STABLE COMPOSITIONS OF UNCOMPLEXED IODINE AND METHODS OF USE

Abstract

The present invention is directed to a composition in solution (often, an aqueous solution) which comprises a combination of molecular iodine (I.sub.2) and an acceptable source of iodate (IO.sub.3), and an acid (inorganic or organic), wherein iodide and iodate are present in the composition at a molar ratio of about 0.1 to about 25, the concentration of uncomplexed molecular iodine is a disinfectant, biocidal and/or antimicrobial (depending upon the end use of the composition) effective amount the concentration of acid in the composition is effective to provide a buffering pH in the composition ranging from about 1.5 to about 6.5. Compositions according to the present invention are storage stable for unexpectedly long periods of time (up to about 5 years), and find use as dis infecting solutions, as germicides and/or biocides (e.g. antiviral, antibacterial, antifungal, antispore etc.) for various surfaces and solutions including living and inanimate surfaces and are particularly useful because of their low cost, their reduced use of iodine, their activity (because of the high concentration of free molecular iodine in solution), their reduced environmental impact, their long term storage stability and their reduced toxicity. They also have particular utility in treating food surfaces to retard spoilage, increase useful shelf-life and minimize the human and economic cost of food waste. The compositions inactivate viruses, bacteria (both gram negative and positive), spores and fungi. Compositions according to the present invention may be used and stored in a variety of materials, given the substantial absence of corrosion (non-corrosive) these compositions display. Dental compositions (e.g. preprocedure rinses and other compositions) and methods related thereto are also disclosed.

Claims

1.-75. (canceled)

76. An aqueous composition adapted for application to keratinous or mucosal tissue of an animal consisting essentially of an antimicrobial effective amount of uncomplexed molecular iodine (I2) formed from a source of iodide (I—) in an effective amount, a source of iodate (IO3-) in an effective amount in molar excess to said iodine and a predetermined amount of an acid, wherein the resulting molar ratio of molecular iodine to iodate in said composition ranges from 0.1 to 25 to 1.5 to 5.0, the molar ratio of iodide (I—) to iodate ranges from 1.25 to 5 to 0.1 to 25 and the concentration of acid in the composition is effective to provide a buffering pH ranging from 1.5 to 6.5, the composition providing a stable concentration of molecular iodine within the range of 0.5 ppm to 500 ppm for a period of at least 2 weeks to 2.5 years, said composition further comprising an effective amount of at least one additional germicidal agent.

77. The composition according to claim 76 wherein said molar ratio of iodide (I—) to iodate in said composition ranges from 1.25 to 5 to 1.5 to 15.0.

78. The composition according to claim 76 wherein said molar ratio of iodide (I—) to iodate in said composition ranges from 1.25 to 5 to 0.5 to 7.5.

79. The composition according to claim 76 wherein the source of iodide is selected from the group consisting of sodium iodide, potassium iodide, lithium iodide, calcium iodide, magnesium iodide, hydroiodic acid and mixtures thereof and the source of iodate is selected from the group consisting of sodium iodate, potassium iodate, lithium iodate, calcium iodate, magnesium iodate, hydroiodic acid and mixtures thereof.

80. The composition according to claim 76 wherein the source of iodide is sodium iodide, potassium iodide and mixtures thereof, and the source of iodate is sodium iodate, potassium iodate and mixtures thereof.

81. The composition according to claim 78 wherein the source of iodide is sodium iodide, potassium iodide and mixtures thereof, and the source of iodate is sodium iodate, potassium iodate and mixtures thereof.

82. The composition according to claim 76 wherein the source of iodide is selected from the group consisting of sodium iodide, potassium iodide and mixtures thereof.

83. The composition according to claim 76 wherein the source of iodate is selected from the group consisting of sodium iodate, potassium iodate and mixtures thereof.

84. The composition according to claim 80 wherein hydroiodic acid is used to complement the source of iodide.

85. The composition according to claim 81 wherein hydroiodic acid is used to complement the source of iodide.

86. The composition according to claim 76 wherein the concentration of uncomplexed molecular iodine ranges from 1 ppm to 300 ppm.

87. The composition according to claim 77 wherein the concentration of uncomplexed molecular iodine ranges from 1 ppm to 300 ppm.

88. The composition according to claim 79 wherein the concentration of uncomplexed molecular iodine ranges from 1 ppm to 300 ppm.

89. The composition according to claim 79 wherein the concentration of uncomplexed molecular iodine ranges from 20 ppm to 250 ppm.

90. The composition according to claim 76 wherein the concentration of uncomplexed molecular iodine ranges from 10 ppm to 300 ppm.

91. The composition according to claim 76 further comprising at least one further component selected from the group consisting of non-aqueous solvents, surfactants, disinfectants, emulsifiers, thickeners/thickening agents, gelling agents suitable for use in the oral cavity, other medicaments, fragrances, preservatives, pigments, dyes, coloring agents and mixtures thereof.

92. The composition according to claim 76 wherein said additional germicidal agent is selected from the group consisting of a peroxide disinfectant, ethanol, isopropanol, propanol, octanoic acid, caprylic acid or a mixture thereof.

93. The composition according to claim 91 wherein said additional germicidal agent is selected from the group consisting of a peroxide disinfectant, ethanol, isopropanol, propanol, octanoic acid, caprylic acid or a mixture thereof.

94. The composition according to claim 76 adapted as a mouthwash composition.

95. The composition according to claim 91 adapted as a mouthwash composition.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0334] The present invention is further described and embellished through the presentation of the following examples. Accordingly, additional understanding of the present invention, including particular aspects and embodiments, as well as their utility and advantages, will be apparent by referring to the detailed description below. The below described examples should not be taken to limit the breadth and application of the present invention in any way.

[0335] The different biocidal properties of complexed versus uncomplexed molecular iodine are well known to one skilled in the art. Gottardi demonstrated that the instability of molecular iodine in an aqueous environment is due to a complex equilibria established after hydration of molecular iodine; more than 6 different iodine species are formed including iodate (Gottardi, W., Iodine and Iodine Compounds, in Disinfection, Sterilization, and Preservation, S.S. Block, Editor. 1991. p. 152-166). Stable aqueous disinfectants based on complexing molecular iodine were developed in the 1800s and theses formulations rely upon high concentrations of iodide that serve to complex molecular iodine, e.g. Lugol's solution. Polyvinylpyrrolidone replaced iodide as the primary complexing agent in iodine-based germicides in the 1950s.

[0336] Complexed molecular iodine per se is not biocidal in contrast to uncomplexed molecular iodine. This stark distinction in biocidal activity led to an outbreak of bacterial infections from a batch of 10% PVP-I that harbored viable bacteria (Favero, M. S., Iodine—champagne in a tin cup. Infect Control, 1982. 3(1): p. 30-32). Formulations based on complexed iodine are commonly referred to as iodophors and all of these compositions contain the vast majority of iodine species in a form that do not contribute biocidal activity. In fact, it has been clearly demonstrated that the biocidal efficacy of an iodine-based germicide is directly proportional to the concentration of uncomplexed molecular iodine. (Gottardi, W., Zentralbl Bakteriol [B], 1980. 170(5-6): p. 422-30).

[0337] The present application teaches compositions and methods that provide uncomplexed formulations of molecular iodine that are stable and capable of being placed into commercial distribution channels. The compositions described in this application can be formulated to provide the optimal concentration for a particular use indication in contrast to iodophor compositions where the concentration of molecular iodine is determined b.sub.y the iodophor equilibrium that provides adequate stability for molecular iodine. The compositions anticipated in this application: (a) provide a constant thiosulfate titratable level of iodine over the shelf-life of the product and (b) exhibit a chemical activity of molecular iodine that is equal to at least about 50% (often at least about 60%) of a pure composition of an equivalent concentration of molecular iodine (i.e. equivalent in terms of total iodine) in a 0.1N HCl solution as measured by the potentiometric method of Gottardi. The compositions described in this application also provide the ability to incorporate other compatible biocides to enhance the use properties of molecular iodine; for example, additional biocides can be selected to complement the spectrum of activity or the rate of biocidal activity. The potential benefits of this formulation approach include: use of less iodine with an associated reduction in environmental burden; lower cost; the ability to provide targeted levels of molecular iodine that are appropriate to different use applications; the ability to incorporate additional biocidal agents; and a reduced potential for negative organoleptic or material incompatibilities.

