or an alkali salt thereof, or a
combination thereof.
28. The method of claim 27, wherein the active ingredient comprises
potassium 2,3-butanedione monoxime.
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation of U.S. application Ser.
No. 13/284,465, filed Oct. 28, 2011, which is a continuation of
U.S. application Ser. No. 12/840,625, filed Jul. 21, 2010, which is
a divisional application of U.S. application Ser. No. 12/017,749,
filed Jan. 22, 2008, the entire disclosure of which is hereby
incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates generally to formulations and
methods for neutralizing chemical agents, and more particularly, to
formulations and methods for neutralizing a broad spectrum of
chemical agents.
BACKGROUND OF THE INVENTION
[0003] The risk of exposure to various chemical and biological
agents is an ever increasing concern for military personnel as well
as civilians. This concern, is particularly heightened in view of
recent terrorist attacks. In particular, terrorist threats
involving such agents are increasing in the United States as well
as abroad. In response to this threat, various countermeasures have
been developed that are capable of neutralizing certain chemical
weapon agents. For example, so called nerve agents, such as sarin,
soman, and tabun are examples of phosphorous containing compounds
which can be altered chemically to remove their toxicity. Since
many of these compounds share a common or similar chemical moiety,
a single chemical countermeasure can be used to neutralize many of
them.
[0004] In addition to chemical and biological agents, there also
exists a wide variety of contaminants such as toxic industrial
chemicals (TIC's) and toxic industrial materials (TIM's) that raise
concerns over public safety. Such contaminants include industrial
chemicals, pesticides, and herbicides and other materials that may
be released in the environment during normal processing, disposal,
waste handling, or accidental discharge. Generally, such
contaminates comprise a broad spectrum of chemical compositions
that are not readily neutralized or destroyed with a single
chemical countermeasure. As a result, exposure to such contaminants
requires that an appropriate countermeasure be selected in order to
effectively neutralize the contaminant. Further, many
countermeasures are only effective if they are applied prior to an
exposure and are unable to effectively neutralize contaminants
after a person has been exposed.
[0005] The problems with selecting an appropriate countermeasure
are of particular concern in environments where a wide variety of
toxic chemicals/materials are being used. For example, many modern
factories use a wide variety of different chemicals and substances
in their every day operation and processes. As a result, there
exists a wide variety of different toxic chemical/materials to
which personnel within the factory may be exposed. Since exposure
to many of these chemicals/materials can result in severe injuries
to the exposed workers, and in some cases death, there is a need to
provide countermeasures that can be used to effectively treat
individuals after exposure.
[0006] Unfortunately, this creates problems with respect to the
feasibility of maintaining an adequate number of the appropriate
countermeasures, as well as problems associated with educating
personnel on selecting the appropriate countermeasure. Such
problems can be heightened in emergency situations after an
exposure has occurred. As a result, it may be difficult to find and
apply the appropriate countermeasure in a timely fashion, which can
result in prolonged exposure and an increase in the severity of the
injury. Further, many chemical countermeasures, such as chemical
disinfectants like hypochlorite solutions are useful but are
corrosive to most metals and fabrics, and to human skin.
Liquid-like foam disinfectants have also been used, and generally
require water and pressurized gases for efficient application. As
such, they are typically not practical under many
circumstances.
[0007] In addition to factories, such problems can also be
experienced in many households across the country. For example, the
typical kitchen sink cabinet may include many different
chemical/materials ranging from household cleaning products to
pesticides. Similar to the chemicals/materials that may be found in
a typical factory, exposure to household chemicals can also result
in severe injury. However, most households today do not even
include the most basic of countermeasures, and as a consequence,
water is often the first choice in an attempt to cleanse exposed
skin or surfaces. Since many chemical/materials do not react or are
insoluble in water, the use of water can further exacerbate the
exposure and severity of the injury by spreading the chemical
materials around and thereby increasing the area of contact with
the toxic chemical/material.
[0008] In addition to chemical countermeasures, physical
decontamination methods can also be used to neutralize many toxic
chemical/materials. Physical decontamination usually involves dry
heat for an extended period of time or steam or super-heated steam
for about 20 minutes. In some cases, UV light can be used
effectively, but it is generally difficult to implement in actual
practice. Such physical decontamination methods cannot be used in
the case of exposure to human skin, and are often impractical to
use under many circumstances. Accordingly, there still exists a
need for effective countermeasures that can be used to neutralize
many of the toxic chemical/materials that may be encountered in
factories, as well as in the home.
