rexresearch.com

TSTO Index


Marvin ANTELMAN

TetraSilver TetraOxide

( Part II )


http://www.thebody.com/Forums/AIDS/Meds/Archive/Alternative/Q169823.html
Nov 16, 2005

Tetrasilver - Not!

What ever happened to the Aids cure Tetrasilver Tetroxide (US Patent #5,676,977) which you commented about a few years ago. The company Marantech is gone from the net and all discussion has stopped.

Response from Dr. Pierone

Although the company appears to have vanished there was a small study reported last year from Kinshasa on Tetrasilver Tetroxide (Imusil). Here is the link.

Actually not all the news was bad. Of the 3 subjects treated, one had a false positive HIV test with a negative HIV viral load at baseline this subject appears to have done quite well after treatment. The other 2 subjects who actually were infected with HIV did not so well with a consistent increase in viral load following Imusil.


http://www.curezone.com/forums/fm.asp?i=1394

Curing AIDS with tetrasilver tetroxide molecular crystal devices


http://www.tetrasilointment.co.uk/

Welcome to TetrasilOintment.co.uk

Introducing the most exciting topical multi purpose skin ointment for years – TETRASIL with active Tetrasilver Tetroxide TST suspended in a soothing and healing natural jojoba oil, palmarosa and organic wax base.

Nothing else works like TETRASIL. TETRASIL is the only skin ointment in the world that contains Tetrasilver Tetroxide TST, a patented, highly stable multivalent silver oxide formed by a combination of four atoms of silver and four atoms of oxygen in a single molecule called TsT.


http://www.thebody.com/Forums/AIDS/Meds/Archive/Alternative/Q154827.html
Feb 24, 2004

Tetrasilver Tetroxide (US Patent #5,676,977)

Dear Dr. Pierone, MD.

Recently you were asked online about the possibility that Tetrasilver Tetroxide was patented as a "cure" for AIDS/HIV. Your response was that it was a pesticide with "little hope" and you gave an EPA reference.

I would invite you to look at Dr. Marvin S. Antelman's background as a world renowned chemist, who patented the Tetrasilver, and now Tetracopper, TetraCobolt, (there are many other) Tetroxides multivalent crystal redox devices...as well as USPTO Patents pertaining to these devices as to their pharmaceutical efficacy against bacteria, fungus and viruses. Because these novel devices are miniature reduction/oxidation devices that have polyvalent cations in their crystall latices, they posess unique electrical activity, and activity against pathogens, unlike the mechanism of action of other anti-virals aimed at fusion inhibition or viral replication via those target sites (eg. cell surface receptors, GP41/GP120 or transcriptases) or the terrible toxic-poisons known as nucleoside-derivates...AZT might as well be the HIV equivalent to Uracil Mustard.

In your expert medical opinions, before to discount Ag404, Could you please review USPTO Patents (5,676,977)(6,645,531)(5,571,520) (5,336,499) & (6,258,385)...all relevant on Imusil (infusion) and Tetrasil(Tetrasil marketed as a topical ointment)..both Ag404...you're previous reference to the EPA compound was one of Dr. Antelman's earlier compounds used as an agent against bacteria in water sources. These newer compounds are formulated and being tested in vitro/vivo against HIV, Herpses, and other viral agents and bacteria and have shown great efficacy against the virus and associated infections in AIDS patients. You can contact Dr. Marvin S. Antelman yourself as well at the Weizmann Institute in Rehovot, Israel. impy@netvision.net.il.

I think its important to look at the data, the science, and the real possibility that the antivirals on the market including Fuzeon (Trimeris) may have a unique competitor that has fewer toxic effects, and a wide spectral activity against many human pathogens.

I would love to see/hear your response after reading thru those patents... If you would like to rephrase the reply to your last questionaire that it "doesn't look promising" after more thorough research, that would be delightful.

Not only is it "promising", it appears to work.

Best, Mark

Response from Dr. Pierone

I first thought that Tetrasil was just another harmless and ineffective treatment promoted by herb merchants. The patent reports are beyond imagination and show that this is really scary stuff!

Data are presented with intravenous infusions of Tetrasil in a clinic in Honduras for people with the "candidiasis etiological category of AIDS". Well, did they have HIV at all? One would never know from this "research report".

"All were terminal, some, however, were in moderate condition, and others in poor" What is this nonsense about terminal AIDS patients?

"...indicates whether hepatomegaly occurred. This was an unfortunate consequence of the treatment which resulted in enlarged livers in all patients except the second one" Unfortunate, indeed!

As I read this patent report detailing the "cure" or AIDS with Tetrasil my overwhelming sense was that the evidence presented would fail a 5th grade science project. But beyond that, the studies detailed were unethical to the exteme.

Stay away from this stuff like the plague!