[0338] The compositions and methods taught here include products that are sold ready to use and those products which are admixed or diluted by the end user prior to use. The dosage forms contemplated in this application include, but are not limited to, solids, pastes, sprays, aerosols, foams, gels, lotions, creams, ointments and liquids. The germicides may be applied directly to surfaces. Other methods of application include, but are not limited to wipes, rinses, drops, gargles, sprays, hose, dips, towel/towelette, cloth, lavage, injection, irrigation, dip, immersion, sponge, mop, vapor or mist. In preferred aspects of the invention, the ready-to-use compositions and methods taught herein provide an activated use-life of at least 1 month and preferably between 6 months and 2 years or even longer (up to about 5 years). During the activated use-life of the compositions anticipated in this application, the thiosulfate titratable iodine does not decrease substantially below the initial concentration and the compositions maintain activity (i.e. they do not become inactive). Maintenance of a minimum concentration for thiosulfate titratable iodine is achieved using three principal formulation strategies: (1) the omission of complexing agents that lower the chemical activity of molecular iodine and (2) incorporation of a molar excess of iodate that provides at least a 10% molar excess of iodate to molecular iodine and as much as a twenty-five-fold molar excess of iodate to molecular iodine and (3) omission of any additive that consumes or causes the reduction of molecular iodine to a measurable degree or that negatively impacts activity.

[0339] It is well known to one skilled in the art that the spectrum of activity and speed of kill for different germicidal agents varies. There is a potential benefit of being able to incorporate more than one germicide into a germicidal composition depending upon which pathogens are of interest. The compositions contemplated in this application are compatible with different germicides provided the additional germicides (1) do not complex molecular iodine (2) do not react with molecular iodine (3) are active at an acid pH and (4) do not reduce the activated use-life of molecular iodine. Representative additional germicides compatible with the formulations contemplated in this application include: hydrogen peroxide; peracetic acid; ethanol; 1-propanol; 2-propanol; and saturated octanoic acid.

[0340] The compositions contemplated in this application are suitable for use over a temperature range of from below 0 degrees to 58 degrees centigrade. The biocidal activity of uncomplexed molecular iodine is more rapid than a comparable concentration of complexed molecular iodine since iodophor compositions lose biocidal activity at low temperatures since the rate at which complexed molecular iodine dissociates from an iodophor limits the availability of the biocidal form of (molecular iodine).

[0341] The pH range for the formulations in this application is between 1.5 and 6.5, often 2.0 and 5.5 with a preferred pH range of about 2.0-3.0 to 5.0. Commonly used weak organic acids are suitable buffering agents for the compositions contemplated in this application including citric acid, lactic acid, acetic acid and formic acid, among others disclosed herein; other commonly used buffering agents such as the sodium phosphates are also compatible with the compositions contemplated in this application.

[0342] It is understood that various inert ingredients or additives will be added to the compositions contemplated in this application including agents that mask odors, increase solubility for actives or inerts, lower liquid-to-liquid or liquid-to-solid interfacial tension, control foaming, increase viscosity, provide detergency or soil release, chelate, act as a dispersant, lower the vapor pressure of molecular iodine by means other than complexation, reduce scaling, prevent flocculation and emulsify. In general, for an additive to be compatible with the formulations contemplated in this application said additive should (a) not lower the chemical activity (as measured potentiometrically) of molecular iodine by more than 5% at the intended use concentrations, (b) not affect the stability of molecular iodine as measured by sodium thiosulfate titration when the test article is stored at 37 degrees centigrade for 6 weeks and (c) not cause the base composition to form a color or present an otherwise unattractive appearance. It is understood that additives that lower the vapor pressure of molecular iodine by means other than complexation can lower the chemical activity of molecular iodine which is acceptable provided the thiosulfate titratable iodine level is not altered and there is no increase in the formation of triiodide. For instance, commonly used surfactants that are compatible with the formulations contemplated in this application include C.sub.10-16 sodium dodecyl benzene sulfonic acid, linear alkylbenzenesulfonates, Dowfax akylphenol ethoxylates, gluconamides, nonylphenoxypolyethyleneoxy ethanol sulfate, Ecosurf EH3, Ecosurf EH6, Ecosurf EH9, nonanoic acid 2,3-dihydroxypropyl ester, dodecanoic acid 2,3-dihydroxypropyl ester and capryllic acid and as otherwise described herein.

Applications of the Present Invention

[0343] The present invention may be used in the following applications or general uses, among others without limitation as disinfectants, sanitizers, antimicrobial agents and/or biocides:

[0344] Low level hard surface disinfectants

Intermediate level hard surface disinfectants
Hospital grade hard surface disinfectant
Sporicides for hard surfaces or medical/dental equipment and instruments
High level disinfectant
Liquid chemical sterilant
Hand sanitizer
Hand wash

Hand rub

[0345] Food contact surface sanitizer
Dairy sanitizer
Prevention of food spoilage
Extension of shelf-life for fruits, vegetables, meats, dairy, seafood and grains
Carcass wash

Poultry dip

[0346] Flower vase life extender
Food spoilage retardant
Food sanitizer
Dish and utensil sanitizer (manual and automatic)
Fruit and vegetable cleaner and sanitizer
Meat sanitizer
Fish sanitizer
Grain sanitizer
Vegetable sanitizer
Fruit sanitizer
Water disinfection
Pool disinfection

Aquaculture

[0347] Animal husbandry

Agriculture

[0348] Oil field biofilm remediation
Seafood processing
Dairy production

Breweries

[0349] Meat packing
Pre-procedural rinse (dental office)

Mouthwash

[0350] Intra-oral irrigation (for use with oral irrigators such as Water Pik)
Sub-gingival irrigation or infusion (dental office professional use)
Biofilm remediation
Hand scrub (surgical pre-operative)

Antiseptic

[0351] Pre-operative patient surgical antiseptic
Ear drops or ear rinse
Eye drops
Contact lens solution
Throat gargle
Throat spray
Oral ingestion for gastrointestinal diseases
Oral ingestion
Wound disinfection
Dialysis equipment disinfection
Vaginal douche
Iodine impregnated medical devices (e.g. catheters and ports)
Iodine impregnated face masks
Iodine impregnated tampons
Iodine impregnated dental floss
Iodine impregnated wound dressings and band-aids
Sinus spray (or rinse)
Nasal spray (or rinse)
Iodine impregnated chewing gum
Iodine impregnated mouth melts
Iodine impregnated lozenges
Iodine toothpaste
Inhalation mist

Inhalers

Vaporizers

[0352] Urinary bladder lavage
Abdominal or thoracic cavity lavage
Skin and scalp treatment
Athlete's foot soak

Eyewash

Teat dip

[0353] Vaginal cream
Ophthalmic ointment
Colonic irrigation
Environmental mold remediation

Humidifiers

[0354] Air conditioning systems
Dental infections
Tissue and organ transplants and grafts
Iodine releasing implants
Disinfecting dental cavity preparations (prior to restoration)
Root canal sealer and irrigant
Egg disinfection
Fish roe disinfection
Condom iodinated lubricant
Oral ingestion for fibrocystic breast disease
Commercial and home dishwashers
Surgical wound closure
Iodine releasing soaps
Government and military use (combating bioterrorism)

