AU778768B2 - Polyoxometalate materials, metal-containing materials, and methods of use thereof - Google Patents

Description

WO 01/34279 PCT/US00/28152 1 POLYOXOMETALATE MATERIALS, METAL-CONTAINING

MATERIALS,

AND METHODS OF USE THEREOF FIELD OF THE INVENTION The present invention relates to materials containing a polyoxonletalate or a metal compound, wherein the metal compound is not a polyoxometalate. The invention further relates to methods for removing a contaminant from an environment by contacting the environment with a polyoxometalate material or a non-polyoxometalate material.

BACKGROUND OF THE INVENTION Decreasing the potential danger of contaminants from the environment has long been a significant issue. For example, the removal of offensive odors originating from cigarette smoke, sweat, cxhaust gases, and rotten food in the work place, the home, and elsewhere would be quite beneficial to the public-at-large. Additionally, materials that can remove highly toxic contaminants, such as chemical warfare agents (CWAs), from the envirotunent can ultimately reduce a soldier's exposure to the agent. Examples of materials that would be useful include creams, powders, coatings, and fabrics.

Creams, also referred to as topical skin protectants (TSPs), have been developed to protect soldiers from the threat of dermal exposure to chemical warfare agents. TSPs require an inert material which can be applied on the skin in a thin layer to form an antipenetrant barrier to CWAs or other contact irritants that will not interfere excessively with normal skin functions. A preferred TSP affords protection against CWAs and other toxic or irritating materials in all of the forms in which they might be encountered liquid, aerosolized liquid and vapor). Perhaps the best-known vesicant CWA is 2,2'-diclilorodiethylsulfide (also known as "HD" or "sulfur mustard"), which was first used during World War I. Improved TSPs, however, are needed for protecting military personnel and civilians from percutaneous exposure to CWAs and protecting the skin from contact dermatitis arising from other sources as well.

WO 01/34279 PCT/US00/28152 2 U.S. Patent No. 5,607,979 to McCreery discloses topical creams formed from about 35% to about 50% thie particulates of certain poly(tetrafluoroethylene)

(PTFE)

resins dispersed in pertluorinated polyether oils having viscosities from about 20 cSt to about 350 cSt. The creams afford protection against chemical warfare agents such as sulfur mustard lewisite sulfur mustard/Lewisite mixtures pinacolyl methylphosphonofluoridate (soman or GD), thickened soman (TGD), and O-ethyl- S-2-diisopropylaminoethyl methylphosphonothiolate These creams, however, can only provide limited exposure to a CWA for a short period of time. Furthennore, the creams cannot convert the CWA to an inactive formnn, which will reduce the overall toxicity of the CWA.

Thus, there is a need for a material, which is also referred to herein as a support, that can remove a contaminant from the environment for an extended period of time.

The incorporation of a polyoxometalate (herein referred to as "POM") into a material such as a cream, coating, powder, or fabric, is one approach to removing a contaminant from an environment. Gall et al. (Chem. Mat. 8, pp. 2523-2527, 1996) disclose the immobilization of HPV,Mo,,O,, on carbon cloth in order to determine the ability of HPV,Mo,,oO 4 u to remove sulfur containing compounds from toluene. Johnson et al.

(Proc. ERDEC Sci. Conf. Chem. Biol. Def. Res., 1998, pp. 393-399) disclose suspending KSi(HO)MnmW,,,39; K 4 Si(H0O)MnVW,, or KComW,Oa,,j in a perflouropolyether barrier cream to determine the creams ability to detect the presence of mustard gas. Johnson et al., however, is not concerned with the removal of the mustard gas from the gas phase.

The prior art also discloses the incorporation of polyoxometalates into powders and coatings. For example, U.S. Patent No. 5,356,469 to Curcio et al. disclose a metal pigment composition suitable for the fonnation of a coating composition. The coating composition is composed of a solvent, a metal pigment, at least one phosphosilicate pigment, and at least one heteropoly anion. The metal pigment particles possess increased stability against attack by water. Japanese patent applicatio number 4054127 to Terumo Corp. discloses the use of heteropoly acid salts as anti-tumor WO 01/34279 PCT/US00/28152 agents. The heteropoly acid salts can be administered in the form of a powder or suspended in solution. Although the prior art discloses a number of different applications of polyoxometalate powders or coatings, the art does not disclose the use of a powder or coating containing a polyoxometalate to remove a contaminant from the environment.

In light of the above, it would be very desirable to have an article and a method of using an article for the removal of toxic and/or malodorous compounds without adding stoichiometric amounts of additives or compounds to the article. The present invention solves such a need in the art while providing surprising advantages. The present invention herein incorporates a polyoxometalate (POM) into a material such as a topical carrier, powder, or coating, which greatly increases the ability of the to remove a contaminant from the environment. The present invention also incorporates a metal compound, wherein the metal compound is not a polyoxometalate, into a in order to remove a contaminant from the environment.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows the consumption of oxygen and formation of CEESO as a function of time.

Figure 2 shows CEESO formation as a function of time using IAu/2Cu/3NO 3 2Cu/3NO 3 and lAu/3NO 3 SUMMARY OF THE INVENTION In accordance with the purpose(s) of this invention, as embodied and broadly described herein, this invention, in one aspect, relates to a polyoxometalate topical composition for removing a contaminant from an environment, comprising a topical carrier and at least one polyoxonetalate, with the proviso that the polyoxomnetalate is not HPVMo,,,O,; K,Si(H,O)Mn m XW,O03 9 KSi(H,O)Mn v "WO0 3 9 or KComW,,O,.

WO 01/34279 PCT/US00/28152 4 The invention further relates to a polyoxometalate topical composition for removing a contaminant from an environment, comprising a topical carrier and at least one polyoxoinetalate, with the proviso that the polyoxometalate is not H,PV,Moo0 4 KsSi(HO)MnMW, 1 O3,; K 4 Si(H.O)Mn" W, K 5 ComW2O or H 6 (PV-Mo04)0.

The invention further relates to a method for removing a contaminant from an environment, comprising contacting the polyoxometalate topical composition of the present invention with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment.

The invention further relates to a method for removing a contaminant from an environment, comprising contacting a polyoxometalate powder or a polyoxometalate coating with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment.

The invention further relates to a modified polyoxometalate, wherein the modified polyoxometalate comprises the admixture of a polyoxometalate and a cerium compound, a silver compound, a gold compound, a platinum compound, or a combination thereof.

The invention further relates to a method for removing a contaminant from an environment, comprising contacting a modified material with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment, wherein the modified material comprises a material and a metal compound comprising a transition metal compound, an actinide compound, a lanthanide compound, or a combination thereof, wherein the metal compound is not a polyoxometalate.

The invention further relates to a modified material for removing a contaminant from an environment, wherein the modified material comprises a material WO 01/34279 PCT/US00/28152 comprising a topical carrier, a powder, a coating, or a fabric, and a metal compound comprising a transition metal compound. an actinide compound, a lanthanide compound, or a combination thereof, wherein the metal compound is not a polyoxometalate.

The invention further relates to an article comprising the modified of the present invention.

Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The advantages of the invention will be realized and attained by means of the elements and combinations. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention.

DETAILED DESCRIPTION OF THE INVENTION The present invention may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the Examples included therein.

Before the present methods and articles are disclosed and described, it is to be understood that this invention is not limited to specific synthetic methods or to particular formulations, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings: The singular forms "an" and "the" include plural referents unless the WO 01/34279 PCT/US00/28152 6 context clearly dictates otherwise.

"Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

In accordance with the purpose(s) of this invention, as embodied and broadly described herein, this invention, in one aspect, relates to a polyoxometalate topical composition for removing a contaminant from an environment, comprising a topical carrier and at least one polyoxometalate, with the proviso that the polyoxometalate is not HPVMo,,04,; K,Si(HO)MnmW,,O, 9

K

4 Si(H,O)Mn'VWj03,,; or KsComW,,O The invention further relates to a modified polyoxometalate, wherein the modified polyoxometalate comprises the admixture of a polyoxometalate and a cerium compound, a silver compound, a gold compound, a platinum compound, or a combination thereof.

The invention further relates to a modified material for removing a contaminant from an environment, wherein the modified material comprises a material comprising a topical carrier, a powder, a coating, or a fabric, and a metal compound comprising a transition metal compound, an actinide compound, a lanthanide compound. or a combination thereof, wherein the metal compound is not a polyoxometalate.

The invention further relates to an article comprising the modified material of the present invention.

Many polyoxometalates known in the art can be used in the present invention to remove a contaminant from an environment. Polyoxometalates are also referred to in the art as heteropoly compounds, heteropoly acids, isopoly compounds, and isopoly acids, which are subsets of polyoxometalates. Examples of polyoxometalates useful in WO 01/34279 PCTIUSOO/28152 7 the present invention are disclosed in Pope, M.T. in Heteropoly and Isopoly Oxometalates, Springer Verlag, 1983. and Chemical Reviews, vol. 98, no. 1, pp. 1-389, 1998, which are incorporated by this reference in their entirety.

The selection of the polyoxometalate used in the present invention is dependent upon the contaminant or contaminants to be removed from the environment. In one embodiment, the polyoxometalate has the formula 1 of [VMo,,,W.NboTapMqXOJY[A], wherein M is at least one f-block element or d-block element having at least one delectron, wherein M is not vanadium, molybdenum, tungsten, niobium, or tantalum; X is at least one or f-block element, wherein X is not oxygen: k is from 0 to 30; m is from 0 to 160; n is from 0 to 160. o is from 0 to 10; p is from 0 to 10; q is from 0 to r is from 0 to 30; s is sufficiently large that y is greater than zero; and y is greater than zero, wherein the sum of k, m, n, o, and p is greater than or equal to four; and the sum of k, m, and q is greater than zero, and A is one or more different counterions. In one embodiment, s is from 19 to 460. The charge on the POM, y, is dictated by the values of k, m. n, o, p, q, r and s. The and f-block elements can exist in any oxidation state.

Generally, M can be any d-block element having at least one d-electron or fblock element having at least one f-electron. Typically, M comprises titanium, chromium, manganese, cobalt, iron, nickel, copper, rhodium, silver, palladium, platinum, mercury, ruthenium, cerium, or europium. In a preferred embodiment, M comprises manganese, cobalt, or ruthenium. In another embodiment, X comprises phosphorus, silicon, aluminum, boron, cobalt, zinc, or iron. When the polyoxometalate has the Keggin structure XM, 2 then it is possible for X and at least one M to be the same d- or f-block element. Not wishing to be bound by theory, it is believed that the metal ion M of the polyoxometalate of the present invention is responsible for removing the contaminant from the gas phase, while X, when present, provides structural integrity to the polyoxometalate.

In one embodiment, the sum of k and q is greater than or equal to one, the sum WO 01/34279 PCT/US00/28152 8 of k, in, u, o, p, and q is 12, and s is 40. In yet another embodiment, k is not zero. In another embodiment, q is not zero.

In a more specific embodiment, when the polyoxometalate has the fonnula 1, the polyoxometalate has the formula [XV 'Mc"Z12-b-.i-Ox,]U[A], wherein X is at least one or f-block element; g is greater than or equal to 2; M is at least one f-block element or d-block element having at least one d-electron, wherein M is not vanadium; h is from 1 to 7; i is from 5 to 6; j is from 4 to 5; x is 39 or 40; Z is tungsten, molybdenum, niobium, or a combination thereof; b is from 0 to 6; c is from 0 to 6; u is from 3 to 9; and A is a counterion. The values of u, x, i, b, c, g, h, and j will vary depending upon the selection of X, M, and Z. The variables are related to one another and can be derived by the following formula: u 2(x) -i(12-b-c) g c(h) b(j) The values of h, i, and j are average charges, and depend upon the selection and number of X, M, Z, and V present in the POM. For example, when Z is Nb+ 5 and Nb^ two Nb atoms present in the POM), the value of i+ is In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [X'Vb ,12-b^OJ" wherein X is at least one phosphorus, silicon, aluminum, boron, zinc, cobalt, or iron; b is from 1 to 6, and u is from 3 to 9.

In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the structure wherein X is at least one phosphorus, silicon, aluminum, boron. zinc, cobalt, or iron; c is from 1 to 6, and u is from 3 to 9.

In a more specific embodiment, when the polyoxometalate has the fonnula 1, the polyoxometalate has the formula wherein X is at least WO 01/34279 PCT/US00/8152 9 one or f-block element: r is greater than or equal to 1; M is at least one f-block element or d-block element having at least one d-electron, wherein M is not vanadium; t is from I to 7; s is from 4 to 5; Z is tungsten, molybdenum, niobium, or a combination thereof: u is from0 to 9; v is from0 to 9; y is from 5 to 6; z is 61 or 62; w is greater than or equal to 4; and A is a counterion. Similar to the formula above, the values of r, s, t, u, v, w, y, and z, will vary depending upon the selection of X, M, and Z. The variables are related to one another and can be derived by the following formula: w 2(z) -y(18-u-v) 2r v(t) u(s) The values of r, s, t, and y are also average charges, and depend upon the selection and number of X, M, Z, and V atoms present in the POM.