See excepts below:

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.


http://www.mefeedia.com/entry/curing-aids-with-tetrasilver-tetroxide-molecular-crystal-dev/12308725/

Video -- http://youtube.com/?v=YfZotd7OG9c

Curing AIDS With Tetrasilver Tetroxide Molecular Crystal

Description:

For several years, Boyd Graves and Leonard Horowitz have spoken about HIV AIDS being manufactured and funded by the US government with the knowledge that it could be used to kill massive populations of humans. Since the mid-1980s, I have maintained that it is a race-specific weapon and even wrote about it being such in 1990-91. It was in 1996 that some scientists found this to be the case, linked to the CCR5 Delta 32 negative genetic mutation making it impossible for millions of whites to contract HIV AIDS. Such is not the case for Africans and Asians, the highest birthrate groups. I also indicated they manufactured a strain of the virus that targeted certain genetic characteristics with white homosexual men. The reason for the targeting of this group was because eugenists discovered that where there is high homosexuality among whites, the birthrates are lower. The case I quoted in 1988-89 was with Denmark and Sweden, having the highest homosexuality rate and the lowest negative birthrate of all Western European countries. This videos main theme is about the patent, proported to be a cure for HIV AIDS. The text of this patent in this video is clear and readable. Barack Obama has stated publicly that it is obsurd to believe the US government created the HIV AIDS. We did not press him about his wrong assumption because had he stated the truth, as most blacks know it to be, it would have politically stopped his run for the presidency. You can't bring about big changes if you're not the president. It is now different and we're going to press this very, very serious issue far more devastating to Blacks around the world. I promise that we shall make this a key agenda in America, far beyond gays wanting to be married. I'm sure millions of blacks dying in Africa, in America and elsewhere is a much more important issue. It is crippling economies all across the African continent with millions of orphaned children and adults too sick to work and build economies.


http://www.aidanceproducts.com/Tetrasilver.html

Test Data

TetraSILVER has been studied for over 10 years, showing that it is, both, very effective and very safe in skin care applications.

In-Vitro Testing:

"In-vitro" means an artificial environment created outside a living organism (e.g., a test tube or culture plate) used in experimental research to study a disease or process. Before tetraSILVER became our products’ unique ingredient it was tested by 14 independent research labs against gram-negative bacteria, gram-positive bacteria, fungi, yeast, and viruses. The labs included Quintiles, Parexel, MDS/Pharma, and other world renowned research organizations. Test after test documented the powerful antimicrobial properties of tetraSILVER.

Toxicity Testing:

In 1966, the US Environmental Protection Agency (EPA) approved tetraSILVER as an effective disinfectant in swimming pools, after extensive tests showed this Silver Oxide was capable of quickly killing a wide spectrum of germs. In the same series of studies, the EPA also determined that TetraSILVER was safe, after passing a series of oral (swallowing), dermal (skin), and ocular (eye) toxicity tests. These tests were very important because some people are in pools every day.

Clinical Testing:

Initial clinical investigations with 328 people (conducted by research dermatologists), in addition to reports from doctors throughout the world, strongly suggest that TetraSILVER, as a key ingredient in skin care products, provides outstanding benefits and supports the body's ability to quickly resolve many common skin problems.


http://www.fda.gov/foi/warning_letters/s6681c.htm

Public Health Service
Food and Drug Administration

One Montvale Avenue Stoneham,Massachusetts 02180
(781) 596-7700
FAX: (781) 596-7896

WARNING LETTER
NWE-09-08

Certified Mail

RETURN RECEIPT REQUESTED

David Goldsmith
Managing Director
Aidance Skincare & Topical Solutions, LLC.
P.O. Box 138
Harmony, Rhode Island 02829

March 3, 2008

Dear Mr. Goldsmith:

This letter concerns your firm’s marketing of the products Tetrasil and Genisil on your websites, www.myskincure.com, www.genisil.com and www.aidanceskincare.com. According to information on your websites, your “Tetrasilver Tetroxide (TST) Ointments,” are intended to prevent, treat, or cure disease conditions. Statements on your websites that document these intended uses include, but are not limited to, the following:

Tetrasil (www.myskincure.com)

    • “Tetrasil's key ingredient, (TST), has a natural attraction to the surface of bacteria, fungi and viruses. These pathogens are responsible for the itching, rashes, redness, burning and other unwanted symptoms of the skin conditions. Upon contact, TST's unique chemical structure releases both a micro electrical charge and oxygen, which immediately begins to kill the pathogens.”

    • “Regardless of the stage of your Genital Herpes, Tetrasil may begin to provide relief in as fast as TWO DAYS.”

    • “Before using Tetrasil, I had tried using Favmir and Valtrex. Each only worsened the length of my outbreaks and their severity. I had tried numerous expensive substances, ointments, and injections, and found myself being a guinea pig for researchers as well. It had been a long, disappointing five-year search only to find nothing worked. Tetrasil, however, was going to be the last thing I tried, and I am glad I did.”

    • “On your lip, Tetrasil's active bio-electro chemistry (TST) surrounds the cold sore and quickly begins to attack the herpes simplex virus (HSV) that causes the tingling, blistering and weeping.”

    • “Tetrasil Spells the End of Herpes Related Breakouts”
    Hello, I am a woman with a history of Herpes Simplex Virus. About every month I would have a severe outbreak on my face caused by the herpes virus. . . I have tried many other treatments for my outbreaks, but only Tetrasil effectively rid me of them.”

