Title of Invention

"A REACTIVE COMPOSITION FOR DECONTAMINATION OF TOXIC CHEMICALS AND A PROCESS THEREOF"

Abstract A reactive composition for decontamination of toxic chemicals and a process thereof comprising of 10-20% of cetyltrimethylammonium bromide, 05-15% of n-butanol, 10-15% of N-methyl pyrilidone, 75-47% of aqueous phase, and the balance, if any, comprising of conventional additives and optional ingredients such as herein described. Further there is provided a process for A composition as claimed in claim 1, wherein said optional ingredients are selected from one or more of hydrogen peroxide and decane. A composition as claimed in claim 2, wherein the said hydrogen peroxide is present in an amount of 1-4%. A composition as claimed in claim 2 or 3, wherein the said decane is present in an amount of upto 3%. A composition as claimed in any of the preceding claims, wherein the optional ingredients are selected from surfactants, Co-surfactants with C2-C6 carbon chain, Organic bases and alkali metal. A composition as claimed in any of the preceding claims, wherein the said surfactant comprises of cationic or anionic surfactants. A composition as claimed in any of the preceding claimswherein the said organic bases selected from ammonium hydroxide, hexamethylene tetramine (eurotropin) or alkyl-amines. A process of making a reactive composition for decontamination of toxic chemicals comprising the steps of making a microemulsion by mixing 10-20% of cetyltrimethlylammonium bromide, 05-15% of n-butanol, 10-15% of N-methyl pyrilidone, 00-03% of decane, 75-47% of Aqueous phase, surfactants, Co-surfactants with C2-C6 carbon chain, Organic bases and Alkali metal; swirling the reactants into a smooth paste; adding water with mild agitation of the said reactants to achieve clarity, opacity and phase separation of the said microemulsion; adding 1-4% of hydrogen peroxide to the said microemulsion.
Full Text PIELD OF INVENTION
The present invention relates to a reactive composition for decontamination of toxic chemicals and a process thereof. More particularly, the present invention relates to the development of oil in water micro emulsion-based formulation using N-methyl pyrilidone as modifier and ammonium carbonate as scavenger of acids generated during decontamination of Chemical Warfare Agents by oxidatively and hydrolytically reactive micro emulsion formulation.
BACKGROUND OF THE INVENTION
Of various known Chemical Warfare Agents (CWAs) nerve agents and sulphur mustard are of particular interest as they are extremely toxic, persistent and largely stockpiled. Sulfur mustard is cytotoxic, alkylating and blistering agent, it is a potent incapacitant and lethal in large quantities. Nerve agents Sarin, Soman, Tabun and Vx impair the respiratory and nervous functions and can kill in minutes.
Decontamination of Chemical Warfare Agents (CWAs) is required in case of chemical attack by adversaries or terrorists. Decontamination of CWAs is achieved either by physically removing the toxic substances from contamination surfaces (materials in the field like vehicles, buildings, equipments, etc, and living objects) or by chemically converting them into relatively less or non-toxic substances (R. Trapp, The detoxification and . Natural Degradation of Chemical Warfare Agents' Stockholm International Peace Research Institute, SIPRI, Taylor & Francis, London and Philadelphia 1985).
For physical removal of CWAs from contamination site, adsorbents like fuller's earth (native aluminium silicate) and detergent/soap solutions are used. Non reactive microemulsions composed of surfactants, oil, alcohols and wetting agents are also used for physical removal of CWAs (US 5695775 V. R Hasso et al and US 5612300 granted to V.B.Haso et al.)- Since these decontaminants do no detoxify the toxic agents, they are not considered as reliable means. Second major problem of physical decontaminants is their safe disposal. Physical decontaminants themselves get contaminated during decontamination operation; their subsequent safe disposal requires further treatment to neutralize CWAs.
Another problem of physical decontaminants is secondary contamination, which is caused by ensuing desorption of adsorbed CWAs. Yet another problem of physical decontaminants like washing solutions is spreading of contaminated area, since during washing operation the solution is spread over contamination surface.
Chemical deactivation of CWAs with chemically reactive decontaminants is better choice of decontamination (Yang Y.C.Chem. Ind. 1995, May 1, 334). Currently used reactive-decontaminants include nucleophile/base-amine mixtures and bleach formulation.
Nucleophile/base-amine based decontaminants are admixtures of bases (alkalimetal hydroxide, limes, potash, etc) and nucleophiles (alkalialcoholate, phenoxides, glycols) with amines like diethylenetriamine, ammonia and monoethanolamine. Most popular and widely used reactive decontaminant is 'Decontamination Solution-2' (DS-2) which is a formulation of 70% diethylenetriamina (H2NCH2CH2NHCH2CH2NH2), 28% ethylene glycolmonomethyl ether (CH3OCH2CH2OHO and 2% sodium hydroxide, DS-2 is very effective in deactivating the CWAs (universal decontaminant) but suffers from many disadvantages (Yang Y. C; Baker J. A.; Ward J. R. Chem. Rev. 1992, 92, 1729). It is highly aggressive and damages the surfaces like paint, plastics rubber and leather materials.