In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [X 2 wherein X is at least one phosphorus, sulfur, silicon, aluminum, boron, zinc, cobalt, or iron; u is from 1 to 9; and w is greater than or equal to 4.

In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [X,"MZ,.Z.,YO 6 2 wherein X is at least one phosphorus, sulfur, silicon, aluminum, boron, zinc, cobalt, or iron; v is from 1 to 9; and w is greater than or equal to 4.

In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [YVZ 12 .pO 4 J[A1, wherein Y is phosphorus, silicon, or aluminum; Z is tungsten or molybdenum; p is from 1 to 6, and A is a counterion. In one embodiment, Y is phosphorus and Z is molybdenum. In one embodiment, Y is phosphorus and Z is tungsten. In one embodiment, Y is silicon and Z is molybdenum. In one embodiment, Y is silicon and Z is tungsten. In one embodiment, Y is aluminum and Z is tungsten. In one embodiment, Y is aluminum and Z is molybdenum.

WO 01/34279 PCT/US00/28152 In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [XVbMh,M" wherein X is at least one or f-block element; g+ is the charge of X: M is at least one f-block element or d-block element having at least one d-electron, wherein M is not vanadium: h+ is the charge of M: Z is tungsten, molybdenum, niobium, or a combination thereof; b is from 0 to 6; c is from 0 to 6, wherein the sum of b and c is greater than or equal to one; u is greater than 3; and A is a counterion.

In a more specific embodiment, when the polyoxometalate has the fonnula 1, the polyoxometalate has the fonnula wherein X is at least one phosphorus, silicon, aluminum, boron, zinc, cobalt, or iron; Z comprises tungsten, molybdenum, niobium, or a combination thereof; b is from 1 to 6; and u is greater than 3.

In a more specific embodiment, when the polyoxometalate has the fonnula 1, the polyoxometalate has the fonnula [XMI'"Z 1 wherein X is at least one phosphorus, silicon, aluminum, boron, zinc, cobalt, or iron; Z comprises tungsten, molybdenum, niobium, or a combination thereof; Mh+ is at least one f-block element or d-block element having at least one d-electron; c is from 1 to 6; and u is greater than 3.

In a more specific embodiment, when the polyoxometalate has the formnnula 1, the polyoxometalate has the formula [Xi+ 2 V.Mi 6 wherein X is at least one or f-block element; i+ is the charge of X; M is at least one d- or f-block element, wherein M is not vanadium; j+ is the charge of M; Z is tungsten, molybdenum, niobium, or a combination thereof; u is from 0 to 9; v is from 0 to 9, wherein the sum of u and v is greater than or equal to one: w is greater than or equal to 4; and A is a counterion.

In a more specific embodiment, when the polyoxometalate has the formnnula 1, the polyoxometalate has the formula 6 wherein X is at least one phosphorus, sulfur, silicon, aluminum, boron, zinc, cobalt, or iron; Z comprises WO 01/34279 PCT/USOO/28152 11 tungsten, molybdenum, niobium, or a combination thereof: u is from I to 9; and w is greater than or equal to 4.

In a more specific embodiment, when the polyoxomnetalate has the formula 1, the polyoxometalate has the fonlula wherein X is at least one phosphorus, sulfur, silicon, aluminum, boron, zinc, cobalt, or iron: Z comprises tungsten, molybdenum, niobium, or a combination thereof: M 1 is at least one d- or fblock element: v is from 1 to 9; and w is greater than or equal to 4.

In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [YV,Z, 2 wherein Y is phosphorus, silicon, or aluminum: Z is tungsten or molybdenum: x is from 1 to 6, and A is a counterion. In one embodiment, Y is phosphorus and Z is molybdenum. In one embodiment, Y is phosphorus and Z is tungsten. In one embodiment, Y is silicon and Z is molybdenum. In one embodiment, Y is silicon and Z is tungsten. In one embodiment, Y is aluminum and Z is tungsten. In one embodiment, Y is aluminum and Z is molybdenum.

Polyoxometalates having an organic group, such as an alkyl group or aryl group, an organosilyl group, or other p- or d-block organomietallic groups bonded to the POM can also be used in the present invention. The organic group can be branched or straight chain alkyl, alkenyl, or alkynyl group or an aryl group of C, to The alkyl group can also be a polyether or polyol. Not wishing to be bound by theory, the organic group is bonded to the polyoxometalate as depicted in Scheme 1, where R is the organic group and Met is generally vanadium, molybdenum, tungsten, niobium, or tantalum: WO 01/34279 PCTIUS00/28152 12 Scheme I

R

ROH

H

-H

2 O Met O Met 1 11 Met Met 1 \YR 3

YLR

3

-HL

Met Met

III

The reaction between an alcohol and the polyoxometalate I results in the loss of water and the formation of the polyoxometalate II, wherein the organic group is bonded to an oxygen atom of the polyoxometalate. Any alcohol known in the art can be used in the present invention. Examples of alcohols that can be used include, but are not limited to, methanol, ethanol, or tris(hydroxymethyl)methane. The polyoxometalates having organic groups bonded to the POM that are disclosed in Gouzerh et al., Chem.

Rev., 98, pp. 77-111, 1998, which is incorporated by reference in its entirety, are useful in the present invention.

In another embodiment, the polyoxometalate I can be reacted with a compound having the generic formula YLoR, wherein Y is silicon, tin, or an other p- or d-block element; L is a leaving group; R is an organic group, such as an alkyl, alkenyl, or alkynyl group or an aryl group of C, to and o is from 1 to 4. Suitable leaving groups for L include, but are not limited to, halides and alkoxides. In Scheme I, the oxygen of polyoxometalate I displaces L from YLR, to form a new Y-O hond (compound III). Any silyl, tin. or organic derivative of a p- or d-block element known in the art can be used in the present invention, provided that the compound has at least WO 01/34279 PCT/US00/28152 13 one leaving group.

The counterion A can be any counterion known in the art. Examples of counterions include, but are not limited to. quaternary arunonium cation, proton, alkali metal cation, alkaline earth metal cation, alumonium cation, d-block cations, f-block cations, or a combination thereof. In one embodiment, the polyoxometalate is an acid, wherein the counterion A is hydrogen In one embodiment, the counterion is a dor f-block metal complex. In one embodiment, the counterion is trimethyltriazacyclononane manganese. In another embodiment, the counterion A is hydrogen, lithium sodium potassium or a combination thereof. In another embodiment, A is not hydrogen or potassium.

In another embodiment, the polyoxometalate comprises a modified polyoxometalate, wherein the modified polyoxometalate comprises the admixture of (1) a pre-modified polyoxometalate and a cerium compound, a silver compound, a gold compound, a platinum compound, a copper compound, a cobalt compound, or a combination thereof. The term "admixture" can refer to the reaction product between the polyoxometalate and the cerium compound, silver compound, gold compound, platinum compound, or a combination thereof For example, the cerium compound, silver compound, gold compound, or platinum compound can undergo ion exchange with the counterion of the polyoxometalate. The cerium compound, silver compound, gold compound, or platinum compound can also react with the polyoxometalate by a redox reaction. The term "admixture" can also refer to when the cerium compound, silver compound, gold compound, or platinum compound do not react at all with the polyoxometalate. For example, the polyoxometalate may absorb the cerium compound, silver compound, gold compound, or platinum compound.

In one embodiment, when the POM is the sodium, lithium, or potassium salt or the acid form (A is the POM can undergo ion exchange with a cerium compound, a silver compound, a gold compound, a platinum compound, or a combination thereof.

For example, Ag,PVMo,,O,,, is produced by the ion exchange of Na.PV,Mo,,O,,, with WO 01/34279 PCTIUS00t28152 14 a stoichiometric amount AgNO,. Any of the POMs described above can undergo lon exchange with a cerium compound. a silver compound, a gold compound, a platinum compound.

Depending upon the type and anmounts of POM and cerium compound. silver compound, gold compound, or platinum compound used, the ion exchange reaction may or may not go to completion. When the ion exchange does not go to completion, there may be small population of Na', Li', or H' in the modified-polyoxoilmetalate.

For example, when H,PV,Mon,,, 0 is admixed with AgNO 3 the resultant POM may be expressed by the formula Ag,H5-PV 2 Mo 1 where x is from I to 5. Here, varying amounts of H' may be present in the POM.

An example of a cerium compound useful in the present invention includes, but is not limited to, (NH 4 ),Ce(NO 3 Examples of silver compounds useful in the present invention include, but are not limited to, AgNO, and AgCIO,. Examples of gold compounds useful in the present invention include, but are not limited to, HAuCI, and salts thereof. An example of a platinum compound useful in the present minvention includes, but is not limited to, H,PtCl,.

In one embodiment, the counterion is cerium, silver, gold, platinum, or a combination thereof. In another embodiment, A is, independently, cerium, silver, gold, or platinum. In another embodiment, A is cerium and silver; cerium and platinum; cerium and gold: or silver and gold.

In another embodiment, A comprises hydrogen, lithium. sodium, potassium, or a combination thereof, and cerium, silver, gold, platinum, or a combination thereof.

In one embodiment, the pre-modified polyoxometalate is HPV 2 Mo,,O 4 NaPV,Mo,O 4 Li 5 PV,Moj,,04,,; KPV,Mo 0

O

4 or a combination thereof, and the cerium compound is (NH In another embodiment, the pre-modified WO 01/34279 WO 0134279PCTUSOO/28152 polyoxoinetalate is H 5 PVMo,,,0 4 Na, VMol 1041; Li~jPV,Moj,04.,,; KYV,Mo,(, 1 0 411 or a combination thereof: the cerium compound is (NH,),Cc(NOI) 6 and tie gold compound is HAuCl, In another embodiment, the pre-modified polyoxonietalate is

H

5 PV,Mo 110411; Na.,PV,Mo LiP\' Mo K,,PV Mo,0 4 or a combination thereof, the cerium comipound is (N11 4 -l),Ce(N0.) 6 and the platinum compound is H,PtC 6 In another einbodinint, the pre-niodifiud polyoxome&talate comiprises Na 4 PVMo,,O,, 1 NaYV MoIA 411' Na(,PV-Mo 904,, NaHPVWO,:, NaPVMo,0,:, Na.CuPW, 0O3,; Na.,CuPW, 039; Na.,MniPW 11 039;, K 5 CoPW 1 0~39; (n1- Dec,),HMnNbP,W 15 0 6 2 or K .,CU 3

(W

9 P0 34 2 and the gold compound is HAuC 4 In another embodiment, the pre-mnodified polyoxometalate is NaPV.Mo,,04,I and the silver compound is ALYNO 3 AoCIO 4 or a combination thereof In another embodiment, the polyoxometalate comprises KCo,W, 1 0 39 KSiCoVW,,,0, 9

K

7 SiCoVWI 1 ,0 39 Na CoW 1 039; Ag 5 PVMo 1,040; AgPV 3 Mo.0 41 AggCoVW 1 104-1; Agl2Ce(PW 1 1039)2 Na 2 Ce(PW 11 031),; K 12 Ce(PW 1 1039)2; Na 5 ,PCuW 1 1 39

HPV

3 Mo 9 0 1 or KCu UPW 1 0 39 In another embodiment, the polyoxometalate is not H 6 P\'Mo0 1 .1 Not wishiniz to be bound by theory, it is believed that some counterions of the present invention can be reduced to the corresponding metal when the polyoxometalate contacts the contaminant. For example, wvhen the cation is Ag' 1 or Au" 3 these cations can be reduced to silver metal or respectively, depending upon die contamrinant that is to be removed. Thus, the counterion. A can exist in multiple valence states.

The phrase "inetal compound" refers to one or more transition metal compounds, actinide compounds, lanthaide compounds, or a combination thereof When the metal compound is only one compound, then the material is directly treated with the metal compound using techniques described below. Mlienx the metal compound is composed of two or more compounds, the mterial can be sequentially treated with the compounds, or alternatively, the metal compounds can be admixed prior to treating the material with the metal compounds. Depending upon the mletal WO 01/34279 PCT/USOD/28152 16 compounds that are selected, the metal compounds may react with one another to fonn a new species, or they may not react at all with each other to produce a composition or mixture. Materials that contain a metal compound of the present invention are referred to herein as "non-POM materials." In one embodiment, the metal compound comprises a cerium compound, a gold compound. a platinum compound, a silver compound, or a combination thereof. Any of the cerium compounds, gold compounds, platinum compounds, or silver compounds listed above can be used as the metal compound. In another embodiment, the metal compound is a cerium compound and a platinum compound, preferably (NH,)2Ce(NO3) 6 and H,PtCl,, respectively. hi another embodiment, the metal compound is a cerium compound and a gold compound, preferably (NH,) 2 Ce(NO 3 6 and HAuCI 4 respectively. In another embodiment, the metal compound is a silver compound and a gold compound, preferably AgNO 3 and/or AgCIO, and HAuCa, respectively. In another embodiment, the metal compound is a cerium compounds, preferably (NH 4 ),Ce(NO 3 6 In another embodiment, the metal compound comprises gold, copper, and nitrate; gold, iron, and nitrate; gold, manganese, and nitrate; gold, titanium, and nitrate: gold. cobalt, and nitrate; gold and nitrate; copper and nitrate; (8) iron and nitrate; gold, vanadium, and nitrate; (10) gold, nickel, and nitrate; (11) gold, silver, and nitrate; or (12) gold, chloride, and nitrate. In a preferred embodiment, the metal compound comprises gold, chloride, and nitrate. In another embodiment, the metal compound comprises mixing (NEt 4 )AuCI, with varying amounts of CuSO 4 MnSO 4

VOSO

4 Ti(SO4) 2 Fe,(SO,) 3 NiSO 4 ZnSO,, Cr 2 (SO4) 3 MgSO 4 CoSO Pd(NO 3 4 Na,SO,, and/or NBu,NO3. In another embodiment, the metal compound is produced by mixing (NEt 4 )AuBr, and NBuNO 2 When the metal compound comprises two or more compounds, the compounds can be admixed using techniques known in the art. In one embodiment, tile metal compound can be produced by admixing two or more metal salts. The aniion of the salt WO 01/34279 PCT/US00/28152 17 can be any anion known in the art. Examples of anions include, but are not limited to, sulfate. carbonate, acetate, nitrate, chloride, and stearate. In one embodiment, when two or more compounds are used to produce the metal compound, the compounds are mixed in the presence of a solvent, preferably an organic solvent. In one embodinent, After the compounds have been sufficiently admixed, the solvent is removed, and the metal compound is optionally dried. In one embodiment, the drying step is by vacuum.