    • “People report success and relief from Shingles using Tetrasil during any of the active stages of the shingles virus (Herpes Zoster).”

    • “Doctor's Report #2: “Tetrasil is effective for the treatment of Erysipelas infections of the skin caused by the A Group B-Hemolytic Streptococcus and healed the skin in a conducive manner."

    • “Tetrasil ointment appeared to be extremely efficient against the opportunistic pathogens present in diabetic feet, as well as the healing of the infection."

Genisil (www.genisil.com)

    • “There is NO CURE for Herpes. RIGHT?
    Think again! If you’ve been looking for a herpes product that actually delivers on its promises, your search is over.”

    • “The silver and oxygen in Genisil will begin to kill the inflammation causing herpes virus quickly and safely upon contact, BEFORE YOU EVER SEE AN OUTBREAK.”

    • “EJC Molecules have a selective attraction to exposed nitrogen groups on the membrane proteins of bacteria, viruses and fungi. Upon contact, EJC's go through an oxidation-reduction (redox) reaction, which studies suggest may be instrumental in speeding wound healing.”

    • “When oxygen is introduced into the area it attacks microbes without a coating and diseased cells with deficient wall enzymes. It [oxidises] them, allowing them to be cleared from the body and replaced with healthy new cells. The broad application of oxygen therapy in medicine is based on the simple principle that diseased cells cannot exist in the presence of oxygen and that cells cannot become diseased if they are supplied with sufficient oxygen.”

    • “Genisil is a uniquely formulated all-natural ointment. It contains a patented compound of the most potent natural anti-virals on earth, plus other ingredients that work FAST to resolve herpes issues.”

    • “With four silver atoms, patented EJC Molecules are significantly more potent than other silvers in the speed with which it kills viruses, bacteria and fungi, including Staphylococcus aureus, responsible for bacterial folliculitis and the yeast responsible for fungal folliculitis.”

Duplicate Testimonials regarding Tetrasil and Genisil; found on each website www.myskincure.com & www.genisil.com:

    • “Doctor's Report
    Two patients with severe recurring genital herpes outbreaks used it, applying the ointment three times daily. Over a period of 2-4 days, the Herpes sores regressed and dried out."

    • “the frequency of herpes outbreaks have been reduced by 50%, as well as their healing time. For me, it has been the ONLY product that has helped to reduce the reoccurrence and severity of my outbreaks.”

    • “An RN: The sore disappeared in 24 hours
    I am a 42 year old female who has suffered from Herpes virus for the last 6 years. Trying most of the pharmaceutical remedies, nothing seemed to work. So I started searching for an alternative. Applying it to an area that was inflamed, red, painful and itchy (signs of an outbreak for me) the sore disappeared within 24 hrs and I have not had a sign of it since. It's almost been a year. Sherry, R.N., Oregon”

Claims for TST Ointments found on www.aidanceskincare.com

    • “TsT’s Interaction on Herpes Simplex Virus: As TST makes contact with the HSV virus, it will start electrocuting the gp-G terminals as well as the entire protein envelope. TST will continue its REDOX reaction and form chelate complexes of silver around the entire viral surface. The combination of electrocution and chelation will prevent the virus from performing its essential life functions and cause its death within minutes.”

    • “In addition to EJC’s anti-microbial properties, the combination of electrical energy and singlet oxygen apparently promote the growth of tissue, thus serving as a potential treatment for burn victims and other applications requiring a stimulus of tissue growth.”

These claims are supplemented by the metatags that you use to bring consumers to your websites. The metatags include “cold sores,” “oral herpes,” “shingles,” “treatment for skin disease or disorder,” “herpes,” “herpes simplex,” “genital herpes,” “herpes simple virus,” “HSV,” “vaginal herpes,” “penal herpes,” “herpes infection,” “bacterial infection,” “viral infection,” and “fungal infection.”

Your “Tetrasilver Tetroxide (TST) Ointments,” including “Tetrasil,” and “Genisil,” are drugs, as defined by section 201(g)(1) of the Federal Food, Drug, and Cosmetic Act (the Act), 21 U.S.C. § 321(g)(1), because they are intended for use in the diagnosis, cure, mitigation, treatment, or prevention of disease. Moreover, these products are new drugs, as defined by section 201(p) of the Act, 21 U.S.C. § 321(p), because they are not generally recognized as safe and effective for their labeled uses. Under sections 301(d) and 505(a) of the Act, 21 U.S.C. §§ 331(d) and 355(a), a new drug may not be introduced or delivered for introduction into interstate commerce unless an FDA-approved application is in effect for it. Your sale of Tetrasil and Genisil without approved applications violates these provisions of the Act.

Furthermore, because Tetrasil and Genisil are offered for conditions, such as herpes, which are not amenable to self-diagnosis and treatment by individuals who are not medical practitioners, adequate directions cannot be written so that a layman can use it safely for their intended uses. Thus, your products’ labeling fails to bear adequate directions for their intended uses, causing them to be misbranded under section 502(f)(1) of the Act, 21 U.S.C. § 352(f)(1).