limitations of existing decontaminants there was dire need of a decontaminant that is rapid, efficient, and universal in detoxifying the CWAs and mild on the delicate surfaces. More importantly, the need was for a decontamination formulation that acts through oxidatively reactive nucleophiles incorporating catalytic action to detoxify the CWAs.
The present invention addresses these disadvantages and other shortcomings of the prior art.
OBJECTS OF THE INVENTION
The most important object of the present invention is to develop oil in water-based microemulsion formulation that rapidly detoxifies the major classes of CWAs. Another important objective of the present invention is to formulate the oil in water microemulsion that is thermodynamically stable and optically transparent. Yet another object of the present invention is to optimize the amounts of constituents of oil in water microemulsion formulation that effectively solubilises both hydrophobic and hydrophilic CWAs.
SUMMARY OF THE INVENTION
Accordingly, towards achieving the stated objectives and meet the disadvantages of the prior art, a reactive composition for decontamination of toxic chemicals and a process thereof comprising of
1. 10-20% of cetyltrimethylammonium bromide, 05-15% of n-butanol, 10-15%
of N-methyl pyrilidone, 75-47% of aqueous phase, and the balance, if any,
comprising of conventional additives and optional ingredients such as herein
described.
2. A composition as claimed in claim 1, wherein said optional ingredients are selected from one or more of hydrogen peroxide and decane.
3. A composition as claimed in claim 2, wherein the said hydrogen peroxide is present in an amount of 1-4%.
4. A composition as claimed in claim 2 or 3, wherein the said decane is present in an amount of upto 3%.
5. A composition as claimed in any of the preceding claims, wherein the optional ingredients are selected from surfactants, Co-surfactants with C2-C6 carbon chain, Organic bases and alkali metal.
6. A composition as claimed in any of the preceding claims, wherein the said surfactant comprises of cationic or anionic surfactants.
7. A composition as claimed in any of the preceding claimswherein the said organic bases selected from ammonium hydroxide, hexamethylene tetramine (eurotropin) or alkyl-amines.