Any POM or metal compound of the present invention can be incorporated into a material in order to remove a contaminant from the environment. Examples of materials include, but are not limited to, a topical carrier, a coating, a powder, or a fabric. As described above, a material as used herein refers to a support that holds the POM or metal compound.

In one embodiment, the polyoxometalate and the metal compound can be incorporated sequentially into the material. In one embodiment, the polyoxometalate is incorporated into the material followed by the incorporation of the metal compound into the material. In another embodiment, the metal compound is incorporated into the material followed by the incorporation of the polyoxometalate into the material.

A wide variety of topical carriers can be used in the present invention. Suitable topically acceptable pharmaceutical carriers are those which typically are used in the topical application of pharmaceuticals and cosmetics. Examples of such carriers include, but are not limited to, lotions, creams, ointments, and gels. Topical carriers are also referred to in the art as barrier creams and topical skin protectants. Any of the topical carriers disclosed in U.S. Patent No. 5,607,979 to McCreery can be used in the present invention, which is incorporated by reference in its entirety. In one embodiment, the topical carrier comprises a pertluorinated polymer. In another embodiment, the topical carrier comprises a perfluoropolyether. An example of a perfluoropolyether (PFPE) useful in the present invention has the general formula CF30[-CF(CF 3 )CFO-](-CF20-)yCF3 In one embodiment, the topical carrier comprises a perflourinated polymer and one or more unfluorinated polymers. In WO 01/34279 PCT/US00/28152 18 another embodiment, the topical carrier comprises a perfluoropolyether and one or more unfluorinated polyethers.

In one embodiment, the topical carrier may further contain saturated or unsaturated fatty acids such as stearic acid, palmitic acid, oleic acid, pahnito-oleic acid, cetyl or oleyl alcohols, stearic acid, tluorinated acids, fluorinated alcohols tetrafluoroethanol), or combinations thereof. The cream may also optionally contain one or more surfactants, such as a non-ionic surfactant.

In one embodiment, the polyoxometalate topical composition is composed of a perfluoropolyether and the counterion A of the POM is silver. In another embodiment, the polyoxometalate topical composition is composed of a perfluoropolyether and the metal compound is a silver compound, a gold compound, or a combination thereof. In another embodiment, the non-POM material comprises a topical carrier composed of a perfluoropolyether and the metal compound comprises a silver compound, preferably AgNO 3 or In another embodiment, the non-POM topical composition is composed a perfluoropolyether and the metal compound comprises a cerium compound, a silver compound, a palladium compound, a platinum compound, or a silver compound.

A wide variety of powders and coatings known in the art can be used as the material of the present invention. In one embodiment, the powder comprises activated carbon.

Any fabric known in the art can be used to produce a polyoxometalate fabric or non-POM fabric of the present invention. In one embodiment, fabrics used to prepare garments, draperies, carpets, and upholstery can be used and articles made from them are a part of this invention. In another embodiment, the fabric can be a knit or nonwoven fabric. Useful fibers include, but are not limited to, polyamide, cotton, polyacrylic, polyacrylonitrile. polyester, polyvinylidine, polyoletfl, polyurethane, WO 01/34279 PCTIUS00/28152 19 polytetrafluoroethylene, or carbon cloth, or a combination thereof. In one embodiment, the fabric is prepared from cotton, polyacrylic, or polyacrylonitile. In one embodiment, the fabric is prepared from a cationic fiber. In another embodiment, the fabric comprises a 50/50 blend of nylon-6.6 and cotton or stretchable carbon blended with polyurethane.

Any celluosic fiber can be incorporated by a POM or metal compound to produce the polyoxometalate fibers or non-POM fibers of the present inventiou.

Examples of useful cellulosic fibers include, but are not limited to, wood or paper. In a preferred embodiment, a polyoxometalate or the metal compound of the present invention can be incorporated in paper in order to remove a contaminant from the gas or liquid phase. In one embodiment, the paper is wallpaper.

The amount of polyoxometalate or metal compound incorporated into the material varies depending upon the contaminant to be removed and the material that is selected. There is no restriction on the amount of POM or metal compound that can be incorporated into the material. In one embodiment, the amount of polyoxometalate or metal compound incorporated in the material is from 0.1 to 95 by weight of the polyoxometalate material or non-POM material. hi one embodiment, the lower limit of polyoxometalate or metal compound by weight is 0.1, 0.5, 1.0, 2.0, 5.0, 10. 15. 20, 35. 40, 45, or 50 and the upper limit is 30, 40, 50, 60, 70, 80, 90, or 95 In one embodiment, when the material is a topical carrier, the polyoxometalate or metal compound is from 5 to 30 c by weight of topical composition.

The present invention is capable of removing a single contaminant or multiple contaminants from an environment. The term "environment" as used herein refers to any media that contains at least one contaminant. In one embodiment, the environment comprises a liquid phase. In another embodiment, the environment comprises a gas phase.

The tenn "remove" refers to. but is not limited to, the degradation of the WO 01/34279 PCT/US00/28152 contaminant, the conversion of the contaminant into another compound that is either less toxic or nontoxic and/or malodorous, or the adsorption of the contaminant by the polyoxometalate or the metal compound. The POM and metal compound can degrade the contaminant by a number of different mechanisms. For example, the POM can aerobically oxidize the contaminant acetaldehyde (CH 3 CHO). Not wishing to be hound by theory, it is believed that the aerobic oxidation of CH 3 CHO proceeds by a radical chain mechanism the inititiion of the radical chain by CH 3 CHO POM,

CH

3 CO* HPOMed).

Contaminants that can be removed by using the present invention include, but are not limited to, an aldehyde, an aliphatic nitrogen compound, a sulfur compound, an aliphatic oxygenated compound, a halogenated compound, an organophosphate compound, a phosphonothioate compound, a phosphorotlioate compound, an arsenic compound, a clloroethyl-amine compound, a phosgene compound, a cyanic compound, or a combination thereof. hi one embodiment, the contaminant is acetaldehyde, methyl mercaptan, ammonia, hydrogen sulfide, methyl sulfide, diethyl sulfide, diethyl disulfide, dimethyl sulfide, dimethyl disulfide, trimethylammie, styrene, propionic acid, n-butyric acid, n-valeric acid, iso-valeric acid, pyridine, formaldehyde, 2-chloroethyl ethyl sulfide, carbon monoxide, or a combination thereof. In another embodiment, the polyoxometalate materials and non-polyoxometalate materials can remove microbial life from the gas or liquid phase. Examples of microbial life include, but are not limited to, bacteria, protozoa, and viruses.

In another embodiment, the contaminant is a chemical warfare agent (CWA).

The chemical warfare agents disclosed in Marrs, Timothy Maynard, Robert. L: Sidell, Frederick Chemical Warfare Agents Toxicology and Treatment: John Wiley Sons: Chichester, England, 1996; Compton, James A. F. Military Chemical and Biological Agents Chemical and Toxicological Properties; The Telford Press: Caldwell, New Jersey, 1988; Somani, Satu M. Chemical Warfare Agents; Academic Press: San Diego, 1992, which are herein incorporated by reference in their entirety, can be removed by the polyoxonetalate materials of the present invention.

WO 01/34279 PCT/USOO/28152 21 The present invention can remove a contaminant from the environment in the gas phase under mild conditions. In one embodiment, the contaminant can be removed from -50 °C to 250 °C at a pressure of from 0.1 ppb to 30 atm, preferably from 25 °C to 105 °C at 1 atm. In another embodiment, the lower temperature limit is -50, -30, -20, -10, 0, 10, 20, 50, 75, 100, or 150 and the upper temperature limit is 100, 125, 150, 175, 200, 225, or 250 In a preferred embodiment, the present ;ivention can remove a contaminant from the environment at room temperature (approximately 25 and at 1 atm. In another embodiment, the present invention can remove a contaminant from the gas phase that has a partial pressure of from 0.1 ppb to 2 atm, 10 ppb to 2 atm, 100 ppb to 2 atm, 200 ppb to 2 atm, and 0.5 ppm to 2 atm.

Similarly, the present invention can remove a contaminant under mild conditions when the environment is a liquid phase. In one embodiment, the contaminant can be removed from a liquid media at from 0 °C to 200 The temperature depends upon the liquid media that is being contacted and the contaminant to be removed.

The POMs and metal compounds are typically used in the presence of an oxidizer to remove a contaminant from the environment. In one embodiment, the POMs and/or metal compounds are used in the presence of air, which oxidizes the POM and/or metal compound. In another embodiment, additional oxidizers can be used in combination with air to oxidize the POM and/or metal compound. Examples of oxidizers include, but are not limited to, peroxides and peracids. In a preferred embodiment, air is used as the oxidizer.

The environment containing the contaminant can be contacted by the polyoxometalate materials or non-POM materials using a variety of techniques. For example, when the contaminant is in the liquid phase, the polyoxometalate material or non-POM material can be dipped or submersed into the liquid phase. Alternatively, the liquid phase can be filtered or passed through the polyoxometalate material or non- POM material. When the contaminant is in the gas phase, the polyoxometalate material or non-POM material is typically placed in an open or closed environment that contains the contaminant(s).

WO 01/34279 PCT/US00/28152 22 The polyoxometalate materials or non-POM materials of the present invention have a number of advantages over the prior art materials that do not use a polyoxometalate to remove a contaminant from the environment. One advantage is that the present invention can remove a contaminant from the environment starting within milliseconds of contact and can remove the contaminant for extended periods of time, ranging from several days to indefinitely. The POMs and metal compounds used in the present invention are capable of being regenerated to an active form that permits the removal of the contaminant. Another advantage is that some POMs and metal compounds can render the material more water resistant and increase the surface area of the material. Finally, when the material is a fabric or cellulosic fiber, the POM and metal compound can enhance the dyeability, light fastness, color fastness, and weaving properties of the fabric or cellulosic fiber.

The polyoxometalate and metal compound can be incorporated into the material using teclniques known in the art. In one embodiment, when the material is a topical carrier, powder, or coating, the polyoxometalate or metal compound is directly added to and admixed with the material. In another embodiment, the material (topical carrier, powder, coating, or fabric) is contacted with a mixture comprising the polyoxometalate or metal compound and a solvent. The polyoxometalate or metal compound can be soluble, partially soluble, or insoluble in the solvent, depending upon the polyoxometalate or metal compound and solvent selected. In one embodiment, the solvent is water. In another embodiment, the solvent can be an organic solvent.

Examples of organic solvents usetul in the present invention include, but are not limited to, acetonitrile, acetone, toluene, carbon dioxide, xylenes, l-methyl-2pyrrolidinone, dimnethyl sulfoxide, or an alcohol, such as methanol, ethanol, 1-propanol, or 2-propanol.

In one embodiment, when the material is a fabric or cellulosic fiber, the polyoxometalate or metal compound mixture is from 0. 1 to 20 by weight polyoxometalate or metal compound and from 80 to 99.9 by weight water, preferably from 0.3 to 15 by weight polyoxometalate or metal compound and 85 to 99.7 WO 01/34279 PCT/US00/28152 23 water. Generally, the fabric or cellulosic fiber is dipped or immersed into the mixture containing the POM or metal compound tor several hours to days at a temperature of from 0 °C to 100 preferably for 2 hours to 2 days at from 25 °C to 80 In another embodiment, the POM or metal compound can he admixed with a resin or adhesive, and the resultant adhesive is applied to the surface of or admixed with the fabric or cellulosic tiber.

Typically, once the material has been contacted with the POM or metal compound mixture, the polyoxometalate material or non-POM material is dried in order to remove residual solvent. In one embodiment, the polyoxometalate materials or non-POM material is heated from 0 C to 220 "C at or below atmospheric pressure, preferably from 25 °C to 100 In another embodiment, the polyoxometalate material or non- POM material is dried in vacuo less than or equal to 10 torr).