Moreover, your Tetrasilver Tetroxide (TST) Ointments, to the extent that they are labeled and promoted for over the counter (OTC) use, are subject to 21 CFR § 310.548, which states that there is a lack of adequate data to establish general recognition of the safety and effectiveness of silver salts for OTC use in the treatment or prevention of any disease. Any OTC drug products containing these ingredients that are promoted, labeled, or represented for the treatment or prevention of any disease are regarded as new drugs within the meaning of section 201(p) of the Act, 21 U.S.C. § 321(p), and require approved applications under section 505 for marketing. Thus, Tetrasil and Genisil are unapproved new drugs and their delivery into interstate commerce violates section 301(d) of the Act, 21 U.S.C. § 331(d).

The issues and violations cited in this letter are not intended to be an all-inclusive statement of violations that exist in connection with your products. You are responsible for investigating and determining the causes of the violations identified above and for preventing their recurrence or the occurrence of other violations. It is your responsibility to assure that your firm complies with all requirements of federal law and FDA regulations.

You should take prompt action to correct the violations cited in this letter. Failure to promptly correct these violations may result in legal action without further notice, including, without limitation, seizure and injunction. Other federal agencies may take this Warning Letter into account when considering the award of contracts.

Within fifteen working days of receipt of this letter, please notify this office in writing of the specific steps that you have taken to correct violations. Include an explanation of each step being taken to prevent the recurrence of violations, as well as copies of related documentation. If you cannot complete corrective action within fifteen working days, state the reason for the delay and the time within which you will complete the correction. If you no longer manufacture or market Tetrasil and Genisil, your response should so indicate, including the reasons that, and the date on which, you ceased production. Additionally, if another firm manufactures the products identified above, your reply should include the name and address of the manufacturer. If the firm from which you receive the products is not the manufacturer, please include the name of your supplier in addition to the manufacturer.

Please direct your response to the U.S. Food and Drug Administration, 1 Montvale Avenue, Stoneham, MA 02180, Attention: Anthony P Costello, Compliance Officer, 781 596-7716.

A description of the new drug approval process can be found on FDA’s internet website at http://www.fda.gov/cder/regulatory/applications/default.htm. Any questions you may have regarding this process should be directed to the Food and Drug Administration, Division of Drug Information (HFD 240), Center for Drug Evaluation and Research, 5600 Fishers Lane, Rockville, Maryland 20857.

Sincerely,

/S/

Mutahar Shamsi
Acting Director,
New England District

Cc:

Marvin Antelman, PhD.
Scientific Affairs
Aidance Skincare & Topical Solutions, LLC.
P.O. Box 138
Harmony, Rhode Island 02829

Rhode Island Board of Pharmacy
Catherine A. Cordy
Executive Director
3 Capitol Hill, Room 205
Providence, RI 02908-5097


http://www.tanningsupplies.co.nz/shop/tetrasil/tetrasil-ointment

Tetrasil Ointment

Tetrasil® is the product that launched Aidance Skincare and that people worldwide use for a wide range of common skin problems on the head, face, neck, arms, chest, back, and legs. The all-natural ingredients in Tetrasil include natural jojoba oil, beeswax, the tetraSILVER® silver oxide, and an essential oil from the palmarosa plant.

Price: NZD $28.83
SKU:  RB004b*

According to the manufacturer:

What is Tetrasil®?

Tetrasil® is a powerful multi-purpose topical ointment. It has been used for the treatment of a wide range of skin conditions. Tetrasil's active ingredient, Tetrasilver Tetroxide, interacts with the surfaces of bacterial, fungal and viral membranes. These pathogens are responsible for the itching, rashes, redness, burning and other unwanted symptoms of the skin conditions.

Upon contact, TETRASIL's unique chemical structure releases both a micro electrical charge and therapeutic oxygen, which immediately begins to kill the pathogens. The result is not just rapid relief, but elimination of the root cause.

Tetrasil is protected by US and international patents, plus additional patents pending.

Tetrasil® is the product that launched Aidance Skincare and that people worldwide use for a wide range of common skin problems on the head, face, neck, arms, chest, back, and legs. The all-natural ingredients in Tetrasil include natural jojoba oil, beeswax, the tetraSILVER® silver oxide, and an essential oil from the palmarosa plant.

Nothing else works like Tetrasil®.

Upon contact, Tetrasil's unique bio-electro chemistry begins to attack the bacterial, viral and fungal skin infections that cause itching, rashes, redness, burning and other unwanted symptoms. Customers say the result is not just rapid relief, but elimination of the root cause. And, with natural ingredients, Tetrasil soothes the skin as it heals.

Chemistry:

Tetrasilver Tetroxide is a charged silver oxide molecular device. Unlike colloidal silver, Tetrasilver Tetroxide is an Electron-Jumping Compound® with a naturally occurring electrical potential many times more powerful than colloidal silver. Further, unlike colloidal silver, Tetrasilver Tetroxide (also called TST™) does not bind with healthy tissue. Therefore it does not produce either temporary or permanent color change to the skin.

TETRASIL contains TST, suspended in an ointment base (organic wax, Jojoba oil). The active ingredient is a small inorganic, semi-conducting molecular crystal that contains two monovalent and two trivalent silver ions that are electrically balanced by four oxygen ions.