8. A process of making a reactive composition for decontamination of toxic chemicals comprising the steps of.
a. making a microemulsion by mixing 10-20% of cetyltrimethlylammonium
bromide, 05-15% of n-butanol, 10-15% of N-methyl pyrilidone, 00-03% of decane,
75-47% of Aqueous phase, surfactants, Co-surfactants with C2-C6 carbon chain,
Organic bases and Alkali metal;
b. swirling the reactants into a smooth paste;
c. adding water with mild agitation of the said reactants to achieve clarity, opacity
and phase separation of the said microemulsion;
d. adding 1-4% of hydrogen peroxide to the said microemulsion.
DESCRIPTION OF THE INVENTION
The present invention will use microemulsions (MEs) as decontamination media for Chemical Warfare Agents (CWAs). According to another embodiment of the present invention, the important feature, that qualifies MEs as decontamination-media, is their ability to dissolve simultaneously considerable amounts of reactive hydrophilic reagents (like hydroxides, hydroperoxides and hypochlorites which remain dispersed in continuous phase of O/W ME) and non polar organic molecules like CWAs, that are localized in oily interior of ME droplet. Thus microemulsions bring hydrophilic and remain immiscible with each other in aqueous medium.
Yet another embodiment of the present invention proposes oxidation and hydrolysis reactions of CWAs to detoxify them. Sulfur mustard, (SM) is preferably detoxified via oxidation rather than hydrolysis. Because, hydrolysis of SM follows SN1 pathway, therefore, increase n nucleophilicity of attacking species does not enhance the rate. Whereas, nerve agents follow SN2 pathway therefore, can effectively be hydrolyzed by stronger nucleophiles. Thus, two entirely different detoxification modes of nerve agents and SM, require development of formulation that can efficiently carryout hydrolysis as well as oxidation reactions. Hypochlorite and hydroperoxide are the
species that passes both, nucleophilicity (owing to a - effect) and oxidizing property; hence can be exploited to deactivate both the classes of lethal CWAs. Peroxides are desirable reactants, owing to their non toxic and non corrosive nature than hypochlorite. Hydrogen peroxide is widely used in green industrial process replacing historical hypochlorite based processes, which is environmentally harmful; that is why, for developing ME based decontaminant, H2O2 was selected as reactive agent in this invention.
According to another embodiment, the rapid oxidation and hydrolysis reaction by H2O2 require its activation by use of appropriate medium and activators; because, as such H2O2 is a slow acting reagent. The oxidative and hydrolytic activation of H2O2 is accomplished by use of bicarbonate and molybdate ions. Activation of H2O2 by bicarbonate takes place via formation of peroxymonocarbonate ion, as per following scheme. Peroxomonocarbonate ion is also a nucleophile, hence facilitates the hydrolytic decontamination of nerve agents.
(Formula Removed)
Molybdate enhances the oxidation potential of hydrogen peroxide by formation of singlet oxygen (102) and tetraperoxomolybdate species. Preference between these two pathways depends on ratio of [H2O2]/[MoO42]. At ratios of [H2O2]/[MoO42] 4 or less singlet oxygen is generated via formation of triperoxomolybdate MoO(OO)32", and at higher ratios tetraperoxomolybdate (Mo(00)42) is formed, both the species are very reactive oxidant against SM. Peroxomolybdte oxidizes the SM to its sulfoxide and itself gets reduced to mono, di or tri-peroxomolybdate. Tetraperoxomolybdate gets regenerated by hydrogen
peroxide in a catalytic cycle. Peroxomolybdate also catalyses hydrolysis of nerve agents by virtue of polarizing the P=0 bond and nucleophilic attact by peroxo function. Both the phenomena are depicted in following scheme.
(Scheme Removed)
HYDROPEROXIDE AIDED HYDROLYSIS OF SARIN IN ME WITH MOLYBDATE AND BICARBONATE
(Scheme Removed)
Yet another embodiment of invention proposes enhancement of hydrolytic detoxification of nerve agents by peroxo ions by use of cationic surfactants. Cationic surfactants like alkyl (C6-C16) trialkyl (C1-C4) ammonium halide, alkyl-pyridinium/piperidinium halide and alkylimidazolium halide enhance the hydrolysis of esters in aqueous medium by 'proximity effect' (to bring nucleophiles and substrates in close contact) by virtue of formation of micelles. Though micelles enhance the hydrolytic deactivation of esters, but their oil solubilising capacity is far less than microemulsions, hence, as mentioned above they do not meet the objective of this invention. That is why microemulsion is selected as medium for hydrogen peroxide aided decontamination of CWAs.
According to further embodiment of invention, nucleophile aided hydrolytic detoxification of nerve agents in cationic O/W ME, require co-solvent to augment the hydrolysis of esters in otherwise slow acting microemulsions. The hydrolysis of esters is slow in MEs than micellar solutions, due to larger interface volumes provided by O/W MEs and distant location of nucleophiles and substrates. In MEs substrates mainly reside in oily interior and nucleophiles (like HOO) remain on outer periphery of ME droplet. This constraint of ME
requires suitable alteration in its composition, to achieve desired hydrolytic activity. Use of co-solvents like N-methyl pyrilidone (NMP) reduce the interfacial tension between the ME droplet and aqueous phase, which facilitates the accessibility of nucleophile to substrate situated in oily core of ME. This phenomenon of NMP is clearly demonstrated by increase in the hydrolytic rate constant of phosphorus ester (shown in table 2 entries 9 & 10) in oil in water microemulsion.
Yet another embodiment of the present invention proposes incorporation of base like ammonium carbonate in O/W ME to scavenge the acids generated by hydrolysis of nerve agents. Each mole of nerve agents Sarin, Soman, Tabun and Vx produces two moles of acids on hydrolysis, e.g. Sarin forms hydrofluoric acid and isopropyl methylphosphonicacid. Accumulation of acids in decontamination media impedes the further inactivation of remaining toxic agent by reducing the pH of medium. Moreover, reversibility of fluoride substitution by peroxide in Sarin and Soman also demands continuous removal of fluoride to drive the reaction in forward direction (as shown in following scheme).