Veterinary use

Horticulture

[0355] Tattoo parlors
Food handlers
Herpes infections
Periodontal rinse
Trans-tympatic (ear drum) injections for otitis media
Iodine releasing drains
Burn spray
Iodine releasing ear drains (tubes)
Iodine releasing periodontal (subgingival) bioresorbable polymer
Blood dialysis
Iodine impregnated tissues (Kleenex)
Iodine tablets for systemic viral infections
Iodine rectal wipes
Iodine releasing anti-inflammatory (steroidal) ointments and creams
Iodine releasing underarm spray or roll-on deodorants
Iodine impregnated dental fillings

Shampoos

[0356] Dental dry socket treatment

Pericoronitis

[0357] Female breast nipple infections
Skin graft infections
Dental laboratories
Combined with monoclonal antibodies for viral targeting
Cold and Flu preventive
Dental water lines (biofilm preventive)

Oral Mucositis

EXAMPLES

Example 1

[0358] The following experiment was performed to demonstrate that a composition of molecular iodine prepared using a molar ratio of iodide to iodate of 5 is not stable in an aqueous environment in the absence of sequestering/binding agents like polyvinylpyrrolidone. The following materials were used for this example: sodium iodide (Acros Organics, Cat. 203182500; Lot A03011333); sodium iodate (Acros Organics, Cat. 201765000 Lot A0322553); sodium carbonate (Fisher Scientific, Cat. 5252-3; Lot3AA12080311A) and citric acid (Fisher Scientific, Cat. A940-500; Lot 252559).

[0359] Control solutions of molecular iodine were prepared in glass 1 liter Teflon-lined screw top bottles. All control solutions contained the following: 0.106 grams of sodium carbonate and 7.5 grams of citric acid. All control solutions were prepared by using a molar ratio of iodide to iodate of 5.0. The concentration of iodide/iodate added to each control solution varied depending upon the desired final concentration of molecular iodine. The final concentrations of molecular iodine prepared in the stock solutions were: 25 ppm (24.5 mg NaI/6.5 mg NaIO.sub.3), 50 ppm (49 mg NaI/13.3 mg NaIO.sub.3), 75 ppm (74 mg NaI/19.6 mg NaIO.sub.3), 100 ppm (99 mg NaI/26.2 mg NaIO.sub.3), 150 ppm (148 mg NaI/39.2 mg NaIO.sub.3) and 250 ppm (208 mg NaI/66.3 mg NaIO.sub.3).

[0360] Aliquots of 100 mL were transferred into ten different 150 mL Teflon-lined screw top bottles The bottles were stored at 30 degrees C. in a laboratory in Boynton Beach, Fla. during the summer of 2013. The following analytical measurements were made on the samples: (1) USP thiosulfate titrations and (2) direct potentiometric measurement of molecular iodine.

[0361] All free molecular iodine values cited in this example and the other examples contained in this application, were determined according to the potentiometric method (W. Gottardi, 1983, Fresenius Z. Anal Chem. 314:582-585). The advantage of the potentiometric method is that the concentration of free molecular iodine is determined directly in solution without subsequent manipulations, such as extraction or equilibrium dialysis; this provides a more accurate measurement. A Fisher reference electrode (Fisher Scientific Company, LLC, Pittsburgh, Pa.; Fisher Catalog No. 13-620-51) and platinum electrode (Fisher Scientific Company, LLC, Pittsburgh, Pa.; Fisher Catalog No. 1 3-620-1 15) were used with a Corning Model 345 pH meter (Nova Analytics Corp., Woburn, Mass.) to make the potentiometric measurements. A cylindrical screw top bottle lid with two holes drilled through the screw top lid was used to make potentiometric measurements. The diameter of one hole was sized to fit the iodide ion selective electrode; another hole was sized to fit the platinum electrode. The third hole was drilled to allow reagent to be added to or removed from the bottle via a syringe if required.

[0362] A standard stock solution of 0.1N sodium thiosulfate (Acros Organics, 1 N, Cat. No. No.: 124270010) was diluted immediately prior to use and then used to titrate 1 mL of the test solution after the potentiometric measurement was completed. The initial concentrations of the stock solutions were confirmed with both potentiometric analysis and titration.

[0363] Thiosulfate titration was conducted as follows: (1) calculate how many μL of a 0.01N sodium thiosulfate was required to titrate 50% of the initial concentration; (2) add the entire volume of 0.01N sodium thiosulfate corresponding to 50% of the initial concentration of molecular iodine and observe if the solution reaches an endpoint; (3) if the sample remains clear for several seconds while stirring then the sample has lost at least 50% of the initial molecular iodine concentration; (4) if the sample remains blue then the sample is still considered to be stable.

[0364] Each day for 49 days a 10 mL sample was withdrawn from two samples of each concentration and titrated with thiosulfate as per the standard USP test. The results were averaged and plotted for each day. For each concentration the first measurement that demonstrated a 50% reduction in thiosulfate titratable iodine was identified. For the standard solutions with initial concentrations of molecular iodine of 100, 150 and 250 ppm a 50% loss was observed at day 21 to 24. For the standard solutions with initial concentrations of molecular iodine of 25, 50 and 75 ppm a 50% loss was observed at day 26 to 29. The concentration of molecular iodine was measured potentiometrically for each concentration on the first day that a sample demonstrated a minimum 50% reduction in thiosulfate titratable iodine. In each instance, the potentiometric measurement of free molecular iodine also demonstrated a minimum 50% loss in free molecular iodine.

Example 2

[0365] The activated use-life for commercial antimicrobial agents is an important product feature. Some products are stable once activated for years. A product that exhibits an abbreviated shelf-life is at a substantial commercial disadvantage. The primary active agent in all of the antimicrobial products contemplated in this application is molecular iodine. Prior examples demonstrate that molecular iodine is not stable in an aqueous environment.

[0366] It was noticed that a single composition in a series of formulations exhibited much greater stability than the others even though there was no chemical basis for this observation since all of the compositions under study were intended to contain a stoichiometric ratio of iodate to iodide. It was speculated that a weighing error may have led to this results. A simple DOE experiment was conducted to explore this observation wherein the weights of the different ingredients were varied higher and lower than the initially used concentrations. It was observed that those samples that received a higher concentration of iodate had enhanced stability. This experiment indicated that the cause of the initial anomalous result was a higher concentration of iodate. This suggested that it is possible to provide a stable minimum level of thiosulfate titratable iodine in uncomplexed molecular iodine formulations by incorporating iodate in molar excess to molecular iodine.

[0367] An experiment was then designed to explore the effect of a molar excess of iodate with respect to extending the aqueous stability of molecular iodine. As previously indicated, if the molar ratio of iodide to iodate of 5 to 1 is used there is a quantitative yield of molecular iodine. i.e. no molar excess. For this experiment the molar ratios of iodide to iodate in the test solutions were: 5.0, 3.32, 2.49, 1.99, 1.66, 1.24 and 1.0; these ratios represent the following relative molar excesses of iodate: to iodide 1.5, 2, 2.5, 3, 4 and 5 fold.

[0368] A series of compositions with different iodide to iodate ratios were prepared as described in experiment 1 using glass 1 liter Teflon-lined screw top bottles. All of these test solutions initially provided 300 ppm of molecular iodine. All solutions contained a 7.5 grams of citric acid. The concentrations of sodium iodate and sodium iodide are shown below in Table 1. The solutions were prepared by dissolving the citric acid in 900 mL of distilled water, then under stirring until a clear solution was formed. Sodium iodide was completely dissolved and then the sodium iodate was added under stirring with the lid on the bottle sealed.

TABLE-US-00001 TABLE 1 Iodate to Iodide Molar Excess Molar Excess of Iodate NaI/IO3 Ratio Molarity NaI Molarity Iodate — 5.0 0.00197 0.000394 1.5 3.3 0.00197 0.000591 2 2.5 0.00197 0.000788 2.5 2.0 0.00197 0.000985 3 1.7 0.00197 0.001182 4 1.2 0.00197 0.001576 5 1.0 0.00197 0.00197

[0369] For each formulation, aliquots of 100 mL were transferred into ten different 100 mL Teflon-lined screw top bottles. The bottles were stored in at an average temperature of 30 degrees C. in a laboratory in Boynton Beach, Fla. starting in May of 2013. Every week, a one mL sample was withdrawn from one of the 100 mL bottles and for each of the different iodide/iodate ratios a USP thiosulfate titration was performed. A single transfer of 0.01N sodium thiosulfate which neutralized 240 ppm molecular iodine was added to test solutions. A potentiometric measurement of molecular iodine was made at the first time point that reached an endpoint by the single thiosulfate addition.

