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TETRASILVER PATENTS



TetraSilver TetrOxide ( TSTO )



The Most Powerful Known Antipathogen !  Available ONLY from Rex Research !  Quantities are extremely limited !
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The Facts : Tetrasilver Tetroxide

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USP Appln 20080233161

DEPOSITION PRODUCTS, COMPOSITE MATERIALS AND PROCESSES FOR THE PRODUCTION THEREOF

BACKGROUND ART

The germicidal properties of silver, even not known as such, have been utilized since the early Mediterranean cultures. It has been known since 1000 BC and possibly before that water kept in silver vessels and then exposed to light and filtered could be rendered potable. Other forms of silver have been used throughout centuries for various applications, such as coatings for prevention of beverages from spoilage or silver plates and foils in the surgical treatments of wounds and broken bones.

The lethal effects of metals towards bacteria and lower life forms were first scientifically described by von Nageli in the late nineteenth century, and this phenomenon has been defined as an "oligodynamic effect" (N. R. Thompson, Silver, in Comprehensive Inorganic Chemistry, Vol. III D, J. C. Bailer, H. J. Emeleus, R. Nyholm and A. F. Trutman-Dickenson, Editors, Pergamon Press, Oxford (1973)). The term oligodynamic effect is typically restricted to describing solutions in which the metal concentration is several orders of magnitude lower than that which would be lethal to higher organisms.

The investigation of the bacteriostatic properties of pure metals such as Fe, Mo, Cu, V, Sn, W, Au, Al, Ta, Nb, Ti, Zr, Ni, Co, Ag and Cr, has proved that Co was the only element which was inhibitory for the bacterial growth under anaerobic conditions (K. J. Bundy, M. F. Butler and R. F. Hochman, "An Investigation of the Bacteriostatic Properties of Pure Metals", Journal of Biomedical Materials Research, Vol. 14 (1980) 653-663). Under aerobic conditions both Cu and Co consistently display inhibitory effects. Some antimicrobial effects have been seen for Ni, Fe and V. However, other metals such as Mo, W, Al, Nb, Zr, Cr and most importantly for the present invention Ag and Sn never showed any tendency to inhibit the growth of Streptococcus mutans.

In the case of silver metal, it was in 1920, when Acel who was the first to attribute the antimicrobial properties of silver to the liberation of Ag.sup.+ ions from the material (D. Acel, "Uber die oligodynamische Wirkung der Metalle", Z. Biochem., 112 (1920) 23).

Gibbard reported in 1937 that pure metallic silver has no antimicrobial activity (J. Gibbard, "Public Health Aspects of the Treatment of Water and Beverages with Silver", Journal of American Public Health, Vol. 27 (1937) 112-119). His experiments showed that if silver is cleaned mechanically with an abrasive cloth or paper it becomes inactive. Similarly, if molten silver is allowed to cool in a reduction atmosphere (e.g. hydrogen), no antimicrobial activity is found. When cooling of molten silver is carried out in air, and formation of surface oxide occurred, an antimicrobial activity may be observed. Similar results were found when silver metal was treated with nitric acid in an air atmosphere (dissolution and formation of an oxide layer). Based on Gibbard's results, pure silver was devoid of activity, but surface oxidized silver was active. Silver oxide, silver nitrate and silver chloride were always active. Also, Gibbard observed that the antimicrobial properties of silver and its compounds were reduced in the presence of proteins or glucose.

Djokie investigated the behavior of silver films, e.g. physical vapor deposited, electrodeposited, electroless deposited and metallurgical in physiological saline solutions (S. S. Djokie and R. E. Burrell, "Behavior of Silver in Physiological Solutions", Journal of the Electrochemical Society, Vol. 145 (5) (1998) 1426-1430). Djokie found that an essential factor leading to an antimicrobial activity of metallic silver is a presence of Ag oxide(s) at the surface of this material. It was demonstrated that only silver films containing silver oxides (most likely Ag.sub.2O) showed an antimicrobial activity. The behavior was attributed to the dissolution of Ag.sub.2O from the "silver" material and formation of Ag.sup.+ or other complexed ions which become antimicrobially active. There was no evidence that pure metallic silver, no matter which way it was produced i.e., physical vapor deposited, electrodeposited or electroless deposited could be dissolved in physiological media, or that these materials would exhibit antimicrobial activity.

It should be noted that when the physical vapor deposition of silver was carried out in an atmosphere containing oxygen the resulted product, as found by the XRD analysis contained silver oxide. Consequently, these samples exhibited antimicrobial activity. Conversely, when the physical vapor deposition was carried out from an argon atmosphere (no presence of oxygen) pure metallic, nanocrystalline silver film was deposited as confirmed by the XRD analysis. However, these films did not dissolve in physiological saline solutions, nor they exhibited antimicrobial activity at all.

For an in depth understanding of structural properties of silver films produced by reactive sputtering, see Djokie et al. (S. S. Djokie, R. E. Burrell, N. Le and D. J. Field, "An Electrochemical Analysis of Thin Silver Produced by Reactive Sputtering", Journal of the Electrochemical Society, Vol. 148 (3) (2001) C191-C196.). To prove the concept that only oxidized silver species are responsible for the antimicrobial activity, Djokie further oxidized pure metallic silver samples (i.e. those produced by the electrodeposition, electroless deposition, physical vapor deposition in an argon atmosphere or metallurgically). The oxidation of these samples was carried out electrochemically in 1 M KOH solutions, using a process very well established in the art. The electrochemically oxidized silver samples were tested for the antimicrobial activity against Pseudomonas Aeruginosa. Clear evidence was found that the electrochemically oxidized silver samples exhibited antimicrobial activity.

The above referenced work shows that only oxidized silver species, but not elemental silver will affect antimicrobial activity. The findings to date show that the "nanocrystalline" or "macrocrystalline" elemental silver does not have antimicrobial activity at all. Elemental silver, either nanocrystalline or "macrocrystalline" may exhibit some antimicrobial activity only if oxidized silver species are present at these surfaces or within the silver metal. Only the formation of silver oxide(s), carbonates or other silver salts (except silver sulfide, due to its extremely low solubility) at the surface or within the material, which may be influenced by an exposure of elemental silver to various bases, acids or due to atmospheric corrosion may lead to an antimicrobial activity of this material.

The use of silver on chronic wounds dates back in the 17.sup.th and 18.sup.th centuries. In the early 19.sup.th century, silver nitrate began to be used on burns and in opthalmology. Concentrations of the solution ranged from 0.20 to 2.5 wt. % with the weaker solutions being reserved for children. Silver has been found to be active against a wide range of bacterial, fungal and viral pathogens. Topical treatment of acute and chronic wounds is a preferred and selective approach to the prevention of infection and healing. In order to achieve these requirements products that are used in the prevention of infections must have certain physical and chemical properties.

When used for topical dressings, silver compounds must have relatively low solubility. This is usually achieved by choosing compounds with a relatively low solubility products (e.g. AgCl, Ag.sub.2SO.sub.4, Ag.sub.2CO.sub.3, Ag.sub.3PO.sub.4, Ag-oxides). Kinetics of dissolution of these compounds in neutral aqueous solutions is quite slow. This property is very convenient for two reasons. First, a sustained release of silver ions from the silver compounds is more likely to provide a prolonged antimicrobial activity. Second, low amounts of the silver ions released into wound exudates may not give rise to transient high tissue blood and urine levels, thus avoiding systemic toxicity. The choice of a particular silver compound will depend upon its reactivity with wound exudates. This reactivity should preferably be minimized in order to achieve the desired effect of the released silver ions (i.e., antimicrobial activity without systemic toxicity).

Besides silver nitrate, one of the most widely used topical antimicrobial materials is silver sulfadiazine (C. L. Fox, "Topical Therapy and the development of Silver Sulfadiazine", Surgery, Gynecology & Obstetrics, 157 (1) (1983) 82-88). This compound is synthesized from silver nitrate and sodium sulfadiazine. Silver sulfadiazine has been used in treatments of burns, leg ulcers and also as a topical antimicrobial agent in the management of infected wounds.

Products such as silver protein (argyrols) or mild silver protein are mixtures of silver nitrate, sodium hydroxide and gelatin. These products are recommended for internal use and are promoted as essential mineral supplements. Although there is no theoretical or practical justification for their use, this class of compounds has been recommended for the treatment of diverse diseases such as cancer, diabetes, AIDS and herpes (M. C. Fung, D. L. Bowen, "Silver Products for Medical Indications: Risk--Benefit Assessment", Clinical Toxicology, Vol. 34 (1) (1996) 119-126).

Silver-zinc-allantoinate has been formulated as a cream and represents a combination of silver, zinc and allantoin (an agent that stimulates debridement and tissue growth (H. W. Margaf, T. H. Covey, "A Trial of Silver-Zinc-Allantoinate in the Treatment of Leg Ulcers", Arch. Surg., Vol. 112 (1977) 699-704). This composition exhibited promising effects in preliminary studies.

In the past few decades several topical dressings containing silver have been developed for wound care. Such materials include Arglaes.TM., Silverlon.TM., Acticoat.TM., Actisorb.TM., and Silver 220.TM..

Antimicrobial coatings and methods of forming same are the subject of U.S. Pat. No. 5,681,575 (Burrell et al) and U.S. Pat. No. 6,238,686 (Burrell et al). The coatings are formed by the physical vapour deposition of biocompatible metal and the preferred biocompatible metal is silver.

U.S. Pat. No. 6,087,549 (Flick) discloses a multilayer laminate wound dressing comprising a plurality of layers of a fibrous material, with each layer comprising a unique ratio of metalized fibers to nonmetalized fibers. In a preferred embodiment the wound dressing consists of three layers and the metal is silver. The wound contact layer has the highest ratio of metalized fibers to nonmetalized fibers, the intermediate layer has a lower ratio of metalized fibers to nonmetalized fibers, and the outer layer has the lowest ratio of metalized fibers to nonmetalized fibers. The wound dressing described by Flick is commercially available under the trade-mark Silverlon.TM..

U.S. Pat. No. 5,211,855 (Antelman), U.S. Pat. No. 5,676,977 (Antelman) and U.S. Pat. No. 6,436,420 (Antelman) teach that tetrasilver tetroxide (Ag.sub.4O.sub.4) containing two monovalent and two trivalent silver ions exhibits bactericidal, fungicidal and algicidal properties. As a result, "tetrasilver tetroxide" is suggested for use for water treatment in U.S. Pat. No. 5,211,855 and for use in destroying the AIDS virus in U.S. Pat. No. 5,676,977.

In U.S. Pat. No. 6,436,420, Antelman describes a method of deposition or interstitial precipitation of tetrasilver tetroxide (Ag.sub.4O.sub.4) crystals within the interstices of fibers, yarns and/or fabrics forming such articles in order to produce fibrous textile articles possessing enhanced antimicrobial properties. The interstitial precipitation of Ag.sub.4O.sub.4 is achieved by immersion of the article to be treated (e.g., fiber, yarn or fabric) in an aqueous solution containing a water soluble silver salt, most preferably silver nitrate. After uniformly wetting the article, the article is removed into a second heated aqueous solution (having a temperature of at least 85 degrees Celsius or more preferably at least 90 degrees Celsius) containing strong alkali (most preferably NaOH) and a water soluble oxidizing agent (most preferably potassium persulfate) for 30 seconds to 5 minutes to facilitate the precipitation of tetrasilver tetroxide.

After the reaction is completed, the article is removed and washed. The article treated in this way is described as exhibiting outstanding antimicrobial resistance towards pathogens such as bacteria, viruses, yeast and algae. The article is also described as being resistant to ultraviolet light and as maintaining its antimicrobial properties after a number of launderings

WO2001/077030
OZONATED SOLUTIONS OF TETRASILVER TETROXIDE

...it appears that in addition to acting as a killing agent in its own right, ozone is surprisingly able to activate the antimicrobial activity of tetrasilver tetroxide, thus yielding a synergistic killing effect exceeding the individual killing effects of either non-activated tetrasilver tetroxide or ozone.

Example 5: Ozone Stability Testing 6.1 mg/L (6.1 ppm) of ozone was provided in deionized, distilled water over a 15 minute period. The solution was allowed to stand with stirring by a magnetic stirrer over a 24-hour period, taking periodic readings of the ozone concentration. By 2 hours, the ozone concentration was 3 ppm and progressively dropped to 0.01 ppm by 18 hours. This represented a half-life of approximately 2 hours. When 2 ppm tetrasilver tetroxide was added, the rate of decay was unexpectedly lengthened, such that 0.12 ppm of ozone was present after 18 hours (approximately an order of magnitude higher than would have been expected in the absence of tetrasilver tetroxide) and by 24 hours, 0.03 ppm of ozone oxidizing activity was still present.