(Scheme Removed)
It requires simultaneous neutralization of generated acid without hampering the detoxification reaction and destabilizing the microemulsion. Cationic ammonium bases are considered to meet this requirement by scavenging the generated fluoride, as they can coexist with cationic surfactants in microemulsion without destabilizing them.
Microemulsion may be applied in different ways. The formulation may be poured or sprayed on the contaminated surface with known spray equipment. The required working microemulsion can readily made by mixing the stock formulation (microemulsion) with hydrogen peroxide in approximately 10:1 ratios by volume. Both the liquids can be provided in a container and combined before use in application apparatus as a lance. If necessary, brushing or other abrasive methods may be applied to ensure complete decontamination.
According to the present invention, the preparation and evaluation of oil in water microemulsion (O/W ME) as decontaminant against Chemical Warfare Agents (CWAs) involve following steps.
a) Composition of oil in water microemulsion, The Detoxifying Formulation (D-TOX)
Microemulsion is a thermodynamically stable optically transparent dispersion of oil in water or water in oil, stabilized with suitable surfactants. For this invention oil in water ME was selected, as it is to be used in large quantities for field application on different delicate surfaces. Thus C7W ME is a mixture of i) surfactant ii) co-surfactant Hi) oil and iv) water. How does one know what proportions of four components to use? For this investigation, composition of microemulsion was optimized by titration. Microemulsions were prepared on 10 gm scale by weighing mixture of n-butanol, cetyltrimethylammonium bromide (CTABr) and decane in to 50 ml flask. This white slurry was swirled into smooth paste. Water was then added with mild agitation to achieve clarity, and formulations which showed opacity and phase separation were disregard as microemulsions. MEs with following compositions (weight/weight) showed optical clarity and stability on storage for prolonged period.
(Formula Removed)
The components of microemulsion with respect to above composition also include the following surfactant, co-surfactant and organic bases.
Cationic surfactants with C6 to C16 hydrocarbon chain. Cationic surfactants with nitrogen and phosphorus (phosphonium) ionic head groups such as alkyl-pyridinium and alkyl-phosphonium halides (fluoride, chloride, bromide, and iodide) and hydroxides.
Co-surfactants (alcohols and ketones) with C2-C6 carbon chain.
Organic bases such as ammonium hydroxide, hexamethylene tetramine (eurotropin) and alkyl-amines. Alkali metal- (sodium, potassium, rubidium and cesium) and ammonium-molybdates.
Anionic surfactants (C6-C16 hydrocarbon chain) such as sodium dodecyl sulphate, which exhibit only oxidative detoxification capability against vesicant class of toxic chemicals.
b) Solubility of CWAs in MEs
Solubility of CWAs was tested in MEs of different compositions, MEs with higher surfactant percentage showed greater solubility of agents. As a typical example the solubility of SM in ME with CTABr 20 %, n-butanol 10%, sodium bicarbonate 0.1 M 67% and decane 3% is given below.
Solubility measurements in ME began by taking 1mL of the liquid in a vial. Drops of SM were then added one at a time, the mixture was shook after each drop. Addition continued until mixture could solubilise no more SM as judged visually by persistent cloudiness. The mixture became from clear to milky with one particular drop. The final added weight of milky suspension minus weight of single drop was taken as solubility of SM in 1mL of ME. SM solubility was 10% (w/w), which is sufficient for practically decontaminating it in field conditions. Similarly the solubility of Vx was found to be 15 %. Solubility of Tabun and Sarin was very high (more than 30 %) as these agents are relatively less hydrophobic.
c) Oxidative reactivity of Microemulsion
Composition of ME for oxidative reactivity was established by studying the oxidation kinetics of non-toxic stimulant, namely, 2-chloroethyl phenyl sulphide (CEPS) (CIC2H4SC6H5), of sulphur mustard.
Composition of ME, for carrying out the oxidation of CEPS is as follows: CTABr 15 %, n-butanol 10 %, water (containing 0.1 M sodium bicarbonate) 65 %, H2O2 (0.02 - 0.4M) and Na2Mo04 (0.001 - 0.01 M). Progress oxidation of CEPS ws monitored by HPLC. It eluted at around 5.4 minutes under the employed HPLC conditions, and reduction in its peak area with respect to time allowed calculating oxidation kinetics. Oxidation profile of CEPS in ME is summarized in table-10. Role of molybdate is evident as catalyst and activator of hydrogen peroxide. Sodium molybdate enhanced the pseudo-first-order oxidation rate constants of CEPS about 25 times, even when taken at half of concentration than that of CEPS (entries 1 and 2). Increment in concentration of molybdate further enhanced the rate
constants (entries 2, 4 & 6); molybdate at 0.01 M concentration increased rate constant by 2 orders of magnitude (entries 1 & 6). Its catalytic action is manifested by constancy of oxidation rates despite varying the substrate concentration over wide range (entries 6-8). H2O2 concentration does not alter the rate constants, if present in sufficiently excess over the substrate (entries 2 & 3; 4 & 5). It clearly demonstrates that H2O2 oxidizes CEPS via tetraperoxomolybdate. In oxidation reactions, ratios of [H2O2] / [MoO42] were kept more than 4, to maintain the predominant formation of Mo (00)42. Tetraperoxomolybdate gets regenerated by hydrogen peroxide; this catalytic behaviour of molybdate is already shown in the scheme.
TABLE-1
Pseudo-first order rate for oxidation of CEPS by H2O2 in microemulsion