[0370] The control solution which had a molar ratio of 5/1 of iodide to iodate demonstrated a minimum 20% or greater loss at day 14. The potentiometric measurement of the control solution indicated a molar ratio of molecular iodine to thiosulfate titratable iodine of 73.4%. In contrast the sample with a molar excess of 1.5 of iodate to iodine did not exhibit loss of thiosulfate titratable iodine over the first 11 weeks. At week 11 the molar ratio of molecular iodine to thiosulfate titratable iodine was 76.1%. All test solutions with a molar excess of iodate of 2 or more beyond the stoichiometric amount did not demonstrate a loss of molecular iodine for 6 months at which point the experiment was terminated. This study demonstrates that a molar excess of iodate to iodide can maintain the concentration of molecular iodine for an extended period of time.

Example 3

[0371] A variation of the experiment described previously was performed. Instead of using iodide, molecular iodine was weighed and added directly to the formulation. After the molecular iodine was dissolved, a molar excess of iodate to molecular iodine was established by adding sodium iodate at a molar ratio of 1.5, 2.0, 2.5, 3.0, 4.0 and 5.0. The control for this experiment did not contain any iodate. The stability of molecular iodine was evaluated over time using thiosulfate titration. The thiosulfate titration was conducted as follows: (1) add a volume of 0.01N sodium thiosulfate which neutralized 75% of the initial concentration of molecular iodine and observe if the solution reaches a transient endpoint; 9(2) if the sample clears for a second or two then the sample has lost at least 25% of the initial molecular iodine concentration; (4) if the sample remains blue then the sample is still considered to be stable.

[0372] The following materials were used for this example: molecular iodine crystals (Puritan Products, Bethlehem, Pa.; ACS Reagent Grade, Lot 069106); sodium iodate (Acros Organics, Cat. 201765000, Lot A0322553); and citric acid (Fisher Scientific, Cat. A940-500; Lot 252559).

[0373] All solutions were prepared by adding 7.5 grams of citric acid to 900 mL of distilled water in a volumetric beaker and the citric acid was dissolved under stirring. Then, in each solution 0.300 grams of molecular iodine was added as crystals and a glass stopper was placed in the mouth of the volumetric to prevent evaporation; water was added to reach 1 liter and then the molecular iodine was stirred until it dissolved. This solution served as the stock solution for the experiment.

[0374] Varying amounts of sodium iodate were added to 100 mL aliquots of the stock solution in Teflon-lined screw top bottles. The control sample did not receive any iodide. The number of milligrams of sodium iodate added to the different experimental samples (100 mL each) was 35.1, 46.7, 58.4, 70.1, 93.6 and 117. The iodate was dissolved after screwing the lids tightly shut and placing the bottles on a rocker. The bottles were stored in a laboratory at 30 degrees C. in Boynton Beach, Fla. during the summer of 2013. The stability of all of the different samples was followed weekly by USP thiosulfate titrations as described above.

[0375] Each week a one mL sample was withdrawn from each of the test solutions and the control solution and titrated with thiosulfate as described above. Any solution that demonstrated a 50% reduction in thiosulfate titratable iodine was considered to have been unstable. For the standard solution a 25% loss was observed at the end of the 3.sup.rd week. The sample with a molar excess of iodate to molecular iodine of 1.5 did not demonstrate a 25% loss until the 12.sup.th week. All other samples had not demonstrated a 25% loss at week 16 which is when the experiment was ended.

Example 4

[0376] A further objective was to combine molecular iodine with other agents to demonstrate compatibility of multiple microbicides contemplated in this application. Enhanced microbicidal activity may be obtained by combining different chemical agents of known germicidal activity in the same formulation. A 300 ppm molecular iodine composition prepared by reacting iodide and iodate at a 5/1 molar ratio in an acidic solution with a molar excess of iodate to molecular iodine of 2; this composition (the base composition) was used to determine if other known biocidal agents would be compatible with this formulation approach.

[0377] To determine if a biocide was compatible, the biocide was added at increasing concentrations to the base solution. If the solution became deeply colored the additive was deemed to be incompatible. If the amount of thiosulfate titratable iodine decreased, the solution was deemed to be incompatible since this indicated that the molecular iodine reacted with the added biocide or that iodine precipitated due to the biocide's interference or interaction with iodine

[0378] The following biocides were tested: phenol/phenate; phenolics; orthophenylphenol; benzyl-4-chlorophenol; ethanol; 1-propanol; iso-propanol; parachlorometaxylenol; hydrogen peroxide; sodium dichloro-s-triazinetrione; amylphenol; phenylphenol; di-isobutyl-phenoxy-ethoxyethyl dimethyl benzyl ammonium chloride; alkyl dimethyl benzyl ammonium chloride; alkyl dimethyl ethylbenzyl ammonium chloride; benzyl-4-chlorophenol; 1-octanaminium-N,N-dimethyl-N-octyl-chloride; octanoic acid; diethyl toluamide; N,N″-bis (4-chlorophenyl)-3,12-diimino-2,4,11,13-tetraazatetradecanediimidamide (2:1); 4-chloro-3,5-xylenol; sodium dichloro-s-acid; and peracetic acid.

[0379] Most of the additional biocides were not compatible with molecular iodine. The addition of most of the phenolics generated increasingly colored solutions and also reduced titratable iodine. The quaternary ammonium compounds generally reduced thiosulfate titratable iodine and some also caused the solution to become colored. Several of the potential biocides did not reduce thiosulfate titratable iodine for the duration of this experiment which was 6 weeks. These included: hydrogen peroxide (3 to 12%); peracetic acid (25 to 50,000 ppm); ethanol (10-95%); 1-propanol (10-95%); 2-propanol (10-95%); and octanoic acid (saturated).

Example 5

[0380] A further objective of this invention was to incorporate surface active agents in the compositions contemplated in this application to enhance the cleaning and wetting properties of said compositions. A series of surface active agents were screened to insure their compatibility with the molecular iodine based composition contemplated in this application. A 985 micromolar concentration of molecular iodine was prepared by dissolving elemental iodine crystals in a sealed glass volumetric flask containing the base composition.

[0381] The base aqueous composition contained 2.0% n-propanol, 3000 ppm peracetic acid, 4.95% hydrogen peroxide, 1.97 millimolar sodium iodate and 0.5% citric acid. Samples of the following surface active agents or classes of surface active agents were obtained from various manufacturers and evaluated for compatibility with molecular iodine. For a surface active agent to be compatible it had to (a) not lower the activity (as measured potentiometrically) of molecular iodine by more than 5% at the lower and upper suggested use concentrations for said surface active agent, (b) not affect the stability of molecular iodine as measured by sodium thiosulfate titration when the test article was stored at 37 degrees centigrade for 6 weeks and (c) not cause the base composition with said surface active agent to form a deep color or otherwise unattractive appearance when the surface active agent was added at increasing concentrations.

[0382] The following classes (or specific compounds) of surface agent agents were tested: C.sub.10-16 sodium dodecyl benzene sulfonic acid, linear alkylbenzenesulfonates, lignin sulfonates, fatty alcohol ethoxylates, C.sub.12-13 ethoxylated propoxylated alcohols, polyethoxylated polyoxypropylenes, alkylphenol ethoxylates, gluconamides, glyceramides (loss of activity), glyceroglycolipids, nonylphenoxypolyethyleneoxy ethanol sulfate, Dowfax, Ecosurf EH3, Ecosurf EH6, Ecosurf EH9, nonanoic acid 2,3-dihydroxypropyl ester, dodecanoic acid 2,3-dihydroxypropyl ester, capryllic acid and polyvinylpyrrolidone.