Manufacturing and Handling:

Procedures and quality controls have been developed and established to ensure that the supply and proper handling of TETRASIL is consistently manufactured to strict standards, following US Food & Drug Administration Good Manufacturing Procedure (GMP) guidelines in GMP-registered facilities.

Tetrasil is used for a wide variety of skin problems, including the following:

Viral infections  //  Oral Herpes  //  Cold sores  //  Genital Herpes  //  Shingles

Bacterial Infections  //  Vaginosis  //  Infected cuts and scraps  //  Impetigo  //  Erysipelas  //  Folliculitis  //  Diabetic Foot and Leg  //  Bedsores

Fungal Infections  //  Tinea Versicolor  //  Ringworm  //  Jock Itch  //  Yeast Infections  //  Toe and Fingernail Fungus  //  Athletes Foot  //  Scalp fungus

Other  //  Psoriasis  //  Eczema  //  Diaper Rash  //  Minor Skin burn  //  Poison Ivy/Oak/Sumac

* Do not use Aidance products if you are allergic to silver.

* Aidance products are for non-oral use only.

* Keep out of reach of children. Consult a physician prior to use with children under 2-years of age.

* Do not use vaginally if you are pregnant or attempting to conceive.

* In case of deep puncture wounds, animal bites or serious burns, consult a physician.

* Discontinue use and consult a physician if condition worsens, if symptoms persist for more than seven days, if symptoms clear up and occur again within a few days, or if a rash or other allergic reaction develops.

* Cover treated area if ointment will be exposed to sunlight. Direct sunlight, immediately after application, may cause ointment to yellow or darken. Discolored ointment is not harmful and can be washed off.

* Use only as directed.

Do not use in combination with other topical ointments, creams or topical medications without physician's approval.


http://81.207.88.128/science/chem/exps/Ni+persulfate/index.html

Oxidation of silver to its +3 oxidation state.

Prepare a solution of silver nitrate or silver oxide in dilute nitric acid. Any concentration of 1 to 2 mol/l for the nitric acid is OK.

Add some solid sodium persulfate to the liquid. Adding a fairly concentrated solution of sodium persulfate also works. When this is done, then the liquid becomes brown and remains clear. The brown color is due to silver (III) ions. The brown color is formed quickly, although not instantaneously. It takes a few seconds.

The two pictures below show the brown liquid and a small quantity of this liquid, diluted in some dilute nitric acid. These picture clearly show the brown color of silver (III) ions (*).    (*) see remark below.

Silver (III) ions are not very stable. Even in the fairly strongly acidic liquids, the compound slowly decomposes. A black precipitate is formed and oxygen is released very slowly. This black precipitate is due to combined hydrolysis and reduction of the silver (III) ions. A mixed silver (I) silver (III) oxide is formed, which precipitates from the liquid as a black solid.

Remarkably, when persulfate is added to a neutral solution of silver nitrate, then no brown color is formed. In that case the liquid first remains colorless, but in the course of a few minutes it slowly turns turbid and a dark brown/black precipitate is formed. Apparently, at higher pH, the brown silver (III) ion is not formed at all and the mixed silver (I) silver (III) oxide is formed immediately.

Addition of sodium hydroxide, quick formation of Ag(I)Ag(III)O2

When the brown liquid is added to a solution of sodium hydroxide, then the process of formation of the black silver (I) silver (III) oxide is almost immediate. As soon as the brown liquid is added to a solution of sodium hydroxide, a dark brown very finely divided precipitate is formed. The solid particles stick together quickly and larger black particles are formed. The black solid slowly evolves oxygen and every few minutes it moves to the surface, due to many small bubbles of oxygen, which are trapped inside the precipitate. When these small bubbles of oxygen are lost, then the solid mass sinks to the bottom again. This 'dance' is repeated several times.

The three pictures below show the liquid, immediately after adding it to a slight excess amount of a solution of NaOH. The second picture shows the same liquid a few minutes later, when the particles of the precipitate stick to each other. The final picture shows the precipitate near the surface, due to lots of trapped bubbles of oxygen. All the pictures clearly show the bubbles of oxygen.

Discussion of the results

Here, the reactions with nickel (II) and silver (I) are covered separately.

 Reaction with nickel

Persulfate oxidizes nickel hydroxide to nickel (IV) oxide in water.

    Ni(OH)2 + 2OH– + S2O82- ? NiO2 + 2SO42- + 2H2O

In the wet environment, the compound NiO2 does not exist as such, as suggested by the simplified equation, given above. In fact a non-stoichiometric compound, which can best be described as NiO2.nH2O is formed, with n some indeterminate number.

On acidification with nitric acid or sulphuric acid, the nickel (IV) compound decomposes again:

    2NiO2.nH2O(s) + 4H+(aq)  ? 2Ni2+(aq) + O2(g) + 2H2O + nH2O

When dilute hydrochloric acid is added, then the liquid gives a strong smell of chlorine. In that case, the chloride ion is oxidized to chlorine. The liquid still bubbles in that case. Probably there will be oxidation of chloride to chlorine and still the decomposition reaction, as described above.