(Table Removed)
d) Hydrolytic reactivity of Microemulsion
To establish the composition of ME for maximum hydrolytic activity against nerve agents, the kinetic investigation was performed with non-toxic stimulant p-nitrophenyl diphenylphosphate (PNPDPP).
The reaction of nucleophile (HOO) and ester (PNPDPP) occurs at the interface of ME and will be sensitive to factors that effect the distribution of nucleophile between various sites in ME and aqueous phase. This constraint of ME requires suitable alteration in its composition, to achieve desired hydrolytic activity.
In this study Hydroperoxide aided esterolytic activity of microemulsions, ME-2 and ME-3 was examined against PNPDPP. Kinetics of PNPDPP hydrolysis was followed spectrophotometrically at 32°C, by monitoring the release of p-nitrophenolate at 40 nm. Reactivity of MEs against PNPDPP can be judged from kinetic date enumerated in table-2.
PNPDPP hydrolyses with almost same rates in MEs (without H2O2) and borate buffer (entries 1, 2 and 9). Addition of H2O2 at relatively higher concentration than substrate enhanced the rate by an order of magnitude (entries 2 and 3). N-methyl pyrilidone (NMP) enhanced the rate constants, with and without H2O2 (entries 3 & 4; 9 & 10).
Increase in rates with NMP may be due to reduction in interfacial tension between ME droplet and aqueous phase, which might facilitate the accessibility of nucleophile (OH or HOO) to substrate situated in oily core of ME. Rate constants seem to be dependent on H2O2 concentration only, but after 0.05 M, further increment in H2O2 concentration does not increase rates significantly. It could be due to restricted diffusion of HOO ions from polar region to hydrophobic core. It is important to note that ME-3 exhibited higher reactivity than ME-2, even though former possessed lower apparent pH (806) than late (10.8). Better reaction rate in ME-3 may be due to formation of peroxymonocarbonate (HC04) ion, which is supposed to be effective nucleophile than HOO at lower pH, as pKa of conjugate acid of HC04 is lower (pKa 3.8) than H20 (pKa 11.7). Hence number of HC04 ions is more than HOO at lower pH. Highest hydrolysis rate was observed on addition of sodium molybdate in ME-3, which was added to activate the oxidizing power of H2O2 against CEPS. Best hydrolytic capability of ME is attributed to generation of tetraperoxomolybdate, this mechanism is already illustrated in scheme.
TABLE-2
Pseudo-first-order rate constants for hydrolysis of PNPDPP by hydroperoxide in microemulsion at 32°C