[0383] Lignin sulfonates, glyceramides (loss of activity), glyceroglycolipids and polyvinylpyrrolidone exhibited negative properties for the formulations anticipated by this application. These surfactants either (a) reduced thiosulfate titratable within 24 hours at room temperature; (b) immediately reduced the chemical activity of molecular iodine by more than 10%; or (c) produced a darkly colored solution.

[0384] C.sub.10-16 sodium dodecyl benzene sulfonic acid, linear alkylbenzenesulfonates and Dowfax were compatible with the compositions contemplated under this application provided the concentration used of these surface active agents was less than 1.5% (w/w) of the final composition. Akylphenol ethoxylates, gluconamides, nonylphenoxypolyethyleneoxy ethanol sulfate, Ecosurf EH3, Ecosurf EH6, Ecosurf EH9, nonanoic acid 2,3-dihydroxypropyl ester, dodecanoic acid 2,3-dihydroxypropyl ester and capryllic acid were compatible at all concentrations tested.

[0385] Microbiological tests (study #130621-204) were initiated on Jul. 2, 2013 and completed on Jul. 16, 2013 at BioScience Laboratories located at 1765 S. 19th Avenue Bozeman, Mont. 59718. The test article was evaluated in a spray application versus glass slide carriers contaminated with Klebsiella pneumoniae (ATCC #4352), Staphylococcus aureus (ATCC #6538), and Trichophyton mentagrophytes (ATCC #9533). The test article contained 200 ppm of molecular iodine, 3% hydrogen peroxide, 0.2% citric acid, 112 mg. monolaurin, 20 ml ethanol, and a molar excess of iodate to molecular iodine of 2.0.

[0386] An initial suspension of each challenge species containing approximately 10.sup.8 CFU/mL was prepared; Fetal Bovine Serum was added to each suspension to produce final challenge suspensions containing a 5% (v/v) soil load. A total of 11 glass slide carriers (microscope slides) were contaminated with a 0.01 mL aliquot of each challenge suspension and dried at 35° c. for approximately 35 minutes. Each dried contaminated carrier was treated with the test solution: the spray bottle containing the test solution was maintained at a 45° angle and sprayed onto each contaminated carrier until the carrier was completely wet.

[0387] Each carrier was maintained in a horizontal position and exposed for either 30 seconds, 1 minute, or 2 minutes (timing of the exposure commenced upon completion of the spray application). Following the selected exposure time, 10 carriers per challenge species were subcultured in separate tubes containing a 40 mL neutralizing broth and incubated. Following incubation, the tubes were examined for the presence of growth, and results were reported as “Growth (+),” or “No Growth (−).”

[0388] One carrier per challenge species per exposure time was evaluated for viable microbial counts, post-treatment: the treated carrier was transferred to a tube containing neutralizing solution, and aliquots were diluted and plated, in duplicate. The plates prepared were incubated in a manner appropriate for each specific test organism; following incubation, the colonies on the plates were enumerated, and the viable CFU/carrier was determined.

[0389] In addition to the testing of microorganisms which are presented in Tables 2 and 3, additional testing of microbes (bacteria or fungus) were also performed. For the primary bacteria, sixty inoculated carriers (stainless penicylinders) are inoculated with the bacteria and dried. The dried cylinders are then sequentially immersed into 10 ml. of the disinfectant and exposed to the disinfectant for a predetermined length of time. The carriers are transferred to a culture media to neutralize the disinfectant. The carriers are incubated and examined for the presence or absence of growth. Other than the primary three bacteria (Tables 2 and 3 hereof), all of the other bacteria are tested on 10 carriers.

[0390] In the fungicidal test (Trichophyton), the disinfectant is inoculated with the fungi in suspension. Exposure is for 5, 10 and 15 minutes. The fungi is removed and neutralized. The cultures are incubated for the presence or absence of growth. No growth must be observed after 10 minutes of exposure to disinfectant.

[0391] In the viral test, the following protocol was used. AOAC use dilution test was modified for virus testing as follows: one surface for each of of two samples, representing two different batches of disinfectant, is tested against a recoverable virus endpoint titer of at least 10 viable viral particles from the test surface for the exposure period specified on the label at less than or equal to ten minutes.

[0392] The results are presented in tables 2-9. In general, the compositions were essentially effective in eliminating/disinfecting bacteria, spores, fungi and viral titer as set forth in the attached tables. The following observations were made for the particular microbes:

[0393] Acinetobacter baumannii. This is a serious hospital based infection of the infirmed Tested by use dilution method (EPA method for multi-use products) must have 0/10 failures to make label claim. The present invention passed in 30 sec. Most prior art compositions take minutes.

[0394] Candida albicans. This is a serious yeast infection. The present invention evidenced 0/10 failures with 30 sec. exposure. Most prior art compositions take minutes and are less effective.

[0395] Klebsiella pneumoniae. This is a highly pathogenic bacterium. It is causative for pneumonia. Again, the present invention evidenced 0/10 failures, with a 30 second kill time. Most prior art products take minutes and are less effective.

[0396] Tricophyton mentagrophytes. This is the causative agent for athletes foot fungus. Test results complied with EPA criteria and showed 0/10 failures with a 30 second kill time. Most products require 5-10 minutes.

[0397] Pseudomonas aeruginosa. This is a problematic hospital infection. EPA requires effective disinfection of this organism to qualify as hospital strength. EPA testing allows up to 6 failures out of 60 in 10 minutes The present compositions passed the EPA test with 1 failure in 45 seconds.

[0398] Salmonella enterica. Same EPA requirements as for Psudeomonas. The present compositions showed only 1 failure out of 60 in 45 seconds, easily surpassing EPA testing criteria of an allowable 10 minutes.

[0399] Staph aureus. Another bacteria required by the EPA to establish a composition as a hospital grade disinfectant. The EPA allows 3 failures in ten minutes; the present composition showed no failures in 30 seconds.

[0400] Hepatitis A virus. This is a non-enveloped virus, very difficult to kill. Most products aren't effective against this virus. The present compositions totally inactivated this virus in 15 seconds and achieved a 4 log kill (compared to 10 minutes allowed by EPA).

[0401] Polio virus. This virus is considered the benchmark for virus killing ability. Generally, if you kill polio, you can kill any virus. The present composition totally inactivated this virus in 90 seconds with a 4 log kill. This kill-time was significantly shorter than the 10 minutes allowed by the EPA.

[0402] Norovirus (murine surrogate). The present compositions showed a complete inactivation of this virus in 30 seconds with a 4 log kill. The allowable EPA kill-time is ten minutes. The results are gleaned from the tables which follow.

TABLE-US-00002 TABLE 2 Qualitative Carrier Evaluation-Results Test Formulation prepared with hard water Challenge Baseline Carrier Number of Suspension Recovery Positive Carriers Challenge Exposur Initial (CFU/untreated per Number                     Klebsiella 30 seconds 3.35 × 10.sup.8 2.78 × 10.sup.3 0/10 pneumoniae 1 minute 1/10 (ATCC #4352) Staphylococcus 30 seconds 6.65 × 10.sup.8 4.42 × 10.sup.6 5/10 aureus 1 minute 1/10 (ATCC 2 minutes 0/10     Trichophyton 30 seconds 1.87 × 10.sup.7 8.60 × 10.sup.2 0/10 mentagrophytes 1 minute 0/10 (ATCC 2 minutes 0/10     1 Prepared with 5% (v/v) added soil load. indicates data missing or illegible when filed