Reaction with silver

In acidic media, persulfate is capable of oxidizing silver (I) ions to silver (III) ions. These silver (III) ions are brown.

    Ag+(aq) + S2O82-(aq) ? Ag3+(aq) + 2SO42-(aq)

Silver (III) ions are not very stable. This liquid slowly looses its color and gives off oxygen. A black precipitate is formed of silver (I) silver (III) oxide. The silver (III) ions slowly oxidize the water, in which they are dissolved.

    4Ag3+ + 6H2O ? 2AgIAgIIIO2 + 12H+ + O2

When the liquid is made more basic, then the reaction proceeds much faster, as the experiment demonstrates. The following reaction occurs in that case.

    4Ag3+ + 12OH– ? 2AgIAgIIIO2 + 6H2O + O2

The compound AgAgO2 in turn also decomposes. It slowly looses oxygen and is converted to simple silver (I) oxide.

   2AgIAgIIIO2 ? 2AgI2O + O2

(*) Remark: Whether the brown color is due to plain Ag3+ or due to some mixed valency complex of silver (I) and silver (III) is not clear to me. It might be that the brown color is due to a mixed valency complex of silver (I) and silver (III). Examples of mixed valency complexes are also given on the following pages: copper (I) / copper (II) and titanium (III) / titanium (IV).

General remarks

Both the silver (III) compounds and the NiO2 compound are very strong oxidizers. Both compounds are capable of oxidizing manganese (IV) and manganese (II) to the +7 oxidation state as permanganate and chromium (III) is oxidized to the +6 oxidation state as dichromate or chromate.

Silver nitrate is a catalyst in many reactions with persulfate in acidic media. Persulfate is a strong oxidizer, but it also is somewhat sluggish. The reaction between silver (I) and persulfate in acidic media, however is quite fast. Silver (III) in turn reacts with manganese (II) or chromium (III) quickly to form permanganate or dichromate, itself being converted to silver (I) again. So, in the presence of a small amount of silver nitrate, the persulfate anion can be used as a fast and very strong oxidizer. The catalytic action of silver is based on the fact that an other pathway for the final redox reaction is provided, with Ag3+ as intermediate species.

A similar catalytic action can be observed with nickel hydroxide in basic solutions. The reaction between nickel hydroxide and persulfate is very fast (instantaneously, at least in terms of human observation). Nickel (IV) oxide in turn is capable of oxidizing e.g. manganese (IV) oxide to permanganate. This property can be used as a sensitive method for detecting manganese.

Another important remark is that in both experiments, the presence of chloride ions should be avoided. Especially with the silver experiment, chloride ions are really disturbing. They make the liquid cloudy, due to formation of silver (I) chloride and they interfere, due to oxidation to chlorine.

For the nickel experiment the presence of chloride is not of a direct concern, but if one wants to use NiO2 for detection of manganese by conversion to the deep purple permanganate, then even small amounts of chloride interfere and make the detection fail.

More info on the interesting and remarkable subject of silver (III) chemistry can be found in the following book: Chemistry of the Elements, second edition, written by Greenwood and Earnshaw, pages 1181 and 1188.


http://www.groupsrv.com/science/about69879.html

Dec 09, 2004 11:23 am
Does anyone know an easy method of producing silver oxide Ag4O4? Other names for this compound are polyvalent silver oxide, Divalent silver
oxide, Sildate, tetrasilver tetraoxide, silver II oxide and CAS #155645-89-9
Thanks,
Marshall

Dec 09, 2004 3:01 pm
I think it is the guy who hopes that this magic remedy "tetrasilver tetraoxide" will cure his cancer. He was trying to hire some chemist here on usenet to make it for him. All on can get from this cure is a nice gray shade in the face from Ag poisoning. (The medical term is argiria.)

I think it is everybody's right to do Darwin award experiments on himself as long as nobody else gets involved. Stay away from this ass.

Dec 09, 2004 3:46 pm 
According to the book "Chemistry of the Elements" of Greenwood, the compound silver (II) oxide is not a true silver (II) compound, but a mixed oxidation state silver (I) silver (III) oxide, hence AgO can better be described as Ag(I)Ag(III)O2, or if you wish Ag(I)2 Ag(III)2 O4.

Silver (III) compounds can even be formed in solution by dissolving some silver nitrate in dilute nitric acid and adding a solution of sodium persulfate or potassium persulfate. The solution becomes brown and remains clear. After a while, however, it becomes lighter again and while doing so, it slowly produces oxygen (I think the Ag(3+) oxidizes the water). I'm not sure whether the brown ion is plain aqueous Ag(3+) or a mixed valency compound of Ag(3+) and Ag(+). When the solution is not sufficiently acidic, then a black precipitate is formed of the above mentioned silver (I) silver (III) oxide.

Dec 09, 2004 4:05 pm 
Quote:
I think it is the guy who hopes that this magic remedy "tetrasilver tetraoxide" will cure his cancer.

What guy? I have not seen any references to cancer here. I certainly do not have cancer. It is insoluble in water, so how would one cure cancer with it?

Quote:
He was trying to hire some chemist here on usenet to make it for him.