(Table Removed)
ME-2: CTABr 15 %, n-butanol 10 %, dodecane 3 %, borate buffer (0.05M pH 8.5) 72 %
ME-3: CTABr 15 %, n-butanol 10 %, dodecane 3 %, NaHCOs (0.1M) 72 %
e) Detoxification of Sarin, Tabun, Vx and Sulfur mustard in ME (D-TOX)
After establishing the hydrolytic and oxidative reactivity of ME against non toxic stimulants of CWAs, its efficiency was tested against real agents. The composition of final working microemulsion was optimized as follows. To this ME formulation aliquot of hydrogen peroxide was added to give concentration of 400mM. On addition of H2O2 to ME forms dark amber colored solution due to formation of tetraperoxomolybdate species.
CTABr :20 %
n-Butanol :15%
NMP :10%
Ammonium carbonate : 10 %
Water containing 2 % NaHC03 + 3 % Na2 Mo04 :45 %
To this ME H2O2 was added to obtain the concentration of H2O2: 400-800mM or (approximately 1.4-2.8 %)
CWAs Sarin, Tabun, Vx and SM lacked spectrophotometrically monitorable groups; hence their detoxification kinetics was monitored by innovatively devised new Flow Injection Tandem Mass Spectrometry (FITMS). In this method, Selected Reaction Monitoring (SRM) technique in tandem electron impact mass spectrometry was used after introducing the sample through GC column. For each agent, a characteristic fragment ion of mass spectrum was selected, and its formation was monitored by SRM. Progress of SM deactivation was followed by monitoring the transition from m/z 158 [M]+ to [M-49]+109, by directly analyzing the reaction mixture at different time intervals without any extraction. Similarly, the transitions selected for Sarin and Tabun were 125 [M-15] + to 99 [M-26] + to 70 [M-90] + respectively. SRM for Vx was from 268 [M+H]+ to 167 [M-100]+ and 128 [M-139]+ in chemical ionization mode (CIMS), as EIMS showed interference from background. Analysis of aliquots from microemulsion reaction mixture, at different time intervals by this technique provided ion - chromatograms with peak area directly proportional to the concentration of analyte being studied. Thus the kinetic data for detoxification of different CWAs in ME were obtained.
Table 3 compares the t1/2 values for these CWAs in working microemulsion and water. It is clearly demonstrated that, half life of these highly persistent agents was significantly reduced to seconds from several hours. It is important to note that highest increase in detoxification reaction was in case of Vx, as it could have been consumed via both oxidation as well as hydrolysis reaction. Thus, the 'oxido-hydrolytic' reactivity of this ME qualifies it as universal detoxification formulation against CWAs. Capacity of microemulsion to detoxify the CWAs was evaluated by taking maximum soluble amount of agents and observing their
consumption. The capacity of ME was found to be at par with currently used DS-2 solution, as shown in table 4.
TABLE-3 Half life of CWAs in water and Working ME

(Table Removed)
CTABr: 20 %, n-Butanol: 15 %, NMP : 10 %, Ammonium carbonate : 10 %, Water containing 2 % NaHCO3 + 3 % Na2MoO4 : 45 % and H2O2 : 400-800mM (1.4-2.8 %)
TABLE-4 Capacity of Microemulsion for Detoxifying the CWAs