Further research showed that neither tetrasilver tetroxide alone nor chemically-activated tetrasilver tetroxide (i. e., activated with potassium monopersulfate as described in the Comparative Examples) gave measurable oxidation as measured by the indigo dye method. Thus, the reduced half-life of ozone in the presence of tetrasilver tetroxide does not appear to be merely an additive effect or an experimental flaw arising from the use of the indigo dye method, but rather appears to be a surprising synergistic effect.

US5336499
Molecular Crystal Device for Pharmaceuticals

Abstract ~ A novel molecular scale device is described which is bactericidal, fungicidal, viricidal and algicidal. The anti-pathogenic properties of the device are attributed to electron activity indigenous to diamagnetic semiconducting crystals of tetrasilver tetroxide ( Ag4O4 ) which contains two monovalent and two trivalent silver ions in each molecular crystal. When the crystals are activated with an oxidizing agent, they release electrons equivalent to 6.4 x 10-19 watts per molecule which in effect electrocute pathogens. A multitude of these devices are effective at such low concentrations as 0.3 PPM used as preservatives in a variety of formulations ranging from cosmetics to pharmaceuticals. Indeed, they are intended as active ingredients for pharmaceuticals formulated to destroy such pathogens as Staphylococcus aureus, and epidermidis, the latter of which it completely destroys in a nutrient broth culture of about 1 million organisms at 0.6 PPM, or Candida albercans, the vaginal yeast infection at 2.5 PPM, and the AIDS virus at 18 PPM.

The electron transfer can be depicted by the following half reactions in which the monovalent silver ion loses an electron and the trivalent silver gains one as follows:

Ag+ -e = Ag+2

Ag+3 +e = Ag+2

The molecular crystal then will become stabilized with each silver ion having a divalent charge.

Stringent testing was performed in which cultures were actually placed in trypticase soy nutrient broth, which allowed the pathogens being tested to replicate without being detached from its own food supply. Under these conditions the devices were able to kill two strains of E. Coli at 2.5 PPM; Micrococcus Luteus at 1.25 PPM; Staphylococcus aureus at 2.5 PPM; Staphylococcus epidermidis at 0.6 PPM; Pseudomonas aeruginosa at 1.25 PPM; and Streptococcus pyogenes at 2.5 PPM.

The devices were then evaluated in analogous nutrient used for yeasts, algae and molds utilizing Sabouraud dextrose broth. The infectious yeast pathogen Candida ALBICANS was totally killed at 2.5 PPM and that of the Saccharomycetpideae variety at 1.25 PPM.

If we are to consider one molecular device in operation, then each molecule would release two electrons having each a charge of 4.8 x 10-10 e.s.u. equivalent to approximately 1.6 x 10-19 coulombs. The EMF given in my Encyclopedia of Chemical Electrode Potentials (Plenum 1982), page 88, for the oxidation of Ag(I) to Ag(II) is 1.98 volts which approximates 2.0 V. The total power output per device can be calculated in watts by multiplying the power output for each electron by 2. Since power is the product of the potential times the charge, P = EI; for each electron it would be

2.0 x 1.6 x 10^-19 = 3.2 x 10^-19 watts ...

US Patent 5,223,149
Trivalent Silver Water Treatment Compositions

Said trivalent silver complexes were subsequently evaluated as to their efficacy in killing gram positive and gram negative bacteria in algae in accordance with the EPA protocols for swimming pools, which require 100% kills of bacteria within ten minutes. The compounds far exceeded the bacteria requirements at concentrations of one PPM or less of silver. They were evaluated with and without persulfate salts at 10 PPM and were effective without persulfates as bactericides.

The complexes, which were colored from deep orange to brown and maroon, were left exposed in clear glass bottles for three months with constant exposure to daylight. The complexes were stable and did not decompose to silver.

Ag(III) complexes were applied to human skin in concentrated form containing as much as 5,000 PPM silver without any silver staining of the skin whatsoever.

US Patent 5,211,855
Method of Treating Water Employing Tetrasilver Tetroxide Crystals
Abstract
A novel molecular scale device is described which is bactericidal, fungicidal and algicidal. The antipathogenic properties of the device are attributed to electron activity indigenous to diamagnetic semiconducting crystals of tetrasilver tetroxide (Ag4O4) which contains two monovalent and two trivalent silver ions in each molecular crystal. When the crystals are activated with an oxidizing agent, they release electrons equivalent to 6.4 x 10-19 watts per molecule which in effect electrocute pathogens. A multitude of these devices are effective at such low concentrations as 0.3 PPM where they can kill 100% of 100 K/cc Streptococcus faecalis, and E. coli colonies in three minutes meeting the ten-minute EPA criteria of 100% kills within ten minutes for swimming pool and hot-tub applications. The devices can be used in utilitarian bodies of water, such as municipal and industrial water reservoirs.

While the formula AgO accurately designates the silver:oxygen ratio, the molecular weight of the compound is actually 495.52. Further elucidation of the molecule's electromagnetic properties revealed that it is a diamagnetic semiconductor. The structure is electronically active because of the trivalent sp2 electron configuration disparity of the electrons within the crystal. The oxide as presented in my patent was actually capable of killing 100% of standardized E. coli and Strep. faecalis colonies in less than five minutes at concentratiors of 0.5 PPM. My independent evaluations of this oxide in areas unrelated to water treatment resulted in the "molecular device" concept which was substantiated by submission of the oxide for testing with a preferred embodiment of the invention (10 PPM of sodium persulfate) at an Environmental Protection Agency (EPA) certified laboratory which revealed that 0.5 PPM of oxide only yielded 0.003 PPM of silver in solution, a silver concentration entirely too low to cause this level of bactericidal activity. Indeed, the killing of the bacteria was analogous to that obtained by electron generating devices utilized in swimming pools or water towers for killing bacteria. It was therefore postulated that the oxide efficacy at low concentrations could only be attributed to regarding each oxide molecule as a device. Further testing was continued on algae and viruses. The accumulated data of efficacy at low concentrations, coupled together with a reinterpretation of silver oxide efficacy, has led to the final development of this invention, namely, a molecular device for killing algae, bacteria and viruses in utilitarian water bodies, such as swimming pools.

This invention relates to a molecular scale device capable of destroying gram positive and gram negative bacteria as well as viruses and algae. Said molecular scale device consists of a single crystal of tetrasilver tetroxide. Several hundred thousand trillion of these devices may be employed in concert for their bactericidal, viricidal, and algicidal properties and applied to industrial cooling towers, swimming pools, hot tubs, and municipal water supplies.

The molecular crystals which are the subject of this invention are commercially available and can be prepared by reacting silver nitrate with sodium or potassium peroxydisulfate according to the following equation:
4AgNO3 + 2Na2 S2 O8 + 8NaOH = Ag4O4 + 4Na2SO4 + 4NaNO3 + 4H2O

The oxide lattice represented by the formula Ag4O4 is depicted in the Drawing FIG. 1. It is a semiconducting electron active diamagnetic crystal containing two monovalent and two trivalent silver ions in combination with four oxygen atoms. The distance between the Ag(III)-O Ag(I)O units equals 2.1 A. Ag(III)-Ag(III) = Ag(I)-Ag(I) = 3.28A and Ag(I)-Ag(III) = 3.19 A. Each trivalent silver ion is coordinated via dsp2 electron bonds to 4 oxygen atoms. The depiction of this lattice is based on several literature references relating to crystallographic studies. Exemplary of this literature are J. A. McMillan's studies appearing in Inorganic Chemistry 13,28 (1960); Nature vol. 195 No. 4841 (1962), and Chemical Reviews 1962, 62,65. Alvin J. Salkind elucidated studies involving neutron diffraction with his coworkers (J. Ricerca Sci. 30, 1034 1960) proving the Ag(III)/Ag(I) nature of this molecule and states in his classic entitled Alkaline Storage Batteries (Wiley 1969), coauthored with S. Uno Falk, that the formula is depicted by Ag4O4  (page 156).

That same year a scientific communication appeared in Inorganic Nuclear Chemistry Letters (5,337) authored by J. Servian and H. Buenafama which maintained that their neutron diffraction studies also confirmed the tetroxide lattice and the presence cf Ag(III) and Ag(I) bonds in the lattice, a conclusion also reported previously by Naray-Szahn and Argay as a result of their x-ray diffraction studies (Acta Cryst. 1965, 19,180). Thus the effects of this invention can be explained in terms of these structural elucidations, namely, that the single molecular semiconductor crystal which inevitably must be electronically active exchanging two electrons per crystals between its mono and trivalent bonds is in reality a device which kills pathogens in the same manner as electrically active large-scale devices utilized in water supplies.

When the tetroxide crystals are utilized to destroy pathogens, they will not do so unless activated by an oxidizing agent. This is analogous to the behavior of single semiconducting photovoltaic molecular devices such as copper indium selenide whose surfaces must be "etched" in order to activate the photovoltaic activity, i.e., for light to facilitate the release of electrons from the molecule. The tetroxide was activated by persulfates [ or: hydrogen peroxide ]. It was found that when the persulfates were tested as a control by themselves, they failed to exhibit any unilateral antipathogenic activity at the optimum level selected of 10 PPM. The persulfates evaluated varied from OXONE (Registered Trademark Du Pont Company) brand potassium monopersulfate to alkali peroxydisulfates.

EXAMPLE 1

Tetrasilver tetroxide (Ag4O4 ) crystals were prepared by modifying the procedure described by Hammer and Kleinberg in Inorganic Syntheses (IV,12).

A stock solution was prepared by dissolving 24.0 grams of potassium peroxydisulfate in distilled water and subsequently adding to this 24.0 of sodium hydroxide and then diluting the entire solution with said water to a final volume of 500 ml. Into 20 ml. vials were weighed aliquots of silver nitrate containing 1.0 g. of silver. Now 50 ml. of the aforementioned stock solution were heated in a 100 ml. beaker, and the contents of one of the vials was added to the solution upon attaining a temperature of 85.degree. C. The beaker was then maintained at 90.degree. C. for 15 minutes. The resulting deep black oxide obtained consisting of molecular crystal devices was washed and decanted four times with distilled water in order to remove impurities.

The purified material was collected for further evaluation and comparison with commercial material.

The commercial material was purchased from Johnson Matthey's Catalog Chemicals Division of the Aesar Group of Ward Hill, Massachusetts, under product code 11607 and generically listed in its materials Safety Data Sheet as both silver peroxide and silver suboxide, having a purity of 99.9%.

Both the prepared and commercial device crystals were submitted for bactericidal evaluation following "good laboratory practice" regulations as set forth in Federal Regulations (FIFRA and ffdca/40 CFR 160, May 2, 1984). The protocols consisted of exposures to Streptococcus faecalis, a gram positive pathogenic bacillus utilizing AOAC (15th) 1990:965:13: at colony densities of 100 000 colonies/cc. and two exposure times of five and ten minutes. The devices were tested at concentrations of 0.3, 0.5 and 1.0 PPM in distilled water adjusted to pH = 7.5 and containing Oxone (Registered Trademark Du Pont Company), which is potassium monopersulfate at a level of 10 PPM. The evaluations were repeated at the same persulfate concentration utilizing commercial grade sodium persulfate manufactured by FMC. 100% kills were actually obtained after three minutes at all the aforementioned device concentrations, there being actually zero colonies at the 0.5 and 1.0 PPM levels after five minutes and at the 0.3 PPM level after ten minutes. Analogous testing employing the same colony density of the gram negative bacillus E. coli were carried out. The same results were obtained. EPA criteria require that 100% kills be obtained within ten minutes for a substance to meet EPA criteria for swimming pool utilizatior. In this case, the devices at 0.3 PPM, equivalent to approximately 360,000 trillion devices, were able to far exceed EPA criteria for sanitizing a swimming pool.

US6485755
Methods of Using Electron Active Compounds for Managing Cancer

The instant inventor also presented a discussion of such results and concepts at a Seminar entitled "Incurable Diseases Update" (Weizmann Institute of Science, Rehovot, Israel, Feb. 11, 1998). The title of this presentation was "Beyond Antibiotics, Non Toxic Disinfectants and Tetrasil.TM. (Trademark of applicant for the tetroxide)."

In this paper, it was reported that the effects of the electron transfer involved with respect to the tetroxide, rendered it a more powerful germicide than other silver entities. The instant inventor holds patents for multivalent silver antimicrobials, e.g., U.S. Pat. No. 5,017,295 for Ag(II) and U.S. Pat. No. 5,223,149 for Ag (III); and while these entities are stronger antimicrobials than Ag (I) compounds, they pale by comparison to the tetroxide and so does colloidal silver that derives its germicidal properties from trace silver (I) ions it generates in various environments. Accordingly, the oligodynamic properties of these entities may be summarized as follows, which is referred to as the Horsfal series:

Ag4O4 > Ag(III) > Ag(II) >>>> Ag(I)

The other unique property of the tetroxide was that it did not stain organic matter such as skin in like manner as Ag(I) compounds do. In addition, it was light stable.

