METHOD FOR THE DETECTION OF CHEMICAL WARFARE AGENTS

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of the filing date of U.S. Provisional Patent Application No. 61/532,883 filed on September 9, 2011 , the contents of which are incorporated herein by reference in their entirety.

FIELD OF THE INVENTION

This invention relates to methods of detecting organophosphorus compounds and toxic industrial chemicals and methods of monitoring decomposition thereof. The invention more particularly relates to metal ion and metal species catalysis of an alcoholysis reaction which converts toxic organophosphorus and industrial chemical compounds into non-toxic compounds in the presence of an indicator compound, which allows a visible indication of where the toxic compounds are located and whether their decomposition is complete.

BACKGROUND OF THE INVENTION

The Chemical Weapons Convention was adopted by the Conference on

Disarmament in Geneva on September 3, 1992, entered into force on April 29, 1997, and calls for a prohibition of the development, production, stockpiling and use of chemical weapons and for their destruction under universally applied international control. Eliminating the hazard of chemical warfare agents is desirable both in storage sites and on the battlefield. Decontamination of battlefields requires speed and ease of application of decontaminant. Surfaces involved pose a challenge for decontamination techniques since some surfaces absorb such agents, making decontamination difficult. Examples of surfaces that could be involved include those of tanks, ships, aircraft, weapons, electronic devices, ground, protective clothing and human skin. The decontaminants should not be corrosive, so that surfaces are not damaged during or following decontamination. An optimum solvent of a decontaminating method should provide ease of application, solubility of the chemical warfare agent, non-corrosiveness, and minimal environmental contamination. Since the establishment of the Convention, considerable effort has been directed toward methods of facilitating the controlled decomposition of organophosphorus compounds.

We have previously reported development of novel and efficient methods for decontamination of organophosphorus agents based on metal ion catalyzed alcoholysis (MICA) in organic media under neutral conditions (see, e.g., Neverov, A.A. and Brown, R.S., Main Group Chemistry (2010), 9:265-281 ; U.S. Patent No. 7,214,836; and U.S. Patent No. 7,875,739). Methods for decomposing an organophosphorus compound by subjecting the organophosphorus compound to an alcoholysis reaction in a medium containing nonradioactive metal ions and at least a trace amount of alkoxide ions have been disclosed. Such methods are useful for decomposing a range of organophosphorus compounds including pesticides, insecticides, chemical warfare agents, and nerve agents such as G- agents and V-agents. It has also been shown using live agent testing in solution that various G- and V- agents are rapidly decomposed, for example in less than 30 seconds, by these decontamination methods (Dupont Durst, H. et al., Abstract no. INOR-396, Abstracts of Papers, 238 ^th ACS National Meeting, Washington, DC, U.S., August 16-20, 2009).

There is an increasing demand for more efficient methods of decontamination and cleanup of accidental or malicious releases of organophosphorus (OP) materials (including pesticides and scheduled chemical warfare agents). One of the deficiencies of current decontamination methods is the lack of any simple visible indication of where the contaminant is located and when the decontamination is complete. Moreover, almost all current instrumental techniques that can be used to determine the presence of nerve agents such as mass spectroscopy, gas chromatography and NMR spectroscopy are expensive and do not allow visualization. There is a need for new methods of detecting chemical warfare agents that are cheaper, portable, and can be used to monitor disposal.

It would be desirable to be provided with a simple method of visualizing contaminants and determining when decontamination is complete In order to facilitate decontamination and cleanup of toxic chemicals.

SUMMARY OF THE INVENTION

According to a first aspect of the invention, there is provided a method for decomposing and monitoring decomposition of an organophosphorus compound, comprising: a) subjecting said organophosphorus compound to an alcoholysis reaction in the presence of an indicator compound in a substantially non-aqueous medium comprising non-radioactive metal ions selected from the group consisting of lanthanide series metal ions, transition metal ions, and combinations thereof, and at least a trace amount of alkoxide ions; wherein said indicator compound possesses UV/visible spectral or fluorescent properties in said medium; wherein said indicator compound binds to said non-radioactive metal ions forming a complex with UV/visible spectral or fluorescent properties which are different from the UV/visible spectral or fluorescent properties of said indicator compound when unbound; and wherein, through said alcoholysis reaction, said organophosphorus compound is decomposed and halogen anions are released, releasing said indicator compound from said complex; and b) determining UV/visible spectral or fluorescent properties of said indicator compound, wherein the UV/visible spectral or fluorescent properties of said indicator compound indicate whether unbound indicator compound is present; and wherein presence of said unbound indicator compound indicates

decomposition of said organophosphorus compound.

According to a second aspect of the invention, there is provided a method for detecting an organophosphorus compound, comprising: a) subjecting said

organophosphorus compound to an alcoholysis reaction in the presence of an indicator compound in a substantially non-aqueous medium comprising non-radioactive metal ions selected from the group consisting of lanthanide series metal ions, transition metal ions, and combinations thereof, and at least a trace amount of alkoxide ions; wherein said indicator compound possesses UV/visible spectral or fluorescent properties in said medium; wherein said indicator compound binds to said non-radioactive metal ions forming a complex with UV/visible spectral or fluorescent properties which are different from the UV/visible spectral or fluorescent properties of said indicator compound when unbound; and wherein, through said alcoholysis reaction, said organophosphorus compound is decomposed and halogen anions are released, such that said indicator compound is released from said complex; and b) determining UV/visible spectral or fluorescent properties of said indicator compound, wherein the UV/visible spectral or fluorescent properties of said indicator compound indicate whether unbound indicator compound is present; and wherein said organophosphorus compound is detected by detecting presence of said unbound indicator compound.

According to a third aspect of the invention, there is provided a method for monitoring decomposition of an organophosphorus compound, comprising: a) subjecting said organophosphorus compound to an alcoholysis reaction in the presence of an indicator compound in a substantially non-aqueous medium comprising non-radioactive metal ions selected from the group consisting of lanthanide series metal ions, transition metal ions, and combinations thereof, and at least a trace amount of alkoxide ions; wherein said indicator compound possesses UV/visible spectral or fluorescent properties in said medium; wherein said indicator compound binds to said non-radioactive metal ions forming a complex with UV/visible spectral or fluorescent properties which are different from the UV/visible spectral or fluorescent properties of said indicator compound when unbound; and wherein, through said alcoholysis reaction, said organophosphorus compound is decomposed and halogen anions are released, such that said indicator compound is released from said complex; and b) determining UV/visible spectral or fluorescent properties of said indicator compound, wherein the UV/visible spectral or fluorescent properties of said indicator compound indicate whether unbound indicator compound is present; and wherein presence of said unbound indicator compound indicates decomposition of said organophosphorus compound.

In some embodiments of these aspects, said halogen anions bind to said nonradioactive metal ions, thereby releasing said indicator compound from said complex.

In some embodiments, said indicator compound is selected from the group consisting of Bromocresol purple, Chlorophenol red, Methyl red, Bromophenol blue, Bromocresol green, Phenolphthalein, Thymolphthalein, Thymol blue, Cresol red, Congo red, Methyl orange and Neutral red 2.

In some embodiments of these aspects, said organophosphorus compound has the following formula (10):

X P Hal

G (10)

where P is phosphorus;

J is O (oxygen), S (sulfur) or a lone pair of electrons;

X and G are the same or different and are selected from the group consisting of A, Q, OQ, QA, OA, SQ.SA, F, CI, Br and C≡N;

Hal is selected from the group consisting of fluoride (F), chloride (CI) and bromide

(Br);

where Q is hydrogen or a substituted or unsubstituted branched, straight-chain or cyclic alkyl group consisting of 1 -100 carbon atoms;

A is a mono-, di-, or poly-substituted or unsubstituted moiety selected from phenyl, biphenyl, benzyl, pyridine, naphthyl, polynuclear aromatics, and 5- and 6-membered aromatic and non-aromatic heterocycles; and

wherein each said substituent is selected from CI, Br, I, F, nitro, nitroso, Q, alkenyl, OQ, carboxyalkyl, acyl, S0 ₃ H, S0 ₃ Q, S=0(Q), S(=0) ₂ Q, amino, alkylamino (NHQ), arylamino (NHA), alkylarylamino, dialkylamino and diarylamino. In some embodiments of these aspects, said organophosphorus compound has the following formula (15): j

X— p— z

G (15)

where:

P is phosphorus;

J is O or S;

X and G are the same or different and are selected from the group consisting of Q, OQ, QA, OA, F, CI, Br, I, QS, SQ, SA and C≡N,

Z is F, CI or Br;

wherein at least one of X and G is not Q or QA;

Q is a substituted or unsubstituted branched, straight-chain or cyclic alkyl group having 1-100 carbon atoms; and

A is a substituted or unsubstituted moiety selected from the group consisting of phenyl, biphenyl, benzyl, pyridyl, naphthyl, polynuclear aromatic, and aromatic and non- aromatic heterocyclic; and

wherein said substituents are selected from the group consisting of CI, Br, I, F, nitro, nitroso, Q, alkenyl, OQ, carboxyalkyl, acyl, S0 ₃ H, S0 ₃ Q, S=0(Q), S(=0) ₂ Q, amino, alkylamino (NHQ), arylamino (NHA), alkylarylamino, dialkylamino and diarylamino.

In some embodiments of these aspects, said organophosphorus compound has the following formula (15):

where:

P is phosphorus;

J is O or S; X and G are the same or different and are selected from the group consisting of Q, OQ, QA, A, OA, F, CI, Br, I, QS, SQ, SA, and C _≡ N;

Z is F, CI or Br;

Q is a substituted or unsubstituted branched, straight-chain or cyclic alkyl group having 1-100 carbon atoms; and

A is a substituted or unsubstituted aryl group selected from the group consisting of phenyl, biphenyl, benzyl, pyridyl, naphthyl, polynuclear aromatic, and aromatic heterocyclic, or a substituted or unsubstituted non-aromatic heterocyclic group;

wherein, when X and G are the same, X and G are not Q; and

wherein said substituents are selected from the group consisting of CI, Br, I, F, nitro, nitroso, Q, alkenyl, OQ, carboxyaikyi, acyl, S03H, S03Q, S=0(Q), S(=0)2Q, amino, alkylamino (NHQ), arylamino (NHA), alkylarylamino, dialkylamino, and diarylamino.

In some embodiments of these aspects, said organophosphorus compound has the following formula (15):

(15)

where:

P is phosphorus;

J is O or S;

X and G are the same or different and are selected from the group consisting of Q, OQ, QA, A, OA, F, CI, Br, I, QS, SQ, SA, and C≡N;

Z is F, CI or Br;

Q is a substituted or unsubstituted branched, straight-chain or cyclic alkyl group having 1-100 carbon atoms; and

A is a substituted or unsubstituted aryl group selected from the group consisting of phenyl, biphenyl, benzyl, pyridyl, naphthyl, polynuclear aromatic, and aromatic heterocyclic, or a substituted or unsubstituted non-aromatic heterocyclic group;

wherein, when X and G are the same, X and G are selected from the group consisting of OQ, OA, F, CI, Br, I, QS, SQ, SA, and C^N; and

wherein said substituents are selected from the group consisting of CI, Br, I, F, nitro, nitroso, Q, alkenyl, OQ, carboxyaikyi, acyl, S03H, S03Q, S=0(Q), S(=0)2Q, amino, alkylamino (NHQ), arylamino (NHA), alkylarylamino, dialkylamino, and diarylamino. In some embodiments of these aspects, said organophosphorus compound has the following formula (15):

(15) where:

P is phosphorus;

J is O (oxygen) or S (sulfur);

X and G are the same or different and are selected from the group consisting of Q, OQ, QA, OA, F (fluoride), CI (chloride), Br (bromide), I (iodide), QS, SQ and C≡N;

Z is F, CI or Br;

where Q is hydrogen or a substituted or unsubstituted branched, straight-chain or cyclic alkyl group consisting of 1-100 carbon atoms;

wherein when X and G are the same, X and G are not Q, and Q is not H;

A is a mono-, di-, or poly-substituted or unsubstituted moiety selected from phenyl, biphenyl, benzyl, pyridine, naphthyl, polynuciear aromatics, and 5- and 6-membered aromatic and non-aromatic heterocycles;

wherein each said substituent is selected from CI, Br, I, F, nitro, nitroso, Q, alkenyl, OQ, carboxyalkyl, acyl, S0 ₃ H, S0 ₃ Q, S=0(Q), S(=0) ₂ Q, amino, alkylamino (NHQ), arylamino (NHA), alkylarylamino, dialkylamino and diarylamino.