Why would anyone do that when it can be purchased?

Quote:
All on can get from this cure is a nice gray shade in the face from Ag poisoning. (The medical term is argiria.)

First it is argyria, not argiria. Second it is not silver posioning, it is silver deposits in the skin which is only a cosmetic condition.

Quote:

I think it is everybody's right to do Darwin award experiments on himself as long as nobody else gets involved. Stay away from this ass.

Just who are you talking about?

Marshall

 Farooq,

According to the book "Chemistry of the Elements" of Greenwood, the compound silver (II) oxide is not a true silver (II) compound, but a mixed oxidation state silver (I) silver (III) oxide, hence AgO can better be described as Ag(I)Ag(III)O2, or if you wish Ag(I)2 Ag(III)2 O4.

That is correct. There are two Ag+ and two Ag+++ in Ag4O4. I have found this documented elsewhere as well.

Quote:

Silver (III) compounds can even be formed in solution by dissolving some silver nitrate in dilute nitric acid and adding a solution of sodium persulfate or potassium persulfate. The solution becomes brown and remains clear. After a while, however, it becomes lighter again and while doing so, it slowly produces oxygen (I think the Ag(3+) oxidizes the water). I'm not sure whether the brown ion is plain aqueous Ag(3+) or a mixed valency compound of Ag(3+) and Ag(+). When the solution is not sufficiently acidic, then a black precipitate is formed of the above mentioned silver (I) silver (III) oxide.

Somewhat similar results can be obtained by mixing a dilute solution of silver hydroxide and hydrogen peroxide from experiments I have run.

Marshall
 
Dec 13, 2004 11:21 am 
The cosmetic results are generally not desirable. Slight argyria gives a rather ashen or pale look to the skin, and severe argyria turns the skin a dark gray blue, sometimes with a slight violet cast. And it can also be deposited unevenly, making one appear very splotchy. Areas exposed to light will tun much more than areas not exposed to light, since this is nothing more than the normal development process anywhere light can reach, including the eyes.

The process is rather interesting though. Silver salts spontaneously reduce to metallic silver upon exposure to light. This is called a virtual image in photography. Then if there is sufficient silver compounds in the blood, and a developer in the blood, more silver will plate out on the particles, cause them to grow rather dramatically. If they grow too large too fast, then they get stuck, and become essentially a permanent tattoo. The other thing required for development to take place is that the blood must be basic, which it is in a healthy person.

Why would someone have a developer in the blood? Well, turns out lots of chemicals are rather effective developers, including caffeine, and tannin. So drinking a cup of coffee after taking silver compounds such as silver nitrate, then going out into the sun can be all that is required to cause this condition. The medical literature says that the condition is not reversible, but experience has shown that to be incorrect. Apparently some substances will do a fair job of chelating silver and reducing this problem over time. IP6 ( Inositol Hexaphosphate ) extracted from rice brand appears to be one such substance.

Marshall


http://msgboard.snopes.com/message/ultimatebb.php?/ubb/get_topic/f/76/t/001200/p/1.html

12 May, 2004 06:00 PM

I'm sure we'd covered this before, but I can't find anything about it through searches.

The patent
The obligitory excitable spam mail
The company website

13 May, 2004 09:16 AM

As soon as I spotten Dusenberg's name in the links, I knew we were dealing with fringe science. These hucksters tack "TETRASIL is currently sold without FDA approval as a no-claim product" in an effort to avoid the FDA approval process, and then make treatment claims for the product: "treat a variety of bacterial, viral, fungal and other skin conditions". Sorry, but any firm that doesn't want to prove that their product works and won't hurt me in the process doesn't get my business. Posts: 88 | From: Metro DC | Registered: Jan 2003  |  IP: Logged | Report this post to a moderator
SoToasty
 
13 May, 2004 11:00 AM
Wow, This stuff is a miracle. It kills bacteria, fungus and viri. Amazing. When/where can I get some stock in the company. This cure-all should not be suppressed by the FDA. They should approve it NOW.
 
14 May, 2004 04:00 AM
Here's an idea: instead of clinical trials, let's have Xtreme Pharmaceuticals - a reality show where contestants with a range of conditions, from life threatening to minor, take an unidentified substance to see if it helps or hurts them.

Watch the bodybuilder's liver implode! Share the drama of the little old lady with arthritis as she realizes she'll never see her grandkids graduate. Jeer the male model with mild acne that winds up disfiguring himself.

There can be twists - when a drug is found that actually works, the contestant has to select their drug from several different sources - which is from an inspected US factory? - which is from an uninspected factory in China? - which was concocted in a garage in Arizona?
Call my agent! Call your attorney!

14 May, 2004 09:06 AM
Chemical Names:(Common Name, Synonym, Trade Names)
CAS REG. NO. 1301-96-8
CAS REG. NO. 155645-89-9
DIVALENT SILVER OXIDE (SILVER II OXIDE)
SILDATE
SILVER OXIDE (AG4O4)
SILVER(II) OXIDE
TETRASILVER TETRAOXIDE (AG4O4)

It is legal to use it in the US--it has been registered since 1996 by the US EPA as a pesticide to disinfect swimming pools and hot tubs. You can buy it as SilSpa and SilDate. That means the registrant had to prove it controls bacteria in pools & spas, as the label claims. The label also talks about not drinking the stuff.