Preferably, the administration provides an amount of the metal oxide sufficient to provide about 1 to about 75 ppm of the metal oxide compound or derivative thereof in the bloodstream. The metal oxide is preferably administered via infusion over a period of time sufficient to inhibit adverse side effects, such as over a time period of from about 30 minutes to about 300 minutes.

The method of the invention is preferably suitable for cancers or dysplastic proliferations including at least one of colon cancer, lung cancer, throat cancer, breast cancer, kidney cancer, pancreatic cancer, bladder cancer, prostate cancer, uterine cancer, brain cancer, liver cancer, skin cancer, testicular cancer, stomach cancer, adrenal gland cancer, cancer of the ovaries, thyroid cancer, bronchial cancer, tracheal cancer, eye cancer, bone cancer, cervical cancer, oral cavity cancer, soft tissue cancer, pituitary gland cancer, myeloma, rectal cancer, esophageal cancer, leukemia, lymphoma, cancerous fibroid tumors, non-cancerous fibroid tumors, or liver cancer. The method is preferably suitable for cancers including skin cancer that has metastasized.

A 3% concentrate was used and evaluated by a certified laboratory employing good laboratory practice (GLP) according to the Code of Federal Regulations for this purpose.

The results were as follows:

Acute Oral Toxicity -- LD.sub.50 Greater than 5,000 mg/Kg
Acute Dermal Toxicity -- LD.sub.50 Greater than 2,000 mg/Kg
Primary Eye Irritation -- Mildly irritating
Primary Skin Irritation -- No irritation
Skin Sensitization -- Non-Sensitizing

US Patent 5,676,977
Method of Curing AIDS with Tetrasilver Tetroxide Molecular Crystal Devices
Abstract
The diamagnetic semiconducting molecular crystal tetrasilver tetroxide ( Ag4O4 ) is utilized for destroying the AIDS virus, destroying AIDS synergistic pathogens and immunity suppressing moieties (ISM) in humans. A single intravenous injection of the devices is all that is required for efficacy at levels of about 40 PPM of human blood. The device molecular crystal contains two mono and two trivalent silver ions capable of "firing" electrons capable of electrocuting the AIDS virus, pathogens and ISM. When administered into the bloodstream, the device electrons will be triggered by pathogens, a proliferating virus and ISM, and when fired will simultaneously trigger a redox chelation mechanism resulting in divalent silver moieties which chelate and bind active sites of the entities destroying them. The devices are completely non-toxic. However, they put stress on the liver causing hepatomegaly, but there is no loss of liver function.
References Cited
U.S. Patent Documents
4415565 ~ Nov., 1983 ~ Wysor ~ 424/618
4915955 ~ Apr., 1990 ~ Gomori~ 424/618
4952411 ~ Aug., 1990 ~ Fox, Jr. et al.~ 424/618
5073382 ~ Dec., 1991 ~ Antelman~ 424/618
5078902 ~ Jan., 1992 ~ Antelman ~ 424/618
5089275 ~ Feb., 1992 ~ Antelman ~ 424/618
5211855 ~ May, 1993 ~ Antelman ~ 424/618
5223149 ~ Jun., 1993 ~ Antelman ~ 424/618
5336499 ~ Aug., 1994 ~ Antelman ~ 424/618
5571520 ~ Nov., 1996 ~ Antelman ~ 424/618
Other References
"Is The AIDS Virus A Science Fiction?" by Peter H. Duesberg and Bryan J. Ellison: Policy Review (Summer 1990), pp. 40-51.
Claims
What is claimed is:
1. A method of treating AIDS-afflicted humans comprising injecting a multitude of tetrasilver tetroxide molecular crystals into the bloodstream of the human subject.
2. A method for increasing white blood cell counts in AIDS-afflicted humans comprising injecting a multitude of tetrasilver tetroxide molecular crystals into the bloodstream of the human subject.
3. Methods of treating AIDS-affilicted humans according to claims 1-2 where the concentration of said molecular crystals is approximately 40 PPM of the total blood weight of the human subject.
Description
BACKGROUND OF THE INVENTION
The present invention relates to the employment of molecular crystals as anti-AIDS devices, but more particularly to the molecular crystal semiconductor tetrasilver tetroxide Ag4O4 which has two monovalent and two trivalent silver ions per molecule, and which through this structural configuration enables intermolecular electron transfer capable of killing viruses and binding them to the resulting silver entity so that a single intravenous injection will completely obliterate acquired immune deficiency syndrome (AIDS) in humans. Furthermore, said devices are capable of killing pathogens and purging the bloodstream of immune suppressing moieties (ISM) whether or not created by the AIDS virus (HIV); so as to restore the immune system.
The present invention is based on concepts previously elucidated in applicant's U.S. Pat. No. 5,336,499 which discloses the destruction and inhibition of bacteria, algae and the AIDS virus in nutrient life supporting systems by using said silver oxide devices. Example 3 of said patent discloses that 18 PPM of said crystal devices could totally suppress the AIDS virus (page 6, line 5). Subsequent to the filing of the aforementioned patent, further testing revealed complete 100% destruction of the AIDS virus in vitro at 20 PPM, and the fact that said devices were harmless when ingested and inhaled, being non-toxic.
Encouraged by these evaluations and successes, applicant obtained permission to evaluate the crystals in vitro against murine acquired immune deficiency syndrome (MAIDS). Only one facility in the State of Israel is licensed for these evaluations, namely, the Kaplan Hospital in Rehovot, Israel, which is affiliated with the Hebrew University-Hadassah Medical School where said evaluations were done.
The initial evaluations entailed experimenting with various silver moieties cited in applicant's aforementioned patent, concentrations, non-reactive buffers and modes of administration. After about 18 months of judicious efforts and initial failures, success was finally achieved in destroying the MAIDS virus in C57BL mice with a single intravenous injection. The results of this test program comprise Example 5 of U.S. Pat. No. 5,336,499. After success with mice, the inventor was able to test the efficacy of said devices on two select etiological groups of terminal AIDS patients in a clinic in Tegucigalpa, Honduras, Central America.
The AIDS patients comprised the etiological subgroups, Candidiasis and Wasting Syndrome. Current indicator diseases for diagnosing AIDS which have been expanded by the CDC, fall into the following five major categories with the approximate percent distribution among AIDS patients:
    ______________________________________
    1. P. carinii pneumonia
                       51%
    2. Wasting syndrome
                       19%
    3. Candidiasis     13%
    4. Kaposi's sarcoma
                       11%
    5. Dementia         6%
    ______________________________________
This invention concerns itself with the treatment and cure of candidiasis and wasting syndrome AIDS patients with Tetrasil*. These two groups account for approximately one third of AIDS cases.
*Trademark of Holipharm Corporation (of Israel) for Ag.sub.4 O.sub.4
Stedman's Medical Dictionary (Williams & Wilken's 26th Ed., 1995) defines wasting syndrome "as a condition of 10% weight loss in conjunction with diarrhea or fever . . . Associated with AIDS (p. 1744)."
OBJECTS OF THE INVENTION
The main object of the invention is to provide for a molecular scale device of a single tetrasilver tetroxide crystalline molecule capable of restoring the immunity of AIDS afflicted humans of the two AIDS etiological subgroups, candidiasis and wasting syndrome.
Another object of the invention is to provide for immunity restoration in said AIDS afflicted humans through a single injection.
Another object of this invention is to destroy ISM in humans manifesting AIDS diseases of said AIDS etiological subgroups irrespective as to whether said ISM was HIV induced, since it is known that humans may manifest AIDS and still be HIV negative, and thus restore the immune system in said humans.
Another object of this invention is to destroy the AIDS virus when present in the systems of said AIDS afflicted humans.
SUMMARY OF THE INVENTION
This invention relates to a molecular scale device not only capable of de33stroying the AIDS virus, but of purging the human bloodstream of pathogens and restoring immunity to AIDS patients of the candidiasis and wasting syndrome categories. Said molecular device consists of a single crystal of tetrasilver tetroxide (Ag4O4). The crystal lattice of this molecule has a unique structure since it is a diamagnetic semiconducting crystal containing two mono and two trivalent silver ions, which in effect are capable of "firing" electrons under certain conditions which will destroy AIDS viruses, other pathogens and immune suppressing moieties (ISM), not only through the electrocution mode, but also by a binding process which occurs simultaneously with electron firing, namely, binding and chelation of divalent silver, i.e., the resulting product of the electron transfer redox that occur when the monovalent silver ions are oxidized and the trivalent ions are reduced in the crystal. The binding/chelation effect occurs at active sites of the AIDS virus, pathogens and ISM. Because of the extremely minute size of a single molecule of this crystal, several million of these devices may be employed in concert to destroy a virus colony to purge a life support system of ISM and pathogens with the consumption of only parts per trillion of the crystal devices. Thus an optimum of 40 PPM of the devices by weight of human blood was found to be sufficient to completely obliterate AIDS. This concentration is slightly over double of the optimum concentration recommended in applicant's aforementioned U.S. patent for the destruction of the human AIDS virus in vitro. Other details concerning the structure of the crystal and its mechanism against pathogens, the AIDS virus and ISM would analogously hold here, and have already been further elucidated in said patent.
The actual destruction of pathogens, ISM and the AIDS virus is effectuated by injection of a suspension of these devices in distilled or deionized water with a non-reacting electrolyte directly, i.e. intravenously, into the bloodstream. A single injection is all that is required under these conditions. Accordingly, humans injected in this manner, upon being inspected after three weeks or more had elapsed and compared with similar humans that had been given placebos, were completely cured of AIDS. The control group still manifested AIDS. Accordingly, the tetrasilver tetroxide device performed in concert with and in full conformity with the ultimate objects of this invention. Furthermore, three out of four wasting syndrome terminal patients and four out of the five candidiasis terminal patients were still alive in 1995 after a year and a half had elapsed from their initial injection. By that time all the AIDS patients had been released from the clinic and allowed to return home.
Other objects and features of the present invention shall become apparent to those skilled in the art when the present invention is considered in view of the accompanying examples. It should, of course, be recognized that the accompanying examples illustrate preferred embodiments of the present invention and are not intended as a means of defining the limits and scope of the present invention.
EXAMPLE 1
Five patients afflicted with AIDS of the candidiasis etiological category were segregated for Tetrasil treatment. The rationale for selecting them was based on facts presented in an article by Peter H. Duesberg and Brian J. Ellison entitled "Is The AIDS Virus A Science Fiction?" (Policy Review, Summer 1990 pp. 40-51). Only the factual presentations of the article were utilized and the hypothesis of the authors was ignored. The facts presented in the article related to the method of selecting AIDS patients based on the five aforementioned etiological subgroups targeted by the CDC, and the evidence presented, that there is AIDS without HIV as well as with it so that an anti-viral agent in most instances will not necessarily restore the immunity system.
Evaluations with Tetrasil were conducted on AIDS patients at Lucha Contra el Sida, Comayaguela, Honduras. The patients two weeks prior to inoculation were removed from their AZT, AIDS therapy. Tetrasil was administered at approximately 40 PPM of blood volume per patient as a suspension in a proprietary buffer solution (pH = 6.5), supplied by Holipharm Corporation.
The results of evaluations with candidiasis are tabulated in Table I under its disease category. All patients evaluated were terminal. Some, however, were in moderate (m) condition and others in poor (p) as designated in the Table. The I and F designations refer to initial and final values as shown. WBC indicates white cell blood count. The H column, following CD 8, indicates whether hepatomegaly occurred. This was an unfortunate consequence of the treatment which resulted in enlarged livers in all patients except the second one. Despite hepatomegaly, there was no interference with liver function.
The onset of hepatomegaly was not spontaneous and varied from patient to patient, being in the range of 4-16 days.
It should also be noted that shortly after injection of Tetrasil there were indications of fever (symbolized by T in the Ag4O4 column), sometimes accompanied by fatigue (F). The body temperature was invariably 38.5.degree. C. (101.3.degree. F.). This was indicative of restoration of the immune response of the body, since normally the body will destroy pathogens when the immune system is functional by raising the temperature. The patient who died; first responded favorably to Diflucan, which previously gave no response. He was cured of his candidiasis, but unfortunately succumbed to his previous body damage. All the other candidiasis syndrome people who previously did not respond to the indicated medications subsequently responded after the Tetrasil treatment. Further evidence of the recovery of the AIDS patients manifested itself 30 days after the initial injection when white blood cell counts were taken. They are shown in Table I under the WBC column, which gives the initial and final WBC. All candidiasis patients showed a dramatic increase in their white blood cell counts, indicative of the restoration of their immunity systems.
EXAMPLE 2
The above protocol of Example 1 was repeated with AIDS patients exhibiting wasting syndrome. The results of their treatment are tabulated in Table I under the disease category of said syndrome. It should be noted that two of the four wasting syndrome patients showed improved white blood counts. The female patient, whose condition improved from poor and terminal to be among the living, showed a decrease in the WBC. However, she showed an increase in body temperature which was indicative of immune response. The test results indicate that one cannot rely on a single factor to indicate the demise of AIDS. The usual HIV marker CD 4 initial and final are irrelevant. ISM suppression appears to be more critical than the destruction of HIV. AIDS was suppressed, any permanent damage that had been done to the patients in the course of their succumbing to AIDS was not obviously cured or corrected by said crystal device treatment, rather said injury persisted and the patient was improved with respect to AIDS but still suffered from said permanent injury or impairment previously inflicted.
                                      TABLE I
    __________________________________________________________________________
    Response of AIDS Patients to Single 40 PPM Ag4O4 Inoculation
                     Date                    Weight
    DISEASE
          PATIENT    Inoc.
                        WBC   CD 4       DEATH
                                             Lbs.
    Group Sex
             Age
                Medictn
                     1994
                        I  F  I  F  CD 8
                                       H 1944
                                             I   F  Ag4O4
    __________________________________________________________________________
    Candidiasis
          M p
             28 Diflucan
                     5/5
                        1,200
                           4,200
                               41
                                 -- 221
                                       + 6/11
                                              82  76
                                                    T
          F m
             33 "    5/5
                        6,000
                           6,700
                              554
                                 872
                                    394
                                       -      98  98
                                                    T
          F m
             33 Ketaconzl
                     5/27
                        2,600
                           3,850
                              248
                                 181
                                    951
                                       +     123 123
                                                    T
          M p
             62 "    6/2
                        3,300
                           3,700
                               89
                                 237
                                     59
                                       +     105  92
                                                    F
          F m
             31 Pentamidn
                     6/2
                        2,400
                           3,050
                               9 181
                                     65
                                       +     121 118
                                                    Pain
    Wasting
          M m
             27      5/27
                        3,600
                           4,600
                               39
                                  14
                                    709
                                       +     119 120
                                                    T
    Syndrome
          M m
             28      5/27
                        2,750
                           --  10
                                 --  60
                                       + 7/19
                                             121 119
                                                    T, F
          F p
             43      5/27
                        3,600
                           2,700
                               68
                                 246
                                    248
                                       +     101  98
                                                    T, F
          M m
             19      5/10
                        3,850
                           5,400
                              137
                                  36
                                     48
                                       +     103 106
                                                    T, F
    _________________________________________________________________________
As this invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, the present embodiments are therefore illustrative and not restrictive, since the scope of the invention is defined by the appended claims rather than by the description preceding them, and all changes that fall within the metes and bounds of the claims or that form their functional as well as conjointly cooperative equivalents, are therefore intended to be embraced by these claims.