In some embodiments of these aspects, said organophosphorus compound has the following formula (15):

(15) where:

P is phosphorus;

J is O (oxygen) or S (sulfur); X and G are the same or different and are selected from the group consisting of Q, OQ, QA, OA, F (fluoride), CI (chloride), Br (bromide), I (iodide), QS, SQ and C≡N;

Z is F, CI or Br;

where Q is hydrogen or a substituted or unsubstituted branched, straight-chain or cyclic alkyl group consisting of 1-100 carbon atoms;

wherein when X and G are the same, X and G are Q or OQ;

A is a mono-, di-, or poly-substituted or unsubstituted moiety selected from phenyl, biphenyl, benzyl, pyridine, naphthyl, polynuclear aromatics, and 5- and 6-membered aromatic and non-aromatic heterocycles;

wherein each said substituent is selected from CI, Br, I, F, nitro, nitroso, Q, alkenyl, OQ, carboxyalkyl, acyl, S0 ₃ H, S0 ₃ Q, S=0(Q), S(=0) ₂ Q, amino, alkylamino (NHQ), arylamino (NHA), alkylarylamino, dialkylamino and diarylamino.

In some embodiments of these aspects, said organophosphorus compound has the following formula (15):

(15) where:

P is phosphorus;

J is O (oxygen) or S (sulfur);

X and G are the same or different and are selected from the group consisting of Q, OQ, QA, OA, F (fluoride), CI (chloride), Br (bromide), I (iodide), QS, SQ and C≡N;

Z is F, CI or Br;

where Q is hydrogen or a substituted or unsubstituted branched, straight-chain or cyclic alkyl group consisting of 1-100 carbon atoms;

A is a mono- di-, or poly-substituted or unsubstituted moiety selected from phenyl, biphenyl, benzyl, pyridine, naphthyl, polynuclear aromatics, and 5- and 6-membered aromatic and non-aromatic heterocycles;

wherein each said substituent is selected from CI, Br, I, F, nitro, nitroso, Q, alkenyl, OQ, carboxyalkyl, acyl, S0 ₃ H, S0 ₃ Q, S=0(Q), S(=0) ₂ Q, amino, alkylamino (NHQ), arylamino (NHA), alkylarylamino, dialkylamino and diarylamino. In some embodiments of these aspects, said organophosphorus compound has at least one phosphorus atom double bonded to an oxygen or a sulfur atom.

In some embodiments of these aspects, said medium is a solution further comprising a solvent selected from the group consisting of methanol, substituted and unsubstituted primary alcohols, substituted and unsubstituted secondary alcohols, substituted and unsubstituted tertiary alcohols, substituted and unsubstituted alkoxyalkanol, substituted and unsubstituted aminoalkanol, and combinations thereof. In certain embodiments, said medium is a solution further comprising a solvent selected from the group consisting of methanol, ethanol, ethanolamine, n-propanol, iso-propanol, n-butanol, 2-butanol, methoxyethanol, and combinations thereof. In certain embodiments, said solution further comprises a solvent selected from the group consisting of nitriles, esters, ketones, amines, ethers, hydrocarbons, substituted hydrocarbons, unsubstituted hydrocarbons, halogenated hydrocarbons, halogenated ethers and combinations thereof.

In some embodiments, said medium further comprises a non-inhibitory buffering agent. In certain embodiments, said buffering agent is selected from the group consisting of anilines, N-alkylanilines, Ν,Ν-dialkylanilines, N-alkylmorpholines, N-alkylimidazoles, 2,6- dialkylpyridines, primary, secondary and tertiary amines, trialkylamines, and combinations thereof.

In some embodiments of these aspects, said medium further comprises alkoxide ions in addition to said at least a trace amount of alkoxide ions. Optionally, the concentration of said alkoxide ions may be about 0.1 to about 2 equivalents of the concentration of the metal ions, about 1 to about 1.5 equivalents of the concentration of the metal ions, about 0.01 to about 2 equivalents of the concentration of the metal ions, about 0.5 to about 1.5 equivalents of the concentration of the metal ions, or about 1 to about 2 equivalents of the concentration of the metal ions.

In some embodiments of these aspects, said medium is prepared by combining a metal salt and an alkoxide salt with at least one of alcohol, alkoxyalkanol and aminoalkanol. In some embodiments of these aspects, said metal ions are selected from the group consisting of lanthanide series metal ions, copper, platinum, palladium, zinc, nickel, yttrium, scandium ions, and combinations thereof. In certain embodiments, said metal ions are selected from the group consisting of Cu ²⁺ , Co ²⁺ , Pt ²⁺ , Pd ²⁺ , Zn ²⁺ , Y ³⁺ , Sc ³⁺ , Ce ³⁺ , La ³⁺ , Pr ^3* , Nd ³⁺ , Sm ³⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , D ^3* , Ho ³⁺ , Er ^3* , Tm ³⁺ , Ni ²⁺ , Yb ³⁺ , and combinations thereof. In certain embodiments, said metal ions are lanthanide series metal ions. In certain embodiments, said lanthanide series metal ions are selected from the group consisting of Ce ³ \ La ³⁺ , Pr ^3* , Nd ³⁺ , Sm ³⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ^3* , Ho ³⁺ , Er ^3* , Tm ³⁺ , Yb ³⁺ , and combinations thereof. In certain embodiments, said metal ions are selected from the group consisting of Cu ² \ Pt ²⁺ , Pd ²⁺ , Zn ²⁺ , and combinations thereof. In certain embodiments, said metal ions are selected from the group consisting of Y ³⁺ , Sc ³⁺ , and combinations thereof. In certain embodiments, said metal ion is La ³⁺ .

In some embodiments of these aspects, said organophosphorus compound is a pesticide, an insecticide, a chemical warfare agent, a phosphonofluoridate G-agent, and/or a nerve agent. In certain embodiments, said agents may be combined with a polymer.

In some embodiments of these aspects, said organophosphorus compound is a toxic industrial chemical (TIC) which releases F , CI ^" or B upon degradation.

In some embodiments of these aspects, said medium further comprises one or more ligands. In certain embodiments, said ligand is selected from the group consisting of 2,2 - bipyridyl, 1,10-phenanthryl, 2,9-dimethylphenanthryl, crown ether, aza crown ether, 1,5,9- triazacyclododecyl, and their substituted forms. In certain embodiments, said ligand further comprises solid support material. In certain embodiments, said solid support material is selected from a polymer, silicate, aluminate, and combinations thereof.

In some embodiments of these aspects, said medium is a solid. In some embodiments of these aspects, said medium is a solution. In certain embodiments, said solution is disposed on an applicator.

In some embodiments of these aspects, said organophosphorus compound is (/- propyl)-0-P(0)(F)CH ₃ (Sarin or "GB"), (Nbutyl)CH(CH ₃ )-0-P(0)(F)CH ₃ (Soman or "GD"), or cyclohexyl-0-P(0)(F)CH ₃ ("GF"). In some embodiments of these aspects, said organophosphorus compound is a pesticide, insecticide, chemical warfare agent, or nerve agent and, through said alcoholysis reaction, said organophosphorus compound is decomposed to a less toxic product.

According to a fourth aspect of the invention, there is provided a kit for decomposing and monitoring decomposition of an organophosphorus compound comprising a

substantially non-aqueous medium for an alcoholysis reaction and an indicator compound, said medium comprising non-radioactive metal ions selected from the group consisting of lanthanide series metal ions, transition metal ions, and combinations thereof, and at least a trace amount of alkoxide ions, and said indicator compound possessing UV/visible spectral or fluorescent properties in said medium and binding to said non-radioactive metal ions to form a complex which has UV/visible spectral or fluorescent properties different from the UV/visible spectral or fluorescent properties of said indicator compound when unbound.

According to a fifth aspect of the invention, there is provided a kit for detecting an organophosphorus compound comprising a substantially non-aqueous medium for an alcoholysis reaction and an indicator compound, said medium comprising non-radioactive metal ions selected from the group consisting of lanthanide series metal ions, transition metal ions, and combinations thereof, and at least a trace amount of alkoxide ions, and said indicator compound possessing UV/visible spectral or fluorescent properties in said medium and binding to said non-radioactive metal ions to form a complex which has UV/visible spectral or fluorescent properties different from the UV/visible spectral or fluorescent properties of said indicator compound when unbound.

According to a sixth aspect of the invention, there is provided a kit for monitoring decomposition of an organophosphorus compound comprising a substantially non-aqueous medium for an alcoholysis reaction and an indicator compound, said medium comprising non-radioactive metal ions selected from the group consisting of lanthanide series metal ions, transition metal ions, and combinations thereof, and at least a trace amount of alkoxide ions, and said indicator compound possessing UV/visible spectral or fluorescent properties in said medium and binding to said non-radioactive metal ions to form a complex which has UV/visible spectral or fluorescent properties different from the UV/visible spectral or fluorescent properties of said indicator compound when unbound.

In some embodiments of these aspects, said medium is contained in an ampule. In some embodiments of these aspects, the kit comprises an applicator bearing the medium, said applicator being adapted so that the medium is applied to the

organophosphorus compound and the compound decomposes. In certain embodiments, the applicator comprises a moist cloth bearing the medium, an absorbent wipe, a brush, a paint brush, a roller, a trowel, a high pressure airless spray gun or a handheld airless spray gun. In certain embodiments, the applicator is a sprayer which is adapted to spray the medium.

In some embodiments of these aspects, said medium further comprises a solvent selected from the group consisting of methanol, substituted and unsubstituted primary, secondary and tertiary alcohols, alkoxyalkanol, aminoalkanol, and combinations thereof. In certain embodiments, said medium comprises aminoalkanol or ethanolamine. In certain embodiments, said medium further comprises a solvent selected from the group consisting of methanol, ethanol, n-propanol, iso-propanol, n-butanol, 2-butanol, methoxyethanol, and combinations thereof. In certain embodiments, said medium further comprises a solvent selected from the group consisting of nitriles, esters, ketones, amines, ethers, hydrocarbons, substituted hydrocarbons, unsubstituted hydrocarbons, halogenated hydrocarbons, halogenated ethers and combinations thereof. In certain embodiments, said medium is prepared by combining a metal salt and an alkoxide salt with at least one of alcohol, alkoxyalkanol and aminoalkanol, optionally ethanolamine. In certain embodiments, said medium further comprises a non-inhibitory buffering agent. In certain embodiments, said buffering agent comprises an aniline, N-alkylaniline, N,N-dialkylaniline, N-alkylmorpholine, N- alkylimidazole, 2,6-dialkylpyridine, primary amine, secondary amine, tertiary amine, trialkylamine, or a combination thereof.

In some embodiments of these aspects, the concentration of said alkoxide ions is about 0.01 to about 2 equivalents of the concentration of the metal ions, about 0.1 to about 2 equivalents of the concentration of the metal ions, about 0.5 to about 1.5 equivalents of the concentration of the metal ions, or about 1 to about 1.5 equivalents of the concentration of the metal ions.

In some embodiments of these aspects, said metal ions are selected from the group consisting of lanthanide series metal ions, copper, cobalt, platinum, palladium, zinc, nickel, yttrium, scandium ions, and combinations thereof. In certain embodiments, metal ions are selected from the group consisting of Cu ²⁺ , Co ²⁺ , Pt ²⁺ , Pd ²⁺ , Zn ²⁺ , Y ³⁺ , Sc ³⁺ , Ce ³⁺ , La ³⁺ , Pr ³ *, Nd ³⁺ , Sm ³⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³ ", Ho ³⁺ , Er ³ , Tm ³⁺ , Ni ²⁺ , Yb ³⁺ , and combinations thereof. In certain embodiments, said metal ions are lanthanide series metal ions. In certain embodiments, said lanthanide series metal ions are selected from the group consisting of Ce ³⁺ , La ³⁺ , Pr ^3* , Nd ³⁺ , Sm ³⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Er ³ *, Tm ³⁺ , Yb ³⁺ , and combinations thereof. In certain embodiments, said metal ions are selected from the group consisting of Cu ²⁺ , Ni ²⁺ , Pt ²⁺ , Pd ²⁺ , Zn ²⁺ , and combinations thereof. In certain embodiments, said metal ions are selected from the group consisting of Y ³⁺ , Sc ³⁺ , and combinations thereof. In certain embodiments, said metal ions comprise La ³⁺ .

In some embodiments of these aspects, said medium further comprises one or more ligands. In certain embodiments, said one or more ligands comprise 2,2'-bipyridyl, 1 ,10- phenanthryl, 2,9-dimethylphenanthryl, crown ether, aza crown ether, 1 ,5,9- triazacyclododecyl, substituted forms thereof, or combinations thereof. In certain embodiments, said one or more ligands are attached via linkages to solid support material. In certain embodiments, said solid support material comprises polymer, silicate, aluminate, or combinations thereof.

In some embodiments of these aspects, said medium is a solid. In some

embodiments of these aspects, said medium is a solution.

In some embodiments of these aspects, said indicator compound is selected from the group consisting of Bromocresol purple, Chlorophenol red, Methyl red, Bromophenol blue, Bromocresol green, Phenolphthalein, Thymolphthalein, Thymol blue, Cresol red, Congo red, Methyl orange and Neutral red 2.

In some embodiments of these aspects, the kit further comprises written instructions for use.

In some embodiments of these six aspects, the organophosphorus compound is neutral.