(Table Removed)
EXAMPLE 1
Preparation of microemulsion (The D-TOX)
Microemulsion for hydrolysis and oxidation reactions were prepared at 100gm level by weighing CTABr 20 gms, n-butanol 15 gms, NMP 10 gms, ammonium carbonate 10 gms, sodium molybdate 1.2 gms and water containing 1% sodiumbicarbonate 45 gms into a 250 ml Erlenmayer flask. To this slurry appropriate amount (400-500 mM) of hydrogen peroxide was added to get working dark amber colored microemulsion. For example 906 mg of 15% H2O2 (approximately 1 mL, equivalent to 4 m Moles) was added to 9.094 gms (total amount of working ME becomes 10 gms) to get 400mM solution of H2O2 in ME. The concentration of aqueous hydrogen peroxide was established using published titrimetric method
Analysis of CEPS oxidation
HPLC analysis of CEPS oxidation was carried out with Hewlitt Packard (model 1100) instrument. Reversed phase (C-18) column was used as stationery phase and CH3CN:H20
(50:50) was taken as mobile phase with 1 ml/min. flow rate. UV detection (254 nm) afforded monitoring of CEPS oxidation.
Reaction mixtures were generated by taking appropriate aliquots of CEPS (Stock solution also prepared in ME) solutions into 2 mL capped vial and making up to 1.0 mL with working ME, 20 uL aliquots of this mixture were run in HPLC at different time intervals for monitoring the oxidation reaction. Linear detector response (UV detection 254 nm) for CEPS concentrations (2-40 mM) was already established in HPLC analysis.
Kinetics of PNPDPP hydrolysis
Kinetics of PNPDPP hydrolysis was followed spectrophotometrically at 400 nm in MEs where molybdate was not used as activator. Reaction mixtures were generated in a 1 cm quartz cuvette with microemulsions ME-2 or ME-3, to give final volume of 3.0 ml. Aliquots of H2O2, were added to get desired concentrations. After equilibrating for 20 min. at 32 = 0.1 0C in a water jacketed cell holder of Chemito Spectrascan 2600 spectrophotometer, an aliquot (30 uL) of substrate solution (in CH3CN) was added. The reaction was monitored at 400nm for release of p-nitrophenoxide ion. The reactions were run in triplicate up to four half lives. For following the hydrolysis of PNPDPP in ME with sodium molybdate, HPLC was used as monitoring technique. The conditions were similar to those used in CEPS oxidation.
Kinetics of CWAs by Selected Reaction Monitoring (SRM)
Characteristic fragment ions of each agent were selected (as defined in description of process) and instrument was tuned to monitor a particular transition. Tandem mass spectrometry experiments were performed on a TSQ 7000 mass spectrometer (Finnegan MAT, USA) coupled to a Varian 3400 GC, at a collision energy of 20 eV using Argon as collision gas at a pressure of 2.1m Torr helium was used as carrier gas at constant flow of 2mL/min. The El experiments were performed at 70 eV using a source temperature of 150°C. CI for Vx was performed using isobutene as reagent gas. In GC, the injector and transfer line temperatures were held at 250°C and column SGE BPX5 (5m x 0.32mm i.d. x 0.25 urn thickness was used) was kept isothermal at 280°C. To obtain the kinetic data of CWAs consumption, 1mL of reaction mixture (ME + H2O2) was equilibrated at 22°C. To this, solution agent sulfur mustard (4.74 mg = 3.7 uL) was added with stirring to obtain desired concentration (25 - 30 mM). 0.02 uL of reaction mixture was analysed immediately and at different time intervals for a particular transition e.g. in case of SM from 158 to 109. The area of obtained ion chromatograms was directly proportional to the concentration of agent. These kinetic runs could be considered as real time monitoring, as time at which aliquots are
analyzed are recorded on ion chromatograms. Linear response of mass detector in required range of concentration of each agent was pre-standardized for their respective transition.
EXAMPLE 2
Preparation of microemulsion (The D-TOX)
Microemulsions for hydrolysis and oxidation reactions were prepared at 200gm level by weighing CTABr 40 gms, n-butanol 30 gms, NMP 20gms, ammonium carbonate 20 gms, sodium molybdate 2.4 gms and water containing 2% sodiumbicarbonate 90 gms into a 500 ml Erlenmayer flask. To this slurry appropriate amount (400-800 mM) of hydrogen peroxide was added to get working dark amber colored microemulsion. For example 1.81 g of 15% H2O2 (approximately 2 mL, equivalent to 8 m Moles) was added to 19 gms (total amount of working ME becomes 20 gms) to get 400mM solution of H2O2 in ME.
Decontamination of Toxic Chemicals by microemulsion:
20 uL of Sarin was dissolved in 1 mL isopropanol in a 2 mL test tube (20000 ppm solution). 100 uL of this solution was diluted to 10 mL isopropanol (200 ppm). It was marked as Ps and analyzed by injecting 1 pL by GC-FID or GC-MS, the peak area of Sarin was noted (19670).
Sample:
20 pL of Sarin was dissolved in 1 mL of working microemulsion (D-TOX) in a 2mL test tube. It was kept for 15 minutes. 100 uL of this reaction mixture was drawn and dissolve in 10 mL isopropanol, and marked as Pd. It was analyzed this by GC-FID or GC-MS by injecting 1 uL solution. The peak area of Sarin was noted (0, as no peak of Sarin was obtained).
Calculation of Decontamination efficiency:
(Formula Removed)
EXAMPLE 3
Preparation of microemulsion (The D-TOX)
Microemulsions for hydrolysis and oxidation reactions were prepared at150gm
level by weighing CTABr 30 gms, n-butanol 22.5 gms, NMP 15 gms,
ammonium carbonate 15 gms, sodium molybdate 1.8 gms and water (containing 2%
sodium bicarbonate) 67.5 gms into a 500 ml Erlenmayer flask. To this slurry
appropriate amount (400-800 mM) of hydrogen peroxide was added to get working dark amber colored microemulsion. For example 0.885 g of 15 % H2O2 (approximately 2 mL, equivalent to 8 m Moles) was added to 14.25 gms (total amount of working ME becomes 15 gms) to get 400mM solution of H2O2 in ME.
Decontamination of Toxic Chemicals by microemulsion:
10 pL of Sulfur mustard (SM) was dissolved in 1 mL isopropanol in a 2 mL test tube (10000 ppm solution). 100 pL of this solution was diluted to 10 mL isopropanol (200 ppm). It was marked as Ps and analyzed by injecting 1 pL by GC-FID or GC-MS, the peak area of SM was noted (3679).
Sample:
10 pL of SM was dissolved in 1 mL of working microemulsion (D-TOX) in a 2mL test tube. It was kept for 15 minutes. 100 pL of this reaction mixture was drawn and dissolve in 10 ML isopropanol, and marked as Pd. It was analyzed this by GC-FID of GC-MS by injecting 1 pL solution. The peak area of SM was noted (0, as no peak of SM was detected).
Calculation of Decontamination efficiency:
(Formula Removed)
Although the invention has been described in details with reference to a preferred embodiment it is to be understood that the above description of the present invention is susceptible to considerable modifications, variations and adaptations by those skilled in the art, such modification are intended to be considered to be within the scope and spirit of the present invention.