US5571520
Molecular Crystal Redox Device for Pharmaceuticals
Abstract
The employment of molecular crystals as bactericidal, viricidal and algicidal devices, and specifically the molecular semiconductor crystal tetrasilver tetroxide Ag4O4 which has two trivalent and two monovalent silver atoms per molecule, and which through this structural configuration generates electronic activity on a molecular scale capable of killing algae and bacteria via the same mechanism as macroscale electron generators.
References Cited
U.S. Patent Documents
4055655 ~ Oct., 1977 ~ Maurer et al ~ 514/495
4695353 ~ Sep., 1987 ~ Jansen et al. ~ 423/604
4717562  ~ Jan., 1988 ~ Jansen et al.~ 423/604
4784991 ~ Nov., 1988 ~ Nimrod et al. ~ 514/495
4835077 ~ May., 1989 ~ Megahed et al. ~ 423/604
4915955 ~ Apr., 1990 ~ Gomori ~ 424/618
4952411 ~ Aug., 1990 ~ Fox, Jr. et al. ~ 424/618
5017295~ May., 1991 ~ Antelman ~ 210/764
5073382 ~  Dec., 1991 ~ Antelman ~ 210/764
5078902 ~ Jan., 1992 ~ Antelman ~ 210/764
5089248 ~ Feb., 1992 ~ Akhtar ~ 423/604
5089275 ~ Feb., 1992 ~ Antelman ~ 424/602
5098582 ~ Mar., 1992 ~ Antelman ~ 210/759
5211855 ~ May., 1993 ~ Antelman ~ 424/618
5223149  ~ Jun., 1993 ~ Antelman ~ 424/618
5336508 ~ Aug., 1994 ~ Marty ~ 424/618
5362735 ~ Nov., 1994 ~ Luengo ~ 514/291
5444052 ~ Aug., 1995 ~ Pieringer et al. ~ 514/738
Claims ~
What is claimed is:
1. A method for curing amoebic dysentery comprising, administering crystals of tetrasilver tetroxide intravenously so as to give a concentration of crystals of 40 PPM in the bloodstream.
2. A method for treating systemic Candida albicans; comprising injecting tetrasilver tetroxide crystals into the blood of humans so as to give a concentration of approximately 40 PPM in the bloodstream.
3. A method for treating Candida albicans according to claim 2 comprising only one single administered injection.
Description ~
BACKGROUND OF THE INVENTION
The present invention relates to the employment of molecular crystals as bactericidal, viricidal and algicidal devices, but more particularly to the molecular semiconductor crystal tetrasilver tetroxide Ag4O4 which has two trivalent and two monovalent silver atoms per molecule, and which through this structural configuration enables electronic activity on a molecular scale capable of killing algae and bacteria via the same mechanism as macroscale electron generators.
The molecular device of this invention is a multivalent silver diamagnetic semiconductor as previously described in my aforesaid pending U.S. application Ser. No. 07/971,933, now U.S. Pat. No. 5,336,499.
OBJECTS OF THE INVENTION
The main object of this invention is to provide a molecular scale redox device of a single tetrasilver tetroxide semiconductor crystal capable of killing viruses, bacteria, fungi and algae when operating in conjunction with other such devices.
Another object of the invention is to provide a molecular device which can be utilized in pharmaceuticals formulated to destroy pathogens.
Other objects and features of the present invention will become apparent to those skilled in the art when the present invention is considered in view of the accompanying examples. It should, of course, be recognized that the accompanying examples illustrate preferred embodiments of the present invention and are not intended as a means of defining the limits and scope of the present invention.
SUMMARY OF THE INVENTION
This invention relates to a molecular scale device capable of destroying gram positive and gram negative bacteria as well as fungi, viruses and algae. Said molecular scale device consists of a single crystal of tetrasilver tetroxide. Several hundred thousand trillion of these devices may be employed in concert for their bactericidal, fungicidal, and algicidal properties and in various pharmaceutical formulations and therapies. The physical chemistry of said tetroxide devices has already been described in my aforesaid pending application Ser. No. 07/971,933, now U.S. Pat. No. 5,336,499 and is incorporated herein by reference.
DESCRIPTION OF THE INVENTION
The crystal lattice of the Ag4O4 device operates by transferring electrons from its two monovalent silver ions to the two trivalent silver ions in the crystal in aqueous media in which it is immersed, and which conducts electrons, contributing to the death of pathogens by traversing the cell membrane surface of the pathogens being "electrocuted", not only by these electrons but also by others emanating from other molecular devices in the vicinity of the pathogen. The device is attracted to the cell membrane surface by powerful covalent bonding forces caused by the well-known affinity of silver to certain elements present in the membrane, such as sulfur and nitrogen.
The electron transfer can be depicted by the following redox half reactions in which the monovalent silver ion loses an electron and the trivalent silver gains one as follows:
Ag+ -e = Ag+2
Ag+3 +e = Ag+2
The molecular crystal then will become stabilized with each silver ion having a divalent charge.
Stringent testing was performed in which cultures were actually placed in trypticase soy nutrient broth, which allowed the pathogens being tested to replicate without being detached from its own food supply. Under these conditions the devices were able to kill two strains of E. coli at 2.5 PPM; Micrococcus luteus at 1.25 PPM; Staphylococcus aureus at 2.5 PPM; Staphylococcus epidermidis at 0.6 PPM; Pseudomonas aeruginosa at 1.25 PPM; and Streptococcus pyogenes at 2.5 PPM.
The devices were then evaluated in analogous nutrient used for yeasts, algae and molds utilizing Sabouraud dextrose broth. The infectious yeast pathogen Candida albicans was totally killed at 2.5 PPM and that of the Saccharomycetpideae variety at 1.25 PPM. These were also evaluated successfully in mice against murine aids, and in humans against Candida albicans both as a douche and intravenously. The devices also were successful externally in humans against Staphylcoccus epidermidis, nail fungus and athlete's foot. Intravenous injections completely cured subjects who were suffering from acute diarrhea of ameobic dysentery.
It was found that oxidizing agents, particularly persulfates, enhance the efficacy of said devices.
EXAMPLE 1
The molecular crystal devices were tested as to whether they could kill pathogenic microorganisms with the intent of utilizing them in pharmaceutical applications. Once it could be determined that the devices inhibited a particular microorganism, the minimal concentration required of the Ag4O4 molecular crystal devices was determined to inhibit the microorganism in nutrient broth. One family of pathogens that are known for their deleterious effects on humans are popularly called "staph" infections. These infections are commonly contracted in hospitals having lax infectious screening procedures. Accordingly, three staph strains were selected as follows for evaluation: Staphylococcus aureus 9027, 27543 and Staphylococcus epidermidis 12228. The inoculum nutrient broth was prepared according to AOAC specifications so as to contain 0.6-1 million organisms per drop of inoculum, each drop being equal to 0.05 ml. The broth itself was trypticase soy broth BBL 11766 prepared according to label instructions. Accordingly, the broth was prestandardized for the microorganisms in question in order to assure that the number of organisms remained constant within the margins of statistical allowance during the test period. Having carried out the procedures with 0.05 ml. of inoculum and having incubated the organisms for 24 hours at 34.degree.-35.degree. C., it was found that staph organism 9027 was inhibited at 2.5 PPM; number 27543 at 5.0 PPM; and the 2228 organism at 0.625 PPM all in the presence of 10 PPM sodium persulfate. This data was utilized to formulate a dermatological cream which would contain 100 PPM sodium persulfate and 10 PPM of device crystals to inhibit staph infections. The cream was applied to a "staph" infection. The infection disappeared overnight. The subject was a 24-year old female.
EXAMPLE 2
The procedures described in Example 1 were analogously followed for the yeast pathogen Candida albicans using strain 16464 excepting that the nutrient broth was changed to accommodate this yeast pathogen to Sabouraud dextrose broth (Difco 038217-9). It was found that 2.5 PPM of molecular crystal devices completely inhibited the growth of this gynecological yeast infection. A gynecological cream and a douche were formulated against yeasts based on the results. The douche which contained 10 PPM of crystals and 40 PPM sodium persulfate was self-administered by a woman in her thirties who had suffered an entire year from the infection and who had taken virtually every prescription medicine for the infection to no avail. After taking two 2-quart douches within 24 hours, all signs of the candida infection had disappeared and her doctor pronounced her completely cured.
EXAMPLE 3
Device crystals were administered intravenously into a person in such a manner as to give a concentration of said tetroxide crystals of 40 PPM in the bloodstream. The person was chronically ill from Candida albicans. The subject, a citizen and resident of Honduras, was a 33-year old female. She was completely cured within a month of taking the crystals intravenously. It should be noted that the subject was close to death as a consequence of exposure to the disease prior to the aforesaid treatment.
EXAMPLE 4
Two patients at the same clinic where Example 3 patient was treated, in San Pedro Sultas, Honduras, were suffering from acute ameobic dysentery with diarrhea and dehydration. They were similarly intravenously treated to a level of 40 PPM of the crystals. Both patients, one a 19-year old male, and the other a 62-year old male, after being given one injection started to show slight improvement after one week. After one month had elapsed, they were completely cured from their condition.
The human dosages of this and the previous example were known to be safe as they were pretested in mice by injecting them with said crystal devices.
EXAMPLE 5
Six C57BL mice were selected that were six months old. One mouse was untreated as a control. Another control mouse was treated with an intravenous injection via its tail with 0.1 ml. of tetrasilver tetroxide devices calculated to contain 40 PPM in the bloodstream of the mouse. Two more control mice were now infected with MAIDS virus designated culture LP-BM5. Two test mice were then infected with culture LP-BM5. The LP-BM5 culture infection was achieved with intra-peritoneal injections of 0.4 ml. of said viral suspension. Subsequent to these vital injections the test mice were injected intravenously with 0.1 ml. (through the tail) of the 40 PPM (0.08 mg.) tetrasilver tetroxide devices. The devices in each case were suspended in distilled water for 3 days prior to injection and conditioned with sodium acetate as the electrolyte of choice. After 4 weeks had elapsed, the untreated and device treated control mice were killed. The untreated control mouse had a spleen weight of 90 mg., and the device treated mouse that of 89 mg. Both mice were seen to be in perfect health. After 3.5 weeks had elapsed, one of the infected control mice was killed and showed signs of MAIDS infection with a spleen weight of 138 mg. After 4 weeks had elapsed, the second infected control mouse was killed. It too showed signs of MAIDS infection with a spleen weight of 158 mg. As for the test mice, the vital suspension injection was injected immediately prior to the silver device treatment. They were then killed after 4 weeks. Both mice showed no signs of MAIDS infection, and their spleens weighed 103 and 95 mg., respectively, which are normal weights for these mice, whose body weight varies between 15-30 g. and whose blood volume is approximately 2.0 ml.
EXAMPLE 6
A 29-year old male suffering from athlete's foot soaked his feet in a solution containing 100 PPM of the crystal devices. The subject was completely cured within 24 hours.
EXAMPLE 7
A 61-year old male who suffered from a toenail fungus was treated with a 25% suspension of said crystal devices. The nail fungus, which had bothered the subject for three years, was gone after a week.
While there is shown and described herein certain specific examples embodying the invention, it will be manifest to those skilled in the art that various modifications and rearrangements of the invention may be made without departing from the spirit and scope of the underlying inventive concept and that the same is not limited to the particular forms herein shown and described except insofar as indicated by the scope of the appended claims.