TABLE-US-00003 TABLE 3 Quantitative Carrier Evaluation-Results Baseline Challenge Carrier Post- Suspension Recovery Exposure Initial (CFU/untreated Carrier Challenge Exposure Population carrier Post- Recovery Microorganism.sup.1                 Klebsiella 30 seconds 3.35 × 10.sup.8 2.78 × 10.sup.3 <4.00 × 10.sup.1 pneumoniae 1 minute <4.00 × 10.sup.1 (ATCC #4352) Staphylococcus 30 seconds 6.65 × 10.sup.8 4.42 × 10.sup.6 <4.00 × 10.sup.1 aureus 1 minute <4.00 × 10.sup.1 (ATCC #6538) 2 minutes <4.00 × 10.sup.1 Trichophyton 30 econds 1.87 × 10.sup.7 8.60 × 10.sup.2 <4.00 × 10.sup.1 mentagrophytes 1 minute <4.00 × 10.sup.1 (ATCC #9533) 2 minutes <4.00 × 10.sup.1     indicates data missing or illegible when filed

TABLE-US-00004 TABLE 4 Qualitative Carrier Evaluation-Results Test Formulation H (see below).sup.b Challenge Baseline Carrier Suspension Recovery.sup.c Number of Challenge Initial (Log.sub.10 Positive Microorganism Exposure Population CFU/untreated Carriers per (ATCC #).sup.a Application Time (CFU/mL) carrier Post-drying) Number Tested Acinetobacter baumannii Use- 30 seconds 1.6550 × 10.sup.9 6.3076 0/10 (ATCC #BAA-747) Dilution.sup.d Candida albicans Use- 30 seconds  3.250 × 10.sup.8 3.6766 0/10 (ATCC #10231) Dilution.sup.d .sup.aPrepared with 5% (v/v) added soil load .sup.bTest formulation was prepared by mixing the following ingredients in sterile Water-for-Irrigation, USP, to produce 1 liter: 495 mL of 10% hydrogen peroxide, 7.5 grams citric acid, 0.112 grams fatty acid (dissolved in 20 mL 70% ethyl alcohol), 9 grams surfactant, 39 mL peracetic acid, and one Vial 2. One 2-liter batch of test formulation was prepared. Resulting formulation was applied via standard Use-Dilution Methodology. .sup.cThree carriers evaluated: mean log.sub.10 recovery reported. .sup.dReference AOAC 955.14.

TABLE-US-00005 TABLE 5 Norovirus type 1 Test Formulation #1 Virus: Murine Norovirus type 1 Host Cell Line: RAW Host Cell Line ATCC #TIB-7.1 Volume Plated per Well 1.0 mL Cell Control Dilution Virus Test Neutralization Initial Cytotoxicity (Negative (−Log.sup.10) Control 30 sec 1 min 2 min Control Population Control Control) −2 NT CT CT CT NT NT ++++ −3 ++++ 0000 0000 0000 ++++ ++++ 0000 0000 −4 ++++ 0000 0000 0000 ++++ ++++ 0000 −5 ++++ 0000 0000 0000 ++++ ++++ NT −6 ++++ 0000 0000 0000 ++++ +++0 NT −7 0000 0000 0000 0000 0000 0000 NT TCID.sub.50 6.50 ≤2.50 ≤2.50 ≤2.50 6.50 6.25 2.50 (log.sub.10) Log.sub.10 N/A ≥4.00 ≥4.00 ≥4.00 Reduction Percent >99.99% >99.99% >99.99% Reduction + CPE (cytopathic/cytotoxic effect) present 0 CPE (cytopathic/cytotoxic effect) not detected NT Not Tested N/A Not Applicable CT Cytotoxicity Present Note: Data has not been QA reviewed

TABLE-US-00006 TABLE 6 Poliovirus Test Formulation #1 Virus/Strain: Poliovirus/Chat (ATCC #VR-1562) Host Cell Line: LLC-MK2 Host Cell Line ATCC #CCL-7.1 Volume Plated per Well 1.0 mL Cell Control Dilution Virus Test Neutralization Initial Cytotoxicity (Negative (−Log.sup.10) Control 30 sec 1 min Control Population Control Control) 0000 −2 NT CT CT NT NT ++++ −3 ++++ 000+ 0000 NT NT 0000 −4 ++++ 0000 0000 ++++ ++++ 0000 −5 ++++ 0000 0000 ++++ ++++ NT −6 ++++ 0000 0000 ++++ ++++ NT −7 0000 0000 0000 00++ ++++ NT −8 0000 NT NT 0000 0000 NT TCID.sub.50 6.50 2.75 2.50 7.00 7.50 2.50 (log.sub.10) Log.sub.10 3.75 4.00 Reduction Percent 99.98% 99.99% Reduction + CPE (cytopathic/cytotoxic effect) present 0 CPE (cytopathic/cytotoxic effect) not detected NT Not Tested N/A Not Applicable
Conclusion: Poliovirus was completely inactivated by the test product at 90 seconds; but not completely inactivated at 60 seconds.

TABLE-US-00007 TABLE 7 Hepatitis A Test Formulation #1 Virus/Strain: Hepatitis A Virus (ATCC #VR-1402) Host Cell Line: FRhK-4 Host Cell Line #CCL-1688 Volume Plated per Well 1.0 mL Cell Control Dilution Virus Test Neutralization Initial Cytotoxicity (Negative (−Log.sup.10) Control 15 sec 30 sec Control Population Control Control) 0000 −2 NT CT CT NT NT ++++ −3 NT 0000 0000 NT NT 0000 −4 ++++ 0000 0000 ++++ ++++ 0000 −5 ++++ 0000 0000 ++++ ++++ NT −6 ++++ 0000 0000 ++++ ++++ NT −7 0000 0000 0000 0+00 ++0+ NT −8 0000 NT NT 0000 0000 NT TCID.sub.50 6.50 2.50 2.50 6.75 7.25 2.50 (log.sub.10) Log.sub.10 4.00 4.00 Reduction Percent 99.99% 99.99% Reduction + CPE (cytopathic/cytotoxic effect) present 0 CPE (cytopathic/cytotoxic effect) not detected NT Not Tested N/A Not Applicable
A complete inactivation of the virus was shown in testing at 15 seconds and 30 seconds.

TABLE-US-00008 TABLE 8 Staph. Aureus Qualitative Carrier Evaluation-Results Test Formulation #1 (see below).sup.b Challenge Baseline Carrier Suspension Recovery.sup.c Number of Challenge Initial (Log10 Positive Microorganism Exposure Population CFU .Math. untreated Carriers per (ATCC #).sup.a Application Time (CFU/mL) carrier Post-drying) Number Tested Staphylococcus Use- 30 4.95 × 10.sup.8 6.2851 3/60 aureus Dilution.sup.d seconds (ATCC #6538) 60 0/60 seconds 90 0/60 seconds .sup.aPrepared with 5% (v/v) added soil load. .sup.bTest Formulation was prepared by mixing the following ingredients in sterile Water-for-Irrigation, USP, to produce 1 liter: 495 mL of 10% hydrogen peroxide, 7.5 grams citric acid, 0.112 grams fatty acid (dissolved in 20 mL 70% ethyl alcohol), 9 grams surfactant, 39 mL peracetic acid, and on Vial 2, One 2-liter batch of test formulation was prepared. Resulting formulation was applied via standard Use-Dilution Methodology. .sup.cSix carriers evaluated; mean log.sub.10 recovery reported .sup.dReference AOAC 955.15-Bacterial Use Dilution Method.