In another embodiment, when the material is a fabric or cellulosic fiber, the POM or metal compound can be incorporated into the fabric or cellulosic fiber by depositing the POM or metal compound on the surface of an existing fabric or cellulosic fiber, covalently bonding the POM or metal compound to the fibers of the fabric or cellulosic fiber, impregnating or intimately mixing the POM or metal compound with the fabric or cellulosic fiber, electrostatically bonding the POM or metal compound to the fabric or cellulosic fiber, or datively bonding the POM or metal compound to the fabric or cellulosic fiber via the coordination of a d- or f- block metal ion on the surface of the POM or metal compound with a functional group on the fabric. Ini the case of electrostatically bonding the POM to the fabric or cellulosic fiber, the positively charged functional groups on the fabric or cellulosic fiber and the negatively charged POM can form an electrostatic bond. In one embodiment, when the counterion of the polyoxometalate is a proton or the metal compound is an acid, the fabric or cellulosic fiber can be protonated by the polyoxometalate or metal compound to produce a positively charged fiber, wlich then electrostatically bonds to the polyoxometalate or metal compound anion. In one embodiment, a cationic polymer can be used as a binding agent to incorporate an anionic polyoxometalate or metal compound into an WO 01/34279 PCT/USOOI28152 anionic fiber.

WO 01/34279 PCT/US00/28152

EXAMPLES

The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compositions, materials, and methods claimed herein are made and evaluated, and are intended to be purely exemplary of the invention and are not intended to limit the scope of what the inventors regard as their invention. Efforts have been made to ensure accuracy with respect to numbers amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, target odorants/toxics are expressed in parts per million, temperature is in °C or is at ambient temperature and pressure is at or near atmospheric.

The term "consumption" or "consumed" refers to the removal or adsorption of a contaminant or contaminants from the environment or the conversion of the contaminant or contaminants to another compound that is nontoxic and/or nonmalodorous.

General Considerations Materials. PFPE #1511 is composed of 35-50 polytetrafluoroethylene thickening agent dispersed in a perfluoropolyether oil with water as a co-surfactant.

PFPE #1511 was provided by Dr. E. H. Braue of the United States Army Medical Research Institute for Chemical Defense.

All reagents used in the examples were obtained fi-om Aldrich Chemical Company, Milwaukee, WI, and were used without further purification. The following reagents were used in the examples (the purity of the reagent is in parenthesis): CEES HPLC grade acetonitrile, tetratluorethylene 1,3-diclhlorobenzene dimethyl sulfoxide (DMSO) AgNO, HAuCl, CuCI, FeCl 3 AgCIO, (NEt 4 )AuCI 2 CuSO, MnSO, VOSO, Ti(SO 4 Fe 2 NiSO, ZnSO, WO 01/34279 WO 0134279PCTIUSOO/28152 26 Cr,(S0 4 3 (99.99957), MgSO, CoSO, (99.998%7), Pd(NO-) 4 (9 NaS0 3 and NBuNO.. (97c7). NBuNO, was purchased fromn Fluka.

Synthesis of Ag Na- ,VAoj Na.PVMol,, 0 a peaed by the literature procedure outlied inl Petterson, Andersson, SeUig, Grate, j. H. Inorg. Chem. 1994, 982.

4 1 was prepared using the following procedure. Ground 1

O

4 11 9- 1.78 x1lO 2 inol) was dissolved in 200 mnL of distilled water. The orange solution was filtered three tims to remove any undissolved POM. Ground AgN0_ (15.2 8.94 Xl10- 2 mnol) was added with vigorous stunimg. The mixture was stirred overnight at room temperature. The product precipitated as a dark red-orange powder and was removed by suction filtration over a mnediumi fritted glass funnel. The product was dried in vacuo overnight. The [R spectrum of the resultant powder confirmed the formation of Ag.,Na5..PVMoIIO 4 o.

Synthesis of Additional Polvoxnetalates The following POMs listed in Table 8 were prepared by literature procedures (the entry number in Table 8 and the bibliographical informnation are in parenthesis): Na 5 CuPW 1 1 0 39 NaMniPW,, KMiiPW, 1 0 3 1; and KCoPW,,O.,: (Entries 2-4 and, 6, respectively; Maksinov, G. Kustova, G. Matveev, K. Lazarenko. T. P Koort Khim. 1989,15S(6), 788-96).

Na 5 PV,Mo and 1- 5 PVMo 1 0 411 (Entries 7 and 20, respectively; O'Donmell1, Stephen E. Pope, Michael T. I. Chem. Soc.. Dalton Trans. 1976, 21. 2290-7).

Na 4 ,PVMo 1 0 4 (Entry 11; So, Hyunsoo. Pope, Michael T. lnorg. Clhem. 1972. 11(6), 1441-3)).

WO 01/34279 WO 0134279PCTUSOO/28152 27 Na 6 PV-,Mo 9 4 ,i and H,,PVMoO, 4 (Entries 8 and 2 1, respectively: Pope, Michael T.; O'Donnell. Stephen Prados, Ronald A. J. Chem. Soc., Chemi. Commun. 1975, 1, 22- NaHP4O,0,ai HPVMoO,, (Entries 9 and 22. respectively: Yurchenko. E. N.

J. Mot. Struct. 1980, 60, 3 25-3 1).

Na 5 FeSiW, 1

O~

9 and KFeSiW, 1

O

39 (Entries 12 and 36, respectively; Peacock, R. D.; Weakley, T. J. R. J. Chemn. Soc. A 1971, 12, 1937-400).

Na 5 SiVW 11

O,

41 (Entry 13, Tourne, Claude: Tourne. Gilbert. Bull. Soc. C/urn. Fr. 1969, 4, 1124-36).

KCo(1I)P_,W,O 61 (Entry 15; Marcu, Gheorghe; Patr-ut, Adrian; Botar, Alexandru.

Rev. Chim. (Bucharest) 1989, 40(11), 870-5).

K

12 Pd 3

(PW

9 O34),: (Entry 16; Kuznetsova, N. Kuznetsova, L. Detusheva, L. G.; Likholobov, V. Fedotov, M. Koscheev, S. Burgina, E. B. Stud. Surf. Sci.

Catal. 1997, 110 0(:rd World Congvress on Oxidation Catalysis, 1997), 1203-12 11).

KCu(II)P,-W 7 0 1 (Entry 17: Harnlaoui, Mohiarned Larbi; Viasseniko, Konstantin; Messadi, Djelloul. C. R. IAcadenzie Sci., Ser. 11 Univers 1990, 311(7), 795-8).

NaP VMol 1 O.,,anid NaPMo,,0 4 (Entries 18 and 19, respectively;, So, Hyunsoo; Pope, Michael T. Jnorg. Chem. 1972, 11(6), 1441-3).

Na 16 PWKMCu 4

O

11 (Entry 24; Huang, Ru-Dan; Bei, Bao-Li; Wang, En-Bo; Li, Bai-Tao; Zhana, Su-Xia. Gaodeug Xutexiao Huaxue Xuebcw 1998, 19(11). 172 1-1723).

Kl,)CecPW,1O 39 2 (Entry 26: Peacock, R. Weakley, T. J. R. 1. C'hem Soc. A 1971, 12, 1937-40).

WO 01/34279 WO 0134279PCTIUSOOI28I 52 28 K7CUSW 1

O

39 and Na 7 CUSiW 1 1 0 39 (Entries 27 and.30, respectively, Teze. Andre; Soucliay, Pierre. C. R. Acad. Sci., Ser. C 1973, 276(19), 1525-8).

Na 5 NiPW 11

O

3 9 (Entry 3 1; Maksimnov, G. Kustova, G. Matveev. K. 1.; Lazarenko, T. P. Koord. Khirn. 1989, 15(6), 788-96).

Na 3 AsW 12

O

4 (Entry 35; Tsygauok, L. Statseuko, V. PD.; Vil'dt, A. L. Zhz. Neorg.

Khijn. 1974, 19(11), 3071-7).

KNiP,W 7

O

6 1 (Entry 37; Hami-laoui, Mohamed Larbi; Viussenko. Konstantin; Messadi, Djelloul. C. R. lMcademie Sci., Ser. 11 Univers 1990, 31 795-8).

(Me 4 N),.JCoS iWqO 4

,H

6 (Entry 38; Nornfiya, Kenji-, Miwa, IMakoto. Polyhedronz 1985, 1407-12).

Na 3 (Entry 40; Preuss, Rosenhiahn, L. J. Inorg. Niw!. Chem. 1972. 34(5), 169 1-703).

K

8

P

2 Wl7(NbO,)0 61 (Entry 42;- Gong, Jian; Li, Guoping-, Wang, Fuquan; Qu, Luuyu.

Wuji Huaxue Xuebao 1995, 11(3), 232-7).

(N1- 4 6 p,FeW 11

O

61 (Entry 43; Peacock, R. Weakley, T. J. R. J. Chem Soc. A,1971, Issue 12, 193 :7-40).

K7Mn(II)P-.W 17 0 6 1 (Entry 44. Marcu, Gheorghie; Patrut, Adrian; Botar, Alexandru. Rev. Chimi. (Bucharest) 1989, 40(11), 870-5).

(NH

4 6

P,

1 0O 6 (Entry 50. Varga, Gideon Jr.; Papaconstantinou., Elias: Pope, Michael T. lnorg. Chem. 1970, 662-7).

Na 9 P V 6 Mo 6

O

41 (Entry 1. Ret'yakov, V. Volkova, L. Zimtseva, G. Rudakov, WO 01/34279 WO 0134279PCTIUSOO/28152 29 E. S. Kinet. Katal. 1993, 34(l), 183).

K

1 2Cu,(W 9

,PQ,)

2 (Entry 10; Weakley, Timothy J. R. Finke, Richard G. lnorg. Chem.

1990. 29(6), 1235-41).

K(NH

4 6 ,RuBW 1

Q

39 (Entry 34: Liu, Huizhauig; Sun, Wenliang; Yue, Bin; Li, Mingxing: Chen, Zhijiang;, Jn, Songlin;, Xie, Gaoyang-: Shao, Qianfen: Wu, Tailiu; Chen, Shiinig; Yan, Xiaoiniing. Wuiji Huaxwue Xuebuo 1997, 13(3), 251-257).

K,,

0 Ni 4

PW

11 0 6 1 (Entry 14; You, David Miller, Warren Novet, Thomas-, Donille, Peter Evitt, Eric; Johnson, David Finke, Richard G. J. Am. Chemn. Soc.

1991, 113(19), 7209-2 1).

KI.Co 4 .P2, 1 (Entry 3 Evans, Howard Tourne, Claude Tourne, Gilbert F.; Wealey, Timothy J. R. J. Chem. Soc., Dalton Trans. 1986, 12, 2699-705).

K10Mn4(PW 9 )3 2 (Entry 41; Gomez-Garcia, C. Coronado, Gomez-Romero,

P.;

Casan-Pastor, N. !norg. Chem. 1993, 32(15), 3378-8 1).

113 u~W 1 6 ~:(Etry45 Weakley, Timothy JI. R. Finke, Richard G. lnorg. Chemn.

1990, 29(6), 1235-4 1).

K

12 p,W,,Ni 3 (Entry 47; Goincz-Garcia, Carlos Coronado, Eugeujio; Ouahiab, Lahcene. Angew. Chem. 1992, 104(5), 660-2).

Na 6

P

4

V

3 ,Mn(TI) 4

O

1 12 (Entry 49; Gornez-Garcia, C. Borras-Almenar, J. J.; Coronado, Quahab, L. Inorg. Chem. 1994, 33(18), 4016&22).

KCoW, 1

O

39 (Entry 29; Walmsley, F. J. Chemn. Ed. 1992, 936-38).

7 Na(NaSbW, 1 )0, 6 (Entry 5 1: Miini, Hiraoka, M. Izumi, Uchida, Y.

WO 01134279 WO 0134279PCTIUSOO/28152 Japanese Patent JP 08113731 A2 1996, Clhem. Abstr 1996, 125, 117542).

Na~H~o 9 4 :(Entry 48: Inouye, Tokutake, Kunihara, .;YsdaT.

Yamase, Nakata, Nakamura, S. Chem. Pharnn. Bull. 1992, 40, 805-807).

KCoVW 11

O,

4 (Entry 28; Bas-Serra, Todorut, et al. Synth. React. Inorg. Met.-Org.

Chemn. 1995, 25(6), 869-82).

H

2 Na,,[Fe(III) 2 (NaHO)(PW 5 O56)21: (Entry 25; Shigeta, Mori, Watanbe, J.; Baba, Khenkin, A. M. Hill, C. Schinazi, R. F. Antiviral Chem. Chemother.

1996. 346-352).

K

6 (Entry 33; Blasecki. J. W. Top. Mol. Org. Eng. 1994, 10, 373-385).

K

8 Cu(II)PW 11 0 6 1 (Entry 17; Marcu, Glieorghe; Patrut, Adrian; Botar, Alexandru. Rev.

Chim. (Bucharest) 1989, 40(11), 870-5).

(n-DeC 4 6 H-MflNb 3

P

2 WisO 6 2 (Entry 5; Gong, Chen, et al. Polyhedron, 1996, 2273-7).

The followinig POMs were prepared by the followig experimental procedures.