BRIEF SUMMARY OF THE INVENTION
[0009] In one alternative embodiment, the present invention is
directed to a formulation and associated method for neutralizing
toxic chemicals and materials, and a broad spectrum of toxic
chemical and/or materials including, but not limited to, toxic
industrial chemicals and toxic industrial materials, such as, for
example, irritants, heavy metals, radioactive metals, acids and
acid irritants, pesticides, and various agricultural chemicals,
(collectively referred to as toxic chemical, materials, or simply
toxins) as well as decontaminating surfaces that have come into
contact with these agents. As a result, the formulation of the
present invention can be used for neutralizing a wide variety of
toxic chemicals and materials.
[0010] In particular, the present invention comprises a formulation
having one or more active moieties that are capable of neutralizing
one or more chemical agents including, but not limited to, acids,
toxic industrial chemicals, toxic industrial materials, metal ions,
and pesticides. In one embodiment, the formulation may include an
active ingredient having a nitrogen oxime moiety and a carbonyl
moiety that is capable of neutralizing a variety of toxins via a
nucleophilic or electrophilic attack. In one embodiment, the active
ingredient comprises 2,3, butanedione monoxime (also known as
diacetyl monoxime (DAM)), and alkali salts thereof such as
potassium 2,3-butanedione monoxime (KBDO). The formulation may also
include a carrier in which the active ingredient is dispersed. In
one embodiment, the carrier may comprise polyethylene glycol (PEG);
monomethoxypolyethylene glycol (mPEG); and combinations and
derivatives thereof.
[0011] In one embodiment, the formulation of the present invention
can be used to neutralize a wide variety of toxic industrial
chemical and materials. In one such embodiment, DAM and its salts,
such as KBDO, include three potentially nucleophilic atoms that are
capable of nucleophilic attack on reactive moieties on the targeted
chemical. For example, the structure of DAM includes three
nucleophilic atoms: the carbonyl oxygen, the oxime nitrogen and, to
a lesser extent, the oxime oxygen. The nucleophilic atoms are
capable of attacking and neutralizing a wide variety of toxic
chemicals. In addition to neutralizing toxins that are susceptible
to nucleophilic attack, DAM and KBDO can be used to neutralize acid
toxins as well. In some embodiments, DAM and KBDO can also be used
to chelate metal ions and thereby can be used to effectively remove
and neutralize the metal ions. In yet a further embodiment, the DAM
and KBDO may be present in a carrier, such as PEG or mPEG, that is
capable of solubilizing and neutralizing various TICs and TIMs.
[0012] In yet another embodiment, the present invention can be used
to neutralize many acids and acid anhydrides that may be
encountered in a manufacturing or production environment, such as,
for example, sulfuric acid (H.sub.2SO.sub.4), hydrochloric acid
(HCl), hydrofluoric acid (HF), perchloric acid (HClO4), hydrobromic
acid (HBr), hydroiodic acid (HI), nitric acid (HNO.sub.3), nitrous
acid (HNO.sub.2), acetic acid, arsine (AsH.sub.3), hydrogen
selenide, hydrogen sulfide (H.sub.2S), acid byproducts of nitrogen
dioxide (NO.sub.2), (sulfur dioxide (SO.sub.2), maleic anhydride,
acetic anhydride, mixed anhydrides, and any salt, ester or
derivative thereof, or any combination thereof, and the like.
[0013] In addition to neutralizing acids, the formulation may also
be used to neutralize a wide variety of irritants that are commonly
used in many industrial circumstances. For example, may toxic
industrial or toxic materials include one or more reactive moieties
that are susceptible of nucleophilic attack by one or more of the
nucleophilic atoms of DAM. Such toxins may include, without
limitation, 1,1'-bi(ethylene oxide), acrylonitriles, allyl
alcohols, allyl chlorides, methyl mercaptan, phosgene, hydrazine,
and the like, and any salt, ester or derivative thereof or any
combination thereof.
[0014] In one embodiment, the formulation of the present invention
may be capable of neutralizing toxins that are soluble in glycols
such as hydrazine, phosphine, and toluene diisocyanates (mixed
isomers). The present invention may also be used to neutralize some
oxidizing and corrosive toxins.
[0015] In one alternative embodiment, the present invention is
directed to a method for neutralizing a broad spectrum of toxic
industrial chemicals and materials in which a composition having an
active ingredient is applied to a toxic Industrial chemical or
material to thereby neutralize the toxic industrial chemical or and
material. In one embodiment, the active ingredient comprises 2,3,
butanedione monoxime or an alkali salt thereof.