In some embodiments of the method aspects, said determining step comprises determining visible spectral properties of said indicator compound. In certain embodiments, said determining step comprises observing the color of said indicator compound. In certain embodiments, a color change in said indicator compound indicates decomposition of said organophosphorus compound. In certain embodiments, said organophosphorus compound is detected by observing a color change in said indicator compound. In certain

embodiments, decomposition of said organophosphorus compound is monitored by monitoring color change in said indicator compound. In certain embodiments, the color of said indicator compound changes from red to yellow, from orange to yellow, from yellow to orange, from fuschia to turquoise, from fuschia to yellow, or from fuschia to green, depending on the indicator compound used.

According to a seventh aspect of the invention, there is provided a method for decomposing and monitoring decomposition of an organophosphorus compound, comprising: a) subjecting said organophosphorus compound to an alcoholysis reaction in the presence of an indicator compound in a substantially non-aqueous medium comprising non-radioactive metal ions selected from the group consisting of lanthanide series metal ions, transition metal ions, and combinations thereof, and at least a trace amount of alkoxide ions; wherein said indicator compound possesses visible spectral properties in said medium; wherein said indicator compound binds to said non-radioactive metal ions forming a complex whose color is different from the color of said indicator compound when unbound; and wherein, through said alcoholysis reaction, said organophosphorus compound is

decomposed and halogen anions are released, such that said indicator compound is released from said complex; and b) determining whether said indicator compound changes color, wherein a change in color of said indicator compound indicates presence of unbound indicator compound and decomposition of said organophosphorus compound.

According to an eighth aspect of the invention, there is provided a method for detecting an organophosphorus compound, comprising: a) subjecting said

organophosphorus compound to an alcoholysis reaction in the presence of an indicator compound in a substantially non-aqueous medium comprising non-radioactive metal ions selected from the group consisting of lanthanide series metal ions, transition metal ions, and combinations thereof, and at least a trace amount of alkoxide ions; wherein said indicator compound possesses visible spectral properties in said medium; wherein said indicator compound binds to said non-radioactive metal ions forming a complex whose color is different from the color of said indicator compound when unbound; and wherein, through said alcoholysis reaction, said organophosphorus compound is decomposed and halogen anions are released, such that said indicator compound is released from said complex; and b) determining whether said indicator compound changes color, wherein said

organophosphorus compound is detected by a change of color of said indicator compound.

According to an ninth aspect of the invention, there is provided a method for monitoring decomposition of an organophosphorus compound, comprising: a) subjecting said organophosphorus compound to an alcoholysis reaction in the presence of an indicator compound in a substantially non-aqueous medium comprising non-radioactive metal ions selected from the group consisting of lanthanide series metal ions, transition metal ions, and combinations thereof, and at least a trace amount of alkoxide ions; wherein said indicator compound possesses visible spectral properties in said medium; wherein said indicator compound binds to said non-radioactive metal ions forming a complex whose color is different from the color of said indicator compound when unbound; and wherein, through said alcoholysis reaction, said organophosphorus compound is decomposed and halogen anions are released, such that said indicator compound is released from said complex; and b) determining whether said indicator compound changes color, wherein a change in color of said indicator compound indicates decomposition of said organophosphorus compound.

In some embodiments of the seventh, eighth and ninth aspects, said halogen anions bind to said non-radioactive metal ions, thereby releasing said indicator compound from said complex.

In some embodiments of these aspects, said indicator compound is selected from the group consisting of Bromocresol purple, Chlorophenol red, Methyl red, Bromophenol blue, Bromocresol green, Phenolphthalein, Thymolphthalein, Thymol blue, Cresol red, Congo red, Methyl orange and Neutral red 2.

In some embodiments of these aspects, said organophosphorus compound has the following formula (15):

where:

J is O or S;

X and G are the same or different and are selected from the group consisting of Q, OQ, QA, OA, F, CI, Br, I, QS, SQ, SA and C≡N,

Z is F, CI or Br;

wherein at least one of X and G is not Q or QA;

Q is a substituted or unsubstituted branched, straight-chain or cyclic alkyl group having 1-100 carbon atoms; and A is a substituted or unsubstituted moiety selected from the group consisting of phenyl, biphenyl, benzyl, pyridyl, naphthyl, polynuclear aromatic, and aromatic and non- aromatic heterocyclic; and

wherein said substituents are selected from the group consisting of CI, Br, I, F, nitro, nitroso, Q, alkenyl, OQ, carboxyalkyl, acyl, S0 ₃ H, S0 ₃ Q, S=0(Q), S(=0) ₂ Q, amino, alkylamino (NHQ), arylamino (NHA), alkyiarylamino, dialkylamino and diarylamino.

In some embodiments of these aspects, said organophosphorus compound has the following formula (15):

where:

J is O or S;

X and G are the same or different and are selected from the group consisting of Q, OQ, QA, OA, F, CI, Br, I, QS, SQ, SA and C≡N,

Z is F, CI or Br;

Q is a substituted or unsubstituted branched, straight-chain or cyclic alkyl group having 1-100 carbon atoms; and

A is a substituted or unsubstituted moiety selected from the group consisting of phenyl, biphenyl, benzyl, pyridyl, naphthyl, polynuclear aromatic, and aromatic and non- aromatic heterocyclic;

wherein said substituents are selected from the group consisting of CI, Br, I, F, nitro, nitroso, Q, alkenyl, OQ, carboxyalkyl, acyl, S0 ₃ H, S0 ₃ Q, S=0(Q), S(=0) ₂ Q, amino, alkylamino (NHQ), arylamino (NHA), alkyiarylamino, dialkylamino and diarylamino.

In some embodiments of these aspects, said organophosphorus compound is a neutral compound.

According to a tenth aspect of the invention, there is provided a method for detecting release of halogen anions during decomposition of an organophosphorus compound, comprising: a) subjecting said organophosphorus compound to an alcoholysis reaction in the presence of an indicator compound in a substantially non-aqueous medium comprising non-radioactive metal ions selected from the group consisting of lanthanide series metal ions, transition metal ions, and combinations thereof, and at least a trace amount of alkoxide ions; wherein said indicator compound possesses visible spectral properties in said medium; wherein said indicator compound binds to said non-radioactive metal ions forming a complex whose color is different from the color of said indicator compound when unbound; and wherein, through said alcoholysis reaction, said organophosphorus compound is

decomposed and halogen anions are released; wherein said halogen anions bind to said non-radioactive metal ions, releasing said indicator compound from said complex; and b) determining whether said indicator compound changes color, wherein a change in color of said indicator compound indicates release of fluoride anions.

According to an eleventh aspect of the invention, there is provided a process for decontaminating and monitoring decontamination of surfaces or solid objects contaminated with an organophosphorus compound comprising: a) treating the surface or solid objects with a solution comprising a substantially non-aqueous medium for an alcoholysis reaction and an indicator compound, said medium comprising non-radioactive metal ions selected from the group consisting of lanthanide series metal ions, transition metal ions, and combinations thereof, and at least a trace amount of alkoxide ions, and said indicator compound possessing UV/visible or fluorescent spectral properties in said medium and binding to said non-radioactive metal ions to form a complex which has UV/visible spectral or fluorescent properties different from the UV/visible spectral or fluorescent properties of said indicator compound when unbound; and b) comparing the UV/visible spectral or fluorescent properties of said solution after treatment of the surface or solid objects with the UV/visible spectral or fluorescent properties of said solution before treatment of the surface or solid objects, wherein a change in the UV/visible spectral or fluorescent properties of said solution after treatment of the surface or solid objects indicates decontamination.

In some embodiments of this aspect, the organophosphorus compound is a neutral compound.

In some embodiments of this aspect, the indicator compound possesses visible spectral properties.

In some embodiments of this aspect, the color of said indicator compound changes when decontamination occurs. According to a twelfth aspect of the invention, there is provided a solution for detecting, decomposing and/or monitoring decomposition of an organophosphorus compound comprising a substantially non-aqueous medium for an alcoholysis reaction and an indicator compound, said medium comprising non-radioactive metal ions selected from the group consisting of lanthanide series metal ions, transition metal ions, and combinations thereof, and at least a trace amount of alkoxide ions, and said indicator compound possessing U /visible spectral or fluorescent properties in said medium and binding to said non-radioactive metal ions to form a complex which has UV/visible spectral or fluorescent properties different from the UV/visible spectral or fluorescent properties of said indicator compound when unbound.

In some embodiments of this aspect, the organophosphorus compound is a neutral compound.

In some embodiments of this aspect, the indicator compound possesses visible spectral properties.

In some embodiments of this aspect, the color of said complex is different from the color of said indicator compound when unbound.

In some embodiments of this aspect, the color of said solution changes when an organophosphorus compound is detected or decomposed.

In some embodiments of the fourth, fifth and sixth aspects, said indicator compound possesses visible spectral properties.

In some embodiments of the fourth, fifth and sixth aspects, the color of said complex is different from the color of said indicator compound when unbound.

In some embodiments of the fourth, fifth and sixth aspects, the color of said unbound indicator compound is yellow, orange, green or turquoise.

In some embodiments of the fourth, fifth and sixth aspects, the color of said medium changes when an organophosphorus compound is detected or decomposed.

In some embodiments of the above method aspects, the halogen anions are fluoride anions (F ). In some embodiments of the above method aspects, the halogen anions are chloride anions (CI ^" )- In some embodiments of the above method aspects, the halogen anions are bromide anions (Br ).

According to a thirteenth aspect of the invention, there is provided a method for decomposing and monitoring decomposition of a toxic industrial chemical comprising: a) subjecting said toxic industrial chemical to an alcoholysis reaction in the presence of an indicator compound in a substantially non-aqueous medium comprising non-radioactive metal ions selected from the group consisting of lanthanide series metal ions, transition metal ions, and combinations thereof, and at least a trace amount of alkoxide ions; wherein said indicator compound possesses UV/visible spectral or fluorescent properties in said medium; wherein said indicator compound binds to said non-radioactive metal ions forming a complex with UV/visible spectral or fluorescent properties which are different from the UV/visible spectral or fluorescent properties of said indicator compound when unbound; and wherein, through said alcoholysis reaction, said toxic industrial chemical is decomposed and halogen anions are released, releasing said indicator compound from said complex; and b) determining UV/visible spectral or fluorescent properties of said indicator compound, wherein the UV/visible spectral or fluorescent properties of said indicator compound indicate whether unbound indicator compound is present; and wherein presence of said unbound indicator compound indicates decomposition of said toxic industrial chemical;

wherein said toxic industrial chemical is an acyl halide, an alkyl sulphonyl halide, an aryl sulphonyl halide, a sulfuryl halide, a phosphorus halide, a phosphorusoxytrihalide, an alkoxymethyl halide, an arlyoxymethyl halide, a triarylmethyl halide, a solvolytically labile organohalide, an aluminum halide, or a solvolytically labile metal halide.

According to a fourteenth aspect of the invention, there is provided a method for detecting a toxic industrial chemical, comprising: a) subjecting said toxic industrial chemical to an alcoholysis reaction in the presence of an indicator compound in a substantially nonaqueous medium comprising non-radioactive metal ions selected from the group consisting of lanthanide series metal ions, transition metal ions, and combinations thereof, and at least a trace amount of alkoxide ions; wherein said indicator compound possesses UV/visible spectral or fluorescent properties in said medium; wherein said indicator compound binds to said non-radioactive metal ions forming a complex with UV/visible spectral or fluorescent properties which are different from the UV/visible spectral or fluorescent properties of said indicator compound when unbound; and wherein, through said alcoholysis reaction, said toxic industrial chemical is decomposed and halogen anions are released, such that said indicator compound is released from said complex; and b) determining UV/visible spectral or fluorescent properties of said indicator compound, wherein the UV/visible spectral or fluorescent properties of said indicator compound indicate whether unbound indicator compound is present; and wherein said toxic industrial chemical is detected by detecting presence of said unbound indicator compound; wherein said toxic industrial chemical is an acyl halide, an alkyl sulphonyl halide, an aryl sulphonyl halide, a sulfuryl halide, a phosphorus halide, a phosphorusoxytrihalide, an alkoxymethyl halide, an arlyoxymethyl halide, a triarylmethyl halide, a solvolytically labile organohalide, an aluminum halide, or a solvolytically labile metal halide.

According to a fifteenth aspect of the invention, there is provided a method method for monitoring decomposition of a toxic industrial chemical, comprising: a) subjecting said toxic industrial chemical to an alcoholysis reaction in the presence of an indicator compound in a substantially non-aqueous medium comprising non-radioactive metal ions selected from the group consisting of lanthanide series metal ions, transition metal ions, and combinations thereof, and at least a trace amount of alkoxide ions; wherein said indicator compound possesses UV/visible spectral or fluorescent properties in said medium; wherein said indicator compound binds to said non-radioactive metal ions forming a complex with UV/visible spectral or fluorescent properties which are different from the UV/visible spectral or fluorescent properties of said indicator compound when unbound; and wherein, through said alcoholysis reaction, said toxic industrial chemical is decomposed and halogen anions are released, such that said indicator compound is released from said complex; and b) determining UV/visible spectral or fluorescent properties of said indicator compound, wherein the UV/visible spectral or fluorescent properties of said indicator compound indicate whether unbound indicator compound is present; and wherein presence of said unbound indicator compound indicates decomposition of said toxic industrial chemical; wherein said toxic industrial chemical is an acyl halide, an alkyl sulphonyl halide, an aryl sulphonyl halide, a sulfuryl halide, a phosphorus halide, a phosphorusoxytrihalide, an alkoxymethyl halide, an arlyoxymethyl halide, a triarylmethyl halide, a solvolytically labile organohalide, an aluminum halide, or a solvolytically labile metal halide.