KSSi(NbO 2 )WLO,, (Entry 46): 1.Og of K 7 HNb 6

O

16 was dissolved in 75-m-L of deionized H,0. To this solution. 2-mL of 3 0 H 2 was added. A few drops of 3M HC1 were added to bring the pH to approxim-ately 6. KSiW 1 0O 39 (15.8 g) was added, which resulted ini gas evolution. To the swirling mixture, 25-miL of H,O followed by 12-mL of 3M HCI were added. The color of the solution was yellow and the pH was approxiniately 1. The mixture was stirred for an additional 30 minutes, then 14 g of solid KCI was added, which resulted iii the formation of a pale yellow solid. The solid 310 was collected by filtration and dried resultingc in 4.7 g of K 5 Si(NbC 2 )W,,O.o WO 01/34279 PCTIUSOO/28152 31 NaSiVNbWiO 39 (Entry 32): 6.64 g of K 7 Hb 6

O

1 9 was dissolved in 800-mL of H,O. To this solution, 80-niL of 30 HO, solution was added and the pH was adjusted to 6.0 with KOH. Solid KISiVWoO, 0 was added slowly to produce a final pH of 8.5. To this mixture, 40-mL of 3M HCI was added dropwise. The addition was stopped occasionally to agitate the solid. The solution was then stirred for 15 minutes.

Additional 3M HCI (40-mL) was added to give a pH of 1.5. The solution was stirred for 1 hour, and 160 g of solid KC! was added. The orange precipitate was filtered off and dried, yielding 40.85 g of KSiVNbW,O 39

K

6 SiVNbW,,0,, and water were passed through an Amberlite IR-120 ion exchange column which was charged with 1 M NaCI. The volatiles were removed from the collected solution by vacuum to produce Na 6 SiVNbW,,O,, as a yellow, crystalline solid. The Amberlite is a product of Rohm and Haas and was purchased from Aldrich.

Instrumentation. Gas chromatography analysis was conducted using a Hewlett-Packard Series 5890 Gas Chromatograph equipped with a flame ionization detector and fitted with a non-polar 5% PHME siloxane, 30 meter column.

Alternatively, the gas chromatograph was equipped with an FID detector and a phenyl methyl silicone capillary column. Mass abundance determinations were performed using a HP 5890 GC with a 5% phenyl methyl silicone capillary column and a 5971 A Mass Selective Detector. Gas chromatography/mass spectroscopy was performed using a Hewlett-Packard Series II 5890 Gas Chromatograph equipped with a 5971A mass selective detector and fitted with a non-polar 5% PHME siloxane, meter column. For both GC and GC-MS, nitrogen was used as the carrier gas. In Examples 5 and 6, all reactions were monitored using a Hewlett-Packard 6890 gas chromatograph with flame ionization detector and HP-5 phenylmethylsilicone capillary column. UV-visible spectra were run on a HP 8452A Diode Array Spectrophotometer. The percentages of O0 of the reaction atmosphere were varied using a Series 810 Mass Trak tlowmeter with dried argon as the other gas.

WO 01/34279 WO 0134279PCTIUSOOI28I 52 32 Exampnle 1: Oxidation of CEES to CEESO by a POMITSP Mixture under Ambient Conditions after 40 Days.

PFPE #1511 (0.525 g) was combined with AgNa..PVMo,,Ou (0.066 g, 3.81 x l0-'nmol) to give a 1% weighlt/weighit POM/cream mixture. ThiePOM/crearnmixture was placed in a 18 mL glass vial fitted with a poly(tetrafluoroethiylefle) (PTFE) stopper.

A sufficient amount of 2-chloroethyl ethyl sulfide (CEES) was added to the mixture to completely submerge the POM/cream mixture. After 40 days, 10 gL of the CEES solution surrounding the POM/cream mixture was removed and diluted into 100 [ItL of 2,2,2-trifluoroethanol (TFE). GC-MS of this solution showed the presence of 2chioroethyl ethyl sulfoxide (CEESO).

WO 01/34279 WOO1/4279PCTI/USOO/28152 3 3 Ex aniple Oxidation of CEES to CEESO by POMITSP MixtureunrAmit Conditions.

The CEES composition used ini all trials was composed of 9.0 mL of CEES combinied with 100 pL of 1, 3-d ichloro benzene, where the 1 ,3-dichlorobenzeiie was added as an internal reference. Each POM/PFPE #1511 cream mixture (approximately 0. 3 g) was smeared at the bottomi of an 18 mrL glass vial and flitted with a PTFE cap.

The CEES composition (1.0 mL) was then added and each vial was left undisturbed for several days under ambient conditions, with periodic GC analysis of the CEES/reference solution to check for CEESO formation. For GC analysis, 10 pL of the CEES/reference solution surrounding the POM/creamn mixture was diluted in 100 jpiL of TFE and analyzed. The results are shown iii Table 1.

Table 1 Entry Catalyst Weight Turnovers after Percent' 9 Days' 1 cream only N/A 0 2 AgNO 3 20.3 0 3 HPV,Mo 5.8 0 4 H.YV,Mo,, 4 20.8 0 5 AgNa,-,PV,MofO,,0, 5.6 0 6 Ag.,Na,.,(PVMo,. 4 20.6 0 7 HAuCI 4 7.1% 0 8 HAuCI 4 AgNO 3 7.6% [gClQ 'Weighit Percent (mass of POM (mass of cream mass of POM x 100 b Turnovers (mol of CEESO/ mol of catalyst) x 100 CThis mnixture was comnposed of 1 equiv. of HAuCl, 1.25 equiv. of AgClO 4 and 0.75 equiv. of AgNO,. The wveight percent is reported as the (weight of all comnponents, g)/(weight of cream, g weight of comrponents, g) x 100 WO 01/34279 PCTUS00128152 3 4 Exampnle 3: Catalytic Oxidation of CEES by POMs in 2,2,2-Trifluoroethaflol after 14 Days under Ambient Conditions.

A CEES solution was prepared by mIiing 85.8 mM of CEES; 1.51 x 10O' to 1.82 x 10O5 mol of catalyst;, 100 pL 1,3-dichilorobenlzenie (initernal standard). and 85 rnL of 2,2,2-trifluoroethaflol, at 25 'C under ambient air. In a typical run, 5.0 mL of the CEES solution was comnbied with enough catalyst to yield a CECES:POM ratio of 20: 1, and the mixture was stirred for 14 days. The results are shown in Table 2.

Table 2 Entry Catalyst CEESO Turnovers' AgN0, 0.42 2 AgH,-PVMor1

O

4 ,n 8.13 .3 Ag,11 4

VMO

1 104() 1.18 4 Na&PV-,Mo,,O,, 0.00 -KCoVW 1 0411 0O.00 6 KCu"PW 11 15.33 7 2 4.47 8 9 Ag..K, ,Cu 1 PW,jO-., 15.21 aTurnovers (mol, of CEESO! mol of catalyst) x 100 WO 01/34279 PCT/US001281 52 Example 4: Aerobic Oxidation of Acetaldehyde Catalyzed by Polyoxonietalates.

In a 20 inL vial, 0.961 inmol acetaldehyde, 2 ing of POM, and pentane (intenal standard) (34.7 uL) were stirred 'i 2 rnL of chlorobenzene under 20 rnL (0.82 rmol) of at 298 K for 24 hours. Under these conditions, the POM was totally insoluble at all times durine the reaction. For the cloth samples, the polyoxometalate was deposited as a 5% by weight solution of H,O and subsequently dried. BHT (2 ,6-di-tert-butyl-pcresol) was used as a radical inhibitor in a 1.2 mol ratio versus POM. The aerobic oxidation of acetaldehyde by the POMs is shown in Table 3.

Table 3 Entiy Catalyst Timie Equivalents Conversion of %Yield TunOloeSd CH3CHI-1 Acetaldehyde b Acetic Acid' I Blank 24 8 0 2 NaCo 2

W

1

O

39 24 1538 97.8 67.2 1033 3 KsSiCOVW 11

O

39 24 1521 95.7 60.2 916 4 K7SiCOVWIf)O1 9 24 1483 92.3 55.8 827 Blank 28.5 37 6 Na 8 Co 2

W

11

O

39 28.5 3075 80.3 70.3 1844 7 KSiCoVW,,O, 28.5 3041 72.1 59.4 1491 7 K 7 SiCOVW 10

O

39 28.5 2966 73.3 62.4 1545 8 Cotton-NaCoW, 1

O

3 9 24 1538 98.2 66.2 815 9 Cotton-KSiCoVW,,0 3 q 24 1521 90.4 50.0 644 1 NaSCoXI 10 3 9 /1.2 BHT 24 1538 17.8 22.4 180 WO 01/34279 PCT/US00/28152 37 Equivalents of Acetaldehyde moles of acetaldehyde (material)/moles of POM. For the last three reactions (Entries 5-8) after 24 h another 0.961 mmol acetaldehyde was added, and the suspension was allowed to stir for an additional 8 h. All values are averages of two experiments.

b Conversion (moles of acetaldehyde consumed/moles of initial acetaldehyde) x 100.

c Yield (moles of acetic acid/moles of initial acetaldehyde) x 100.

d Turnovers [moles of acetic acid (in the run with catalyst) moles of acetic acid (in the blank run without catalyst)]/moles of catalyst.

Example 5: Aerobic Oxidation of Tetrahydrothiophene in Liquid Phase by Modified Polyoxometalates and Metal Compounds.

Tetrahydrothiophene (THT) (0.445 mmol, 0.64 M) and 1,3-dichlorobenzene (internal standard) in the presence or absence of the polyoxometalate and/or metal compound were stirred in 4 mL of acetonitrile in 20 mL vials under Iatm 0. at room temperature. The aerobic oxidation of THT by modified polyoxometalates and metal compounds is shown in Table 4. In Entries 3-7 and 12, 2 x 10-6 mol of polyoxometalate or metal compound was placed in the vial before adding the reagent and internal standard. In Entries 8-14, the polyoxometalate and metal compound (Entries 11 and 14)or the metal compounds were placed in the vial before the addition of the reagent and the internal standard. In Entries 8-14, 2 x 10- mol of each POM or metal compound was used in a 1/1 ratio.

WO OIC4279 WOO1/4279PCTIUS0012815S2 Table 4 Entry Catalyst Tine (hi) Yield Turnover' I Blaakc 3. 5 0- 2 Blank' 72d0 3. H 5

PV

1 Mo,,0 4 1 3.5 0 0 4 I-AuCl 4 3.5 0 0 HAuC1, 2 0 0 6 (NH,),Ce(N0 3 6 3.5 14 12 7 (NH 4 )2Ce( NO3 6 72d26 100 8 (NH,),Ce(NOI)6 3.5142

H

5 PV,Mo IC1040) 9 (NH{ 4 )2Ce(N0 3 6 3.5 67 57 HAuCI, (NHj 2 Ce(N0 3 6 72d76 293 HAuC1 4 11 (NH,)2Ce(N0 3 6 3.5 65 56 HAuC I, H 5 PVIMo 1 0 4 1 12 H,PtC1 6 3 0 0 13 (NI- 4 )Ce(N0 3 6 3 25 21 H,PtC 16 14 (NH,)2Ce(N0 3 6 3 26 23 ____H,PtC1 6 HPV,MolO,. I04 Moles of THTO moles of initial THT.

'Moles of THTO moles of catalyst.

'No catalysts.

d More THT and 0, added to the reaction system after 24 hir of initial reaction.

WO 01/34279 WO 0134279PCTIUSOOI281 52 39 EXaRInol 6. Aerobic Oxidation of CEES in Liquid Phase by Modified Polyoxornetalates and Metal Compounds.

CEES (0.337 minol, 0.64 M) and 1,3-dichlorobenzefle (internal standard) in the presence or absence of the polyoxometalate and/or metal compound were stirred in 4 ml of acetonitrile in 20 rnL vials under I atm of 0, at roomn temperature. The aerobic oxidation of CEES by m-odified p-yxmtltsand metal conpouinds is shown in Table 5- In Entries 2, 3 5. and 6, 2 x 10.6 inol of polyoxometalate or metal compound was placed in the vial before addig the reagent. In Entries 4 and 7-12, the polyoxon-etalate and/or the metal compound(s) (2 x 10.6 inol) were placed in the vial before adding the reagent solution.

WO 0134279 WO 0134279PCT/USOO/28152 Table Entry Catalyst Time Conversion Yield %b Tumnoverc (day) I Blankd 0 0- 2 HAuCl 4 3 0 00 3 HPV,Mo,o04 o 4 HAuC1 4

H

5

PV

2 Mo 0

O

4 o 3 12 3 2

(NH

4 2 Ce(N0 3 6 1 16 8 6 (NH 4 )2Ce(N0 3 6 3 26 18 12 7 (NI-1 4 ),Ce(N0 3 6 HAuC1 4 1 28 9 6 8 (NH 4 2 Ce(N0 3 6 HAuC 1, 3 57 36 24 9 (NI- 4 )Ce(N0 3 6 1 47 24

H

5

PV

2 Mo 11104,

(NH

4 2 Ce(N0 3 6 3 64 41 27

H

5

PV

2 MoinO 4 0 11 (NH 4 2 Ce(N0 3 6 HAuCl 4 1 53 43 28 H.,PV,Mo,, 1 0o~ 12 4 2 Ce( N0 3 6 HAuCl 4 3 82 70 46 HPV,Mo( 1

O

40 a Moles of CEES consumed I moles of initial CEES.

b Moles of CEESO (the GC response factor of CEESO is assumed the same as that of CEES) moles of initial CEES.