[0016] In one alternative embodiment, the formulation of the
present invention can be used to neutralize various metals and
radionuclides, such as heavy metals, lead, transition metals,
radioactive metals, Pu, Th, U, Zr, Nb, Ru, actinides, lanthanides,
rare earth elements and combinations thereof, for example, via a
chelating or ring forming reaction. In this embodiment, the DAM
acts as a chelating agent to form a chelate complex in which the
metal is bound to two or more atoms of the chelating agent. In one
embodiment, DAM is capable of chelating with metal ions to form a
live to seven member ring.
[0017] In one alternative embodiment, the present invention
provides a method for neutralizing or sequestering metal atoms in
which a composition having at least one nucleophilic carbonyl
moiety and at least one nucleophilic oxine nitrogen moiety is
reacted with a metal. Reaction of the composition and the metal
chelates the metal to form a ring structure in which the at least
one nucleophilic carbonyl moiety and at least one nucleophilic
oxime nitrogen moiety are bonded to the metal.
[0018] In one alternative embodiment, the formulation of the
present invention may also be used to neutralize a wide variety of
pesticides. In one embodiment, formulations of the present
invention can be used to neutralize pesticides containing
organophosphates (OPs), pyrethroids (SP), carboxy moieties, and
carbamates, or any combination thereof. In one embodiment a first
DAM molecule reacts with a pesticide containing OP to produce a
phosphorylated oxime. In a subsequent reaction, a second DAM
molecule then reacts with the phosphonylated oxime to produce a
non-toxic substituted phosphonic acid. In one embodiment, OPs
pesticides that can be neutralized with DAM include, but are not
limited to, azinphos-methyl, chlorpyrifos, diazinon, disulfoton,
ethoprop, fonofos, malathion, methyl parathion, parathion, phorate,
and terbufos.
[0019] In a further embodiment, the formulation of the present
invention may also be used to neutralize pesticides containing
carbamates, such as 2-methyl-2-(methylthlo)propionaldehyde
O-methylcarbamoyloxime (Aldicarb);
2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate
(carbofurna, furadan, or curator); 3-hydroxycarbofuran; ethyl
N-[2-(4-phenoxyphenoxy)ethyl]carbarnate (fenoxycarb); 1-naphthyl
methylcarbamate (carbaryl also known under the tradename Sevin),
ethienocarb, examples: 3-hydroxycarbofuran, aldicarb sulfone,
aldicarb sulfoxide, butylate, S-ethyl dipropylthiocarbamate (EPTC),
methiocarb, methomyl, molinate, oxamyl, pebulate, propham,
propoxur, thiobencarb, triallate, and 2-(1-methylpropyl)phenyl
N-Methylcarbamate.
[0020] In one alternative embodiment, the present invention is
directed to a method of neutralizing a broad spectrum of
pesticides, such as organophosphates, carbamates, organochlorine,
and pyrethroids, in which a composition containing 2,3, butanedione
monoxime or an alkali salt thereof is reacted with a pesticide to
thereby neutralize the pesticide.
[0021] In one embodiment, the composition containing the active
ingredient is applied in an amount that ranges from about 1:1 to
20:1 to the amount of pesticide to which a person or surface has
been exposed. In some embodiments, the amount may range from about
2:1 to 15:1, and in particular from about 5:1 to 10:1. Following
treatment of the toxin with the active ingredient, water may be
used to remove any residual of the toxin and formulation from a
suffice or skin of a person that has been treated.
[0022] In one embodiment, the formulation can be provided as a
topical skin protectant (TSP), such as a lotion or cream, that can
be applied to human skin prior to, or after exposure to toxic
chemicals or materials. In some embodiments, the formulation can be
provided in the form of a liquid, gel, powder, emulsion, foam,
spray, and the like. In one embodiment, the formulation can be used
to decontaminate surfaces that have been exposed to toxic chemicals
or materials, including but not limited to metal surface, stone
surfaces, and plastic surfaces.
DETAILED DESCRIPTION OF THE INVENTION
[0023] The present invention now will be described more fully
hereinafter with reference to the accompanying drawings, in which
some, but not all embodiments of the inventions are shown. Indeed,
these inventions may be embodied in many different forms and should
not be construed as limited to the embodiments set forth herein;
rather, these embodiments are provided so that this disclosure will
satisfy applicable legal requirements. Like numbers refer to like
elements throughout.