The thirteenth, fourteenth, and fifteenth aspects comprise all embodiments described above with respect to the first to twelfth aspects according to the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

For a better understanding of the invention and to show more clearly how it may be carried into effect, reference will now be made by way of example to the accompanying drawings, which illustrate aspects and features according to preferred embodiments of the present invention, and in which:

Figures 1-10 shows UV-visible spectra obtained for various combinations of lanthanide ion salts, indicators and buffer solutions added to fluoride anion in solution.

Curve 1 shows the spectrum obtained from a solution containing 20 mM HOTf

(trifluoromethane sulphonic acid) and 40 mM amine buffer; Curve 2 shows a spectrum obtained after addition of 0.1 mM indicator to the solution; Curve 3 shows a spectrum obtained after addition of 1 mM lanthanide triflate; Curve 4 shows a spectrum obtained after addition of 1 mM tetrabutylammonium fluoride ( (Bu ₄ N ⁺ )F ); Curve 5 shows a spectrum obtained after addition of another 1 mM (Bu N ⁺ )F ^" ; Curve 6 shows a spectrum obtained after addition of another 1 mM (Bu ₄ N ⁺ )F ^~ ; Curve 7 shows a spectrum obtained after addition of another 1 mM (Bu ₄ N ⁺ )F ^" ; Curve 8 shows a spectrum obtained after addition of another 1 mM (Bu ₄ N ⁺ )F\ "Abs" stands for absorbance.

In Figure 1 , curve 1 shows a spectrum obtained where the buffer is 4- ethylmorpholine (EtMo); curve 2 shows a spectrum obtained where the indicator compound is Bromocresol purple; curve 3 shows a spectrum obtained where the lanthanide triflate is lanthanum trifluoromethanesulfonate (La(OTf) ₃ ); curve 4 shows a spectrum obtained after addition of (Bu N ⁺ )F; curve 5 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F ^" ; and curve 6 shows a spectrum obtained after another addition of (Bu ₄ N ^* )F ^~ .

In Figure 2, curve 1 shows a spectrum obtained where the buffer is 4- ethylmorpholine (EtMo); curve 2 shows a spectrum obtained where the indicator compound is Chlorophenol red; curve 3 shows a spectrum obtained where the lanthanide triflate is lanthanum trifluoromethanesulfonate (La(OTf) ₃ ); curve 4 shows a spectrum obtained after addition of (Bu N ⁺ )F; curve 5 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F ^~ ; curve 6 shows a spectrum obtained after another addition of (Bu ₄ N ^* )F ^~ ; and curve 7 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F\

In Figure 3, curve 1 shows a spectrum obtained where the buffer is 4- ethylmorpholine (EtMo); curve 2 shows a spectrum obtained where the indicator compound is Methyl red; curve 3 shows a spectrum obtained where the lanthanide triflate is lanthanum trifluoromethanesulfonate (La(OTf) ₃ ); curve 4 shows a spectrum obtained after addition of (Bu ₄ N ⁺ )F ^~ ; curve 5 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F; curve 6 shows a spectrum obtained after another addition of (Bu N ⁺ )F; curve 7 shows a spectrum obtained after another addition of (Bu N ⁺ )F; and curve 8 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F ^~ . In Figure 4, curve 1 shows a spectrum obtained where the buffer is 2,6-lutidine (Luti) (reagent plus 98%); curve 2 shows a spectrum obtained where the indicator compound is Bromophenol blue; curve 3 shows a spectrum obtained where the lanthanide triflate is lanthanum trifluoromethanesulfonate (La(OTf) ₃ ); curve 4 shows a spectrum obtained after addition of (Bu N ⁺ )F ^" ; curve 5 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F; curve 6 shows a spectrum obtained after another addition of (Bu N ⁺ )F ^~ ; curve 7 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F ^" ; and curve 8 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F ^~ .

In Figure 5, curve 1 shows a spectrum obtained where the buffer is 4- ethylmorpholine (EtMo); curve 2 shows a spectrum obtained where the indicator compound is Bromocresol green; curve 3 shows a spectrum obtained where the lanthanide triflate is lanthanum trifluoromethanesulfonate (La(OTf) ₃ ); curve 4 shows a spectrum obtained after addition of (Bu ₄ N ⁺ )F ^~ ; curve 5 shows a spectrum obtained after another addition of (Bu N ⁺ )F ^" ; curve 6 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F ^~ ; and curve 7 shows a spectrum obtained after another addition of (Bu N ⁺ )F ^~ .

In Figure 6, curve 1 shows a spectrum obtained where the buffer is 4- ethylmorpholine (EtMo); curve 2 shows a spectrum obtained where the indicator compound is Bromocresol purple; curve 3 shows a spectrum obtained where the lanthanide triflate is samarium trifluoromethanesulfonate (Sm(OTf) ₃ ); curve 4 shows a spectrum obtained after addition of (Bu ₄ N ⁺ )F ^" ; curve 5 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F ^" ; curve 6 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F ^" ; and curve 7 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F ^~ .

In Figure 7, curve 1 shows a spectrum obtained where the buffer is 4- ethylmorpholine (EtMo); curve 2 shows a spectrum obtained where the indicator compound is Methyl red; curve 3 shows a spectrum obtained where the lanthanide triflate is samarium trifluoromethanesulfonate (Sm(OTf) ₃ ); curve 4 shows a spectrum obtained after addition of (Bu N ⁺ )F ^" ; curve 5 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F ^~ ; curve 6 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F ^~ ; curve 7 shows a spectrum obtained after another addition of (Bu N ⁺ )F ^~ ; and curve 8 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F ^~ .

In Figure 8, curve 1 shows a spectrum obtained where the buffer is 4- ethylmorpholine (EtMo); curve 2 shows a spectrum obtained where the indicator compound is Chlorophenol red; curve 3 shows a spectrum obtained where the lanthanide triflate is samarium trifluoromethanesulfonate (Sm(OTf) ₃ ); curve 4 shows a spectrum obtained after addition of (Bu ₄ N ⁺ )F ^~ ; curve 5 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F ^" ; curve 6 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F ^' ; and curve 7 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F.

In Figure 9, curve 1 shows a spectrum obtained where the buffer is 2,6-lutidine (Luti) (reagent plus 98%); curve 2 shows a spectrum obtained where the indicator compound is Bromophenol blue; curve 3 shows a spectrum obtained where the lanthanide inflate is samarium trifluoromethanesulfonate (Sm(OTf) ₃ ); curve 4 shows a spectrum obtained after addition of (Bu ₄ N ⁺ )F ^" ; curve 5 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F ^" ; curve 6 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F ^" ; curve 7 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F; and curve 8 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F\

In Figure 10, curve 1 shows a spectrum obtained where the buffer is 2,6-lutidine (Luti) (reagent plus 98%); curve 2 shows a spectrum obtained where the indicator compound is Bromocresol green; curve 3 shows a spectrum obtained where the lanthanide triflate is samarium trifluoromethanesulfonate (Sm(OTf) ₃ ); curve 4 shows a spectrum obtained after addition of (Bu ₄ N ⁺ )F ^" ; curve 5 shows a spectrum obtained after another addition of (Bu N ⁺ )F ^" ; and curve 6 shows a spectrum obtained after another addition of (Bu ₄ N ⁺ )F ^~ .

Figures 11-18 show UV-visible spectra obtained for various combinations of lanthanide ion salts, indicator compounds and buffer solutions. "Indicator system": spectra obtained from a solution of buffer (20 mM HOTf and 40 m amine),0.1 mM indicator and 1 mM La(OTf) ₃ or Sm(OTf) ₃ as indicated below; "Indicator system + BnzF": spectra obtained after adding 62.5 ml of a 5 mM benzoyl fluoride (BnzF) stock solution (200 ml in acetonitrile) to the indicator system. The UV-visible spectrum was recorded from 800 to 200 nm, every 1.2 minutes. "Abs" stands for absorbance.

In Figure 1 , spectra are shown where the indicator compound is Bromocresol purple, the buffer is EtMo, and La(OTf) ₃ is used; cycle time was 1.2 min.

In Figure 12, spectra are shown where the indicator compound is Bromocresol purple, the buffer is EtMo, and Sm(OTf) ₃ is used; cycle time was 1.2 min.

In Figure 13, spectra are shown where the indicator compound is Methyl red, the buffer is EtMo, and La(OTf) ₃ is used; cycle time was 1.2 min.

In Figure 14, spectra are shown where the indicator compound is Methyl red, the buffer is EtMo, and Sm(OTf) ₃ is used; cycle time was 1.2 min. In Figure 15, spectra are shown where the indicator compound is Bromophenol blue, the buffer is Luti, and La(OTf) ₃ is used; cycle time was 1.2 min.

In Figure 16, spectra are shown where the indicator compound is Bromophenol blue, the buffer is Luti, and Sm(OTf) ₃ is used; cycle time was 1.2 min.

In Figure 17, spectra are shown where the indicator compound is Bromocresol green, the buffer is EtMo, and La(OTf) ₃ is used; cycle time was 1.2 min.

In Figure 18, spectra are shown where the indicator compound is Bromocresol green, the buffer is EtMo, and Sm(OTf) ₃ is used; cycle time was 1.2 min.

DETAILED DESCRIPTION OF THE INVENTION

According to a broad aspect of the invention there is provided a method of detecting a toxic compound, e.g., an organophosphorus compound or an industrial chemical, by detecting the presence of decomposition products. In an aspect, there is provided a method of detecting the presence of a toxic, e.g., an organophosphorus, compound. In another aspect, there is provided a method of monitoring decomposition of a toxic, e.g., an organophosphorus, compound. In yet another aspect, there is provided a method for decomposing and monitoring decomposition of a toxic, e.g., an organophosphorus compound.

We have previously reported methods of decomposing organophosphorus agents using metal ion catalyzed alcoholysis (MICA) in organic media under neutral conditions and ambient temperatures (Neverov, A.A. and Brown, R.S., Main Group Chemistry (2010), 9:265-281 ; U.S. Patent No. 7,21 ,836; and U.S. Patent No. 7,875,739). For example, methods of decomposing an organophosphorus compound by combining the

organophosphorus compound with a substantially non-aqueous medium comprising alcohol, alkoxyalkanol or aminoalkanol, metal ions and at least a trace amount of alkoxide ions, have been described. When so-combined the organophosphorus compound undergoes an alcoholysis reaction and forms a less toxic or non-toxic compound.

Methods of increasing the rate of decomposition of an organophosphorus compound by combining the compound with a catalytic species formed in a substantially non-aqueous medium comprising metal ions; alcohol, alkoxyalkanol or aminoalkanol; and alkoxide ions were also described (see, e.g., Neverov, A.A. and Brown, R.S., Main Group Chemistry (2010), 9:265-281 ; U.S. Patent No. 7,214,836; and U.S. Patent No. 7,875,739). Live agent testing in solution conducted by ECBC (Edgewood Maryland, USA) and TNO in the

Netherlands (using a 1 :50 challenge; 1 part agent and 50 parts solution, v:v) has shown that various G- and V-agents are rapidly decomposed by the decontamination solution, for example decontamination can occur in less than 30 seconds (Dupont Durst, H. et al., Abstract no. INOR-396, Abstracts of Papers, 238th ACS National Meeting, Washington, DC, U.S., August 16-20, 2009).

We report herein the development of a halogen anion detection system, i.e., a fluoride anion (F ), chloride anion (CI ), and/or bromide anion (Br ) detection system, compatible with metal ion based decontamination methods (i.e., with the formulations of the MICA solutions) and with the chemistry of decomposition of a substrate material that produces a halogen anion for detection. We have developed a system capable of producing a visual optical response at sub-millimolar (<0.001 M) concentration of inorganic F ^" . The detection system is based, at least in part, on the fact that metal cations (e.g., lanthanide cations (Ln ^3*" )) have high affinity for halogen anions, e.g., F ^" , particularly in solvents of lower polarity such as alcohols that are used in the MICA decontamination method (methanol and ethanol being two common examples).

A main component of the detection techniques and solutions described herein is a complex between a non-radioactive metal ion, e.g., a lanthanide (Ln ³⁺ ) cation or lanthanum methanesulfonate, and an indicator compound, where such complex has specific UV/visible spectral or fluorescent properties. Without wishing to be bound by theory, in the presence of a sufficient amount of halogen anion, e.g., F ^" , the halogen anion binds to the metal ion (e.g., l_n ³⁺ )/indicator complex thereby releasing the indicator compound to produce a chromophore or fluorophore that has different spectral properties from the original metal ion (e.g., Ln ³⁺ )/indicator complex.