WE CLAIM:
1. A reactive composition for decontamination of toxic comprising of 10-20% of cetyltrimethylammonium bromide, 05-15% of n-butanol, 10-15% of N-methyl pyrilidone, 75-47% of aqueous phase, and the balance, comprising of conventional additives such as bases selected from ammonium or alkali metal carbonates and bicarbonatcs, optional ingredients selected from surfactants, Co-surfactants with C2-C6 carbon chain, Organic bases and alkali metal.
2. A composition as claimed in claim 1, wherein said optional ingredients are selected from of hydrogen peroxide and dccanc.
3. A composition as claimed in claim 2, wherein the said hydrogen peroxide is present in an amount of 1-4%.
4. A composition as claimed in claim 2 or 3, wherein the said dccanc is present in an amount of upto 3%.
5. A composition as claimed in any of the preceding claims, wherein the said surfactant comprises of cationic or anionic surfactants.
6. A composition as claimed in any of the preceding claims, wherein the said organic bases selected from ammonium hydroxide, hexamethylene tetramine (eurotropin) or alkyl-amincs.
7. A composition as claimed in claim 1, wherein the process of composition for decontamination of toxic chemicals, comprising the steps of:
a. making a microemulsion by mixing 10-20% of cetyltrimethlylammonium
bromide, 05-15% of n-butanol, 10-15% of N-methyl pyrilidone, 00-03% of
decanc:, 75-47% of Aqueous phase, surfactants, Co-surfactants with C2-C6
carbon chain, Organic bases and Alkali metal;
b. swirling the reactants into a smooth paste;
c. adding water with mild agitation of the said reactants to achieve clarity
opacity and phase separation of the said microemulsion;
d. adding 1-4% of hydrogen peroxide to the said microemulsion.

Documents:

1439-DEL-2005-Abstract-(02-02-2012).pdf

1439-del-2005-Abstract-(11-09-2012).pdf

1439-del-2005-abstract.pdf

1439-DEL-2005-Claims-(02-02-2012).pdf

1439-del-2005-Claims-(08-05-2013).pdf

1439-del-2005-Claims-(11-09-2012).pdf

1439-del-2005-claims.pdf

1439-DEL-2005-Correspondence Others-(02-02-2012).pdf

1439-del-2005-Correspondence Others-(06-06-2011).pdf

1439-del-2005-Correspondence Others-(09-05-2011).pdf

1439-del-2005-Correspondence Others-(11-09-2012).pdf

1439-del-2005-correspondence-others.pdf

1439-del-2005-correspondence-po.pdf

1439-DEL-2005-Description (Complete)-(02-02-2012).pdf

1439-del-2005-description (complete).pdf

1439-del-2005-description (provisional).pdf

1439-DEL-2005-Form-1-(02-02-2012).pdf

1439-del-2005-form-1.pdf

1439-del-2005-form-18.pdf

1439-DEL-2005-Form-2-(02-02-2012).pdf

1439-del-2005-form-2.pdf

1439-del-2005-form-26.pdf

1439-del-2005-form-3.pdf

1439-del-2005-form-5.pdf

1439-del-2005-GPA-(06-06-2011).pdf

1439-del-2005-Hearing-Discussion-(09-04-2013).pdf


Patent Number 256244
Indian Patent Application Number 1439/DEL/2005
PG Journal Number 21/2013
Publication Date 24-May-2013
Grant Date 22-May-2013
Date of Filing 03-Jun-2005
Name of Patentee DIRECTOR GENERAL, DEFENCE RESEARCH & DEVELOPMENT ORGANISATION
Applicant Address MINISTRY OF DEFENCE, GOVT OF INDIA, WEST BLOCK-VIII, WING 1, SEC-1, RK PURAM, NEW DELHI-110066, INDIA.
Inventors:
# Inventor's Name Inventor's Address
1 MEEHIR PALIT JRDE, JHANSI ROAD, GWALIOR-474 002, INDIA.
2 DEVENDRA KUMAR DUBEY JRDE, JHANSI ROAD, GWALIOR-474 002, INDIA.
3 DEEPAK PARDASANI JRDE, JHANSI ROAD, GWALIOR-474 002, INDIA.
4 ARVIND KUMAR GUPTA JRDE, JHANSI ROAD, GWALIOR-474 002, INDIA.
5 KRISHNAMURTHY SEKHAR JRDE, JHANSI ROAD, GWALIOR-474 002, INDIA.
PCT International Classification Number C11D 3/39
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA