Multichannel Deactivation of Noxious Chemical and Biological Agents

Abstract

Germanium-doped titania semiconductors, which are capable of photocatalyzed electron transfer are coated with electronic deficient fluorinated phthalocyanines capable of energy transfer. The combination of these pathways results in a broad spectrum photocatalyst useful for deactivating harmful chemical and biological agents.

Claims

1. A composition for detoxification of chemical war agents, comprising: an effective amount of titania doped with an effective amount of GeO.sub.2 using a solid-state technique; and an amount of solution of a fluorophthalocyanine applied thereto to form a catalyst.

2. The composition of claim 1 wherein the catalyst composition is at least F.sub.64PcZn/P25 Ti(Ge)O.sub.2 or F.sub.64PcZn/Ti(Ge)O.sub.2.

3. The composition of claim 2, wherein decomposition of chloroethyl ethyl sulfide (CEES) with the catalyst results in a half-life of CEES photodegradations for about 10 min for F.sub.64PcZn/P25 Ti(Ge)O.sub.2, and about 11 min for F.sub.64PcZn/Ti(Ge)O.sub.2.

4. A process for making a composition for detoxification of chemical war agents, comprising: doping titania with GeO.sub.2 using a solid-state technique; applying a solution of a solvent of fluorophthalocyanine; and drying of a resulting hybrid material by removing the solvent.

5. The process of claim 4 further comprising: dissolving chemical and biological agents, in a solvent directly deposited on the resulting hybrid material; and illuminating the resulting hybrid materials with white light for reduction in concentration of the agents.

6. The process of claim 4, wherein the resulting hybrid material is coated on fabric selected from a group consisting of nonwoven fabric, cotton, polyester, woven fabric, dacron, nylon, Kevlar, and any combination thereof.

7. The process of claim 4 wherein the doping further comprises: using a fumed aeroxide P25 having a particle size of about 20 nm, and a surface area of about 50 m.sup.2/g suspended in water, or a titania gel having a particle size of about 100 nm and a surface area of about 10 m.sup.2/g; and reacting the resulting hybrid material with an aqueous solution of Ge(OH) 4 at about a pH4.

8. The process of claim 4 wherein, germania, GeO.sub.2, in Ti(Ge)O.sub.2 is at the level of about 1-5% by mass.

9. The process of claim 4, further comprises loading a germania-coated titania with Zinc (II) 1,4,8,11,15,18,22,25-octafluoro-2,3,9,10,16,17,23,24-octakisperfluoro (isopropyl) phthalocyanine, F.sub.64PcZn, via precipitated deposition of about 3% loading.

10. The process of claim 4, wherein the hybrid material includes F.sub.64PcZn/P25 Ti(Ge)O.sub.2, F.sub.64PcZn/Ti(Ge)O.sub.2, or a combination thereof.

11. A process for making a composition for detoxification of chemical war agents, comprising: doping titania with GeO.sub.2; applying a solution of a solvent of fluorophthalocyanine to form F.sub.nPcMetal/Ti(Ge)O.sub.2 or F.sub.nPcMetal/P25 Ti(Ge)O.sub.2, wherein / stands for coated on, and the Metal is Zn or a diamagnetic material; and n is 16 or 64, and drying of a resulting hybrid material by removing the solvent, wherein the resulting hybrid material is a photocatalyst.

12. The process of claim 11, further comprises coating the photocatalyst on fabric selected from a group consisting of nonwoven fabric, cotton, polyester, woven fabric, dacron, nylon, Kevlar, and any combination thereof.

13. The process of claim 12, further comprises deactivating a chemical agent, biological agent, or combination thereof with the photocatalyst.

14. The process of claim 13, wherein the chemical agent, biological agent is chloroethyl ethyl sulfide (CEES).

15. The process of claim 14, wherein a half-life of CEES photodegradations is about 10 min for F.sub.64PcZn/P25 Ti(Ge)O.sub.2, and about 11 min for F.sub.64PcZn/Ti(Ge)O.sub.2.

16. The process of claim 11, wherein when the Metal=zinc (Zn) and n is 64 there is a lowering of the weight-loss temperature of about 50 C; and when the Metal=zinc (Zn) and n is 16 there is a weight-loss temperature of over 200 C.

17. The process of claim 11, wherein a content of germania, GeO.sub.2, in Ti(Ge)O.sub.2 is at the level of 1-5% by mass.

18. The process of claim 11, wherein the solvent of fluorophthalocyanine is Zinc (II) 1,4,8,11,15,18,22,25-octafluoro-2,3,9,10,16,17,23,24-octakisperfluoro (isopropyl) phthalocyanine.