TABLE-US-00009 TABLE 9 Pseudomas and Salmonella Baseline Carrier Recovery.sup.c Number of Challenge (Log.sub.10 Positive Challenge Suspension Initial CFU/untreated Carriers Per Microorganism Date of Exposure Population carrier Post- Number (ATCC #).sup.a Application Evaluation Time (CFU/mL) drying) Tested seudomonas Use- Jan. 17, 2014 45 seconds 2.69 × 10.sup.9  5.49 1/60 aeruginosa Dilution Jan. 24, 2014 1 minute 3.85 × 10.sup.9  6.96 4/60 (ATCC #15442) Salmonella Use- Jan. 17, 2014 45 seconds 1.06 × 10.sup.10 6.01 0/60 enterica Dilution Jan. 24, 2014 1 minute 1.17 × 10.sup.10 7.92.sup.d .sup. 3/60.sup.d serovar Choleraesuis (ATCC #10708) Qualitative Carrier Evaluation - Results Test Formulation I (see below).sup.b .sup.aPrepared with 5% (v/v) added soil load .sup.bTest formulation was prepared by mixing the following ingredients to produce a 1 liter batch: 737 mL peracetic acid (Peraclean 0.4%), 165 mL hydrogen peroxide (30%), one vial of each of sodium iodate and sodium iodide, one vial of fatty acid (dissolved in 20 mL ethyl alcohol), 7.5 grams citric acid, 9 grams surfactant, and 69 grams of sterile Water-for-Irrigation, USP. One 3-liter batch of formulation was prepared on each day of testing. .sup.cThree carriers evaluated: mean log.sub.10 recovery reported. .sup.dChallenge species to be retested due to high baseline barrier recoveries.

Example 6—Corrosion

[0403] In this example, mild steel and aluminum were exposed to concentrations of peracetic acid (PAA) ranging from 25-2950 ppm for one week. In all cases, the steel either rusted completely or was severely blackened in one week at 88 deg. F. Aluminum became severely discolored but did not corrode. Acidified peroxide at 3 & 4.95% rusted steel. Brass became pitted with 500 ppm PAA. When steel and aluminum were exposed to a formulation, according to this invention, containing 25-2950 ppm PAA, no corrosion or discoloration was observed on steel after one week. Brass exposed for one week to the same composition resulted in no discoloration. In another composition according to the present invention with acidified peroxide plus I.sub.2 on steel, no rust was evidenced.

[0404] Following the successful result for the present invention, the composition was modified such that three ingredients were systematically omitted from a formula (which contained peracetic acid as a base composition), leaving only one of the components in the composition. The three were EH-6, monolaurin and H.sub.2O.sub.2. These compositions were formulated with 500 ppm PAA in the formula, but iodine and acid were not present.

Variable Compositions and Results:

[0405] H2O2 only—no corrosion steel [0406] EH-6 only (the preferred range of EH-6 in the formula is 0.25-2.0%, optimal range of 0.75-1.0%)—resulted in severe discoloration, but no rust [0407] Monolaurin only—severe discoloration, but no rust. [0408] Monolaurin, H.sub.2O.sub.2 and EH removed-severe rust (these experiments run only on steel).
When mild steel is immersed in a solution of peracetic acid (any concentration ranging from about 25 to 5000 ppm), it begins to rust at room temperature in less than 30 minutes. In contrast the composition of the present invention with the identical concentration of peracetic acid, does not show any signs of corrosion, even after one week which is an unexpected result. Likewise, if you acidify hydrogen peroxide with citric acid, at the same levels used in the present invention, the steel sample will rust in hours or days. Moreover, citric acid itself will result steel without any other components.

Example 7 Food Preservation

[0409] An additional embodiment of this invention is the inhibition of deterioration or spoilage of foodstuffs. This experiment demonstrates that compositions of the invention can extend the useful life of various foods. The following materials were used for this example: sodium iodide (Acros Organics, Cat. 203182500; Lot A03011333); sodium iodate (Acros Organics, Cat. 201765000 Lot A0322553); sodium carbonate (Fisher Scientific, Cat. S252-3; Lot3AA12080311A) and citric acid (Fisher Scientific, Cat. A940-500; Lot 252559).

[0410] A solution of molecular iodine was prepared in a sterile glass 1 liter screw top bottle that contained 0.5 grams of sodium carbonate, 2.5 grams of citric acid, 24.5 mg of sodium iodide and 3.25 mg NaIO.sub.3. The final concentration of molecular iodine was 25 ppm as determined by the direct potentiometric measurement of molecular iodine.

[0411] These experiments were intended to prove the hypothesis that compositions of the invention could extend the useful life of various foods. These are examples only and by no means limit the variety of foods or the extent to which spoilage is inhibited.

[0412] In the testing, the refrigerated shelf life of fruits and vegetables was significantly extended and mold formation was prevented compared to controls. Testing by an independent laboratory of a food-safe composition of the present invention confirmed its effectiveness against foodborne pathogens, destroying Listeria, E-coli, Salmonella and the Norovirus in 90 sec., achieving over 5 log kill (easily passing the EPA requirement for effectiveness as a food sanitizer). See below. This reduction in spoilage also extends to foods such as chicken and other meats and dairy products and grains among others. Independent laboratory testing of the present invention on chicken breasts confirmed significant pathogen reduction as well as an absence of sensory signs of spoilage.

[0413] In addition, testing with the present invention which contained iodine at lower concentrations (e.g. about 10-50 ppm, preferably about 20-30, often about 25 ppm) can be useful for treating viral and mucosal infections (including colds, influenza and yeast infections, among others). Independent laboratory testing of a safe for human use, 25 ppm iodine formula according to this invention against Rhinovirus and Coronavirus (the viruses most frequently responsible for colds and sore throats) demonstrated complete inactivation and 4 log kill in 30 sec (see below). These results clearly support the use of the present invention for treating oral mucosa, throat and nasal passages to prevent or ameliorate colds and sore throats.

Study Results for Development Test RKY01010714.FCAL (A16207) (Feline Calicivirus)

Test Substances: Formula L, Formula I+Ecolab Fruit and Vegetable

Treatment, and Ecolab Fruit and Vegetable Treatment

Test Request Form Number: RKY01010714.FCAL

Project Number: A 16207

Test Substance Preparation: Prepared by Independent Lab

Virus: Feline Calicivirus, Strain F-9 (ATCC VR-782)

[0414] Organic Soil Load: 1% fetal bovine serum (FBS)
Exposure Time: 90 seconds
Exposure Temperature: Room temperature (21.0° C.)
Cell Cultures: CRFK (feline kidney cells)

Virus Control Results

[0415] Feline Calicivirus=7.25 log.sub.10

Cytotoxicity Control Results:

[0416] Formula L=Cytotoxicity present at 3.50 log.sub.10
Formula L+Ecolab Fruit and Vegetable Treatment=Cytotoxicity present at 2.50 log.sub.10
Ecolab Fruit and Vegetable Treatment=No cytotoxicity present ≤1.50 log.sub.10

[0417] The cytotoxicity control is used to determine if the test substance has any cytotoxic effects on the cell cultures used in the study. The percent and log reduction take into account any cytotoxicity observed.

Test Results:

Formula L (Present Invention)

[0418] Complete inactivation of the test virus was demonstrated.
A ≥99.98% reduction in viral titer was demonstrated. The log reduction was ≥3.75 log.sub.10.

Formula L+Ecolab Fruit and Vegetable Treatment

[0419] Complete inactivation of the test virus was demonstrated.
A ≥99.998% reduction in viral titer was demonstrated. The log reduction was ≥4.75 log.sub.in.

Ecolab Fruit and Vegetable Treatment

[0420] Complete inactivation of the test virus was not demonstrated.
Test virus was detected at 2.25 log.sub.10.
A 99.999% reduction in viral titer was demonstrated. The log reduction was 5.00 log.sub.10.
Study Results for Development Test RKY01010713.TK.3 IA16206) (Listeria monocytogenes)

Test Substance: Formulation L, Formulation L+Ecolab Fruit and Vegetable Treatment,

Ecolab Fruit and Vegetable Treatment

Protocol Number: RKY01010713.TK.3

Project Number: A 16206

Test Substance Preparation: Prepared by ATS Labs

[0421] Organism: Listeria monocytogenes (ATCC 19117)
Exposure Time: 90 seconds
Soil: No organic soil load

Actual Exposure Temp: 20.9° C.

[0422] Neutralizer: Letheen Broth with 0.07% Lecithin and 0.5% Tween 80

Carrier Population Control Results: 6.1 O log 10

[0423] All controls were acceptable.