US6258385
Tetrasilver Tetroxide Treatment for Skin Conditions
Abstract
The invention relates to the use of electron active molecular crystals comprising tetrasilver tetroxide (Ag.sub.4 O.sub.4) for the treatment and cure of dermatological skin conditions (diseases) ranging from dermatitis, acne and psoiasis to herpes and skin ulcers.

US Patent 5,078,902
Divalent Silver Halide Bactericide
Abstract
Divalent silver halides provide a source for divalent bactericidal silver ions in the presence of persulfate. The halides are especially effective when applied to water used in industrial cooling installations, hot tubs and swimming pools and will conform to stringent EPA requirements for waters utilized for bathing as in tubs and pools of 100% kills of 100 K/cc E. Coli coliforms within 10 minutes, exemplary of which are the chloride and bromide which give 100% kills within 5 minutes. The halides, of course, can be used in salty water since they are solids immune from halide action that would otherwise precipitate soluble divalent silver from solution.

US Patent 5,073,382
Divalent Silver Alkaline Bactericide Compositions
Abstract
Solid alkaline bactericidal compositions are disclosed suitable for compounding alkaline end products such as food and dairy cleaners and surgical scrubbing soaps, formed by the neutralization of acid stabilized inorganic divalent silver complexes and capable of effecting 100% kills upon cultures of anaerobic bacteria colonies of 100K/cc. within 5 minutes.


US20080233161

DEPOSITION PRODUCTS, COMPOSITE MATERIALS AND PROCESSES FOR THE PRODUCTION THEREOF

Abstract
A composite material comprising a substrate and a deposition product and the use of a deposition product for providing an antimicrobial effect. The substrate of the composite material is a medical device. Further, in each of the composite material and the use, the deposition product consists essentially of at least one oxidized silver species and wherein the deposition product is comprised of a compound having the formula Ag.sub.7O.sub.8X, where X is an anion.



http://europepmc.org/patents/PAT/CN101336640

CN101336640
Tetrasilver tetroxide bactericide, preparation method and use thereof


Abstract
The present invention discloses a tetrasilver tetroxide fungicide, a preparing method and an application thereof. The tetrasilver tetroxide fungicide comprises the following components by weight part: weak alkaline solution 800-1200 parts, tetrasilver tetroxide 0.1-0.5 parts, and polyvinyl alcohol 8-20 parts. The preparing method of the tetrasilver tetroxide fungicide comprises the following steps: using the weak alkaline solution with pH value of 7.0-7.5 as dissolvent, fetching 800-1200 parts of weak alkaline solution, and adding 0.1-0.5 parts of tetrasilver tetroxide, sufficiently diluting and uniformly mixing 8-20 parts of polyvinyl alcohol with the obtained solution in which the polyvinyl alcohol is used as carrier, and then the tetrasilver tetroxide fungicide is prepared. The invention also discloses the application of the tetrasilver tetroxide fungicide as a disinfection additive. The preparing method of the tetrasilver tetroxide fungicide according to the invention is simple and is suitable for large-scale production.

Technical field
The present invention relates to a four silver oxide bactericide, its preparation and application.

Background technique
At present, the research and application of bactericides mainly focus on the medicaments for preventing and curing the diseases caused by fungi, and the research and development of medicaments for preventing and curing diseases caused by bacteria and viruses is not enough. Silver bactericidal effect has long been found in recent years, people in the process of sterilizing silver sterilization, but also gradually want to apply the principle of sterilizing silver products to go, but the market has not yet as a bactericide to prevent bacteria and viruses , And the example applied to the product appears. In the July 2005 issue of "Chinese Journal of New Drugs and Clinical Medicine", "Progress in the research of medicinal silver tetraoxide" was reported, indicating that it is expected to become a novel antimicrobial agent and be used in the treatment of AIDS, cancer and other diseases .

Content of the invention
Object of the Invention: The purpose of the present invention is to provide a four-silver tetrabasic bactericide prepared from tetra-silver tetraoxide, a preparation method thereof and its use as a bactericidal additive.

Technical solution: a silver tetrabasic fungicide, which comprises the following components in weight: 800 to 1200 parts of weak alkaline solution, 0.1 to 0.5 parts of silver tetraoxide, and 8 to 20 parts of polyvinyl alcohol.

Four silver tetrafluoroborate bactericide includes the following components by weight: 1000 parts of weak alkaline solution, 0.2 parts of silver tetraoxide, and 10-15 parts of polyvinyl alcohol.

Preparation of tetrabasic silver fungicides, which comprises the following steps:

(1)Take weak alkaline solution with PH value of 7.0-7.5 as solvent, take weakly alkaline solution of 800-1200 parts and add 0.1-0.5 parts of silver tetraoxide to dilute thoroughly;

(2)8 to 20 parts of polyvinyl alcohol as a carrier, polyvinyl alcohol and the solution obtained in step (1) were uniformly mixed to obtain a tetrad silver oxide bactericide.

The weakly alkaline solution in step (1) is ammonia, sodium hydroxide or potassium hydroxide.

Four silver oxide fungicides as bactericidal additives.

Application of Four Silver Oxide Bactericide as Antibacterial Additive in Antibacterial Plastic Products.
Application of Four Silver Tetraoxide Bactericide as Antibacterial Additive in Antibacterial Fiber Products.
Application of Four Silver Oxide Bactericide as Antibacterial Additive in Antibacterial Fabric.
Application of Tetraoxysilver Antibiotics as Bactericidal Additives to Plant Diseases Caused by Microbes of Various Pathogens.
Application of Four Silver Oxide Bactericide as Antibacterial Additive in Antibacterial Coatings.

According to two kinds of fungicide mechanism of action: ① by interfering with the respiratory process of germs, inhibit the production of energy to kill bacteria. ② interfere with microbial life substances such as proteins, nucleic acids, alcohols and other biosynthesis to kill bacteria. Tetraoxide silver tetraoxide prepared four silver fungicides as fungicides belong to the second type of mechanism of action. The mechanism of Ag4O4 was analyzed. The antibacterial order of Ag4O4 was: Ag <3 +> Ag <2 +> Ag <1+>, and Ag4O4 was a kind of Ag4O4 with A unique conformation of "multivalent silver" oxide that redox reactions with exposed 2N and 2S groups on the protein surface produces electrical kill and chelation that result in altered protein conformation. Its mechanism of action is different from the general antimicrobial agents, the mode of action is not easy to cause the pathogen resistance or mutation, no toxicity to normal tissues, with anti-microbial and anti-inflammatory cells.

Beneficial effects: Four silver tetraoxide interferes with the function of preventing biosynthesis of bacterial cells, especially bacteria and viruses, and antimicrobial plastic products, antimicrobial fiber products, antibacterial fabrics , Against various pathogenic microorganisms caused by plant diseases, medical equipment and reagent additives, antibacterial coatings and antibacterial ware widely used in these fields, with good inhibition of bacteria, viruses, the preparation method of the present invention is simple, suitable for large Scale industrial production, application method is simple and practical.

Detailed description
The present invention will be further described below in combination with specific embodiments.

Example 1: Preparation of tetrad silver oxide bactericide.
(1)To PH value of 7.0 ammonia (NH3) solution 1 kg solvent, adding 200 mg of silver tetraoxide fully diluted;

(2)0.01 kg of polyvinyl alcohol as a carrier, and the solution obtained in step (1) were uniformly mixed to obtain 1 kg of silver tetrafluoroborate fungicide.

Example 2: Four silver tetrabasic bactericides as bactericidal additives in antimicrobial plastic products.
The reagent containing the silver tetrafluoroborate obtained in Example 1 was sprayed on the air filter element to naturally cure and dry the air filter element with antibacterial effect. Tetraoxide silver fungicide can also be added in the form of plastic coupling agent, about to dissolve the solution of tetrad silver anti-bacterial agent sprayed on the plastic particles, and then dried to use.

After testing, spray sterilized four four silver oxide air-conditioning filter in Escherichia coli, Staphylococcus aureus, Klebsiella pneumoniae, Aerobacter aerogenes, Campylobacter brevis, the survival rate of mixed strains were 0 , Which shows that four silver antimicrobial agent has the role of killing bacteria and mold.

Example 3: Four silver tetrabasic bactericides as bactericidal additives in antimicrobial plastic products.
The tetracycline antimicrobial agent obtained in Example 1 was directly combined with the air conditioning case in the form of a mist or coating on the formed air conditioning case. Because the exterior of the air conditioning is very smooth, you can use corona treatment, that is, under the action of high voltage electric field, the electron current exerts a powerful impact on the surface of the air conditioning enclosure, which can make the surface of the enclosure furred, roughened and increase the surface area. When in contact with its surface, it will create a good wetting that will penetrate into the furrows that have been pulled, and will be firmly anchored to the plastic shell by anchoring. Use this principle, the corona treatment will be four silver tetrachloride bactericide spray applied or coated by the temperature of 60 ~ 80 C for 8 to 12 minutes to dry, so that the four silver tetrachloride bactericide by complexation Fixed on the plastic shell surface.

After testing, spraying four tetra-antimicrobial tetracycline in the air-conditioned housing Escherichia coli, Staphylococcus aureus, Klebsiella pneumoniae, Aerobacter aerogenes, Bacillus crillium, species mixed survival rate was 0 , Which shows that four silver antimicrobial agent has the role of killing bacteria and mold.

Example 4: Preparation of tetrad silver oxide bactericide.
(1)To PH value of 7.2 sodium hydroxide solution 0.5 kg as solvent, add 100 mg of silver tetraoxide fully diluted;

(2)With 0.006 kg of polyvinyl alcohol as a carrier, the solution obtained in step (1) was uniformly mixed to obtain 0.5 kg of silver tetrafluoroborate bactericide.

Example 5: Tetraoxide silver fungicide as bactericidal additives in the application of antibacterial fiber products.
The PP brushed fiber products and 60 ~ 85 C dissolved in Example 4 was prepared four tetrabutyl silver fungicide solution warm water cross-linked, and then dried to obtain a bactericidal antibacterial fiber products.

After testing, coated silver tetrabuicides disinfectant PP drawing grade fiber products Escherichia coli, Staphylococcus aureus, Klebsiella pneumoniae, Aerobacter aerogenes, Campylobacter sp., A mixture of strains Survival rate is 0, we can see that four silver tetrabasic fungicides have the role of killing bacteria and mold.

Example 6: Use of Tetraoxysilver Antibiotics as Antibacterial Additives in Antibacterial Fiber Products.
The tetrad silver oxide bactericide obtained in Example 4 is added to the hot melt adhesive, and the child with a bactericidal effect can be made to be wet by the coating method.

After testing, children coated with silver tetrasulfate antimicrobial agents used in diabetics, Staphylococcus aureus, Klebsiella pneumoniae, Aerobacter aerogenes, Campylobacter crispus, bacteria mixed kind of survival The rate is 0, we can see that four silver tetrabasic fungicides have the role of killing bacteria and mold.