Moles of CEESO (the GC response factor of CEESO is assumed the sarme as that of CEES) moles of catalyst.

No catalyst.

WO 01/34279 WO~h/4279PCTUSOO/28152 41 Example 7: Aerobic Oxidation of CEES in Liquid Phase by a Polyoxometalate and HAuC1 4 j.

Each POM (9.61 x 10.6 mol); HAuCI 4 (4.8 x 10- 5 mol); 1,3-dichlorobenzefle (9.61 x 10-' ruol), and CEES (9.61 x 10-' inol) were stirred in 4 rnL of acetonitrile under rnL (0.82 rnrnol) of 0, at 298 K. The aerobic oxidation is shown in Table 6.

Table Entry Catalyst Tinr Turnovers 0 Tine Turnovers b 011) of CEESO (Ii) of CEESO .0 1 NaPVMo 1 4 0 11 1.1 2 NaPV,Mo 1 0

Q-

0 4 5.0 11 10.6 3 NaEpV 3 Mo0 0 4 7.0 11 18.3 4 NaH,PV 4

W

8 O 4 4.4 11 14.2 Na 9 PVMoO 40 4 5.6 11 20.7 6 Na 5 CuPW 11

O

39 4 59.2 11 83.6 7 HAuCI 4 4 0 11 0 aTurnovers (moles of CEESO (catalyst rn) moles of CEESO (blank run.))/mioles of catalyst.

WO 01/34279 PCT/US00/28152 42 Example 8: Aerobic Catalytic Oxidation of CEES to the Sulfoxide (CEESO) using AgNO/HAuCI, System (non-POM system).

A metal compound solution was prepared by combining AgNO3 (1.0 x 10- 5 mol) and HAuC1, (5.0 x 10- 6 mol) in 1 mL of acetonitrile. To this solution was added CEES x 10- mol). Upon addition of CEES to the solution, a white precipitate immediately formed. The precipitate is believed to be a silver containing salt. possibly coordinated to CEES. The solution was allowed to stir for 100 hours, at which time there was loss of CEES in the solution based on gas chromatography. The filtrate was taken to dryness, and a solution containing excess CEES in acetonitrile was added to the yellow oily residue. Gas clromatography of the solution confinned the formation of CEESO. The results are shown in Table 7 (entries 1-7).

Example 9: Aerobic Catalytic Oxidation of CEES to the Sulfoxide (CEESO) using AgNOJAgCIOjHAuCl, System (non-POM system).

A 20 mL vial fitted with a PTFE septum was purged with I atm of To this vial were added by syringe, 0.035 mL of AgNO 3 (0.1013 M in acetonitrile); 0.060 mL of AgCIO, (0.1138 M in acetonitrile); and 0.100 mL HAuClI (0.0477 M in acetonitrile), and the total volume was adjusted to 1 mL with the addition of HPLC grade acetonitrile.

To this solution, 0.36 mL (2.86 x 10- 3 mol) of CEES were added to the solution, and the formation of CEESO was monitored over time by gas chromatography using 1,3dichlorobenzene as the internal reference. The results are summarized in Table 7 (Entries 8-11).

WO 01/34279 WO 0134279PCTIUSOOI28152 Table 7 Entry Catalyst Tunie TurnoverA (hrs) I 2 AgNO 100 0 2 2 AgCO 4 100 0 3 1 HAuCl, 100 0.9 4 2 AgNO-, 1 HAuC 4 L 113.0 2 AgNO, IHAuCl, 2 2 1.3 6 12AuNO, IHAuCl, 24 83.5 7 2 AgNO, I HAuC. 100 146.3 8 0.75AgNO- 1.25AgCl, IHAuC1 4 1 3 8. 3 9 0.75AgNO, 1.25AgC1 4 1HAuCI 4 2 50.2 0.75AgNO, .25AgC], IHAuCb, 24 141.9 1-I1 10.75AgNO, 1.25AgCl, IHAuCl, 100 208.7 a Moles of CEESO/ moles of catalyst (catalyst is based on moles of HAuC 4 used).

WO 01/34279 W00114279PCT/USO 0/28152 44 Example 10: Aerobic Oxidation of CEES by POMIHAUCI 4 and Metal ConipoundIHAuC, Systems.

One equivalent of the POM or mnetal compound was combined with five equivalents of HAuCI 4 in acetonitrile, wherein the total volume was 1 nil. To this solution, 100 equivalents of CEES was added. The reaction was conducted under one atm of 0. at 298 K. The number of turnovers were calculated at 4 and 11I hours, and the results are summarized in Table 8a.

t0 Table 8a Entry POM or Metal Compound Turnovers' Turnoversb 1 Na.)PVMo,0A,. 5.6 20.7 2 Na.CuPW,,O,, 59.2 83.6 31 NajvMnPW,,0.

0 6.5 29.0 4 K,CoPW,,O,, 38.9 71.9 (n-Dec,),,HMnNbP,W,,O,,, 5.1 27.9 6 KPMnW,,O 10 51.8 76.5 7 Na V,Mo,, 0 4 1 5.0 10.6 8 Naj'VMoO,,n 7.0 18.3 209 Na.H.PV.MoO, 1 4.4 14.2

K,

1 Cul,(WQP0,), 5.1 12.2 11 NaPVW, ,0 2 Qt 1.6 8.7 12 NaFeSiW,,QfI, 0.9 4.6 13 Na.SiVW,,0Afl 0.0 2.3 14 K,ONi 3.5 K.Co(II)P ,W17061 1.02.

16 4.2 6.4 17_ KCu(II)P,W, 7 2.0 4.7 18_ NaPVMo,,O, 10 0.0 1.2 19 NaPMo,,O,, 0.0 0.1 H.XV,W,,OII 0.0 1.4 21 H 6 PV.IWO4!, 0.0 1.2 22_ HPV4WO,, 0.0 0.9 23 HAuCLd 0.0 0.0 24 Na,,PW,,(CuO,, .51.

H,Na, 4 f[e(fl),(NaHO),(P 9

W

1 O.,j~l 1.0 1.6 26 K,,Ce(PW, 0.6 0.7 27_ K 7 CuS iW,, 0.4 1.0 1.1 28 K.,CoVW,,Odr, 1.3 1.1 29 K.Co,W,, 1.5 Na 7 ,CuSiW 1 ,Oo 1.1 1.1 31 Na,NiPW,,O,, 0.6 0.9 32_ NaSiV~bW,,0,, 0.7 0.6 33 K,,SiTiW,.O.A,_ 0.6 0.4 WO 01/34279 WO 0134279PCT/USOO/28152 34 K(NH-1)RuBWIO,, 0.7 0.9 Na,AsW,,Os,, 0.7 0.2 36 K,,FeS]W, 1 0. 0.9 0.7 37 K Ni ,W,0O1 0.90.

38 1.8 1.9 39 KfCo 1

P,W"O

6 q 1.3 1.6 4 1.8 1.7 41 K,,Mfl,(PWg)O,), 1.3 1.4 42 1K.P,W, 7 (NbO,) 1.1 0.9 43 (NH4),PFeW, 7 0. 44 KMn(II)P.,W7 Of 1.0 0.8

K

1 YPW,,,CuO, 1. 1.9 46_ KSi(NbO,)W,,lIl) 0.9 0.7 47 -K,,P.W,NiO~q 1.0 1.8 48_ Na.,HMoO- 0.8 0.9 49 Na,,n(DO, 1.1 1.4 (NH,),P,WIxOhI 0.0 0.3 51 (NH,),,Na(NaSb0 0.5 1.8 52 CuCi., 0.0 0.4 53- Fed, 0.3 a Turn~overs after 4 hours b Turnovers after I11 hours Additional POM and/or me~tal compounds that were tested can be found in Table Table 8b Entry Compound A Compound B 1 HAuC 4 2 Na 4 P)Mo 1 4 3 Na 4 PVMo,,O 4 n 5 HAuCI 4 4 NaPVMo,,1O 4

A

NaPV,Mo,,0 4 0 5 HAuC 4 6 NaPVMo,,Ov, 7 NaPVMo 9

O,

4 5 HAuC1 4 8 NaH,PVMo,0 4 ,n 9 NaH,PV 4 MoRO 4 A 5 HAuC1 4 NaPVMoO,, I I NLiVoO( 5 H Audi, 13 Na.IP 0 i w- 5HAuC14 14 Na,PMo 1 Wo 01/34279 WO 0134279PCTIUSOO/28152 NaPMo,.04 4 5 HAuCl, 16 NaCuPW 1 ,Ot. 5 HAuCl, 17 (TBA),CuPW,,O,, 5 HAuCI4 18 NaMnPW,,O,, 19 Na.NnPW,,O,, 5 HAuCi, Na.FeSiW, 0 21 Na.FeSiW,1 0 22) 23 Na.SiVW,,O,, 5 HAuC1 4 24 NaPV,WflO 4 NaPV,W,O, 4 5 HAuCI 4 26 NaPV,WO 4 27 NaPVW,,O,(, 5 HAuCI, 28 Na.7PV 4

WO,.

29 Na 7 PVW,0O 4 5 HAuC1 4 Na,P 4 WnCuJ 4 0i, 31 Na,;P.,W.znCu 4

O

11 5 HAuCI.

32 H,.NaAFe(III),(NaHO),(P,W,O,), 33 5 HAuCL 34 K,,,Ce(PW 1 09)- 5 HAuCI 4 -36

K

7 37

K

7 CuSiW,,O 19 5 HAuO 4 38 KCoVW, 1 O, 39 K,,CoVW,,O,, 5 HAuCl 4 KCoPW,,O~ 9 42 KCo-,W, 01 9 43 K Co,W ,OAQ 5 HAuCI 1 44 (Ne4,F~ibPW,, (NDecj,),HMnNNP,W,,O 6 5 HAuCl, 46 Na 7 CuSiW 47 NaC~W,, 5 HAuCl 4 48 49 NaNiPW,,Oig 5 HAuCI 4 NaSiVNbW,,Og______ 51 NaSiVNbW10O., 0 ul 52 KPMiiW,, 53 -KPMnW,,O~ 9 5 HAuCL 4 54 K.,SiTiW,,O 4 KSiiWO. 5 HAuCl 4 56 K(NI-1 1 ),RuBW, 1 0 9 57

K(NII

1 5 HAuC1 4 58 Na,AsW 1 WO 01/34279 WO 0134279PCT/USOOI28152 59 Na,AsW,,O, 4 5 HAuCI, 61 KFeSiW,,O, 9 5 HAuCI, 62 K.NiP,W,70 6 63 K,,NiP,W, 7 0, 5 HAuCI, 64 (Me 4 N),,(CoSiW,,O,.H 6 (me 4 N) (CoSiW,,0 4

.H

6 5 HAuCi.

66 67 K,,,Co.

4

P

1

W~O

6 s 5 HAuCi.

68 NaVJOO,R 69 NaVA001 5 HAuCi, 71 K,,(Mn,)(PWqO) 5 HAuCI 4 72 K,,Cu,(W,,PO, 4 73 K,,Cu,(W,,PO, 4 5 HAuCI, 74 K,,Ni 4

PIWI

1 7

O

K,,Ni.PW, 7 Otj 5 HAuCI.

76 77

KP.,

7 (NbO,) 78 (NI{ 4 6 PFeW 7 0 6 79 (NH,),PFeW, 7 0 6 1uI K,Co(II)P,W,0 81 KCo(II)PW, 7 0 6 5 HAuC1 4 82 K,,Pd,(PW 0 83 K,,Pd,(PW 0 1 4 )i 5 HAuC1 4 84 K7Mn(II)P,W, 7 5 HAuC1 4 K,,,PW,,Cu 4 0s 5 HAuC1 4 86 K,.Cu(II)P,W, 7 0 6 5 HAuC1 4 87 K.,Si(NbO,)W,,O 4 n 5 HAuC 4 88 KlP,WtNi,% 6 g 5 HAuC1 4 89 NHMo, 5 HAuCI 4 II),O,,,5Hu1 91 6 ,+5HAuC 4 5 HAuC 1 92 (NI- 4 ),Na(NaSbQW,,)Op6 5 H-AuCl., 93 5 Cu(acetate), 94 Na.PV,MoAnOA, 5 Cu(acetate), 5 Co(II)Acac 96 NaPVMo, 4 o 5 Co(IT)Acac 97 5 Fe(III)Acac 98 NaPV,MoAo 4 l) 5 Fe(III)Acac 99 5 MnO, 100 NaPV,Mo 0 0n, 5 MnO, 101 SCuCI, 102 NaPV,Mo, 1 5 CuCl.