Based on this methodology for detection of halogen anion, a method for the detection of certain substrates was created which, upon decomposition in the MICA solution, release halogen anion (referred to herein as a "relay indicating technique"). The most common examples of such substrates are the so-called fluoride containing G-agents (e.g., sarin (1) and soman (2)), acyl fluorides such as benzoyl fluoride (BnzF) and organophosphorus fluorides of general structure such as (RO) ₂ PF, (RO) ₂ P(=0)F, R ₂ PF, R(RO)P(0)F, and R ₂ P(=0)F). Other examples of such substrates are toxic industrial chemicals (TICs) which release fluoride, chloride or bromide anions upon degradation. Non-limiting examples of such TICs include acyl halides, alkyl and aryl sulphonyl halides, sulfuryl halides, phosphorus halides such as PX ₃ (where X = F, CI, Br), and phosphorusoxytrihalides such as P(0)X ₃ , solvolytically labile organohalides, aluminum halides, easily solvolyzed organohalides such as alkoxymethyl halides, arlyoxymethyl halides, triaryimethyl halides, and solvolytically labile metal halides such as AIX ₃ (where X = F, CI, Br).

Sarin (GB) 1 Soman (GD) 2 GF

As a demonstration of the principle, we used benzoyl fluoride as an example of materials which release F ^" upon decomposition in MICA solution and as a model compound for phosphonofluoridate G-agents such as sarin and soman. The process is shown in Scheme 1 below.

(Ln ^¾+ ) _q ( R) _k F- + In

Scheme 1. Schematic mechanism for the production of a visual response from an indicator compound (In) which is released from complexation by F ^" which binds to the Ln ³⁺ (ln) complex. The designators r,p,q,k,n,m in the formulae in Scheme 1 refer to the relative stoichiometry for the various components of the complex. r=1-2, p=1-2, q=1-2, n=1-5, m=1- 5, k=1-5.

The metal ion catalyzed alcoholysis (MICA) decontamination solution contains catalyst [(Ln ³⁺ ) _p ( OR) _m ] that promotes the solvolysis of benzoyl fluoride during which inorganic fluoride anion is released. Its presence is detected by the change of the visible spectral properties of solution, or more accurately a Ln ³⁺ /indicator complex ((Ln ³⁺ ) _r (OR) _n (ln)) which is present in the solution in low concentration. The initial response time for the detection of the so-produced F ^" depends upon the reactivities of the substrates, and in the case of benzoyl fluoride is less than 30 seconds. Application of the indicating decontamination solution results in a clearly defined visual response at the site of contamination.

It should be noted that the principle is not limited to the detection of F ^" from benzoyl fluorides, but also a wide variety of carbonyl-containing compounds which upon

decomposition in the medium produce halogen anions (e.g., F, CI ^" , or Br ^" ) (see Scheme 2).

{( ^x+ )(OR) _n (L) _m } _s

HOR (Ln ³⁺ ) _r ( R)n(L) _m (ln)

Ln ^d+ (OR) _n (L) _m Ha|- + In

Scheme 2. Schematic mechanism for the production of a visual response from an indicator compound (In) which is released from complexation by halide (Hal) which binds to the Ln ³⁺ (ln) complex. The halide in Scheme 2 is produced from alcoholysis of an acyl halide, or thioacyl halide. The designator R' refers to alkoxy, aryioxy, alkyl, or aryl substituents; J refers to O (oxygen) or S (sulphur); Hal refers to F (fluoride), CI (chloride) or Br (bromide); and the designators n,m in the formulae for (Ln ³⁺ )( OR) _n (L) _m (ln) _s refer to the relative stoichiometry for the various components of the complex. In {(M ^x+ )( ^" OR) _n (L) _m } _s , where M is a metal selected from lanthanide series metals or transition metals; x is the charge on the metal which may be 1 to 9, most preferably 2 to 4; ^" OR is alkoxide; n is the number of associated alkoxide ions and may be 1 , 2, n -1, n, n+1 , n+2, ...n+6, most preferably 1 to n-1 ; s is 1 to 100; L is ligand; m is the number of ligands complexed to the metal ion, and may be 0 to 9; where m is greater than 1 , the ligands may be the same or different.

It should be noted that the principle is applicable to the wide variety of

organophosphorus compounds which upon decomposition in the medium produce halogen anions (e.g., F ^" , CI ^" , or Br ^" ) (see Scheme 3). ) _r (OR) _n (L) _m (ln)

Ln ³⁺ ( R) _n (L) _m Ha|- + In

Scheme 3. Schematic mechanism for the production of a visual response from an indicator compound (In) which is released from complexation by Hal ^" which binds to the Ln ³⁺ (ln) complex. The halide is released from the (R') ₂ P(0)Hal or (R') ₂ P(S)Hal or (R') ₂ PHal substrates by a metal ion catalyzed alcoholysis reaction. The designator R' refers to alkoxy, aryloxy, alkyl, or aryl substituents and can also include F, CI or Br substituents; J refers to O (oxygen), S (sulphur) or lone pair of electrons; Hal refers to F (fluoride), CI (chloride) or Br (bromide); and the designators n,m in the formulae for (Ln ³⁺ )(OR) _n (L) _m (ln) refer to the relative stoichiometry for the various components of the complex. In {(M* ⁺ )(OR) _n (L) _m } _s where M is a metal selected from lanthanide series metals or transition metals; x is the charge on the metal which may be 1 to 9, most preferably 2 to 4; ^" OR is alkoxide; n is the number of associated alkoxide ions and may be 1 , 2, n -1, n, n+1 , n+2, ...n+6, most preferably 1 to n-1 ; s is 1 to 100; L is ligand; m is the number of ligands complexed to the metal ion, and may be 0 to 9; where m is greater than 1 , the ligands may be the same or different.

The same principle is applicable to the wide variety of organosulfur compounds which upon decomposition in the medium produce halogen anions (e.g., F ^" , CI ^" , Br ^" ). An example is shown in Scheme 4.

) _r (OR) _n (L) _m (ln)

Ln ^3t ( R) _n (L) _m Ha|- + In

Scheme 4. Schematic mechanism for the production of a visual response from an indicator compound (In) which is released from complexation by Hal ^" which binds to the Ln ³⁺ (ln) complex. The halide is released from the R'S(0 ₂ )Hal or R'S(0)Hal or R'SHal substrates by a metal ion catalyzed alcoholysis reaction. The designator R' refers to alkoxy, aryloxy, alkyl, or aryl substituents; J refers to O (oxygen), S (sulphur) or lone pair of electrons; Hal refers to F (fluoride), CI (chloride) or Br (bromide); and the designators n, m in the formulae for (Ln ³⁺ )(- OR)n(HOR) _m (ln) refer to the relative stoichiometry for the various components of the complex. In {(M ^x+ )(-OR) _n (L) _m } _s where M is a metal selected from lanthanide series metals or transition metals; x is the charge on the metal which may be 1 to 9, most preferably 2 to 4; - OR is alkoxide; n is the number of associated alkoxide ions and may be 1 , 2, .... n -1 , n, n+1 , n+2, ...n+6, most preferably 1 to n-1 ; s is 1 to 100; L is ligand; m is the number of ligands complexed to the metal ion, and may be 0 to 9; where m is greater than 1 , the ligands may be the same or different.

It should be appreciated that in certain cases, the metal ion serving as the catalytic species responsible for the alcoholysis of the substrate should be matched to the substrate. For such matching, we use the concept of hard and soft metal ions and substrates (M. B. Smith, M.B. and March, J., Advanced Organic Chemistry, Fifth Ed., Wiley Interscience, New York (2001 ), pp. 338-342). Substrates containing the 'soft' sulphur atom such as those containing P=S or C=S units do not react rapidly with hard metal ion alcoholysis catalysts such as the lanthanides (Ln ³⁺ ), but react well with softer metal ions and their complexes containing such metal ions as Cu ²⁺ , Zn ²⁺ , Pt ²⁺ and particularly palladium in the form of Pd ²⁺ or in a palladacycle (Lu, Zhong-Lin et al., Org. Biomol. Chem. (2005), 3: 3379 - 3387). On the other hand, substrates containing the 'hard' oxygen atom positioned in P=0, C=0 or S=0 units of the substrates in Schemes 2 and 3 will be readily susceptible to alcoholysis promoted by hard cations such as the lanthanides (Ln ³⁺⁾ .

In some cases, a second metal ion may be needed for the alcoholysis reaction. For example, it will be appreciated that lanthanum may not work with a phosphorothioate substrate in the absence of palladium, copper or the like. In addition, it should be appreciated that in certain cases the metal ion should be matched to the halogen anion as some metals will work better with certain anions. For example, it may be expected that palladium or copper, but not lanthanum, will work well with bromide, whereas lanthanum works well with fluoride. Thus the choices of metal and indicator compound should be optimized for both the substrate and the type of anion released.

Thus, the techniques and solutions provided herein can be used to detect chemical warfare and/or toxic agents and to monitor their decontamination. In an aspect, the techniques and solutions allow verification that decontamination is complete.

It should be noted that the principle is not limited to the detection of F ^" from phosphonofluoridates or acyl fluorides, but is also applicable to the detection of other counter anions, such as halides. The former can be produced from the solvolysis of lachrymators; non-limiting examples of lachrymators include acyl chlorides and bromides (RC(=0)X, where X = CI or Br), alkyl and aryl sulphonyl halides, sulfuryl halides, phosphorus halides such as PX ₃ (where X = F, CI, Br), and phosphorusoxytrihalides such as P(0)X ₃ , , (RO) ₂ PX , RPX ₂ , R ₂ PX, as well as easily solvolyzed organohalides such as alkoxymethyl halides, arlyoxymethyl halides, triarylmethyl halides, and solvolytically labile metal halides such as AIX ₃ (where X = F, CI, Br).

The indicator compound used in the methods and solutions of the invention may be any compound known in the art to have chromogenic and/or fluorogenic properties, as long as the indicator compound is compatible with metal ion based decontamination methods (i.e., with MICA solutions) and is capable of binding to a non-radioactive metal ion to produce a complex having UV/visible spectral and/or fluorescent properties different from those of the unbound indicator compound. Non-limiting examples of indicator compounds include Bromocresol purple, Chlorophenol red, Methyl red, Bromophenol blue, Bromocresol green, Phenolphthalein, Thymolphthalein, Thymol blue, Cresol red, Congo red, Methyl orange and Neutral red.

In an embodiment, the indicator compound has UV/visible spectral properties. In another embodiment, the indicator compound has fluorescent properties. In yet another embodiment, the indicator compound has both UV/visible spectral and fluorescent properties. In one embodiment, the indicator compound is a triarylmethane compound with UV/visible spectral or fluorescent properties at the pH of the reaction medium. It will be appreciated that the choice of indicator compound will depend on several factors including pH, the metal ions being used, the substrate and so on. For example, it will be appreciated that in order to visualize an indicator, the color must be manifest at the pH at which the reaction occurs, i.e., the pH of the medium. In some embodiments, the color of the indicator compound will persist even if the medium or solution has evaporated, i.e., even when the indicator compound is "dry." It should be understood that reference to determining the UV/visible spectral or fluorescent properties, e.g., color, of a relay-indicating medium or solution containing indicator compound, as used herein, encompasses the UV/visible spectral or fluorescent properties, e.g., color, of the dried medium or solution or the residue from said medium or solution after drying.

As used herein, the term "alcohol" means a compound which comprises an R-OH group, for example, methanol, primary alcohols, and substituted or unsubstituted secondary alcohols, tertiary alcohols, alkoxyalkanol, aminoalkanol (e.g., ethanolamine), or a mixture thereof.

As used herein, "substantially non-aqueous medium" means an organic solvent, solution, mixture or polymer. As it is very difficult to obtain anhydrous alcohol, a person of ordinary skill in the art would recognize that trace amounts of water may be present. For example, absolute ethanol is much less common than 95% ethanol. However, the amount of alcohol present in a medium or solution according to the invention should not have so much water present as to inhibit the aicohoiysis reaction, nor should a substantial amount of hydrolysis occur.

As used herein, the term "organophosphorus compound" includes compounds which comprise a phosphorus atom doubly bonded to an oxygen or a sulfur atom. In preferred embodiments such organophosphorus compounds are deleterious to biological systems, for example, a compound may be an acetylcholine esterase inhibitor, a pesticide or a chemical warfare agent. In some embodiments, the organophosphorus compound is a neutral compound, i.e., the sum of the oxidation states of all the atoms or ions in the compound is zero. In other embodiments, particularly suited to toxic industrial chemicals (TICs) and toxic industrial materials (TIMs), the organophosphorus compounds may not be doubly bonded to an oxygen atom or sulfur atom.

As used herein, the term "decomposing an organophosphorus or toxic compound" refers to rendering a deleterious organophosphorus or toxic compound into a less toxic or non-toxic form.

In an aspect, the relay indicating techniques and solutions described herein can be used to identify or detect toxic, e.g., organophosphorus, compounds, e.g., to indicate where contaminant is located. In another aspect, the relay indicating technique described herein is used to monitor the progress of decontamination. For example, the indicator techniques and solutions described herein can be applied to a surface which has been decontaminated to verify that the contamination is complete. Any residual contaminants can be detected, e.g., visualized, using the indicator techniques and solutions of the invention.