[0024] In one embodiment of the invention, the formulation provides
one or more decontaminants that can be used to neutralize a broad
spectrum of toxic chemicals and materials. In the context of the
present invention, the term "neutralization" includes the
detoxification, decontamination, mitigation, or otherwise
substantial destruction of toxins so that they reduce the acute
adverse effects in humans or animals. Methods of neutralization
include, but are not limited to, nucleophilic attack, electrophilic
attack, chelating reactions, acid-base reactions, solubilization,
sequestration, and combinations thereof.
[0025] In one embodiment, the formulation includes an active
ingredient having a nitrogen oxime moiety and a carbonyl moiety
that is capable of neutralizing a variety of toxins via a
nucleophilic or electrophilic attack. In another embodiment the
active ingredient includes a nitrogen oxime moiety and a carbonyl
moiety. In yet another embodiment, the active ingredient comprises
2, 3, butanedione monoxime, also known as diacetyl monoxime (DAM),
and salts thereof inducing, but not limited to, alkali salts such
as potassium 2,3-butanedione monoxime (KBDO) and sodium
2,3-butanedione monoxime, and alkaline earth salts such as calcium
2,3-butanedione monoxime The structure of DAM is illustrated by
formula (1) below.
##STR00001##
In one alternative embodiment, additional oximes that may be used
in the practice of the invention include derivatives of DAM in
which the alkyl group of DAM includes four to six carbon atoms. For
example, in one embodiment, the active ingredient may include one
or more of 2,3 pentandione monoxime, 3,4 pentandione monoxime, 3,4
hexanone monoxime, 2,3 hexananone monoxime and 4,5 hexanone
monoxime (alternate names may include 2,3. pentanedione 3-oxime
(CAS 609-29-0) 2 oximo pentane-3-one, 3, loom pentane -4-one,
2,3-Pentanedione, 3-oxime, 2,4-Pentanedione oxime,
Pentane-2,3-dione 2-oxime, 2,3,4-Pentanetrione, 3-oxime,
2,4-Pentanedione, dioxime, 2,4-Pentanedione, 2,4-dioxime, and
combinations thereof. Unless otherwise stated, the reference to DAM
herein includes diacetyl monoxime, 2,3-butanedione monoxime, salts
thereof, as well as derivatives thereof. When the formulation is
applied to a susceptible toxin, one or more of the reactive
moieties reacts with the targeted toxin to thereby neutralize the
toxin. In one embodiment, the toxin is at least substantially
decomposed into end products that can be removed with water or by
other means.
[0026] In one embodiment, the formulations of the present invention
can be delivered and applied to the toxins in a variety of manners
and phases to provide the necessary detoxification and
decontamination. For example, the formulation can be in the form of
a topical skin protectant (TSP), such as a lotion or cream, a
liquid solution or suspension, a foam, and the like. In one
alternative embodiment, formulations of the present invention may
be in the form of a gel or coating. Gels and coatings suitable for
the present invention are generally known in the art.
[0027] As discussed in greater detail below, an alternative
embodiment of the present invention may generally comprise an
activated solution or product that can be applied to a surface or
skin of an individual in need thereof, or dispersed into the air to
neutralize or other wise detoxify one or more toxic
chemicals/materials.
[0028] In one embodiment, the formulation may generally include one
or more active ingredients that are capable of binding, absorbing,
solubilizing, or otherwise neutralizing a targeted chemical
compound. The formulation may also typically include a carrier in
which the active ingredient is dispersed. In one embodiment, the
carrier comprises polyethylene glycol (PEG);
monomethoxypolyethylene glycol(mPEG); and combinations and
derivatives thereof. In one embodiment, the active ingredient may
be dispersed in a base comprising a macrocycle chosen from
1,4,7,10,13,16-hexaoxacyclooctadecane and
4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane together
with a carrier chosen from dioxolane, tetraglyme, dimethoxyethane,
a polyethylene glycol, or a polyethylene glycol mono- or di-ether.
In another embodiment, the formulation may also include water or
other solvent in amounts sufficient to ensure dissolution of the
active ingredient in the base.
[0029] In one alternative embodiment, the base contains
substantially equal amounts of the macrocycle and of the active
ingredient. The amount of water or solvent present in the
formulation is generally dependent on the desired end use of the
formulation. For example, in creams and similar applications, the
amount of water included may be small, such as less than about 5%
of the base. In other embodiments, it may be desirable that the
amount of water present be kept to a minimum as otherwise unwanted
side reactions between the active ingredient and the water or
solvent may occur. In some embodiments, the formulation w111
contain 110 water or solvent at all.