19. The process of claim 11, wherein the doping further comprises using either a fumed aeroxide P25, or a titania gel to react with an aqueous solution of Ge(OH) 4 at about a pH 4.

20. The process of claim 11, wherein the fumed aeroxide P25 has particle size of about 20 nm and surface area of about 50 m.sup.2/g suspended in water; and the titania gel has particle size of about 100 nm and a surface area of about 10 m.sup.2/g.

Description

BRIEF DESCRIPTION OF FIGURES

[0013] So that those having ordinary skill in the art will have a better understanding of how to make and use the disclosed composition and methods, reference is made to the accompanying figures wherein:

[0014] FIG. 1 is a schematic of the photochemical basic mechanism of reactivity of the proposed invention; the Oxygen that acquired energy, termed singlet oxygen, decays to produce radicals and other reactive oxygen species (ROS) that destroy the noxious agents

[0015] FIG. 2a-2g. Structural progression of light-absorbing structures from Chlorophyll to fluorinated F.sub.16PcM (II) and F.sub.64PcM (II), M stands for a Metal dication.

[0016] FIG. 3a illustrates oxidic supports used in the present invention, and FIG. 3b illustrates the encapsulation, E, and capping C of a trapped Pc using tetraethoxysilane (TEOS). A semipermeable silicate network that prevents Pc leaching is produced.

[0017] FIG. 4a is a graph illustrating the relationship between temperature and weight percentage for TGA pure phthalocyanines, and FIG. 4b is a graph illustrating the relationship between temperature and weight percentage for TGA phthalocyanines supported on P25 of the proposed invention; and

[0018] FIG. 5 is a graph illustrating binding energy of the Zn 2p orbital using the principles of the proposed invention.

DETAILED DESCRIPTION

[0019] The present disclosure is directed to a new composition, a process, and novel strategy for solutions to enable the Warfighter to deter, prevent, protect against, mitigate, and respond to Chemical and Biological (CBN) threats and effects that are needed. A particularly desired solution is the invention of self-detoxifying technologies, which is a wearable protective material that does not require additional chemicals, often harmful, for example bleach, to assist in the detoxification effect.

[0020] The use of the terms a, an, the, and similar referents in the context of describing the present invention (especially in the context of the claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. Use of the term about is intended to describe values either above or below the stated value in a range of approximately 10%; in other embodiments, the values may range in value above or below the stated value in a range of approximately 5%; in other embodiments, the values may range in value above or below the stated value in a range of approximately 2%; in other embodiments, the values may range in value above or below the stated value in a range of approximately 1%. The preceding ranges are intended to be made clear by context, and no further limitation is implied. The use of any and all examples, or exemplary language (e.g., such as) provided herein, is intended merely to better illuminate the invention, and does not pose a limitation on the scope of the invention unless otherwise stated. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

[0021] The core of the intended self-detoxifying reactivity approach is to construct materials that transfer electrons and hydrolyze chemical bonds, while also harvesting light and injecting its energy into oxygen from air to generate reactive oxygen species (ROS). ROS detoxify agents by attacking them chemically. The CF bonds of the materials that generate ROS will protect them from self-destruction. The prototype is constructed by depositing a photosensitizer from the class phthalocyanines, Pc, on a support. The basic mechanism of photo reactivity is shown in FIG. 1. The energy of light is transferred by the photosensitizer to ground-state .sup.3O.sub.2 from air to generate reactive singlet oxygen, 102, in a process remarkably similar to the established photodynamic therapy to treat cancers.

[0022] FIG. 1 illustrates the photodynamic generation of ROS: ground-state, singlet .sup.1Pc.sub.0 absorbs light to yield an excited state: .sup.1Pc.sub.0+h.fwdarw..sup.1Pc.sub.1, which becomes a triplet .sup.3Pc.sub.1 via intersystem crossing, IC, .sup.1Pc.sub.1.fwdarw..sup.3Pc.sub.1. The energy-reach .sup.3Pc.sub.1 transfers its energy to ground-state, triplet .sup.3O.sub.2 to generate .sup.1O.sub.2 and regenerate .sup.1Pc.sub.0: .sup.3Pc.sub.1+.sup.3O.sub.2.fwdarw..sup.1Pc.sub.1+.sup.1O.sub.2, to complete the catalytic cycle. In summary .sup.1O.sub.2.fwdarw.ROS.fwdarw.degradation of noxious chemicals.