The solutions of the invention can be applied to the contaminated surface or area using conventional techniques, of which many are known in the art. Possible methods of application include, for example, spraying, surface coating or direct application. Non-limiting examples of applicators include high pressure airless spray guns, handheld airless spray guns, absorbent wipes, moist cloths bearing the medium or solution, brushes (e.g., paint brushes), rollers and trowels.

In a further aspect, the indicator solutions provided herein are used for simultaneous decomposition and detection of toxic, e.g., organophosphorus, compounds. That is, the indicator solutions can be applied to a toxic, e.g., an organophosphorus, contaminant. The contaminant will decompose by MICA, and the decomposition can be monitored by the detection of the F ^" or halide which is released during decomposition. Thus, there are provided herein decontamination solutions with the ability to detect or monitor decomposition (referred to as "agent disclosure decontamination solutions"). The capability to allow monitoring of decomposition and to provide assurance of complete decontamination is an advantage over other decomposition methods known in the art. Thus, in an embodiment, there is provided a method for decomposing an organophosphorus compound comprising metal ion catalyzed alcoholysis (MICA) in the presence of an indicator compound. In another embodiment, there is provided a method for decomposing and monitoring decomposition of an organophosphorus compound comprising metal ion catalyzed alcoholysis (MICA) in the presence of an indicator compound.

Decomposition of a toxic compound using MICA may be carried out in solution form, or in solid form. Examples of such decomposition include, applying catalyst as a solution directly to a solid chemical warfare agent or pesticide. Such a solution would be, for example, an appropriately buffered alcoholic, alkoxyalkanoiic or aminoalkanolic solution comprising metal ions and alkoxide ions, in which one or more catalytic species forms spontaneously, which may be applied to a surface which has been contacted with an organophosphorus agent.

As used herein, the term "catalytic species" means a molecule or molecules, comprising metal ions and alkoxide ions, whose presence in an alcoholic, alkoxyalkanoiic or aminoalkanolic solvent containing a toxic, e.g., an organophosphorus compound or a toxic industrial chemical, increases the rate of alcoholysis of the organophosphorus compound relative to its rate of alcoholysis in the solvent without the catalytic species.

As used herein, the term "appropriately buffered" means that the 'pHof a solution is controlled by adding non-inhibitory buffering agents, or by adding about 0.1 to about 2.0 equivalents of alkoxide ion per equivalent of metal ion. As used herein, the term " 'ρΗ " is used to indicate pH in a non-aqueous solution (Bosch et al., J. Chem. Soc (1999), Perkin Trans. 2,1953; Rived, F. et al., Anal. Chim. Acta (1998), 374, 309; Bosch, E. et al., Anal. Chem. (1996), 68, 3651 ). One skilled in the art will recognize that, if a measuring electrode is calibrated with aqueous buffers and used to measure pH of an aqueous solution, the term

™ pH is used. If the electrode is calibrated in water and the 'pH' of a neat methanol solution is then measured, the term _w ^s pH is used, and if the latter reading is made, and a correction factor (2.24 in the case of methanol) is added, then the term * pH is used.

As used herein, the term "non-inhibitory agent or compound" means that the agent or compound does not substantially diminish the rate of a catalyzed reaction when compared to the rate of the reaction in the absence thereof.

As used herein, the term "inhibitory agent or compound" means that the agent or compound does substantially diminish the rate of a catalyzed reaction when compared to the rate of the reaction in the absence thereof.

As used herein, the term "metal species" means a metal in an oxidation state of zero to 9.

As used herein, the term "mononuclear" or "monomeric" means a species comprising one metal atom.

In an embodiment, the catalytic species used for MICA is a metal alkoxide species of the stoichiometry {M" ⁺ (OR) _m L _g } _s where M is a metal selected from lanthanide series metals or transition metals; n is the charge on the metal which may be 1 to 9, most preferably 2 to 4; OR is alkoxide; m is the number of associated alkoxide ions and may be 1 , 2, ... , n -1, n, n+1 , n+2, ...n+6, most preferably 1 to n-1 ; s is 1 to 100; L is ligand; g is the number of ligands complexed to the metal ion, and may be 0 to 9; where g is greater than 1 , the ligands may be the same or different. Examples of this embodiment include the lanthanum dimer {La ³⁺ (OMe)} ₂ and copper monomer {Cu ²⁺ ( OMe)L}. As used herein, the term "ligand" means a species containing a donor atom or atoms that has a non-bonding lone pair or pairs of electrons which are donated to a metal centre to form one or more metal-ligand coordination bonds. In this way, ligands bond to coordination sites on a metal and thereby limit dimerization and prevent further oligomerization of the metal species, thus allowing a greater number of active mononuclear species to be present than is the case in the absence of ligand or ligands.

As used herein, the term "{M ⁿ⁺ :L: ^" OR}" (which differs from the above described system, {M"*(OR) _m L ₉ } _s , by the use of the symbol ":" between constituents of the brace "{ }") is used when no stoichiometry is defined for a system comprising metal ions (M" ⁺ ), ligand (L), and alkoxide (OR). This technique is meant to encompass any and all catalytically active stoichiometries thereof including but not limited to dimers, trimers and longer oligomers, monoalkoxides, dialkoxides, polyalkoxides, etc.

In another embodiment, the catalytic species used for MICA has the general formula

20:

where Z ¹ and Z ² are the same or different non-radioactive lanthanide, copper, platinum or palladium ions;

R ¹ , R ² , R ³ and R ⁴ are each independently alkyl groups selected from a branched, cyclic or straight-chain hydrocarbon containing 1-12 carbon atoms, preferably 1-4 carbon atoms;

p is a number from 1-6; and m and q are each independently zero or 1 or more, preferably 1 -5, such that the dimer has a net charge of zero.

In another embodiment, the catalytic species used for MICA has the general formula

20,

where Z ¹ and Z ² are the same or different non-radioactive lanthanide series metal ions, copper, platinum or palladium ions;

R ¹ , R ² , R ³ and R ⁴ are each independently alkyl groups selected from a branched, cyclic or straight-chain hydrocarbon containing 1-12 carbon atoms, preferably 1-4 carbon atoms;

p is a number from 1-6; and

m and q are each independently zero or 1 or more, preferably 1 -5, such that the dimer has a net charge of zero.

In another embodiment, the catalytic species used for MICA has the general formula

20,

where Z ¹ and Z ² are the same or different non-radioactive lanthanide series metal ions, and/or transition metal ions;

R ¹ , R ² , R ³ and R ⁴ are each independently alkyl groups selected from a branched, cyclic or straight-chain hydrocarbon containing 1-12 carbon atoms, preferably 1 -4 carbon atoms;

p is a number from 0-6; and

m and q are each independently zero or 1 or more, preferably 1-5, such that the dimer has a net positive charge.

In another embodiment, the catalytic species used for MICA has the general formula

20,

where Z and Z ² are the same or different non-radioactive lanthanide series metal ions, and/or transition metal ions;

R , R ² , R ³ and R ⁴ are each independently alkyl groups selected from a branched, cyclic or straight-chain hydrocarbon containing 1-12 carbon atoms, preferably 1-4 carbon atoms;

p is a number from 1 -6; and

m and q are each independently zero or 1 or more, preferably 1-5, such that the dimer has a net positive charge. In another embodiment, the catalytic species used for MICA has the general formula

30: a(R ² 0) Z ¹ (OR ³ ) _b

(30)

where Z ¹ is a non-radioactive lanthanide, copper, platinum or palladium ion;

R ² and R ³ are each independently alkyl groups selected from a branched, cyclic or straight-chain hydrocarbon containing 1-12 carbon atoms, preferably 1-4 carbon atoms; a is a number from 1-3; and

b is zero or 1 or more, such that the catalytic species has a net charge of zero.

In another embodiment, the catalytic species used for MICA has the general formula

30,

where Z ¹ is a non-radioactive lanthanide series metal ion or a transition metal ion; R ² and R ³ are each independently alkyl groups selected from a branched, cyclic or straight-chain hydrocarbon containing 1-12 carbon atoms, preferably 1-4 carbon atoms; a is a number from 1-3; and

b is zero or 1 or more, such that the catalytic species has a net positive charge. In another embodiment, the catalytic species used for MICA has the general formula

30,

where Z ¹ is a non-radioactive lanthanide series metal ion or a transition metal ion; R ² and R ³ are each independently alkyl groups selected from a branched, cyclic or straight-chain hydrocarbon containing 1-12 carbon atoms, preferably 1-4 carbon atoms; a is a number from 1-3; and

b is zero or 1 or more, such that the catalytic species has a net positive charge; wherein unoccupied coordination sites on the metal may be occupied by one or more ligands.

In another embodiment, the catalytic species used for MICA has the general formula

40:

(40)

where Z ¹ , Z ² and Z ³ are the same or different non-radioactive lanthanide, copper, platinum or palladium ions;

R ¹ , R ² R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently alkyl groups selected from a branched, cyclic or straight-chain hydrocarbon containing 1-12 carbon atoms, preferably 1 -4 carbon atoms;

p is a number from 1-4;

m, d, q and t are each independently zero or 1 or more, preferably 1 -5, such that the oligomer has a net charge of zero; and

r is a number from 0 to 100, or in the case of polymeric material may be greater than

100.

In yet another embodiment, the catalytic species used for MICA has the general formula 40:

where Z ¹ , Z ² and Z ³ are the same or different non-radioactive lanthanide series metal ions, or transition metal ions or combinations thereof;

R ¹ , R ² R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently alkyl groups selected from a branched, cyclic or straight-chain hydrocarbon containing 1-12 carbon atoms, preferably 1 -4 carbon atoms;

p is a number from 1-4;

m, d, q and t are each independently zero or 1 or more, preferably 1 -5, such that the oligomer has a net positive charge; and

r is a number from 0-100, or in the case of polymeric material may be greater than

100.

The alcoholic solution for ICA comprises a primary, secondary or tertiary alcohol, an alkoxyalkanol, an aminoalkanol, or a mixture thereof. In one embodiment, a non- inhibitory buffering agent is added to the solution to maintain the ^ H at the optimum range of * pH , for example in the case of La ³⁺ in methanol, * pH 7 to 1 1. Examples of non- inhibitory buffering agents include: anilines; N-alkylanilines; Ν,Ν-dialkylanilines; N- alkylmorpholines; N-alkylimidazoles; 2,6-dialkylpyridines; primary, secondary and tertiary amines such as trialkylamines; and their various derivatives.

In another embodiment, for MICA the non-inhibitory buffering agents are not added, but additional alkoxide ion is added in the form of an alkoxide salt to obtain metal ions and alkoxide ions in a metakalkoxide ratio of about 1 :0.01 to about 1 :2, for some embodiments preferably about 1 :1 to about 1 :1.5, for other embodiments preferably about 1 :0.5 to about 1 :1.5. A person skilled in the art will recognize that an alcoholic solution contains trace amounts of alkoxide ions. This concept is analogous to water containing a trace amount of hydrogen ions and hydroxide ions, thus water of pH 7 contains, by definition, [H ⁺ ] = 1 x 10 ^"7 M and [OH ] = 1 x 10 ^~7 M. For this reason, when alkoxide salts are added according to this embodiment of the invention, they are referred to as "additional" alkoxide ions. Suitable non- inhibitory cations for the alkoxide salts include monovalent ions such as, for example, Na ⁺ , K\ Cs ⁺ , Rb\ NF and N ⁺ R'R"R"'R"" ⁺ (where R', R", R"\ and R"" may be the same or different and may be hydrogen or substituted or unsubstituted alkyl or aryl groups) and divalent ions such as the alkali earth metals, and combinations thereof.

To obtain the metal ions, metal salts are added to the solution. Preferably, the metal ion is a non-radioactive lanthanide series metal ion. Suitable lanthanide series metal ions include, for example, Ce ³⁺ , La ³⁺ , Pr ^3* , Nd ³⁺ , Sm ³⁺ , Eu ³⁺ ,Gd ³⁺ , Tb ³⁺ , Dy ^3* , Ho ³⁺ , Er ³ ', Tm ³⁺ and Yb ³⁺ and combinations thereof or complexes thereof. Suitable non-lanthanide series metal ions include, for example, divalent transition metal ions such as, for example, Cu ²⁺ , Pd ²⁺ ,Pt ²⁺ , Zn ²⁺ , and trivalent transition metal ions such as, for example, Sc ³⁺ and Y ³⁺ , as well as combinations thereof or complexes thereof, including combinations/complexes of those with non-radioactive lanthanide series metal ions. While La ³⁺ ( ^* pKa ¹ = 7.8) has good catalytic efficacy from *pH 7.3 to 10.3, other metal ions which have lower ^* pKa values (for example

Ho ³⁺ and Eu ³⁺ have ^* pKa i values of 6.6, while Yb ³⁺ has a ' pKa _! value of 5.3 (Gibson, G. et al., Can. J. Chem. 2003, 81 , 495)) may be efficacious at lower *pH .