Example 7: Use of Tetraoxysilver Antibiotics as Antibacterial Additives in Antibacterial Fiber Products.
The tetrafluoroborate antimicrobial agent obtained in Example 4 was added to the hot melt adhesive, and the sanitary napkin and the panty liner with bactericidal effect were prepared by the coating method.

After testing, coated with four silver tetrasulfide disinfectant sanitary napkins, sanitary pads in Escherichia coli, Staphylococcus aureus, Klebsiella pneumoniae, Aerobacter aerogenes, Bacillus crillium, mixed species Survival rate is 0, we can see that four silver tetrabasic fungicides have the role of killing bacteria and mold.

Example 8: Use of a silver tetraborate antimicrobial agent as an antimicrobial additive in an antimicrobial fabric.
The medical staff and patient clothing were immersed in the solution of the silver tetrabasic fungicide prepared in Example 4, and the antibacterial effect of medical staff and patient clothing were obtained by centrifuging and recovering the solution, drying and drying.

After testing, infiltration of tetrabenzene antimicrobial tetracycline antibacterial agents and patient clothing Escherichia coli, Staphylococcus aureus, Klebsiella pneumoniae, Aerobacter aerogenes, Campylobacter brevis, the survival rate of mixed species Are 0, we can see that four silver tetrabasic fungicides have the role of killing bacteria and mold.

Example 9: Use of Tetraoxysilver Antibiotics as Antibacterial Additives in Antibacterial Fabrics.
The wound paste was immersed in a solution of the silver tetraborate antimicrobial agent obtained in Example 4, and the wound paste with antibacterial effect was obtained by centrifugal dehydration recovery solution, drying and drying.

After testing, infiltrated four antimicrobial silver tetrazolium agents in the wound paste E. coli, Staphylococcus aureus, Klebsiella pneumoniae, Aerobacter aerogenes, Campylobacter brevis, the survival rate of mixed strains were 0 , Which shows that four silver antimicrobial agent has the role of killing bacteria and mold.

Example 10: Preparation of tetrad silver oxide bactericide.
(1)To PH value of 7.5 potassium hydroxide solution 2 kg solvent, add 400 mg of silver tetraoxide fully diluted;

(2)With 0.03 kg of polyvinyl alcohol as a carrier, the solution obtained in step (1) was uniformly mixed to obtain 2 kg of silver tetrafluoroborate bactericide.

Example 11: Application of Tetraoxotetra Fungal Bacteria in Plant Resistance to Diseases Caused by Various Pathogenic Microorganisms.
When watering wheat, the silver tetrabasic bactericide prepared in Example 10 can be diluted at a concentration of 10 to 30 ppb, and diseases caused by various pathogenic microorganisms can be effectively prevented by spraying or pouring.

After testing, pouring over the water containing four tetrabasic silver disinfectant of wheat, Escherichia coli, Staphylococcus aureus, Klebsiella pneumoniae, Aerobacter aerogenes, Campylobacter crispus, the survival rate of mixed strains Are 0, we can see four silver oxide bactericide has the effect of killing bacteria and fungi, thereby effectively inhibiting the pathogenic microorganisms caused by the disease.

Example 12: Application of Tetraoxide Tetraoxide Bactericide in Plant Resistance to Diseases Caused by Various Pathogenic Microorganisms.
The silver tetraborate antimicrobial agent prepared in Example 10 was diluted to a concentration of 10 to 30 ppb and sprinkled onto apple trees by spraying or pouring to effectively prevent apple tree diseases caused by various pathogenic microorganisms.

After testing, poured over the water containing four tetrasulfan antimicrobial apple trees, Escherichia coli, Staphylococcus aureus, Klebsiella pneumoniae, Aerobacter aerogenes, Campylobacter crispus bacteria, mixed species of survival The rate is 0, we can see that four silver tetrabasic fungicides have the role of killing bacteria and fungi, which effectively inhibit the disease caused by pathogenic microorganisms.

Example 13: Use of Tetraoxide Tetraoxide Bactericide in Plant Diseases Against Various Pathogenic Microorganisms.
The silver tetraborate antimicrobial agent obtained in Example 10 was diluted to a concentration of 10 to 30 ppb and sprinkled onto the lawn by spraying or pouring to effectively prevent the lawn disease caused by various pathogenic microorganisms.

After testing, after pouring water containing tetra-oxystericum water after the lawn, Escherichia coli, Staphylococcus aureus, Klebsiella pneumoniae, Aerobacter aerogenes, Campylobacter sp., The survival rate of mixed species Are 0, we can see four silver oxide bactericide has the effect of killing bacteria and fungi, thereby effectively inhibiting the pathogenic microorganisms caused by the disease.

Example 14: Use of Tetraoxysilver Antibiotics as Antibacterial Additives in Antibacterial Coatings.
The silver tetraborate antimicrobial agent obtained in Example 10 was added to the paint and paint at a concentration of 10 to 50 ppm, and the paint or paint was sprayed on handrails, computers, telephones, toys, wood floors and the like frequently. More bacteria were used Of the items, so that spray paint, paint items with antibacterial effect.

After testing, spray paint containing antifouling agent of tetraoxide, paint handrails, computers, telephones, toys and wooden floors, etc., Escherichia coli, Staphylococcus aureus, Klebsiella pneumoniae, Aerobacter aerogenes, orange Gram-positive bacteria, bacteria mixed kind of survival rates are 0, we can see that four silver tetrabuicides kill bacteria and fungi have the role.



US5098582
Divalent Silver Oxide Bactericides

Abstract
Divalent silver oxide provides a source for divalent bactericidal silver ions in the presence of persulfate. This oxide is especially effective when applied to water used in industrial cooling towers, hot tubs and swimming pools and conforms to stringent EPA requirements of 100% kills of 100K/cc Streptococcus faecalis within 10 minutes. The oxide also can be used in water with exceptionally high salt content without halide curdy precipitate formation and will not stain the skin of users who may inadvertently be exposed to it.



US5089275
Stabilized Divalent Silver Bactericides

Abstract
Solid bactericidal compositions are disclosed based on divalent silver (Ag(II)) as the active sanitized agent. The compositions are prepared by reacting acid liquid Ag(II) complexes with anhydrous calcium sulfate so as to form a solid matrix in which the bactericide is entrapped in the resulting hydrated calcium sulfate. Optimum compositions are described consisting of Ag(II) phosphate dissolved in phosphoric acid where the ratio of solid (by weight) to liquid (by volume) is 5:2. The resulting solid bactericides can be used in water cooling installations. They are capable of causing 100% kills within 10 minutes of E. Coli conforms in conformity with EPA protocols, allowing them to quality as swimming pool and hot tub sanitizers. Since the compositions are based on calcium sulfate, they are also suitable as mineralizers, thus providing a dual function.


AU2002346065
Methods of using electron active compounds for managing conditions afflicting mammals


Also published as:  WO03003809 // WO03003809  (A3)
Abstract
The present invention relates to a method of preventing, treating, or managing a condition of an animal, such as a mammal. The animal is administered with a therapeutically effective amount of at least one electron active compound, or a pharmaceutically acceptable derivative thereof, that has at least two polyvalent cations, at least one of which has a first valence state and at least one of which has a second different valence state, to prevent, treat, or manage the condition, or a symptom thereof. A multivalent metal oxide, such as Ag(I,III), Cu(I,III), Pr(III,IV), and Bi(III, V) oxides or a pharmaceutically acceptable derivative thereof, may be administered to the animal in an amount and for a period of time which is therapeutically effective to prevent, treat, and/or manage such a condition(s) afflicting the animal.


AR029184
MULTIVALENT ELECTRON ACTIVE COMPOSITIONS AND METHODS OF MAKING AND USING SAME


Abstract
The present invention is directed to pharmaceutical compositions that include a therapeutically effective amount of at least one electron active compound, or a pharmaceutically acceptable derivative thereof, that has at least two polyvalent cations, at least one of which has a first valence state and at least one of which has a second, different valence state. Preferred compounds include Bi(III,V) oxide, Co(II,III) oxide, Cu(I,III) oxide, Fe(II,III) oxide, Mn(II,III) oxide, and Pr(III,IV) oxide, and optionally Ag(I,III) oxide. These compounds may be in a crystalline state having metallic cations of two different valences, or electronic states, in the inorganic crystal. In addition, the invention relates to methods for prevention, management, or treatment of a condition using these compounds or pharmaceutical compositions including the same.


US2006105057
Compositions using tetrasilver tetroxide and methods for management of skin conditions using same


Abstract
Pharmaceutical compositions including tetrasilver tetroxide (Ag&lt;SUB&gt;4&lt;/SUB&gt;O&lt;SUB&gt;4&lt;/SUB&gt;), such as in crystalline form, and methods of using such compositions for the prevention, treatment, and management various of dermatological skin conditions and diseases. In one embodiment, these compositions are substantially free of added persulfates. These dermatological conditions and diseases that may be prevented, treated, or managed with the compositions of the invention vary and include, but are not limited to, eczema, psoriasis, dermatitis, disease-induced skin ulcers, undefined tropical diseases, shingles, rashes, bedsores, cold sores, blisters, boils, herpes simplex, acne, pimples, skin chafing, skin cracking, itchiness, skin peeling, and warts.


US2004265877
Methods for detecting presence of cellular constituents


Abstract
The invention is directed to methods for detecting, monitoring and/or diagnosing aberrant cellular proliferation, and disorders associated therewith, such as cancer, and/or infection by microorganisms. The detection, monitoring and/or diagnosis comprises contacting a compound of the invention with a cell or fluid sample. Compound binding confirms the presence of an abnormal cell or a protein associated with an abnormal cell or infection by one or more microorganisms, and/or disorders associated with infection by one or more microorganisms.


US2004022868

Compositions using tetrasilver tetroxide and methods for management of skin conditions using same


Abstract
Pharmaceutical compositions including tetrasilver tetroxide (Ag4O4), such as in crystalline form, and methods of using such compositions for the prevention, treatment, and management various of dermatological skin conditions and diseases. In one embodiment, these compositions are substantially free of added persulfates. These dermatological conditions and diseases that may be prevented, treated, or managed with the compositions of the invention vary and include, but are not limited to, eczema, psoriasis, dermatitis, disease-induced skin ulcers, undefined tropical diseases, shingles, rashes, bedsores, cold sores, blisters, boils, herpes simplex, acne, pimples, skin chafing, skin cracking, itchiness, skin peeling, and warts.


ZA200205146
Compositions and methods for facilitating skin growth and managing skin conditions.


WO03043537
IMPROVEMENTS IN CURING AIDS WITH TETRASILVER TETROXIDE MOLECULAR CRYSTAL DEVICES


Abstract
A cure for treatment of AIDS which specifically represents an improvement over the instant inventor's U.S. Patent 5,676,977 entitled Method of curing aids with tetrasilver tetroxide molecular crystal devices. The improvement embodies curing non-terminal AIDS patients with 15 PPM of the tetroxide, as well as curing terminal patients by the administration of slow injections at 40 PPM so as to reduce side effects such as benign hepatomegaly. Only a single injection is required to achieve a cure.




WO0172275
OXIDATIVE FLUORINATOR COMPOUNDS AS ANTIMICROBIALS

2001-10-04
Abstract
The invention relates to a method and composition for destroying or inhibiting proliferation of microbes using oxidative fluorinator compounds. Fluoride salts that do not dissociate completely in aqueous solutions, such a tri- or tetravalent transition metal fluorides, inert gas fluorides, or tri- or tetravalent rare earth fluorides, are effective antimicrobial agents event at levels up to about 20 ppm, when used alone or in conjunction with a strong oxidizer.


US2003095932
OXIDATIVE FLUORINATOR COMPOUNDS AS ANTIMICROBIALS

Abstract
The invention relates to a method and composition for destroying or inhibiting proliferation of microbes using oxidative fluorinator compounds. Fluoride salts that do not dissociate completely in aqueous solutions, such as tri- or tetravalent transition metal fluorides, inert gas fluorides, or tri- or tetravalent rare earth fluorides, are effective antimicrobial agents even at levels up to about 20 ppm, when used alone or in conjunction with a strong oxidizer.


WO0149115
HIGH PERFORMANCE SILVER (I, III) OXIDE AND COBALT (II, III) OXIDE ANTIMICROBIAL TEXTILE ARTICLES


Abstract

Fibrous textile articles possessing enhanced antimicrobial properties are prepared by the deposition or interstitial precipitation of tetrasilver tetroxide (Ag4O4) or cobalt (II, III) oxide (Co3O4) crystals within the interstices of fibers, yarns, or f abrics forming such articles, as well as methods of preparing the same.