Controlling bacteria in water is a far cry from curing AIDS in people. I found a lot of good studies where silver oxide is being evaluated as a surface coating on medical devices, such as urinary catheters, and may be a good disinfectant for that.

December, 2004 09:35 PM
I've used Tetrasil and it works. It's the best anti-fungal cream I've ever used. Athletes foot gone on day 2, and it never came back.

People who say the people making it are evil for making false claim and providing false hope know nothing.

There have been clinical trials regarding AIDS patients and Tetrasil does work as claimed.


http://earth1.epa.gov/pesticides/foia/reviews/129097/129097-001.pdf
 

EFFICACY EVALUATION AND TECHNICAL MANAGEMENT SECTION
EFFICACY REVIEW
ANTIMICROBIAL PROGRAM BRANCH

IN 06/30/95 OUT 10/05/95

EPA Reg. No. or File Symbol 3432-AU
LAN Code
EPA Petition or EUP No. OPP Identification Number 165250
Date Division Received 06-16-95
Type Product Swimming Pool Water Disinfectant
MRID No (s) 431365-01. 434656-01. & 434583-02
Product Manager PM 32 (Douglas)
Product Name SILDATE
Company Name N. Jonas & Co.
Submission Purpose Application for New Registration with
Field Test Data and proposed label
Type Formulation Liquid

Active Ingredient (s); —%—

Silver Oxide II (AgO) 2. 05
Contains 2.73 Ounce Silver Oxide II. Equivalent to 2.38 ounce
Silver as Elemental per Gallon.

Activator;

Energize (Potassium Persulfate) (1 pound per 10,000 gallons)

Recommendations

Efficacy Supported By The Data:

The submitted Field Test data are acceptable and meet the efficacy data requirements/criteria established by the Environmental Protection Agency for Swimming Pool Water Disinfectants as outlined in the Pesticide Assessment Guidelines, Subdivision G - Product Performance 91-8(c) at a concentration of 1 ppm Sildate in the presence of 10 ppm Energize.

Labeling;

Under the heading "Directions for Use", in the first paragraph, revise the statement " — add Energize at the rate of 1 lb per 10,000 swimming pool water" to read "...add Energize at the rate of 1 lb per 10,000 gallons of swimming pool water." Under the heading "Directions for Use", in the third paragraph, revise the statement "If the pool volume is knot known " to read "If the pool volume is not known..." Include Ingredient Statement on Energize label and specify percent Potassium persulfate.

Reviewed by Srinivas Gowda Date 10/05/95


Basic Chemical Information for Silver oxide (Ag4O4)

 
Chemical Name --  Silver oxide (Ag4O4
Microbiocide, Fungicide, Herbicide
 
Synonyms
Chemical versus Common Names

129097 (US EPA PC Code) , 1301-96-8 (CAS Number) , 1301968 , 1301968 (CAS Number) , 155645-89-9 (CAS Number) , 155645899 , 155645899 (CAS Number) , Divalent silver oxide (silver II oxide) , Sildate , Silver oxide (Ag4O4) , Silver oxide (Ag4O4) (9CI) (CA INDEX NAME) , Silver(II) oxide , SilveroxideAg4O4 , Tetrasilver tetraoxide (Ag4O4)


http://www.scorecard.org/chemical-profiles/product.tcl?reg_nr=00343200064&prod_name=SILDATE

 CHEMICAL PROFILES|Product Profile
Product:  SILDATE
EPA Registration Number:  00343200064

This pesticide is used as a:

* DISINFECTANT

This pesticide is registered for unrestricted use.

This pesticide's toxicity code is 3, which corresponds to a toxicity category of Caution.

Active Ingredients in this Product  Percentage by Mass
SILVER OXIDE (AG4O4)  2%


http://www.njonas.com/products.htm

N. Jonas & Co., Inc.
4525 Adams Cir.
Bensalem, PA 19020-0425, USA
Phone: 2156398071 or 8005236533
Fax: (800) HOT-ASAP


PATENTS

http://v3.espacenet.com

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

2007-12-20
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

2003-06-18
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

2006-05-18
Abstract
Pharmaceutical compositions including tetrasilver tetroxide (Ag<SUB>4</SUB>O<SUB>4</SUB>), 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

2004-12-30
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

2004-02-05
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.

2003-06-26


WO03043537
IMPROVEMENTS IN CURING AIDS WITH TETRASILVER TETROXIDE MOLECULAR CRYSTAL DEVICES

2003-05-30
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

2003-05-22
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

2001-07-12
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

2001-07-10
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

2001-05-08
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

2002-08-20
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.


IL127287

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

2001-11-25
Corresponding document:  WO 9745133  (A1)
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

2002-11-26
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 37°C 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.


http://www.faqs.org/patents/app/20080233161

DEPOSITION PRODUCTS, COMPOSITE MATERIALS AND PROCESSES FOR THE PRODUCTION THEREOF

Stojan Djokic

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.