An embodiment is a catalytic system comprising mixtures of metal ions, for example, mixtures of lanthanide series metal ions which would be active between the wide *pH range of 5 to 11. Lanthanide series metal ions and alkoxide may form several species in solution, an example of which, species forming from La ³⁺ and methoxide is shown in the figures. In the case of La ³⁺ , a dimer containing 1 to 3 alkoxides is a particularly active catalyst for the degradation of organophosphorus compounds. In the case of non-lanthanide series metal ions, such as, for example Zn ²⁺ and Cu ²⁺ , a mononuclear complex containing alkoxides is an active catalyst for the degradation of organophosphorus compounds.

In some embodiments, there is limiting of dimerization and prevention of further oligomerization by addition of ligand such as, for example, bidentate and tridentate ligands. By coordination at one or more sites on a metal, a ligand limits dimerization and prevents further oligomerization of a metal species, thus allowing a greater number of active mononuclear species than is the case in the absence of ligand. Although not meant to be limiting, examples of such ligands are 2,2 -bipyridyl ("bpy"), 1,10-phenanthryl ("phen"), 2,9- dimethylphenanthryl ("diMephen") and 1,5,9-triazacyclododecyl ("[12]aneN ₃ "), crown ether, aza crown ether, and their substituted forms. Such ligands may be attached via linkages to solid support structures such as polymers, silicates or aluminates to provide solid catalysts for the alcoholysis of organophosphorus compounds which are decomposed according to the invention. The point of attachment of the metal:ligand:alkoxide complex to the solid support is preferably at the 3 or 4 position in the case of bipyridyl or the 3, 4 or 5 position in the case of phenanthrolines using linking procedures and connecting spacers which are known in the art. In the case of aza ligands, such as, for example, [12]aneN ₃ , the point of attachment of the complex to the solid support would preferably be on one of the nitrogens of the macrocycle, using methods and connecting spacers known in the art. Such attachment to solid supports offers advantages in that the solid catalysts may be conveniently recovered from the reaction media by filtration or decantation. In an embodiment wherein ligands are attached to solid support structures, organophosphorus compounds may be decomposed by running a solution through a column such as a chromatography column. In another embodiment wherein ligands are attached to solid support structures, organophosphorus compounds may be decomposed by contact with a polymer comprising metal species and alkoxide ions.

Suitable anions of the metal salts are non-inhibitory or substantially non-inhibitory and include, for example, CI0 ^" , BFV, Γ, CF ₃ S0 ₃ ^" (also referred to herein as "triflate" or "OTf") and combinations thereof. Preferred anions are CI0 ₄ ^" and CF ₃ S0 ₃ ^~ .

The relay indicating decontamination solutions of the invention comprise solvents, wherein preferred solvents are alcohols, including primary and secondary alcohols such as methanol, ethanol, n-propanol, so-propanol, n-butanol, 2-butanol and methoxyethanol, and combinations thereof. Most preferably the solution is all alcohol or all alkoxyalkanol or all aminoalkanol; however, combinations with non-aqueous non-inhibitory solvents can also be used, including, for example, nitriles, ketones, amines, ethers, hydrocarbons including halogenated hydrocarbons, halogenated ethers, chlorinated hydrocarbons, fluorinated ethers, and esters. In the case of esters, it is preferable that the alkoxy group is the same as the conjugate base of the solvent alcohol. In some embodiments, esters may cause side reactions which may be inhibitory.

In some embodiments methanol is used. Methanol is closest to water in terms of structure and chemical properties and is readily available. However, methanol is less desirable than other solvents due to its toxicity and its relatively low boiling point of 64.7 °C which makes it volatile and prone to evaporation from open vessels. Use of higher alcohols such as ethanol, n-propanol and iso-propanol is also encompassed. Ethanol, n-propanol and iso-propanol are substantially less volatile (boiling points 78, 97.2 and 82.5 °C respectively), are less toxic, and have better solubilizing characteristics for hydrophilic substrates. The higher boiling points mean that these solvents are more amenable to field conditions since there would conveniently be less evaporation and thus less solvent would be lost to the atmosphere.

Other preferred solvents include n-butanol and 2-butanol since they have higher boiling points than the lower alcohols.

In an embodiment, the solvent is ethanolamine.

In an aspect, for MICA the metal ion species catalyzes an alcoholysis reaction of an organophosphorus compound or a mixture of organophosphorus compounds represented by the following general formula (10):

where P is phosphorus;

J is O (oxygen), S (sulfur) or a lone pair of electrons;

X and G are the same or different and are selected from the group consisting of A, Q, OQ, OA, OA, SQ.SA, F, CI, Br and C≡N;

Hal is selected from the group consisting of fluoride (F), chloride (CI) and bromide

(Br); where Q is hydrogen or a substituted or unsubstituted branched, straight-chain or cyclic alkyl group consisting of 1-100 carbon atoms;

A is a mono-, di-, or poly-substituted or unsubstituted moiety selected from phenyl, biphenyl, benzyl, pyridine, naphthyl, polynuclear aromatics, and 5- and 6-membered aromatic and non-aromatic heterocycles;

wherein each said substituent is selected from CI, Br, I, F, nitro, nitroso, Q, alkenyl, OQ, carboxyalkyl, acyl, S0 ₃ H, S0 ₃ Q, S=0(Q), S(=0) ₂ Q, amino, alkylamino (NHQ), arylamino (NHA), alkylarylamino, dialkylamino and diarylamino.

In an aspect, for MICA the metal ion species catalyzes an alcoholysis reaction of an organophosphorus compound or a mixture of organophosphorus compounds represented by the following general formula (15):

x— P— z

(15)

G where P is phosphorus;

J is O (oxygen) or S (sulfur);

X and G are the same or different and are selected from the group consisting of Q, OQ, QA, OA, F (fluoride), CI (chloride), Br (bromide), I (iodide), QS, SQ and C≡N;

Z is F, CI or Br;

where Q is hydrogen or a substituted or unsubstituted branched, straight-chain or cyclic alkyl group consisting of 1-100 carbon atoms;

wherein when X and G are the same, X and G are not Q, and Q is not H;

A is a mono-, di-, or poly-substituted or unsubstituted moiety selected from phenyl, biphenyl, benzyl, pyridine, naphthyl, polynuclear aromatics, and 5- and 6-membered aromatic and non-aromatic heterocycles;

wherein each said substituent is selected from CI, Br, I, F, nitro, nitroso, Q, alkenyl, OQ, carboxyalkyl, acyl, S0 ₃ H, S0 ₃ Q, S=0(Q), S(=0) ₂ Q, amino, alkylamino (NHQ), arylamino (NHA), alkylarylamino, dialkylamino and diarylamino. In another aspect, for MICA the metal ion species catalyzes an alcoholysis reaction of an organophosphorus compound or a mixture of organophosphorus compounds represented by the following general formula (15):

X P z

(15)

G where P is phosphorus;

J is O or S;

X and G are the same or different and are selected from the group consisting of Q, OQ, QA, OA, F, CI, Br, I, QS, SQ, SA and C≡N;

Z is F, CI or Br;

Q is a substituted or unsubstituted branched, straight-chain or cyclic alkyl group having 1 -100 carbon atoms; and

A is a substituted or unsubstituted moiety selected from the group consisting of phenyl, biphenyl, benzyl, pyridyl, naphthyl, polynuclear aromatic, and aromatic and non- aromatic heterocyclic;

wherein, when X and G are the same, X and G are not Q; and

wherein said substituents are selected from the group consisting of CI, Br, I, F, nitro, nitroso, Q, alkenyl, OQ, carboxyalkyl, acyl, S0 ₃ H, S0 ₃ Q, S=0(Q), S(=0) ₂ Q, amino, alkylamino (NHQ), arylamino (NHA), alkylarylamino, dialkylamino and diarylamino.

In yet another aspect, for MICA the metal ion species catalyzes an alcoholysis reaction of an organophosphorus compound or a mixture of organophosphorus compounds represented by the following general formula (15):

where P is phosphorus;

where:

J is O or S;

X and G are the same or different and are selected from the group consisting of Q, OQ, QA, A, OA, F, CI, Br, I, QS, SQ, SA, and C≡N;

Z is F, CI or Br;

Q is a substituted or unsubstituted branched, straight-chain or cyclic alkyl group having 1-100 carbon atoms; and

A is a substituted or unsubstituted aryl group selected from the group consisting of phenyl, biphenyl, benzyl, pyridyl, naphthyl, polynuciear aromatic, and aromatic heterocyclic, or a substituted or unsubstituted non-aromatic heterocyclic group;

wherein, when X and G are the same, X and G are selected from the group consisting of OQ, OA, F, CI, Br, I, QS, SQ, SA, and C≡N; and

wherein said substituents are selected from the group consisting of CI, Br, I, F, nitro, nitroso, Q, alkenyl, OQ, carboxyalkyi, acyl, S03H, S03Q, S=0(Q), S(=0)2Q, amino, alkylamino (NHQ), arylamino (NHA), alkylarylamino, dialkylamino, and diarylamino.

In a further aspect, for MICA the metal ion species catalyzes an alcoholysis reaction of an organophosphorus compound or a mixture of organophosphorus compounds represented by the following general formula (15):

x— P— z

where P is phosphorus;

where:

J is O or S;

X and G are the same or different and are selected from the group consisting of Q, OQ, QA, A, OA, F, CI, Br, I, QS, SQ, SA, and C≡N;

Z is F, CI or Br; wherein at least one of X and G is not Q or QA;

Q is a substituted or unsubstituted branched, straight-chain or cyclic alkyl group having 1-100 carbon atoms; and

A is a substituted or unsubstituted aryl group selected from the group consisting of phenyl, biphenyl, benzyl, pyridyl, naphthyl, polynuclear aromatic, and aromatic heterocyclic, or a substituted or unsubstituted non-aromatic heterocyclic group; and

wherein said substituents are selected from the group consisting of CI, Br, I, F, nitro, nitroso, Q, alkenyl, OQ, carboxyalkyl, acyl, S03H, S03Q, S=0(Q), S(=0)2Q, amino, alkylamino (NHQ), arylamino (NHA), alkylarylamino, dialkylamino, and diarylamino.

In a further aspect, for MICA the metal ion species catalyzes an alcoholysis reaction of an organophosphorus compound or a mixture of organophosphorus compounds represented by the following general formula (15):

where:

P is phosphorus;

J is O (oxygen) or S (sulfur);

X and G are the same or different and are selected from the group consisting of Q, OQ, QA, OA, F (fluoride), CI (chloride), Br (bromide), I (iodide), QS, SQ and C≡N;

Z is F, CI or Br;

where Q is hydrogen or a substituted or unsubstituted branched, straight-chain or cyclic alkyl group consisting of 1-100 carbon atoms;

wherein when X and G are the same, X and G are Q or OQ;

A is a mono-, di-, or poly-substituted or unsubstituted moiety selected from phenyl, biphenyl, benzyl, pyridine, naphthyl, polynuclear aromatics, and 5- and 6-membered aromatic and non-aromatic heterocycles;

wherein each said substituent is selected from CI, Br, I, F, nitro, nitroso, Q, alkenyl, OQ, carboxyalkyl, acyl, S0 ₃ H, S0 ₃ Q, S=0(Q), S(=0) ₂ Q, amino, alkylamino (NHQ), arylamino (NHA), alkylarylamino, dialkylamino and diarylamino. In a further aspect, for MICA the metal ion species catalyzes an alcoholysis reaction of an organophosphorus compound or a mixture of organophosphorus compounds represented by the following general formula (15):

where:

P is phosphorus;

J is O (oxygen) or S (sulfur);

X and G are the same or different and are selected from the group consisting of Q, OQ, QA, OA, F (fluoride), Ci (chloride), Br (bromide), I (iodide), QS, SQ and C≡N;

Z is F, CI or Br;

where Q is hydrogen or a substituted or unsubstituted branched, straight-chain or cyclic alkyl group consisting of 1-100 carbon atoms;

A is a mono-, di-, or poly-substituted or unsubstituted moiety selected from phenyl, biphenyl, benzyl, pyridine, naphthyl, polynuclear aromatics, and 5- and 6-membered aromatic and non-aromatic heterocycles;

wherein each said substituent is selected from CI, Br, I, F, nitro, nitroso, Q, alkenyl, OQ, carboxyalkyl, acyl, S0 ₃ H, S0 ₃ Q, S=0(Q), S(=0) ₂ Q, amino, alkylamino (NHQ), arylamino (NHA), alkylarylamino, dialkylamino and diarylamino.

As used herein, the term "heterocycle" means a substituted or unsubstituted 5- or 6- membered aromatic or non-aromatic hydrocarbon ring containing one or more O, S or N atoms, or polynuclear aromatic heterocycle containing one or more N, O, or S atoms.

A potential advantage of the relay indicating techniques and solutions of the invention is that the solvent, being hydrophobic, relative to water, permits good solubility of organophosphorus agents such as soman (GD), sarin (GB), GF, hydrophobic polymers, insecticides, pesticides and certain toxic industrial chemicals. Another possible advantage of the relay indicating techniques and solutions of the invention is that they provide a non-aqueous solution and reaction products that can be easily and safely disposed of by incineration. It will thus be appreciated that the relay indicating techniques and solutions of the invention can be used for a broad range of chemical warfare agents or toxic industrial chemicals, or mixtures of such agents, or blends of such agents with polymers, as well as other toxic compounds such as insecticides, pesticides and related organophosphorus agents in general.