US6258385
Tetrasilver tetroxide treatment for skin conditions


Abstract
The invention relates to the use of electron active molecular crystals comprising tetrasilver tetroxide (Ag4O4) for the treatment and cure of dermatological skin conditions (diseases) ranging from dermatitis, acne and psoiasis to herpes and skin ulcers.


US6228491
High performance cobalt (II,III) oxide antimicrobial textile articles

Abstract
Fibrous textile articles possessing enhanced antimicrobial properties are prepared by the deposition or interstitial precipitation of cobalt (II, III) oxide (Co3O4) crystals within the interstices of fibers, yarns and/or fabrics forming such articles.


US6436420
High performance silver (I,III) oxide antimicrobial textile articles

Abstract
Fibrous textile articles possessing enhanced antimicrobial properties are prepared by the deposition or interstitial precipitation of tetrasilver tetroxide (Ag4O4) crystals within the interstices of fibers, yarns and/or fabrics forming such articles.


WO 9745133
USE OF TETRASIL VER TETROXIDE MOLECULAR CRYSTALS IN THE PREPARATION OF A MEDICAMENT FOR TREATMENT OF AIDS


Abstract
The diamagnetic semiconducting molecular crystal tetrasilver tetroxide (Ag4O4) is utilized for destroying the AIDS virus, destroying AIDS synergistic pathogens and immunity suppressing moieties (ISM) in humans. A single intravenous injection of the devices is all that is required for efficacy at levels of about 40 PPM of human blood. The device molecular crystal contains two mono and two trivalent silver ions capable of "firing" electrons capable of electrocuting the AIDS virus, pathogens and ISM. When administered into the bloodstream, the device electrons will be triggered by pathogens, a proliferating virus and ISM, and when fired will simultaneously trigger a redox chelation mechanism resulting in divalent silver moieties which chelate and bind active sites of the entities destroying them. The devices are completely non-toxic.; However, they put stress on the liver causing hepatomegaly, but there is no loss of liver function.


US6485755
Methods of using electron active compounds for managing cancer


Also published as:  WO0149303 // US6669966 //  US6645531 //  WO0149302 // WO0149301
Abstract -

The present invention provides methods for preventing, treating, and/or managing one or more cancerous conditions in a patient, such as a human. A multivalent metal oxide, such as Ag(I,III), Cu(I,III), Pr(III,IV), and Bi(III,V) oxides or a pharmaceutically acceptable derivative thereof, may be administered to the patient in an amount and for a period of time which is therapeutically effective to prevent, treat, and/or manage such condition(s). These cancerous conditions include systemic and external cancers, and may also include conditions and symptoms associated with cancer. The present invention also provides a pharmaceutical composition suitable for treating such cancerous conditions. The compositions of the invention may be adapted for at least one of subcutaneous injection, intramuscular injection, intravenous injection, infusion, transdermal, or topical application.


WO/2001/077030
OZONATED SOLUTIONS OF TETRASILVER TETROXIDE

SPECIFICATION

FIELD OF THE INVENTION

This invention relates to compositions containing multivalent silver compounds that have been exposed to ozone, and more particularly to aqueous solutions containing ozone-activated tetrasilver tetroxide.

BACKGROUND OF THE INVENTION

It is conventionally understood that water, particularly standing bodies of water, can be an effective breeding ground or reservoir for a variety of undesirable microbes. Thus, a wide variety of water treatment systems have been developed to disinfect potable water and/or maintain it at a safe level.

Perhaps the most common disinfection method for drinking or recreational water is chlorination. However, it has been found that chlorine has an objectionable odor, and can cause skin irritations and serious eye irritations to users of recreational bodies of water, such as pools, spas, etc. More importantly, chlorine forms trihalomethanes in the presence of organic materials and these compounds present a potential health threat due to their carcinogenicity and mutagenicity. Because of the long term health threat and objectionable physical properties of chlorine, a number of alternate water treatment systems that operate without chlorine have been developed in recent years.

Another gas used to disinfect water is ozone. According to U. S. Patent No. 4,176,061 to Stopka, the ability of ozone to purify drinking water has been appreciated for some time.

Stopka cites a number of references that teach the advantages of using ozone rather than chlorine to decontaminate water. What Stopka does not disclose is that ozone, like chlorine, has some disadvantages. Perhaps most significant of these disadvantages is that ozone, as a gas, can dissipate from water over time, leaving the water once again susceptible to contamination by various pathogens.

A number of water disinfection systems rely on the oligodynamic effect provided by the addition to water of, e. g., transition metals such as silver.

For example, U. S. Patent No. 4,608,247 to Heinig, Jr. discloses water treatment systems comprising exposing the water to a material which erodes to provide particulate silver in the water. Although the particulate silver is said to be ionic, and the patent does not disclose the valency of the ions formed by erosion, other references, such as Antelman,"Silver (II, III) Disinfectants,"Soap/Cosmetics/Chemical Specialties, pp. 52-59 (March 1994) at page 52, third paragraph, suggest that trace ions formed from silver metal are monovalent.

U. S. Patent No. 5,352,369 to Heinig, Jr. acknowledges that water treatment systems like that disclosed in Heinig's earlier 247 patent are only partially effective in avoiding the use of chlorine as an antimicrobial agent, in that such systems often require the addition of reduced amounts of chlorine to water treated by such systems. The 369 patent purports to avoid this limitation on prior silver-based systems, in providing a method of treating water by generating an active oxidizer in the water which is capable of attacking and killing a wide range of microorganisms therein. The method comprises exposing the water to a silver catalyst in the presence of oxygen to form an active oxidizer in the water and, in some instances to also release silver ions (presumably monovalent silver ions as discussed above) therein via an erosion process similar to that set forth in Heinig's 247 patent. The silver catalyst utilized in the method comprises an alumina matrix having between approximately 0.1% and 5% by weight of elemental silver chemically deposited thereon. The oxygen utilized in the method preferably also comprises ozone.

U. S. Patents Nos. 5,017,295,5,073,382,5,078,902, 5,089,275,5,098,582,5,211,855 and 5,223,149 to Antelman disclose water treatment methods comprising adding multivalent silver compounds to water.

U. S. Patent No. 5,211,855 to Antelman discloses and claims a water treatment method comprising adding tetrasilver tetroxide to water bodies, such as reservoirs. At column 1, Antelman discloses that his previous patents were incorrect in identifying the antimicrobial agent as silver (II) oxide (i. e., AgO), when it is actually tetrasilver tetroxide (i. e., Ag404), wherein each molecule comprises one pair of monovalent silver atoms and one pair of trivalent silver atoms.

U. S. Patent No. 5,223,149 to Antelman discloses the use of trivalent silver compounds as bactericidal and algicidal agents in water treatment. Antelman asserts that these trivalent silver compounds are an improvement over his earlier divalent silver compounds, which are disclosed and claimed in his earlier U. S. patents identified above. Antelman at the paragraph bridging columns 1-2 teaches that oxidizing agents are not required to be used with the trivalent silver compounds.

Despite the foregoing developments, there is still room in the art for improved water treatment systems.

All references cited herein are incorporated herein by reference in their entireties.

SUMMARY OF THE INVENTION

The invention provides an ozonated form of the compound tetrasilver tetroxide, a water disinfection method employing the ozonated tetrasilver tetroxide and compositions comprising the ozonated tetrasilver tetroxide. Examples of compositions of the invention include beverages and disinfectants.

In addition, the invention provides a method for increasing the half-life of ozone in water, said method comprising providing tetrasilver tetroxide in the water along with the ozone.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be described in conjunction with the following drawings in which like reference numerals designate like elements and wherein: Figs. 1,2 and 3 are Multiple Angle Light Scattering (MALS) graphs of log intensity vs. angle.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The inventor has discovered that the ozonated form of the compound tetrasilver tetroxide has an antimicrobial effect greater than that of non-oxidated tetrasilver tetroxide. Prior to the inventor's discovery, it was known that potassium monopersulfate could activate the antimicrobial effect of tetrasilver tetroxide, but the inventor is unaware of any suggestion in the prior art that ozone is also capable of activating this effect. In embodiments of the invention, ozonated tetrasilver tetroxide has an antimicrobial effect at least equal to that of potassium monopersulfate-activated tetrasilver tetroxide. Moreover, activating tetrasilver tetroxide with ozone avoids the drawbacks of using potentially hazardous and/or toxic chemicals as activation agents.

Although there has been some confusion in the art regarding the precise nature of tetrasilver tetroxide, U. S. Patent No. 5,211,855 describes tetrasilver tetroxide as a molecule, Ag404, having one pair of monovalent silver atoms and one pair of trivalent silver atoms. While not necessarily wishing to be bound by this theory in its entirety, the term"tetrasilver tetroxide"as used herein is intended to identify the compound Ag404.

Tetrasilver tetroxide is the most preferred oligodynamic compound of the invention; however, it is contemplated that the other oligodynamic compounds, such as trivalent silver (see, e. g., U. S. Patent No. 5,223,149 to Antelman), multivalent copper (see, e. g., U. S. Patent No. 5,336,416 to Antelman), and other multivalent heavy metal compounds, can be substituted for tetrasilver tetroxide in certain embodiments of the invention.

Tetrasilver tetroxide is ozonated by a process comprising providing non-activated tetrasilver tetroxide and ozone in a fluid medium. The medium can be ozonated before, during and/or after addition of tetrasilver tetroxide thereto. Water is the preferred fluid medium, but other liquid or gaseous media in which ozone can be solubilized can be suitable for use in the invention, e. g., various peroxides, ethers, alcohols or acids, such as peracetic acid.

The initial ratio of ozone to tetrasilver tetroxide provided in the medium is preferably 1: 10 to 10: 1, more preferably at least 1: 2, most preferably at least 1: 1. The amount of ozone is preferably from 0.5 to 7.0 ppm, and more preferably from 4 to 6 ppm. The concentration of non-activated tetrasilver tetroxide is preferably from 0.5 to 7.0 ppm, and more preferably from 2 to 6 ppm. Greater amounts of either ingredient might be wasteful or cause undesirable side effects.

Lesser amounts of either ingredient might not be sufficiently microcidal to achieve a desired antimicrobial effect.

Although it is preferred to initially provide ozone in the above-identified concentrations, such concentrations need not be maintained throughout the life of the resulting composition. In embodiments, ozone is actively removed or passively dissipates from the composition over time, yielding a composition substantially devoid of ozone in which ozone-activated tetrasilver tetroxide continues to function as an antimicrobial agent.

In view of the heretofore unknown ability of ozone to activate tetrasilver tetroxide, it is not necessary to provide other activating agents in the composition, such as potassium monopersulfate.

Compositions of the invention are suitable for a wide variety of purposes. For example, the compositions can be consumed as beverages (e. g., as bottled water, municipal tap water, etc.) or can be applied as cleaning agents to substrates in need of cleaning (i. e., disinfection, etc.). The concentration of tetrasilver tetroxide and/or ozone may be adjusted according to the intended use. For example, the concentration of at least one ingredient might be raised above the preferred concentrations mentioned above to prepare a disinfectant composition unsuitable for human consumption. Of course, such a composition would preferably be packaged in a container labeled as a cleaning product so as to avoid accidental human consumption.

Water disinfection is the most preferred use for ozonated tetrasilver tetroxide of the invention. water disinfection according to the invention can be as simple as providing ozonated tetrasilver tetroxide in water. This can be done in accordance with the methods described above for providing ozonated tetrasilver tetroxide compositions. The water decontaminated can be used for consumption (e. g., via municipal water distribution systems), recreation (e. g., in pools), manufacturing (e. g., as a raw material, solvent, etc.), etc.

The water disinfection method of the invention enjoys several advantages over conventional water treatment methods employing ozone without tetrasilver tetroxide or tetrasilver tetroxide without ozone. In addition to the unexpected activation of tetrasilver tetroxide by ozone described above, tetrasilver tetroxide has an unexpected effect on ozone. The inventor has discovered that the half-life of ozone in water is increased by tetrasilver tetroxide. As the dissipation of ozone from treated water over time and distance has posed a major limitation on the use of ozone in municipal water treatment, the ability of tetrasilver tetroxide to extend the half-life of ozone in water is a very significant advantage of the invention.

The combined effects of ozone and tetrasilver tetroxide also facilitate the use of lesser amounts of at least one of the two ingredients relative to prior art methods using only one of the two ingredients. This can improve the quality of the product of the method (e. g., by minimizing the undesirable odor of ozone), while decreasing production costs.

Embodiments of the invention are useful to kill pathogens, including but not limited to: vegetative bacteria and spores, such as Clostridium or Bacillus species; viruses; protozoans; and protozoan cysts and oocysts, such as Giardia and Cryptosporidium. Non-pathogenic simulants, such as Bacillus subtilis and Bacillus stearothermophilus spores, are used to demonstrate the efficacy of treatment because they are more resistant to disinfection than any known water-borne pathogens.