[0023] FIGS. 2a-2g Structural progression from Chlorophyll to fluorinated F.sub.16PcM (II) and F.sub.64PcM (II), M stands for a Metal dication. Color code: F, green; N, blue, C, gray. a) Chlorophyll a; M=Mg is shown as a sphere; b) UV-Vis spectrum of Chlorophyll a; c) structural formula of F.sub.64PcM (II) exhibiting iso-perfluoroalkyl and aromatic F groups, M=Zn; d) X-ray structure of F.sub.64PcM (II), M=Zn; e) structural formula of F.sub.16PcM (II); f) X-ray structure of F.sub.16PcM (II); g) UV-Vis spectrum of F.sub.16PcM (II), M=Zn.

[0024] The HOMO-LUMO, like in chlorophyll, are located on the organic macrocycle. Fluorination hinders molecular electron loss, imparts thermal stability to 300 C., and chemical resistance. To complete self-detoxifying reactivity, a simultaneous reactivity pathways imparted by the oxidic supports is introduced. The supports and Pc encapsulation in metal-inorganic frameworks strategy are shown in FIGS. 3a and 3b, respectively.

[0025] The panchromaticity advantage. TiO.sub.2, the semiconductor solid-state support of the fluorinated photosensitizer yields electron-hole pairs under illumination, and abstract electrons from agents leading to their destruction. The activity of TiO.sub.2 is well known. The electron-transfer detoxifying reactivity channel complements the energy-transfer one supported by the Pc. Importantly, the absorbance in the UV-Vis region of the Pc, 600-800 nm, which dominates its spectrum, FIG. 2g, does not interfere with the UV region necessary for TiO.sub.2 activation. Thus, the entire Solar spectrum is utilized more efficiently, leading to panchromatic self-detoxification.

[0026] The catalyzed hydrolytic advantage. Basic metal oxides, BMO, for example alumina Al.sub.2O.sub.3, and zirconia, ZrO.sub.2, catalyze the hydrolytic degradation of P-based agents, less so the S-based ones. The BMOs use no light for their reactivity. Consequently, their use as supports for result in a dual hydrolytic-oxidative reactivity combination, ultimately yielding a material that should be capable of broad self-detoxification against HD, VX and GD, and thus defense against attacks that use mixtures of agents.

[0027] It should be pointed that the proposed inorganic supports are nanoscale metal-inorganic frameworks, without the diffusion and other issues of metal-organic framework, and exhibiting relatively favorable resistance to aggressive chemical agents such as ROS, which perform detoxification. The nano dimensions ensures high surface areas.

[0028] As shown in FIG. 4a and FIG. 4b the composition of matter, F.sub.nPcMetal/Ti(Ge)O.sub.2 (/ stands for coated on) is based on F.sub.nPcMetal/TiO.sub.2, with dopant GeO.sub.2 providing additional modifications. There are specific interactions between the surface of the bulk TiO.sub.2 and the F.sub.nPcMetal. Thermogravimetric analyses results obtained under inert Nitrogen for F.sub.nPcMetal/TiO.sub.2 vs. bulk, pure F.sub.nPcMetal, n=16 and 64, Metal=Zinc had data that show a surprising result: there is a lowering of the weight-loss temperature of about 50 C for n=64, but for n=16 the temperature decreases by over 200 C. These results point toward specific interactions that rule out a simple physical mixture of the organic and inorganic support, thus the formation of a new phase.

[0029] As shown in FIG. 5, the Zn2p signal observed via X-ray photoelectron spectroscopy for a) bulk F.sub.16PcZn, b) F.sub.16PcZn/TiO.sub.2, and c) F.sub.16PcZn/Ti(Ge)O.sub.2. The Ge dopant does not significantly alter the host structure.

[0030] The reactivity of the materials of the present invention is of interest, as evaluated for the degradation of CEES, an HD simulant. Thus, the ability of the bare oxides and dopes oxides coated with a Pc was compared. The half-lives of degradation of CEES using bare P25 TiO.sub.2, Tronox and GeO.sub.2 were 173, 105 and 72 minutes, respectively. On the other hand, F.sub.64PcZn/P25 Ti(Ge)O.sub.2 and F.sub.64PcZn/Tronox (Ge) O.sub.2 produced half-lives of degradation of CEES of 10 and 11 minutes, respectively, an acceleration of about one order of magnitude under otherwise identical conditions.

[0031] While in the foregoing specification the present invention has been described in relation to certain embodiments thereof, and many details have been put forth for the purposes of illustration, it will be apparent to those skilled in the art that the invention is susceptible to additional embodiments and that certain of the details described herein can be varied considerably without departing from the basic principles of the invention.

[0032] The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and, accordingly, reference should be made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention.

[0033] Although the invention herein has been described with reference to embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the appended claims.