[0030] As discussed above, the formulation may include a carrier,
such as polyethylene glycol, monomethoxypolyethylene glycol, or
polyethylene glycol ether. These compounds have the formula
R--O--CH.sub.2CH.sub.2O).sub.nCH.sub.2CH.sub.2OR in which either R
may be hydrogen or an alkyl group, including but not limited to
methyl or ethyl, and "a" indicates the chain length. In one
alternative embodiment, "n" can have a range of values. Generally,
as "a" increases, the compound becomes more viscous. For example,
in cream applications it may be desirable for the formulation to be
relatively thick and viscous, and therefore it may be desirable to
include a thickening agent. Generally, at value of "n" that
represents a molecular weight of 1500 no thickening agent may be
needed for the formulation to be in the form of a cream. In one
embodiment, at least one of the R groups, and most preferably both,
are other than hydrogen, and are typically methyl or ethyl.
[0031] In one embodiment, the formulation may be in the form of oil
in water or water in oil emulsions. Other components of such
emulsions may include emulsifying agents and oils conventionally
used in barrier creams or lotion type formulations such as mineral
or silicone oils.
[0032] In some embodiments, the formulation may also include one or
more additional additives, such as surfactants, moisturizers,
fragrances, fillers, coloring agents, emulsifiers, thickening
agents, and the like provided the additives are inert to the active
ingredient. In one alternative embodiment, the formulation may
include a pharmaceutically acceptable inert solid as a thickener,
which is also inert toward the active ingredient. Typical usable
solids may include silicas, titania, fuller's earth, clays,
bentonite and the like.
[0033] Neutralization of Toxic Industrial Chemicals and
Materials
[0034] In one embodiment, formulations of the present invention can
be used to neutralize a wide variety of toxic industrial chemical
and materials, commonly referred to as TICS and TIMS, respectively.
Many TICS and TIMS may include acids and skin irritants that can
cause burning and irritation to the skin. In one embodiment, the
formulation of the present invention may be used to neutralize
and/or mitigate the harmful effects of these various toxins and
thereby help ameliorate burns and skin irritations that may result
from exposure thereto. In some embodiments, the formulation of the
present invention may also be formulated to be applied to surfaces
that have been exposed to TICS and TIMS. TICS and TIMS may include
chemical materials found in manufacturing, production, and
maintenance facilities and do not necessarily include chemical
warfare agents such as, for example, vesicants (e.g., mustard gas)
and nerve gas.
[0035] DAM and its salts, such as KBDO, include three potentially
nucleophilic atoms that are capable of nucleophilic attack on
reactive moieties on the targeted chemical. For example, the
structure of DAM includes three nucleophilic atoms: the carbonyl
oxygen, the oxime nitrogen and, to a lesser extent, the oxime
oxygen. The nucleophilic atoms are capable of attacking and
neutralizing a wide variety of toxic chemicals. In addition to
neutralizing toxins that are susceptible to nucleophilic attack,
DAM and KBDO can be used to neutralize acid toxins as well. In some
embodiments, DAM and KBDO can also be used to chelate metal ions
and as a result can be used to effectively remove and neutralize
various metal ions. In yet a further embodiment, the DAM and KBDO
may be present in a carrier, such as PEG or mPEG, that is capable
of solubilizing and neutralizing various TICs and TIMs.
[0036] In some embodiments, formulations in accordance with the
present invention can be used to neutralize many acids and acid
anhydrides that may be encountered in the work place. Such acids
may include, without limitation, sulfuric acid (H.sub.2SO.sub.4),
hydrochloric acid (HCl), hydrofluoric acid (HF), perchloric acid
(HClO4), hydrobromic acid (HBr), hydroiodic acid (HI), nitric acid
(HNO.sub.3), nitrous acid (HNO.sub.2), acetic acid, arsine
(AsH.sub.3), hydrogen selenide, hydrogen sulfide (H.sub.2S), acid
byproducts of nitrogen dioxide (NO.sub.2), sulfur dioxide
(SO.sub.2), fluoroacetic acid, chloroacetic acid, malonic acid,
formic acid, phosphoric acids, acid anhydrides such as maleic
anhydride, acetic anhydride, and the like. In this embodiment, the
active ingredient (e.g., DAM) and its salt KBDO are basic and are
capable of reacting with acids to thereby neutralize them. In some
cases, workers exposed to an acid have attempted to remove the acid
by applying water, which only exacerbates the situation. In the
present invention, the formulation can be applied to the skin in
order to quickly neutralize the acid component and thereby help
prevent further injury to the worker.