The invention will be illustrated in more detail with reference to the following Examples, but it should be understood that the present invention is not deemed to be limited thereto.

Comparative Examples Efficacy of tetrasilver tetroxide on E. coli K12 Culture E. coli has long been recognized for its association with fecal contamination of water and the presence of many enteric pathogens. A sample of E. coli K12 strain was grown on TSA (tryptic soy agar) at 37C for 24 hours for use as a test organism. The following measurements were obtained after 24 hours: Acridine Orange Direct Count: 1.05 x 108 cells/mL; Plate Count on TSA: 3.95 x 108 cells/mL; Stock Culture Plate Count: 2.27 x 108 cells/mL; and 1 hour culture in water: 2.71 x 107 cells/mL (untreated control).

The efficacy of tetrasilver tetroxide (SILDATE, N. & Co., Bensalem, PA) in the absence of ozone was evaluated by performing TSA plate counts on E. coli K12 strain samples having the following additives: (A) 1 ppm tetrasilver tetroxide + 10 ppm potassium monopersulfate (PMP); (B) 2 ppm tetrasilver tetroxide + 20 ppm of PMP; (C) 5 ppm tetrasilver tetroxide + 50 ppm of PMP; and (D) 10 ppm tetrasilver tetroxide + 100 ppm of PMP.

PMP is a compound known to activate the antimicrobial effect of tetrasilver tetroxide. The counts were taken at various time intervals. The results are tabulated in Table 1.

Table 1: TSA plate counts (E. coli K12 survival) Plate Count (cells/mL) over Time (in minutes) Additive 5 10 20 30 60 A---5. 1 x 103 0 B-1. 5 x 106 0-- C 2.5 x 106 0--- D0---- It was observed that 10 ppm tetrasilver tetroxide activated with 100 ppm PMP kills 100% of the test pathogen at five minutes or less. Other studies have indicated that 10 ppm or less tetrasilver tetroxide kills 100% of E. coli K12 strain within 30 minutes. Tetrasilver tetroxide (5 ppm) activated with 50 ppm PMP kills 90% in 5 minutes and 100% in 10 minutes. Tetrasilver tetroxide (2 ppm) activated with 20 ppm PMP kills 95% in 10 minutes and 100% in 20 minutes. Tetrasilver tetroxide (1 ppm) activated with 10 ppm PMP kills 4 logs in 30 minutes and 100% in 1 hour.

Efficacy of Ozone The efficacy of ozone in the absence of tetrasilver tetroxide was evaluated by challenging Bacillus subtilis spores with 2 ppm ozone and measuring the survival rate over time by MALS, acridine orange direct counts (AODC) and by counting colony forming units (CFU) at 24 hours. The results are tabulated in Table 2. The resulting MALS graphs are shown in Fig. 1.

Table 2 Treatrnent MALS AODC 24-Hour Count Time intensity % control spores/mL % control cfu/mL % control % AODC 0 2436. 6 100 2. 34X106 100 2. 10x106 100 100 5 1591. 92 65. 33 1. 6X106 68.3 1. 23X106 58.5 76.9 101264. 26 51.89 1. 16X106 49.5 1. 68X105 8.0 14. 5 15 1039. 64 42.67 1. 29X106 55.1 1. 80X103 0.09 0.14 20 851. 5 34.94 4. 87X105 20.8 1. 82X102 0.009 0.04 30 681. 2 27. 96 5. 03X105 21. 5 10 0.00005 0.002 Fig. 1 shows a reduction in the log intensity as a direct function of increasing time of exposure to ozone, thus demonstrating the killing effect of ozone in water. Similar results were obtained using a spore suspension of B. stearothermophilus. Water suspensions of bacterial spores were chosen because they are the most resistant form of microbes known, even more resistant than oocysts of Cryptosporidium and cysts of Giardia, neither of which is inactivated by chlorine.

Ozone is, of course, effective against enteric pathogens.

For example, adding 3.2 ppm 03 to a test culture kills 1.95 x 106 cells/mL of E. coli in 1 minute and kills 1.5 x 106 cells/mL of P. aeruginosa in 1 minute.

Example 1: Ozone-Activated Tetrasilver Tetroxide with Ozone Removed An ozone generator was used to study the effects of ozonated tetrasilver tetroxide (OTT) on E. coli K12 Survival.

The ozone generator for all of the examples was a Model CD-1B generator supplied by AQUA-FLO, Inc., 6244 Frankford Ave., Baltimore, MD 21206. Ozone was generated from oxygen supplied from a tank with oxygen purity of more than 99.9%. The generator was fitted with a voltage regulator and an oxygen flow regulator which enabled the oxygen flow/voltage parameters to be precisely set so that the desired concentration of ozone could be maintained continuously or a given level attained and allowed to revert back to oxygen based on its half-life. When oxygen flowed through the generator, high voltage converted it to ozone, which was bubbled into water. Excess (head) ozone passed through a platinum catalyst that converted it back to oxygen.

By use of toggle switches, the ozone was directed through glass spargers into either of two specially designed 2-liter Erlenmeyer flasks containing 1 liter of water. Either a solution of a test chemical or a suspension of microorganisms or both could be introduced into the flasks via tubes at the top which passed through a rubber stopper (which seals off the system).

Samples could be withdrawn at the bottom of the flask by opening a stopcock.

Ozone concentrations were measured by a chemical oxidation of indigo dye by using an indigo dye colorimeter manufactured by HACH, Inc.

Water containing 6 ppm tetrasilver tetroxide was ozonated with 3 ppm ozone for 15 minutes, followed by 40 minutes of vigorous aeration to remove ozone from the water. The ozone concentration was measured by a HACH POCKET COLORIMETER using ACCUVAC ampules by the indigo dye oxidation method. The initial ozone concentration of 3.0 mg/L (i. e., 3 ppm) was reduced to 0. 09 mg/L after 40 minutes of aeration and was further reduced to undetectable levels before the ozone-activated tetrasilver tetroxide solution was used to challenge E. coli K12.

E. coli overnight cultures were challenged with either 3.0 or 6.0 ppm of ozone-activated (i. e., ozonated) tetrasilver tetroxide and plated onto TSA after each exposure time. The results are tabulated in Table 3.

Table 3: Survival of E. coli K12 following treatment with ozone-activated tetrasilver tetroxide OTT Concentration Exposure Time Count Percent (ppm) (min) (cfu/mL) Survival 0 0 2. 14 x 106 100 3 5 4. 5 x 106 100 3 10 1. 59 x 106 76 3 15 3. 6 x 105 17. 2 3 20 8. 1 x 104 3. 9 3 30 0 0 6 5 1. 77 x 106 85. 2 6 10 8. 8 x 104 4. 2 6 15 1. 7 x 102 0. 08 6 20 0 0 6 30 0 0 This example demonstrates that the antimicrobial effect of tetrasilver tetroxide can be activated by ozone, and persists after separation of the ozone from the tetrasilver tetroxide.

Example 2: Ozone-Activated Tetrasilver Tetroxide and 0.03 ppm Ozone 6 ppm tetrasilver tetroxide was ozonated in water at an ozone concentration of 5.7 ppm for 16 minutes and aerated vigorously for 30 minutes to provide a final ozone level of 0.03 ppm. An E. coli K12 overnight culture (22 hours) was then treated with 0,1,2 or 6 ppm of the activated tetrasilver tetroxide for 0,10,20 or 30 min. The results are tabulated in Table 4.

Table 4: Effect of ozone-activated tetrasilver tetroxide on E. coli K12 with varying times of exposure OTT Concentration Exposure Time Count Percent (ppm) (min) (cfu/mL) Survival 6 10 0 0 6 20 0 0 6 30 0 0 2 10 1. 1 x 104 2. 3 2 20 0 0 2 30 0 0 1 10 1. 7 x 105 36 1 20 1. 02 x 104 2 1 30 55-100 <0.02 0 0 4. 7 x 105 100 0 60 3. x x 105 76 Example 3: Ozone-Activated Tetrasilver Tetroxide and 0.04 ppm Ozone 6 ppm of tetrasilver tetroxide was ozonated at an ozone concentration of 6.6 ppm for 16 min in water and vigorously aerated for 30 minutes to provide a final ozone concentration of 0.04 ppm. An E. coli K12 overnight culture (22 hours) was then treated with 1 or 2 ppm of the activated tetrasilver tetroxide for 0,10,20 or 30 min. The results are tabulated in Table 5.

Table 5: Effect of ozone-activated tetrasilver tetroxide on E. coli K12 with varying times of exposure OTT Concentration Exposure Time Count Percent (ppm) (min) (cfu/mL) Survival 2 10 1. 02 x 106 27 2 20 1. 47 x 104 0. 7 2 30 1. 25 x 102 0.02 1 10 3. 2 x 106 85 1 20 2. 21 x 106 58 1 30 1. 14 x 104 1 0 10 3. 75 x 106 100 0 20 2. 12 x 106 57 0 30 1. 05 x 106 28 0 (No 03) 0 6. 5 x 106- 0 (No 03) 45 6. 4 x 106 Example 4: 2 ppm Tetrasilver Tetroxide and 0.32 ppm Ozone Bacillus subtilus spore suspensions in water were challenged with 2 ppm tetrasilver tetroxide and 0.32 ppm ozone to evaluate the killing efficacy of the combination. The survival rate over time was measured by MALS, AODC and counting colony forming units at 24 hours. The results are tabulated in Table 6. The resulting MALS graphs are shown in Fig. 2.

Table 6: Effect of ozone (0.32 ppm) and tetrasilver tetroxide (2 ppm) on spores of B. subtilis at varying times of treatment Treatment MALS AODC 24-Hour Count (cfu) Time intensity % control spores/mL % control cfu/mL % control* % AODC 0 1754. 33 100 2. 07X106 100 1. 47X106 91 _ 1754. 33 78.3 2. 05X106 88.7 1. 38X106 85 67.3 10 1203. 75 53.0 1. 19X106 57.5 2. 38X105 14 0.20 15 724. 2 32.0 5. 36X10s 25.9 7. 14X102 0.6 0.13 20508. 08 22.7 2. 81X105 13.3 0. 95Xl02 0.005 0.03 25 443. 68 19.8 2. 18X105 10.3 0. 30X102 0.002 0.016 30 485. 86 21.7 1. 90X105 9.0 0. 35X102 0.002 0.018 35 502. 86 22.4 2. 31X105 10.9 0. 20X102 0.001 0.087 * Control cfu was 1.62 x 106 cfu/ml Fig. 2 shows a reduction in the log intensity as function of increasing time of exposure to ozone and tetrasilver tetroxide, thus demonstrating the antimicrobial effect of ozonated tetrasilver tetroxide in water.

Fig. 3 is a MALS graph showing the antimicrobial effects of: (a) a sixty-minute treatment with 2 ppm tetrasilver tetroxide; (b) a twenty-minute treatment with 0.3 ppm ozone; and (c) a twenty-minute treatment with 0.3 ppm ozone and 2 ppm tetrasilver tetroxide. The tetrasilver tetroxide alone (a) was little more effective than the untreated control (d). Twenty minutes of ozone alone (b) produced a significant killing effect, but the combination of ozone and tetrasilver tetroxide (c) was much more potent than either compound alone.

Without wishing to be bound by any theories, it appears that in addition to acting as a killing agent in its own right, ozone is surprisingly able to activate the antimicrobial activity of tetrasilver tetroxide, thus yielding a synergistic killing effect exceeding the individual killing effects of either non-activated tetrasilver tetroxide or ozone.

Example 5: Ozone Stability Testing 6.1 mg/L (6.1 ppm) of ozone was provided in deionized, distilled water over a 15 minute period. The solution was allowed to stand with stirring by a magnetic stirrer over a 24-hour period, taking periodic readings of the ozone concentration. By 2 hours, the ozone concentration was 3 ppm and progressively dropped to 0.01 ppm by 18 hours. This represented a half-life of approximately 2 hours. When 2 ppm tetrasilver tetroxide was added, the rate of decay was unexpectedly lengthened, such that 0.12 ppm of ozone was present after 18 hours (approximately an order of magnitude higher than would have been expected in the absence of tetrasilver tetroxide) and by 24 hours, 0.03 ppm of ozone oxidizing activity was still present.

Further research showed that neither tetrasilver tetroxide alone nor chemically-activated tetrasilver tetroxide (i. e., activated with potassium monopersulfate as described in the Comparative Examples) gave measurable oxidation as measured by the indigo dye method. Thus, the reduced half-life of ozone in the presence of tetrasilver tetroxide does not appear to be merely an additive effect or an experimental flaw arising from the use of the indigo dye method, but rather appears to be a surprising synergistic effect.

While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.



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