Test Results:

[0424] Formulation L (Present Invention): >99.999% (>5.40 log 10) Reduction at 90 seconds
Formulation L+Ecolab Fruit and Vegetable Treatment: >99.999% (>5.40 log.sub.10) Reduction at 90 seconds.
Ecolab Fruit and Vegetable Treatment: >99.999% (>5.40 log.sub.10) Reduction at 90 seconds
Formulation L, Ecolab Fruit and Vegetable Treatment, and Formulation L+Ecolab Fruit and Vegetable Treatment all demonstrated an identical >99.999% reduction at 90 seconds. All three
test substances had identical 100% kill rates on all test recovery plates.
Study Results for Development Test RKY01010713.TK.2 (A16205I) (Escherichia coli)

Test Substance: Formulation L, Formulation L+Ecolab Fruit and Vegetable Treatment, Ecolab Fruit and Vegetable Treatment

Protocol Number: RKY01010713.TK.2

Project Number: A 16205

Test Substance Preparation: Prepared by ATS Labs

[0425] Organism: Escherichia coli (ATCC 11229)
Exposure Time: 90 seconds
Soil: No organic soil load

Actual Exposure Temp: 20.9° C.

[0426] Neutralizer: Letheen Broth with 0.07% Lecithin and 0.5% Tween 80

Carrier Population Control Results: 6.33 log 10

[0427] All controls were acceptable.

Test Results:

[0428] Formulation L (Present invention): >99.999% (>5.63 log 10) Reduction at 90 seconds Formulation L+Ecolab Fruit and Vegetable Treatment: >99.999% {>5.63 log 10) Reduction at 90 seconds
Ecolab Fruit and Vegetable Treatment: >99.999% (>5.63 log 10) Reduction at 90 seconds
Formulation L, Ecolab Fruit and Vegetable Treatment, and Formulation L+Ecolab Fruit and Vegetable Treatment all demonstrated an identical >99.999% reduction at 90 seconds. All three
test substances had identical 100% kill rates on all test recovery plates.
Study Results for Development Test RKY01010713.TK.1 fA162041 (Salmonella enterica)

Test Substance: Formulation L, Formulation L+Ecolab Fruit and Vegetable Treatment, Ecolab Fruit and Vegetable Treatment

Protocol Number: RKY01010713.TK.1

Project Number: A 16204

Test Substance Preparation: Prepared by ATS Labs

[0429] Organism: Salmonella enterica (ATCC 10708)
Exposure Time: 90 seconds
Soil: No organic soil load

Actual Exposure Temp: 20.9° C.

[0430] Neutralizer: Letheen Broth with 0.07% Lecithin and 0.5% Tween 80

Carrier Population Control Results: 6.21 log 10

[0431] All controls were acceptable.

Test Results:

[0432] Formulation L: >99.999% (>5.51 log 10) Reduction at 90 seconds
Formulation L+Ecolab Fruit and Vegetable Treatment: >99.999% (>5.51 log 10) Reduction at 90 seconds
Ecolab Fruit and Vegetable Treatment: >99.999% (>5.51 log 10) Reduction at 90 seconds

[0433] Formulation L, Ecolab Fruit and Vegetable Treatment, and Formulation L+Ecolab Fruit and Vegetable Treatment all demonstrated an identical >99.999% reduction at 90 seconds. All three test substances had identical 100% kill rates on all test recovery plates.

TABLE-US-00010 TABLE 7A Test Product #1 25 pm Virus/Strain: Rhinovirus type 14/1059 (ATCC Cat #VR-284) Host Cell Line: MRC-5 Host Cell Line ATCC #CCL-171 Dilution Virus Exposure Time Cytotoxicity Neuturalization Cell Control (−Log.sup.10) Control 30 Seconds Control Control (Negative Control) 0000 −2 NT CT ++++ NT −3 ++++ 0000 0000 ++++ −4 ++++ 0000 0000 ++++ −5 ++++ 0000 NT ++++ −6 ++++ 0000 NT +0++ −7 0000 0000 NT 0000 TCID.sub.50 6.50 2.50 2.50 6.25 (log.sub.10) Log.sub.10 N/A 4.00 N/A Reduction Percent 99.99% Reduction + CPE (cytopathic/cytotoxic effect) present 0 CPE (cytopathic/cytotoxic effect) not detected NT Not Tested N/A Not Applicable CT Cytotoxicity [0434] Conclusion: The test product #1 of the present invention completely inactivated Rhinovirus type 14 above the cytotoxicity level following exposure for 30 seconds.

TABLE-US-00011 TABLE 7B Test Product #1 25 pm Virus/Strain: Coronavirus/229E (ATCC Cat #VR-740) Host Cell Line: MRC-5 Host Cell Line ATCC #CCL-171 Dilution Virus Exposure Time Cytotoxicity Neuturalization Cell Control (−Log.sup.10) Control 30 Seconds Control Control (Negative Control) 0000 −2 NT CT ++++ NT −3 ++++ 0000 0000 ++++ −4 ++++ 0000 0000 ++++ −5 ++++ 0000 NT ++++ −6 ++++ 0000 NT +++0 −7 0000 0000 NT 0000 TCID.sub.50 6.75 2.50 2.50 6.25 (log.sub.10) Log.sub.10 N/A 4.25 N/A Reduction Percent 99.99% Reduction + CPE (cytopathic/cytotoxic effect) present 0 CPE (cytopathic/cytotoxic effect) not detected NT Not Tested N/A Not Applicable CT Cytotoxicity [0435] Conclusion: The test product #1 of the present invention completely inactivated Coronavirus strain 229E above the cytotoxicity level following exposure for 30 seconds.

Further Examples—Food Preservation

[0436] Two pints of strawberries were treated with the present invention (a solution) by immersing 1 pint of each of the test articles in 300 mL of the 25 ppm solution for 5 minutes. Each of the treated test articles was allowed to air dry at room temperature and then placed in a refrigerator alongside the untreated control articles. At the end of one month, both treated and untreated samples were evaluated. In each case the untreated strawberries were coated with fungi; in contrast, the treated strawberries did not exhibit any fungi and appeared fresh with favorable organoleptic qualities. Furthermore, the treated strawberries exhibited the same luster and firm texture as when they were purchased. The untreated strawberries were dull in color, less firm and began to shrivel. This experiment is just one example of the large range of foods that can be treated with compositions of this application to prevent spoilage.

[0437] In yet another experiment, mushrooms were immersed in the same composition as the strawberries for five minutes and allowed to air dry before being placed in the refrigerator alongside the untreated control. The untreated mushrooms began to shrivel, exuding liquid. By the end of one month the untreated mushrooms had lost most of their moisture, had shrunken significantly in volume and had significantly darkened. In contrast to this, the treated mushrooms retained their original texture, color and volume.

[0438] In still another experiment, blackberries were treated in the same manner for five minutes as were the strawberries and mushrooms. The treated berries and the untreated control berries were then refrigerated. Initial signs of mold formation were evident on the untreated berries within one week. Mold growth continued under refrigeration until, by the 49.sup.th day the untreated berries had softened and were completely overgrown with mold, while the treated berries exhibited no signs of deterioration or mold growth by day 49 when the experiment was terminated.

Example—Spores

[0439] The present invention was tested against spores to determine the effectiveness. The present invention was tested at an independent laboratory against Bacillus subtilis and Clostridium sporogenes at 50 degrees c. and had 0/10 failures on each pathogen, with a 5 min. exposure time according to an EPA protocol. This qualifies the present invention as sporicidal. The present compositions are also effective against spores at room temperature, but exposure is generally for a longer period of time. To inhibit and/or eliminate spores on surfaces or in solution, compositions often are used at a temperature between about 5 degrees and 58 degrees Celsius.

[0440] The formula used was the same one for all of our standard testing. This is significant, since no other intermediate level hospital grade disinfectant can make such a claim. The present compositions have efficacy against the same EPA required spores at room temperature, having been evaluated and having demonstrated spore kill at 10 min. on porcelain penicylinders according to an EPA protocol.