A further potential advantage of the relay indicating techniques and solutions of the invention is that destruction of toxic, e.g., organophosphorus, agents occurs with or without the addition of heat. An ambient temperature reaction is cost-efficient for large scale destruction of stockpiled organophosphorus material such as chemical weapons, insecticides or pesticides. The catalyst species can catalyze the alcoholysis over the full temperature range between the freezing and boiling points of the solvents or mixture of solvents used.

Another potential advantage of the relay indicating techniques and solutions provided herein is that decomposition of a toxic, e.g., an organophosphorus, compound can be achieved and monitored at the same time, with the application of one solution. That is, the relay indicating solutions of the invention decompose a toxic, e.g., an organophosphorus, compound by MICA, and the decomposition is monitored by detection of F released. Thus, the relay indicating solutions described herein can be considered, in one aspect, as "agent disclosure" decontamination solutions. The capability to allow monitoring of decomposition and to provide assurance of complete decontamination is an advantage over other decomposition and decontamination methods known in the art. Thus in an embodiment, there is provided a method for decomposing a toxic, e.g., an organophosphorus compound or toxic industrial chemical, and monitoring decomposition of the organophosphorus compound or toxic industrial chemical comprising metal ion catalyzed alcoholysis (MICA) in the presence of an indicator compound.

The invention also provides a kit for detecting a toxic, e.g., an organophosphorus compound or a toxic industrial chemical, for monitoring decomposition of a toxic, e.g., an organophosphorus compound or a toxic industrial chemical and/or for decomposing and monitoring decomposition of a toxic, e.g., an organophosphorus compound or a toxic industrial chemical, comprising a substantially non-aqueous medium for an alcoholysis reaction, said medium comprising non-radioactive metal ions and at least a trace amount of alkoxide ions, and an indicator compound. The kit may include a container, e.g., an ampule, which is opened so that the medium can be applied to the toxic, e.g., organophosphorus, compound. Alternatively, the kit may include an applicator bearing the medium, wherein the applicator is adapted so that the medium is applied to the toxic, e.g., organophosphorus compound and the compound consequently decomposes. The applicator may comprise an absorbent wipe or a moist cloth, i.e., a cloth bearing a solution according to the invention. The applicator may be a sprayer which sprays medium according to the invention on the organophosphorus compound, e.g., a high pressure airless spray gun or a handheld airless spray gun. In other embodiments, the applicator is a brush (e.g., a paint brush), a roller or a trowel. In some embodiments, the kit further comprises written instructions for use.

Examples

The present invention will be more readily understood by referring to the following examples, which are provided to illustrate the invention and are not to be construed as limiting the scope thereof in any manner.

Unless defined otherwise or the context clearly dictates otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It should be understood that any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the invention.

In the Examples, benzoyl fluoride was used as an example of materials which release fluoride anion upon decomposition and as a model compound for

phosphonofluoridate G-agents. The metal ion based decontamination method used herein promotes the solvolysis of benzoyl fluoride during which inorganic fluoride anion is released. The presence of the inorganic fluoride anion is detected by a change in the visible spectral properties of the solution.

Additional experiments were performed where hard and porous surfaces were contaminated with the model compound for G-agents. Briefly, a hard, porous surface (in this case, cardboard) was "spot-contaminated" with about 25 ul of benzoyl fluoride (as a model compound for fluoride containing G-agents). Indicating solution consisting of 1mM Methyl red, 40mM EtMo buffer (20 mM HOTf and 40 mM EtMo), and 1 mM La(OTf) ₃ was sprayed on the surface and within 10 sec bright red spots developed in the areas which were contaminated with benzoyl fluoride. Application of the relay indicating decontamination solution described herein resulted in a clearly defined visual indication at the site of contamination. For the examples described herein, the following materials were purchased from Aldrich: Methanol, anhydrous (EMD); lanthanum trifluoromethansulfonate (La(OTf) ₃ ); , 2- picoline 98% (Pico); 2,6-lutidine reagent plus 98% (Luti); triethylamine, > 99% (Et ₃ N); 4- etyhlmorpholine (EtMo); 1-methylimidazole (Melm); trifluoromethanesulfonate (HOTf); tetrabutylammonium fluoride ((Bu ₄ N ⁺ )F ^" ); tetrabutylammonium chloride ((Bu ₄ N ⁺ )CI );

tetrabutylammonium nitrate ((Bu ₄ N ⁺ )(N0 ₃ ^~ )); tetrabutylammonium bromide ((Bu N ⁺ )Br ); tetrabutylammonium acetate ((Bu ₄ N ⁺ )(CH ₃ C0 ₂ )); and benzoyl fluoride (BnzF).

Samarium trifluoromethansulfonate (Sm(OTf) ₃ ) and tetrabutylammonium hydrogen sulfate ((Bu N ⁺ )(HS0 ₄ ^~ )) were purchased from Acros Organics. Tetrabutylammonium perchlorate ((Bu ₄ N ⁺ )(CI0 ₄ )) was purchased from Fluka.

The indicator compounds phenolphthalein, thymolphthalein, cresol red, chlorophenol red, methyl red, Congo red, methyl orange, neutral red, bromocresol purple, and bromocresol green were purchased from Aldrich; bromophenol blue was purchased from Matteson Coleman & Bell Manufacturing Chemists; and thymol blue was a Baker Analyzed Reagent.

For the kinetic studies, stock solutions of 50 mM La(OTf) ₃ and Sm(OTf) ₃ were prepared in methanol. Also, 20 mM solutions of the indicator compounds and 350 mM HOTf were also prepared in methanol.

UV-visible (UV/vis) spectra were recorded by a Cary 100 and UV/vis

spectrophotometer. The temperature was controlled at 25 °C.

Example 1. Fluoride anion detection

Various combinations of lanthanide ion salts, indicator compounds and buffer solutions were tested for their ability to provide spectral response to various concentrations of fluoride anion in solution. The experiments were performed in the following way: 2.5 ml. of corresponding buffer comprised of 20 mM HOTf and 40 mM amine was placed into a UV cell and a UV/vis spectrum was recorded (generally from 800 to 200nm; see curve no. 1 in Figures 1- 10). Then 12.5 μΙ of stock solution of indicator compound was added to the same cell (concentration in the cell 0.1 mM) and the UV/vis spectrum was recorded (see curve no. 2 in Figures 1-10). 50 pi of lanthanide triflate stock solution (La(OTf) ₃ or Sm(OTf) ₃ ) was then added into the same cell (concentration in the cell 1mM) and the UV/vis spectrum was recorded (see curve no. 3 in Figures 1-10). Spectral effects of fluoride anion present in solution were studied by sequential addition of 12.5 μΙ stock solution of tetrabutylammonium fluoride ((Bu ₄ N ⁺ )F) (200mM) to the same UV cell already containing buffer, indicator and lanthanide triflate, so that the change in fluoride concentration after each addition was approximately 1 mM. UV/vis spectra were recorded after each addition and additions were continued until no further spectral change was observed (between 3-5 aliquots added; see curve no. 4 and higher in Figures 1-10). Differences between curve no. 3 (corresponding to the indicating solution or system) and curves obtained after addition of aliquots of fluoride anion demonstrate the ability to detect a spectral response to the presence of fluoride anion in solution.

Figures 1 -10 contain sets of UV/visual spectra obtained as described above for various combinations of lanthanide ion salts, indicator compounds and buffer solutions, and spectral variations in the presence of added F .

The color of the solutions was also observed visually. Results were as follows:

For each figure, the solution number corresponds to the curve number for the corresponding spectrum. For example, solution no. 1 is the solution for which the spectrum is shown in curve no. 1 ; solution no. 2 is the solution for which the spectrum is shown in curve no. 2; solution no. 3 is the solution for which the spectrum is shown in curve no. 3; solution no. 4 is the solution for which the spectrum is shown in curve no. 4; and so on.

In Figure 1 , the color of solution no. 2 was yellow; solution no. 3 was red; solution no. 4 was red; solution no. 5 was yellow; and solution no. 6 was yellow.

In Figure 2, the color of solution no. 2 was yellow; solution no. 3 was orange; solution no. 4 was orange; solution no. 5 was orange; solution no. 6 was orange/yellow; and solution no. 7 was yellow.

In Figure 3, the color of solution no. 2 was orange; solution no. 3 was yellow; solution no. 4 was yellow; solution no. 5 was yellow; solution no. 6 was yellow; solution no. 7 was orange; and solution no. 8 was orange.

In Figure 4, the color of solution no. 2 was green; solution no. 3 was fuchsia; solution no. 4 was fuchsia; solution no. 5 was purple; solution no. 6 was purple; solution no. 7 was green; and solution no. 8 was green.

In Figure 5, the color of solution no. 2 was turquoise; solution no. 3 was fuchsia; solution no. 4 was purple; solution no. 5 was purple/blue; solution no. 6 was blue/turquoise; and solution no. 7 was turquoise. 00837

In Figure 6, the color of solution no. 2 was yellow; solution no. 3 was fuchsia; solution no. 4 was fuchsia; solution no. 5 was fuchsia; solution no. 6 was yellow; and solution no. 7 was yellow.

In Figure 7, the color of solution no. 2 was orange; solution no. 3 was yellow; solution no. 4 was yellow; solution no. 5 was yellow; solution no. 6 was yellow; solution no. 7 was orange; and solution no. 8 was orange.

In Figure 8, the color of solution no. 2 was yellow; solution no. 3 was orange; solution no. 4 was orange; solution no. 5 was orange; solution no. 6 was yellow; and solution no. 7 was yellow.

In Figure 9, the color of solution no. 2 was green; solution no. 3 was fuchsia; solution no. 4 was fuchsia; solution no. 5 was purple; solution no. 6 was purple/grey; solution no. 7 was green; and solution no. 8 was green.

In Figure 10, the color of solution no. 2 was yellow; solution no. 3 was fuchsia;

solution no. 4 was fuchsia/purple; solution no. 5 was brown; and solution no. 6 was yellow.

The following systems were successful at detecting fluoride ion in solution:

Bromocresol purple and La(OTf) ₃ with Luti and EtMo; Chlorophenol red and La(OTf) ₃ with Melm and EtMo; Methyl red and La(OTf) ₃ with Luti, Melm and EtMo; Bromophenol blue and La(OTf) ₃ with Luti and EtMo; Bromocresol green and La(OTf) ₃ with pico, Luti, and EtMo;

Bromocresol purple and Sm(OTf) ₃ with pico, Luti and EtMo; Chlorophenol red and Sm(OTf) ₃ with pico, Luti and EtMo; Methyl red and Sm(OTf) ₃ with Luti and EtMo; Bromophenol blue and Sm(OTf) ₃ with Luti and EtMo; and Bromocresol green and Sm(OTf) ₃ with pico, Luti, and EtMo. Selected examples are shown in Figures 1-10.

Example 2. Detection of benzoyl fluoride

Various solutions or systems (referred to as "indicating" solutions or systems) were tested for their ability to provide spectral response to the presence of benzoyl fluoride. The experiments were performed in the following way: Indicating solution was formulated by placing into a UV cell 2.375 mL of buffer (comprised of 20 mM HOTf and 40 mM amine), 12.5 μΙ of indicator stock solution (10mM) and 50 μΙ La(OTf) ₃ or Sm(OTf) ₃ stock solution (50mM). The UV/vis spectrum was recorded, generally from 800 to 200 nm (labeled as "indicator system" on the spectra in Figures 11-18). Then 62.5 pL of benzoyl fluoride stock solution (200 pL in acetonitrile) was added to the cell and the UV/vis spectra were recorded every 1.2 minutes. Figures 11 -18 show sets of spectra obtained as described above for various combinations of lanthanide ion salts, indicator compounds and buffer solutions, and demonstrate the real time detection of F ^" produced from the catalytic solvolysis of benzoyl fluoride.

Differences between the relay "indicator system" spectra and spectra obtained after addition of aliquots of benzoyl fluoride anion demonstrate the ability of the system to detect a spectral response to the presence of benzoyl fluoride in solution that underwent MICA.

The results shown in Figures 1 1-18 show that the following systems were successful at determining presence of benzoyl fluoride in solution: Bromocresol purple, EtMo and La(OTf) ₃ ; Bromocresol purple, EtMo and Sm(OTf) ₃ ; Methyl red, EtMo and La(OTf) ₃ ; Methyl red, EtMo and Sm(OTf) ₃ ; Bromophenol blue, Luti and La(OTf) ₃ ; Bromophenol blue, Luti and Sm(OTf) ₃ ; Bromocresol green, EtMo and La(OTf) ₃ ; and Bromocresol green, EtMo and Sm(OTf) ₃ .

Although this invention is described in detail with reference to preferred embodiments thereof, these embodiments are offered to illustrate but not to limit the invention. It is possible to make other embodiments that employ the principles of the invention and that fall within its spirit and scope as defined by the claims appended hereto.

The contents of all documents and references cited herein are hereby incorporated by reference in their entirety.