[0037] In addition to neutralizing acids, the formulation may also
be used to neutralize a wide variety of irritants that are commonly
used in many industrial circumstances. For example, many toxic
industrial chemicals or toxic industrial materials include one or
more reactive moieties that are susceptible of nucleophilic attack
by one or more of the nucleophilic atoms of DAM. Typical reactive
moieties that are susceptible to nucleophilic attack may include,
carbonyls, allyls, epoxides, amides, nitriles, acid anhydrides, and
the like. Such toxins may include, without limitation,
1,1'-bi(ethylene oxide), acrylonitriles, allyl alcohols, allyl
chlorides, methyl mercaptan, acetic anhydride, fluoroacetic acid,
and the like. In one embodiment, the formulation of the present
invention may also be used to neutralize phosgene via a
nucleophilic attack by one or more of the nucleophilic atoms of
DAM.
[0038] In one alternative embodiment, formulations of the present
invention can also be used to neutralize toxins that are soluble in
alcohols, such as glycols. In this embodiment, the active
ingredient is typically present in a glycol based carrier such as
PEG or mPEG. In this embodiment, the carrier is capable of
solubilizing and thereby neutralizing the toxin. In one embodiment,
the formulation of the present invention may be capable of
neutralizing toxins such as hydrazine, phosphine, and toluene
diisocyanates (mixed isomers).
[0039] In the case of hydrazine, it is believed that the active
ingredient of the formulation (e.g., DAM) reacts with the basic
hydrazine to help neutralize hydrazine's basicity while the glycol
based carrier concomitantly assists the active ingredient by at
least substantially solubilizing hydrazine. As a result, the
formulation of the present invention can be used to help safely
neutralize hydrazine so that the hydrazine can be removed by
washing the exposed skin or surface with water.
[0040] In some embodiments, the formulation may also be used to
neutralize corrosive toxins, including but not limited to, ammonia,
anhydrous ammonia, and oxidizing toxins, such as chlorine.
[0041] Generally, the amount of the formulation that is needed to
neutralize the toxic industrial chemicals or materials will depend
on the amount of the toxic industrial chemicals or materials to
which the person or surface has been exposed. In one embodiment,
the composition containing the active ingredient may be applied in
an amount that ranges from about 1:1 to 20:1 to the amount of toxic
industrial chemicals or materials to which a person or surface has
been exposed. In some embodiments, the amount may range from about
2:1 to 15;1, and in particular from about 5:1 to 10:1. In one
embodiment, after application of the formulation to the toxic
industrial chemical or material, water can be used to remove any
residual from the skin or surface that has been treated.
[0042] Neutralization of Heavy Metals and Radioactive Metals
[0043] In one alternative embodiment, the formulation of the
present invention can be used to neutralize various metal and
radionuclides, such as heavy metals, lead, transition metals:
radioactive metals Pu, Th, U, Zr, Nb, Ru, actinides, lanthanides,
rare earths and combination thereof, for example, via a chelating
or ring forming reaction. In this embodiment, the DAM acts as a
chelating agent to form a chelate complex in which the metal is
bound to two or more atoms of the chelating agent.
[0044] The structure of DAM can form a stable 5 to 7 ring structure
with transition metals, actinides, lanthanides and heavy metals.
For example, 2,3-butanedione monoxime may form a 5 membered ring
with various metals, and derivatives of DAM, such as 2,4
hexanedione 2 oxime, may form 6 member ring structures. Generally,
the resulting ring structure having between 5 and 7 sides provides
a relatively stable reaction product in which the metal is
effectively bound by the DAM. As shown in Formula (1) above, DAM
includes a carbonyl oxygen and an oxime nitrogen moiety. These
moieties can function as ligands that each form a bond or
coordinate with the metal at more than one of the metals
coordination sites. For example in the case of a lead atom, the
.dbd.N and 'O of DAM bind to a separate coordinate site of Pb to
form a stable 5 membered ring.
[0045] Generally, metals having an empty or partially empty outer
electron shell can coordinate with DAM to form a chelate complex.