WO 01/34279 WO 0134279PCTUSOO/28152 103 5 FeCl, 104 NaPV.Mof)O 4 5 FeCL, 105 5 CrC, 106 NaPV,Mo,)O., 5 CrCI, 107 5 CeC1, 108 NaPV,MoO,s 4 5 CeCh 109 NaPV 6 MoO 4 5 FeCi., 110 Na ,PV 6 MoO4 5 CuCI, lit Na,,PV 6 MoO 4 112 5 FeC1 2 113 K,,Pd,(PWQO,), 5 CuCi, 114

K,

9 Pd,(PW 0 115 Na.CuPW,,O, 9 116 -Na.CuPW,,O,, 5 Cr(NO) 117 5 CrNO, 118 NaCupw,,Oln 5 Co(N04, 119 5 Co(NO.).

120 5 Zn(NQ4, 121 Na.CuPW 1 0,49 5 Zn(NOO, 122 Na.,CuPW,,O,, 5 Cu(NO)d2 123 5 Cu(NO,), 124 NaCuPW,,O~ 9 5 Zn(N03)3 125 Na.CuW,,Otq 5 Cu(acetate), 126 NaCuW, 11 O9 5 Fe(acetate), 127 NaCuW I 10, 5 MnO, 128 5 NaNO, 129 LiPVW,, 4 )ul 130 AgNO, 131 AgNO, 5 HAucI' 132 NaNO, 5 HAuC 4 133 NaC1O 4 5 HAuCI 4 134 Ag-CIO, 5 HAuC., ~135 LiC10 4 5 HAuCI 4 136 5 (NH-1),Ce(ND 1

)A

137 Na,,PN~o 1

O

4 0 5 (NH ),Ce(NO,) 6 138 Na.CuPW, 1 O,o 5 (NH,),Ce(NO) 139 NaPVMo,,04,1 5 CoSO, 140 Na,,CuPW,,Ozr, 5 CoSO 4 11NaPVMo,, 4 n 5 Ce(S0 4 142 Na,,CuPWjj,O 1 5 143 NaPVMO,,Ojrn 5 H,PtCIL 144 Na.CuPW11R 0 5 H,PtC1 145 NaPVMoi,0 4 f, 5 Pd(NO,), 146 NaCUPWI,01(o 5 Pd(NO-) WO 01/34279 PCT/USOO/28152 49 147 NaPVMo, Od 5 RhC, 148 INaCuPW,,O,, 5 RhCl, 149 INaY VMo,,O 4 5 ReQ, 150 Na.CuPW,,O,,, 5 ReQ., WO 01/34279 PCT/US00/28152 Example 11: Oxidation of CEES to CEESO by Metal Compounds (non-POM).

Deternining the Stoichiometry of O, in the Catalytic Oxidation of CEES. A Schlenk flask fitted with septum was attached to a manometer and purged with To the flask containing 1.36 mL of acetonitrile, solutions (all in acetonitrile) of 0.200 mL of (NEt4)AuC 2 (5.0 x 10 6 mol), 0.188 mL of AgCIO 4 solution (1.0 x 10 mol), 0.094 mL NBu 4

NO

3 solution (5.0 x 10.6 mol), 0.166 mL 1,3-dichlorobenzene x 10 4 mol) (internal standard for GC), and 0.084 mL CEES (3.8 x 10" mol) were added.

The consumption of 02 was recorded, and aliquots were periodically taken and injected into the GC. The stoichiometry of 02 consumption was established using a manometer to determine the amount of 0, consumed while simultaneously monitoring CEESO formation with a gas chromatograph. Figure 1 reveals that one equivalent of the CEESO formed corresponds to 0.5 equivalents of 02.

Cream Formulation Reactions. Experiments were performed using the perfluorinated oil, Galden D02, and Fomblin perfluorinated polyether oil as "solvent," both of which are components of the cream. Samples were prepared by adding components together, dissolving in a minimal amount of acetonitrile, stirring for minutes, and then removing the solvent by vacuum.

In all the cases where (NEt 4 )AuCI 2 was used as the gold compound, 1.25 x 10 mol of the gold compound was used. The other components which were varied in quantities were NBu 4

NO

3 (1.25 x 10- 5 1.25 x 10- mol), and a CuSO, (1.25 x 1.25 x 10' 4 mol) (Table The gold, copper, and/or nitrate salts were admixed in acetonitrile, then the solvent was removed by vacuum. After the mixture was dried by vacuum in a Schlenk flask, the flask is attached to the manometer and the apparatus is purged with 02. After purging, 7.0 mL of the perfluorinated fluid was added to the flask. The system was equilibrated to atmospheric pressure then sealed from any external atmosphere. Through the septum 0.05 mL (4.2 x 10"' mol) of CEES was added and the system was monitored for 02 consumption. Table 9 shows CEESO formation after 1 hour using various cream formulations (7.0 mL Galden D02).

WO 01/34279 WO 0134279PCr[US0Or28152 TABLE 9' [Aul

[CU+

2 I [CEESO formed] 0 1.25 1.25 3.62 1.25 1.25 1.25 5.80 o 2.50 2.50 5.00 1.25 2.50 2.50 8.06 0 5.00 7.25 8.06 1.25 5.00 7.25 16.20 0 10.00 12.50 10.60 1.25 10.00 12.50 18.70 'All concentrations expressed in 10V mol.

Another experiment was performed using Fomnblin as the "solvent." In this case, mL of Fomnblin, 0.005g of (NEt,)AuC 2 (1.25 x i0 5 mol), was admixed in with varying amounts of CuSO 4 MnSO 4

VOSO

4 Ti(S0 4 2 Fe,(S0 4 NiSO 4 ZnSO 4 Cr 2 (S0 4 3 MgSO 4 CoSO 4 NaSO 3 and/or NBu 4

NO

3 The catalyst was prepared and the experiment was performed using the same method as earlier reported- Table 10 reveals CEESO formation in PFPE Surfactant (1.0 mL Fomrblin) using various metal compounds. The mnetal compounds are abbreviated for simplicity sake. For example, mnetal compounid 1 Au/lCu(II)/l NO 3 was prepared by mixing one equivalent each of (NEt,)AuCI., CuSO 4 anid NBuNO,.

WO 01134279 ~VO 0134279PCT/USOO/28152 TABLE Metal Compound Turnovers of CEESO after 10 min (based on Au) 1Au/lCu(fl/1N0 3 17 1AuI2Cu(II)flNO 3 28 3 115 lAuI2Cu(II)/2N0 3 155 I Au/i Cu(II)/3N0 3 155 1AuIlFe(III)/3NO, 142 IAuI2M n(II)/3N0 3 164 I Au/2Ti(IVI)/3N0 3 142 1AuI2Co(I1V3N0 3 177 1AuI4NO 3 185 lAuI2Cu(II)/3N0 3 181 1 AuI2Cu(II)/4N0 3 195 lAuI3Cu(II)/3N0 3 165 2Cu(II)13N0 3 28 IAu/3NO, 150 I Fe(III)13N0 3 19 1AuI2V(IV)/3N0 3 160 lAt./2Ni(II)/3N0 3 140 IAuI2Ag(II)/3NO., 184 Figure 2 shows CEESO formation as a function of time for lAuI2Cu(II)/3N.,, 2Cu(II)/3N0 3 and I1AuI3NO.,. From the data in Table 10 and Figure 2, it is clear that there was a synergistic effect when certain redox active metals were added to the Au/NIO, systemn. For example, one of the most active systems, IlAu/2Cu(II)/3N0 3 was -3.8 and 6.5 time~s more effective after 10 minutes of reaction time than when only 2 of WO 01/34279 PCT/US00/28152 53 the components were used, 1Au/3N0 3 and 2Cu(II)/3NO 3 respectively. Also, Figure 2 shows that iiiibition was less pronounced in the three component system. Another important aspect of this system is that the oxidation terminates to the sulfoxide without continued oxidation to yield the sulfone. This is important as it relates to toxicity issues as it is believed that the sulfoxide of mustard gas is significantly less toxic than the corresponding sulfone.

WO 01/34279 PCT/US00/28152 54 Example 12: Synthesis, Characterization, and Reactivity of Organo-Modified POMs Synthesis of AgVO,,((OCH,),CCH,). (Ag Me cap) Na[VO 3

((OCH,)

3

CCH

3 2 (Na Me cap, 0.480 g) was dissolved in 4 mL of distilled water. This was filtered over a medium fritted funnel to remove any undissolved POM. To the dark red-orange solution was added AgNO, (0.215 g) with stirring. An orange-red precipitate formed immediately. The crude product was separated by suction filtration over a medium frit, washed with room temperature water and ether. The product was dried over night in vacuo. Crystals were grown by diffusing ether into an acetonitrile solution of the crude product at room temperature.

V NMR (0.04 g dissolved in 2.0 mL of MeCN) -499.232 ppm (singlet). Solid-state IR (KBr pellet, 1400 400 1452.11 1390.47 1200.43 1128.53 1015.5 953.9 820.36 794.68 712.5 614.91 584.09 424.87 Synthesis of Co[V,O,((OCII),CCH,),1 (Co Me cap) The same procedure for the synthesis of Ag 2

[V

6

,O

3

((OCH,)

3

CCH

3 was followed, except CoCI, was added to form the Co salt of the POM. Crystals were grown from diffusing isopropyl alcohol into a MeCN solution of crude product. 5

'V

NMR (0.04 g dissolved in 2.0 mL of MeCN) -500.3 ppm (singlet). Solid-state IR (KBr pellet, 1400- 400 cm") 1452.11 1390.47 1200.43 1128.53 1015.5 953.9 820.36 794.68 712.5 614.91 584.09 424.87 Reactivity of Organo-Modified POMs Table 11 lists the oxidation of tetrahydrothiophene (THT) by tbutylhydroperoxide (TBHP) catalyzed by the transition metal salts of Me-capped V 6

,O

3 The oxidations were performed by dissolving the particular salt in acetonitrile to give lightly colored orange-yellow solutions. The solutions were placed in 24-mL vials WO 01/34279 PCT/USOO/28152 fitted with PTFE septa. THT and TBHP were then syringed in and the reactions were monitored by quantitative GC. Reactions were stirred at room temperature.

Table 11. Room Temperature Oxidation of THT to THTO by TBHP Catalyzed by Transition Metal Salts of Me Capped V,,0 3 after 48 Hours.

Catalyst Mols of Mols of Turnover catalyst. xl10 THTO. xl0 5 number' Na Me cap 1.76 6.03 34.3 Ag Me cap 1.87 5.59 30.0 Co Me cap 1.61 6.33 39.3 AeNO, 14.1 1.06 0.754 CoCL, 39.5 2.25 0.570 blank" NA 0 0 "blank reaction: 3.0 mL of MeCN, 0.018 mL of THT, 0.010 mL of internal reference.

Turnover number (mols of THTO)/(mols of catalyst) x 100 Throughout this application, various publications are referenced. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which this invention pertains.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only.

Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

The reference to any prior art in this specification is not, and should not be taken as, an acknowledgement or any form of suggestion that the prior art forms part of the common general knowledge in Australia.

Se *oo *oo **o

Claims (61)

1. A polyoxometalate topical composition for removing a contaminant from an environment, comprising a topical carrier and at least one polyoxometalate, with the proviso that the polyoxometalate is not H 5 PV 2 Molo0 40 K Si(H 2 0)Mn"Wi 1039; K 4 Si(H20)Mn VW 1039; K 5 Co1'Wi 2 0 40 or H(,(PV3MoO40) wherein the topical carrier is selected from the group consisting of lotions, creams, ointments and gels.

2. The composition of claim 1, wherein the polyoxometalate has the formula 1 of [VkMo,,WnNBoTapMqXrO]'[A], wherein M is at least one f-block element or d- block element having at least one d-electron, wherein M is not vanadium, molybdenum, tungsten, niobium, or tantalum; X is at least one or f-block element, wherein X is not oxygen; k is from 0 to 30; m is from 0 to 160; n is from 0 to 160; o is from 0 to 10; p is from 0 to 10; q is from 0 to 30; r is from 0 to 30; s is sufficiently large that y is greater than zero; and y is greater than zero, wherein the sum of k, m, n, o, and p is greater than or equal to four; and the sum *I of k, m, and q is greater than zero, and A is one or more different counterions.

3. The composition of claim 2, wherein M comprises a d-block element having at least one d-electron or a f-block element having at least one f-electron.

4. The composition of claim 2, wherein M comprises titanium, chromium, manganese, cobalt, iron, nickel, copper, rhodium, silver, palladium, platinum, 0 mercury, or ruthenium. The composition of claim 2, wherein M comprises manganese.

6. The composition of claim 2, wherein M comprises cobalt. 6. The composition of claim 2, wherein M comprises cobalt. 0

7. The composition of claim 2, wherein M comprises ruthenium. WO 01/34279 PCT/US00/28152 57

8. The composition of claim 2, wherein M comprises copper.

9. The composition of claim 2, wherein X comprises phosphorus, silicon, aluminum, boron, cobalt, zinc, or iron. The composition of claim 2, wherein A comprises a quaternary ammonium cation; proton; alkali metal cation; alkaline earth metal cation; ammonium cation; d- or f-block metal complex, or a combination thereof.