In one embodiment, DAM can coordinate with metals, such as
transition metals, heavy metals, and actinide and transuranic
metals to form a bi-dentate ligand. DAM has three nucleophilic
atoms, the carbonyl oxygen, the oxime nitrogen and, to a lesser
extent, the oxime oxygen. The potassium salt oximate (KBDO) has
these same nucleophilic atoms and is generally believed to be more
strongly nucleophilic than the neutral oxime. For example, in one
embodiment DAM may chelate with Pb to form a square planar
coordination complex. In yet another embodiment, a possible lead
and DAM or KBDO complex is depicted below. The two dashed lines
from the Pb to the oxime N and carbonyl O are the coordination
bonds that form a five membered ring. In some embodiments, another
molecule of DAM or KBDO can be accommodated by the Pb atom, using
remaining sp3d2 orbitals to make a square planar complex as
depicted below.
##STR00002##
[0046] In another embodiment. DAM and KBDO may be used to complex
with actinide and transuranic metals to remove them from solutions
and/or surfaces. It is believed that this is especially effective
in decontaminating surfaces which have been exposed to radioactive
materials from a radiological weapon or radiological dispersal
device (RDD), or other form of spreading radioactive materials on
surfaces/areas.
[0047] Generally, the amount of the formulation that is needed to
neutralize the metals will depend on the amount of the metal to
which the person or surface has been exposed. In one embodiment,
the composition containing the active ingredient may be applied in
an amount that ranges from about 1:1 to 20:1 to the amount of metal
to which a person or surface has been exposed. In some embodiments,
the amount may range from about 2:1 to 15:1, and in particular from
about 5:1 to 10:1. In one embodiment, after application of the
composition to the metal, water can be used to remove any residual
from the skin or surface that has been treated.
[0048] Neutralization of Pesticides
[0049] In one alternative embodiment, the formulation of the
present invention may also be used to neutralize a wide variety of
pesticides. Pesticides used in the United States are generally
categorized in several major classes: organophosphates, carbamates,
organochlorine, and pyrethroids. In one embodiment, formulations of
the present invention can be used to neutralize pesticides
containing organophosphates (OPs), pyrethroids (SP), carboxy
moieties, and carbamates. Pesticides generally include chemicals
and materials commonly used in insecticides, and do not necessarily
include chemical warfare agents such as vesicants and nerve
gas.
[0050] It is believed that in the neutralization of OP pesticides,
the nitrogen oxime of DAM react with active phosphorus center of
the OP in a nucleophilic attack. The nucleophilic attack results in
the OP compound decomposing into reaction byproducts. In this
reaction, a first molecule of DAM reacts with the OP to produce a
phosphorylated oxime. In a subsequent reaction, a second DAM
molecule then reacts with the phosphonylated oxime to produce a
non-toxic substituted phosphonic acid. In one embodiment, OPs
pesticides that can be neutralized with DAM include, but are not
limited to, azinphos-methyl chlorpyrifos, diazinon, disulfoton,
ethoprop, fonofos, malathion, methyl parathion, parathion, phorate,
and terbufos.
[0051] Pesticides containing carbonyls, such as carbamates, can
cause cholinesterase inhibition poisoning by reversibly
inactivating the enzyme acetylcholinesterase. In a further
embodiment, the formulation of the present invention may also be
used to neutralize pesticides containing carbamates, such as
2-methyl-2-(methylthio)propionaldehyde O-methylcarbamoyloxime
(Aldicarb); 2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate
(carbofuran, furadan, or curator); 3-hydroxycarbofuran; ethyl
N-[2-(4-phenoxyphenoxy)ethyl]carbamate (fenoxycarb); 1-naphthyl
methylcarbamate (carbaryl also known under the tradename Sevin);
ethienocarb, 3-hydroxycarbofuran; aldicarb sulfone; aldicarb
sulfoxide; butylate: S-ethyl dipropyithiocarbamate (EPTC);
methiocarb; methomyl; molinate; oxamyl; pebulate; propham;
propoxur; thiobencarb; triallate; and 2-(1-methylpropyl)phenyl
N-methylcarbamate. It is believed that the carbonyl at the center
of the carbonate is electrophilic and therefore susceptible to
nucleophilic attack by the oxime of DAM.
[0052] In some embodiments, the carrier may also provide an
effective means for neutralizing carbamates by removing or
sequestering the carabate. In one embodiment, the carrier may
comprise a polyglycol, such as PEG or mPEG, that is capable of
solubilizing carbamates to thereby remove and neutralize the
carbamate.