11. The composition of claim 2, wherein A comprises cerium, silver, gold, platinum, or a combination thereof.

12. The composition of claim 2, wherein A comprises hydrogen, lithium, sodium, potassium, or a combination thereof.

13. The composition of claim 2, wherein A comprises hydrogen, lithium, sodium, potassium, or a combination thereof, and cerium, silver, gold, platinum, or a combination thereof.

14. The composition of claim 2, wherein A is silver. The composition of claim 2, wherein A is gold.

16. The composition of claim 2, wherein A is platinum.

17. The composition of claim 2, wherein A is cerium.

18. The composition of claim 2, wherein A is cerium and silver.

19. The composition of claim 2, wherein A is cerium and platinum WO 01/34279 PCT/US00/28152 58 The composition of claim 2, wherein A is cerium and gold.

21. The composition of claim 2, wherein A is silver and gold.

22. The composition of claim 2, wherein A is not hydrogen or potassium.

23. The composition of claim 2, wherein s is from 19 to 460.

24. The composition of claim 2, wherein the sum of k and q is greater than or equal to one, the sum of k, o, p, and q is 12, and s is The composition of claim 2, wherein k is not zero.

26. The composition of claim 2, wherein q is not zero.

27. The composition of claim 1, wherein the polyoxometalate has the formula [Xg Vbi+M c"Z2-.b.-c i 0OU[A], wherein X is at least one or f-block element; g is greater than or equal to 2; M is at least one f-block element or d-block element having at least one d-electron, wherein M is not vanadium; h is from I to 7: i is from 5 to 6;j is from 4 to 5; x is 39 or 40; Z is tungsten, molybdenum, niobium, or a combination thereof; b is from 0 to 6; c is from 0 to 6; u is from 3 to 9; and A is a counterion.

28. The composition of claim 27, wherein the polyoxometalate has the formula [Xg+VbZ1.b''i+O 4 wherein X is at least one phosphorus, silicon, aluminum, boron, zinc, cobalt, or iron; b is from 1 to 6, and u is from 3 to 9.

29. The composition of claim 27, wherein the polyoxometalate has the structure [X wherein X is at least one phosphorus, silicon, aluminum, boron, zinc, cobalt, or iron; c is from I to 6, and u is from 3 to 9. WO 01/34279 PCTIUS00/28152 59 The composition of claim 1, wherein the polyoxometalate has the formula MI".'+ZIU- wherein X is at least one or f-block element; r is greater than or equal to 1; M is at least one f-block element or d-block element having at least one d-electron, wherein M is not vanadium; t is from I to 7: s is from 4 to 5: Z is tungsten, molybdenum, niobium, or a combination thereof; u is from 0 to 9: v is from 0 to 9; y is from 5 to 6; z is 61 or 62; w is greater than or equal to 4; and A is a counterion.

31. The composition of claim 30, wherein the polyoxometalate has the formula [X wherein X is at least one phosphorus. sulfur, silicon, aluminum, boron. zinc, cobalt, or iron; u is from I to 9; and w is greater than or equal to 4.

32. The composition of claim 30, wherein the polyoxometalate has the formula wherein X is at least one phosphorus, sulfur, silicon, aluminum, boron, zinc, cobalt, or iron; v is from 1 to 9; and w is greater than or equal to 4.

33. The composition of claim 1, wherein the polyoxometalate has the formula [YV,Z 2 wherein Y is phosphorus, silicon, or aluminum; Z is tungsten or molybdenum; p is from 1 to 6, and A is a counterion.

34. The composition of claim 1, wherein the polyoxomnetalate further comprises an organic group, an organosilyl group, an other p-block organometallic group, or a d-block organometallic group, wherein the organic group, the organosilyl group, the other p-block organometallic group, or the d-block organometallic group is bonded to the polyoxometalate. The composition of claim 1, wherein the polyoxometalate comprises KCoW,,0,; KSiCoVW,,O 39 K,SiCoVW 0 O 39 NaCo 2 W,03,; Ag,PV 2 AgPV,MoO,,; AgLCoVW,,O,; Ag,,Ce(PW,O03,)2; WO 01/34279 WO 0134279PCTIUSOOI28I 52 Na 12 ,Ce(PW 1 1039)2; K, 2 Ce(PW 1 0~39)2; NaPCuW,,0,q H 6 PV 3 Mo 9 0 4 or K.CuaPW 11 019.

36. T-he composition of claim I whereini the polyoxometalate comprises a modified polyoxoietalate, wherein the modified polyoxometalate comprises the admixture of a pre-modified polyoxomnetalate and a cerium compound, a silver compound, a gold compound, a platinum compound, a copper com pound, a cobalt compound, or a combination thereof.

37. Thie composition of claim 36, wherein the pre-modified polyoxometalate is H 5 PV,Mo 11 0 4 and the cerium compound is (NI-1) 2 Ce(N0 3 6

38. The composition of claim 36, wherein the pre-modified polyoxomewtalate is HSPV 2 Mo 1 10 41 the cerium compound is (NH,),,Ce(N0 3 6 and the gold compound is HAuC 4

39. The composition of claim 36, wherein the pre-modified polyoxoi-etalate is H 5 PV,Mo 0 the cerium compound is (NH-Ij,Ce(N0 3 6 and the platinum compound is H 1 PtCI 6 The composition of claim 36, wherein the pre-modified polyoxomnetalate is Na,,PV 2 Mo, 1 ,O and the silver compound is AgNO 3 AgCIO 4 or a combination thereof.

41. The composition of claim 36. wherein the pre-modified polyoxornetalate comprises NaPVMo, 104,,; Na 5 PV,_Mo, 11 Na 6 PV 1 Mo 9 0 4 3 Na 5 H 2 P V 4 W,0 4 Na 9 PV 6 Mo 6 O 4 Na.,CuPW 1 ,039; Na.,CuPW,,O,,4-; Na.,MnPW 1 ,04g); K 3 CoPW 11 O 39 (ndeCC) 6 HMiNbP.Ws062; or K, 1 Cu,(W 9 P0 3 and the gold compound is HAuCl,.

42. The composition of claim 1, wherein the topical carrier comprises a WO 01/34279 PCITUS00/28152 61 perfluorinated polymer.

43. The composition of claim 1, wherein the topical carrier comprises a perfluorinated polymer and at least one unfluorinated polymer.

44. The composition of claim 1, wherein the topical carrier comprises a pertluoropolyether. The composition of claim 1, wherein the topical carrier comprises a perfluoropolyether and at least one unfluorinated polyether.

46. The composition of claim 1, wherein the polyoxometalate is from 0.01 to 95 by weight of the polyoxometalate topical composition.

47. The composition of claim 2, wherein the topical carrier is a perfluoropolyether and A is silver.

48. A method for removing a contaminant from an environment, comprising contacting the polyoxometalate topical composition of claim 1 with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment.

49. A method for removing a contaminant from an environment, comprising contacting the polyoxometalate topical composition of claim 36 with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment. The method of claim 48, wherein the environment comprises the gas phase.

51. The method of claim 48, wherein the environment comprises the liquid phase.

52. The method of claim 48, wherein the contaminant comprises a chemical warfare agent.

53. The method of claim 48, wherein the contaminant comprises an aldehyde, an aliphatic nitrogen compound, a sulfur compound, an aliphatic oxygenated compound, a halogenated compound, an organophosphate compound, a phosphonothioate compound, a phosphorothioate compound, an arsenic compound, a chloroethyl-amine compound, a phosgene compound, a cyanic compound, or a combination thereof.

54. The method of claim 48, wherein the contaminant comprises acetaldehyde, methyl mercaptan, ammonia, hydrogen sulfide, methyl sulfide, diethyl sulfide, diethyl disulfide, dimethyl sulfide, dimethyl disulfide, trimethylamine, styrene, propionic acid, n-butyric acid, n-valeric acid, iso-valeric acid, pyridine, formaldehyde, 2-chloroethyl ethyl sulfide, carbon monoxide, or a combination thereof. The method of claim 48, wherein when the environment is the gas phase, the contaminant is removed from the gas phase at from -50 °C to 250 °C and at a pressure of from 0. 1 ppb to 30 atm.

56. The method of claim 48, wherein when the environment is the gas phase, the contaminant is removed from the gas phase at from 0 °C to 105 °C and at 1 atm.

57. A modified polyoxometalate, wherein the modified polyoxometalate comprises the admixture of(1) a pre-modified polyoxometalate and a cerium, silver, gold or platinum compound, or a combination thereof, wherein the pre- modified polyoxometalate is selected from the group consisting of HPV 2 Moo0040; NasPV 2 MoIo040; Li5PV 2 Mo00O 4 0; K 5 PV 2 Mo 1 oO 4 0; Na 4 PVMon 04o; NaPV 3 Mog0 4 o; Na 5 H 2 PV 4 WO040; NaoPV 6 Mo 6 OAo; :o Na 5 CuPW O039; NasMnPW 11040; KsCoPWI 1039; (n-Dec 4 6 HMnNb 3 P 2 Wi50 6 2 or KI 2 Cu;(WqPO3,) 2 or a combination thereof, and the cerium, silver, gold or platinum compound, or a combination thereof, is selected from the group consisting of (NH,) 2 Ce(NO3) 6 HAuCI 4 H 2 PC1 6 AgNO 3 63

58. The modified polyoxometalate of claim 57, wherein the pre-modified polyoxometalate is H 5 PV 2 Mo 1 00o 4 o; NaSPV 2 Moo 0 O40; LikPV 2 Mo 1 o 4 0: KPV 2 MooO 4 or a combination thereof the cerium compound is (NH 4 2 Ce(NO 3 and the gold compound is HAuCI 4

59. The modified polyoxometalate of claim 57, wherein the pre-modified polyoxometalate is H 5 PV 2 Moloo 4 0 o; NaPV 2 Mo, 0 0o 4 o; LiPV 2 MojoO 4 o; 2 Mo 0 0o 4 0 or a combination thereof the cerium compound is (NH):Ce(NO3) and the platinum compound is HIPIC1 6 The modified polyoxometalate of claim 57, wherein the pre-modified polyoxometalate is H 5 PV 2 Mo 0 0o 40 Na 5 PV 2 Moo 0 0 4 0 Li 5 PV 2 MO 10 0 4 0 K 5 PV 2 Mooo 0 0 40 or a combination thereof, and the silver compound is AgNO 3

61. The modified polyoxometalate of claim 57, wherein the pre-modified polyoxometalate independently comprises Na 4 PVMo i040; NasPV 2 Mo 1 oO 4 n; NaPV 3 MoO0; NaH 2 PV 4 Ws4 0 NaOPV 6 MooOao; Na5CuPW O30;3 NasMnPW 04o(); K5CoPW 1039; (n-Dec 4 6 HMnNb 3 P2WI 5 06 2 or .a Ki 2 Cu 3 (W9PO34)?, and the gold compound is HAuCIl 4 *62. A polyoxometalate comprising K 8 SiCoVW 1 oO 3 9; K 7 SiCoVWoO 3 9 .3 Ag 5 YPV 2 Mo 90O4; Ag 6 PV3Mo 9 0 4 0 AgsCoVW 1040: or Ag I 2 Ce(PWi 1039)2.

63. A modified material for removing a contaminant from an environment, wherein the modified material comprises a material comprising a topical carrier, and a metal compound comprising a transition metal compound, an actinide ~compound, a lanthanide compound, or a combination thereof, wherein the metal compound is not a polyoxometalate and the topical carrier is selected from the S group consisting of lotions, creams, ointments and gels. .64. The modified material of claim 63, wherein the metal compound comprises a cerium compound, a platinum compound, a silver compound, a gold compound, or a combination thereof. The modified material of claim 63, wherein the metal compound is a gold compound. 64

66. The modified material of claim 63, wherein the metal compound is a platinum compound.

67. The modified material of claim 63, wherein the metal compound is a cerium compound.

68. The modified material of claim 63, wherein the metal compound is a silver compound.

69. The modified material of claim 63, wherein the metal compound is a cerium compound and a platinum compound. The modified material of claim 63, wherein the metal compound is a cerium compound and a gold compound.

71. The modified material of claim 63, wherein the metal compound is a silver compound and a gold compound.

72. The modified material of claim 63, wherein the topical carrier is a perfluoropolyether and the metal compound is a silver compound, a gold compound, or a combination thereof. 0

73. The modified material of claim 63, wherein the topical carrier is a *perfluoropolyether and the silver compound is AgNO 3 AgCIO 4 or a combination thereof. as** 0

74. The modified material of claim 63, wherein the metal compound comprises gold, chloride, and nitrate. a

75. The modified material of claim 63, wherein the metal compound comprises mixing (NEt 4 AuCI 2 and CuSO4, MnSO4, VOSO4, Ti(S0 4 2 Fe 2 (SO4),, NiSOa, ZnSO 4 Cr 2 (SOa) 3 MgSO 4 CoSO 4 Pd (NO 3 4 Na 2 SO 3 or NBu 4 or a combination thereof.

76. A method for removing a contaminant from an environment, comprising contacting a modified material of claim 63 with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment.

77. A topical composition substantially as herein described with reference to the Examples. *see &V 0 a46 0 0 e :so.