[0053] Generally, the amount of the formulation that is needed to
neutralize the pesticides will, depend on the amount of the
pesticide to which the person or surface has been exposed. In one
embodiment, the composition containing the active ingredient may be
applied in an amount that ranges from about 1:1 to 20:1 to the
amount of pesticide to which a person or surface has been exposed.
In some embodiments, the amount may range from about 2:1 to 15:1,
and in particular from about 5:1 to 10:1. In one embodiment, after
treatment of the pesticide with the formulation, water can be used
to remove residual from the skin or surface that has been
treated.
[0054] As discussed above, formulations in accordance with the
invention can be formulated to be delivered and applied to toxins
in a variety of manners and phases. For example, the formulation
can be provided as a topical skin protectant (TSP), such as a
lotion or cream, that can be applied to human skin prior to, or
after exposure to toxic chemicals or materials. In some
embodiments, the formulation can be provided in the form of a
liquid, gel, powder, emulsion, foam, spray, and the like. In one
embodiment, the formulation can be used to decontaminate surfaces
that have been exposed to toxic chemicals or materials.
[0055] Generally, the amount of active ingredient in the
formulations is from about 1 to 90; 1 to 50; or 1 to 25 weight
percent, based on the total weight of the formulation. In one
embodiment, the amount of active ingredient in the formulation is
between about 2 and 20 weight percent, and in particular between
about 4 and 18 weight percent, and more particularly between about
5 and 15 weight percent, based on the total weight of the
formulation.
[0056] Tables 1 and 2 below describe exemplary, non-limiting
embodiments of the present invention in which the formulation is in
the form of a cream.
TABLE-US-00001 TABLE 1 Cream Formulation Concentration Composition
Ingredient (Wt. %) Carrier MPEG 550 60 to 95 Active Ingredient
KBDO/DAM 0.5 to 20 Water Water 5 to 15
TABLE-US-00002 TABLE 2 Cream Formulation Ingredient Wt. % KBDO 14.7
.+-. 0.5 DAM 0.78 to 0.95 MPEG 550 75.98 Purified Water 8.44
[0057] As noted above, formulations of the present invention may be
in the form of a aerosols, lotions, creams and gels. Generally, the
desired viscosity of the formulations will depend on the intended
use, which can be readily ascertained by one skilled in the art.
For example, gels will generally have a viscosity that is greater
than the viscosity of a lotion, cream, or aerosol. Table 3 below
lists some exemplary viscosities for formulations that are in
accordance with embodiments of the present invention.
TABLE-US-00003 TABLE 3 Representative Viscosities Viscosity Range
Form [cp] Aerosol <100 Lotion 100 to 5,000 Cream 5,000 to 25,000
Gel >25,000
[0058] In one embodiment, formulations in accordance with the
present invention may have a viscosity between 140 and 180 cp at
+25.degree. C.
[0059] In one alternative embodiment, formulations in accordance
with the present invention may be produced by varying blends of
MPEG. For example, in one embodiment, mPEGs of varying viscosity
can be blended in proportions to increase or decrease the resulting
viscosity of the end product.
[0060] In one embodiment, the formulation's viscosity may be
increased by physico-mechanical process of emulsification. Tables 4
and 5 below illustrate non-limiting, exemplary formulations that
are in accordance with embodiments of the present invention.
TABLE-US-00004 TABLE 4 Lotion base, example of formula Ingredient
Wt. % Mineral oil 25 Dioctyldodecyl dodecanedioate 2 Dimethicone 1
Glyceryl stearate 6 Cetyl esters 1 Polysorbate 60 4 Cetyl alcohol 1
Glycerin 5 Water 55
TABLE-US-00005 TABLE 5 Cream base, example of formula Ingredient
Wt. % Emulsifying wax 2 Dioctyldodecyl dodecanedioate 5 Cetearyl
alcohol (and) ceteareth 20 2 Glyceryl stearate (and) PEG 100
stearate 1 C12-15 alcohol benzoate 2 Glyceryl stearate 2 Cetyl
alcohol 2 Montmorillonite 1 Water 80
[0061] Many modifications and other embodiments of the inventions
set forth herein will come to mind to one skilled in the art to
which these inventions pertain having the benefit of the teachings
presented in the foregoing descriptions and the associated
drawings. Therefore, it is to be understood that the inventions are
not to be limited to the specific embodiments disclosed and that
modifications and other embodiments are intended to be included
within the scope of the appended claims. Although specific terms
are employed herein, they are used in a generic and descriptive
sense only and not for purposes of limitation.
* * * * *