PL223968B1 - Aqueous solutions of the borate complexes of citrate-silver(I), copper(II) and zinc(II) and a method for preparing aqueous solutions of the borate complexes of citrate-silver(I), copper(II) and zinc(II) - Google Patents

Description

The subject of the invention is aqueous solutions of citrate-borate complexes of silver (I), copper (II) and zinc (II) and a method of obtaining aqueous solutions of citrate-borate complexes of silver (I), copper (II) and zinc (II).

Aqueous solutions of silver (I), copper (II) and zinc (II) complex compounds with boron citrate have a strong biocidal effect against harmful microorganisms (bacteria, fungi and viruses). Aqueous solutions of silver (I), copper (II) and zinc (II) complexes in a properly selected concentration are non-toxic to humans, animals, fish and plants and will be used in all areas of the economy.

Silver citrate complexes are already known from the patent literature, there are also known chemical and electrochemical methods of preparation and their use in disinfecting various surfaces and aqueous solutions.

US Patent No. 6,838,095 and US applications No. 2002 025 344, 2002 150 628 and 2005 118 281 disclose water-soluble, non-toxic complexes of silver with organic hydroxy acids. As organic hydroxy acids, glycolic acid, lactic acid, malic acid, tartaric acid, citric acid or mandelic acid are mentioned. Citric acid and its salts are particularly preferred, as shown in the Examples of Chemical Preparation of Silver Citrate Complexes.

In US patent applications 2005 202 066, 2005 245 605, 2006 100 273 and 2007 185 350 compositions are described containing anhydrous silver dihydrogen citrate and citric acid. The citric acid is at least five times molar excess to the silver dihydrogen citrate. The above biocidal compositions can be diluted with water in any ratio depending on the needs, e.g. when disinfecting water in various systems or food.

In the patent applications Nos. 2006 051 430 and 2006 1154 40 there are described cosmetics for the care of the human body, where the main biocidal and preservative agent is silver dihydrogen nitrate plus conventional ingredients in the presented cosmetic compositions.

U.S. Patent Nos. 6,197,816, 6,583,173, and 7,601,755 disclose aqueous disinfectants including silver citrate which was obtained by electrolytic (anodic) dissolution of metallic silver in aqueous citric acid and optionally 20% ethyl alcohol.

Another US Patent No. 7,261,905 discloses an aqueous disinfectant consisting of organic silver complexes also obtained by electrolytic dissolution of a silver anode in aqueous solutions of citric acid and other hydroxy acids and amino acids. The above process of electrolytic dissolution of silver can also take place in the presence of 20% ethyl alcohol.

US Patent Application No. 2005 274 624 discloses an aqueous disinfectant in the form of an extended shelf life concentrate comprising an aqueous silver citrate solution obtained by anodic dissolving silver metal in a citric acid solution. The silver anode is digested in a 5-10% aqueous solution of citric acid, the electrolytically obtained silver ions are at a concentration of 0.05-0.1% by volume.

Another US patent application No. 2007 269 530 discloses an aqueous disinfectant, non-toxic - especially environmentally friendly, the 0.5-0.1% solution of which is effective in destroying bacteria, viruses, fungi and other pathogenic organisms. Also in this patent application, the silver anode is electrolytically digested in aqueous 5-10% citric acid solutions, possibly other organic hydroxy acids, amino acids, optionally in the presence of 20% ethyl alcohol. This patent application discloses a very wide use of electrolytically obtained silver biochelates.

In SG Patent No. 163,461, the authors describe a formulation consisting of a mixture of silver dihydrogen citrate with any chelating agent or hydrogen peroxide, resulting in the formation of a silver ion complex as a disinfectant.

On the other hand, US patent application No. 2010 040 699 describes a method of producing silver citrate as an antibacterial preparation.

The authors of AU patent application No. 2009 251 057 presented a composition containing silver dihydrogen citrate in combination with another compound from the group of ammonium compounds, oxidants or halides (Cl, Br, I) as a natural antibiotic with excellent antibacterial activity.

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In US Patent Application No. 2009,099,257, electrolytically generated silver citrate has been used as an ingredient in cosmetic products such as gel, soap, emulsion, lotion to treat acne.

In turn, in the patent application WO 2010 145 922 silver citrate together with complexes of citric acid with silicic acids has been used in dermatological preparations and cosmetic waters.

The authors of the patent application WO 2011 044 916 used nano-silver in combination with water peroxide, nano-gold, quaternary ammonium salts, iodine source, citrates, surface compounds and terpene oils as a very powerful disinfectant, effective in the elimination of microorganisms such as Staphylococcus aureus , Cholerasuis salmonella, Pseudomonas aeruginosa and the H1N1 virus.

The authors of US Patent Application No. 2011,078,928 used silver dihydrogen citrate as an antibacterial agent to impregnate shoe insoles.

Despite the assurances of the authors of the above-cited applications and patents that silver citrate complexes have an extended shelf life, in practice it turned out that the concentrates and aqueous solutions of these complexes turn yellow after some time (about several dozen days), and then a spongy, gray-black precipitate is released. silver. Therefore, the manufacturer of silver citrate complexes recommends storing these solutions in a dark, cool place and in dark glass packaging.

It is known to those skilled in the art that the citric acid used in the above-cited applications and patents, like other organic acids containing a hydroxyl group (-OH), easily reduces ionic silver to metallic (colloidal), which is commonly used in the preparation of colloidal solutions. silver.

In US patent application No. 2009 0149 592 a method of reducing metal ions, with particular emphasis on silver ions, in a trisodium citrate dihydrate environment is presented.

The authors of US patent application no. 2009 236 570 disclosed methods for the preparation of time-stable silver colloids using a lithium citrate solution.

US Patent No. 7,786,178 describes a method of obtaining silver colloids by reducing silver ions in an aqueous solution of sodium citrate and iron (II) sulfate.

It is impossible to list all the applications of silver compounds, both patented and resulting from the user's creativity. Medical research confirms the effectiveness of ionic silver against over 650 diseases. These include: AIDS, allergies, leukemia, diarrhea, diphtheria, Lyme disease, Candida, cholera, lymphoma, sinus diseases, diabetes, melanoma, dysentery, boils, yeast infection, plague, eczema, rheumatism, flu, A H1N1 influenza, avian flu (H5N1), tuberculosis, mycosis, oral infections, parasitic, viral and fungal infections, trachoma, hay fever, syphilis, whooping cough, lichen, dandruff, psoriasis, seborrhea, malaria, bone sarcoma, indigestion, frostbite, burns, herpes, prostate , sepsis, shingles, colds, skin cancer, breast cancer, gonorrhea, salmonella, anal itching, thyroid gland, acne, rosacea, scarlet fever, leprosy, lupus, rheumatism, insect bites, SARS, multiple sclerosis, gastric ulcer, arthritis, inflammation bladder, colitis, conjunctivitis, keratitis, cystitis, meningitis, pleurisy pneumonia, staphylococcal and streptococcal infections.

Copper (II) citrate complexes are quite rare in the literature.

US Patent Application No. 2010,099,758 describes a composition containing copper and silver ions electrolytically generated in a citric acid solution, which further comprises potassium carbonate, used to accelerate wound healing without excessive scarring.

The authors of the NZ Patent No. 552,451 disclosed the chemical composition of the composition used in the production of a drug for the treatment of cancer, psoriasis, myelodysplasia diseases, hyperproliferative disorders of the body cells, viral, bacterial, protozoal, parasitic, infectious, fungal diseases and immunodeficiency (HIV) diseases. Among the many ingredients of this preparation rich in copper compounds, copper citrate is mentioned.

In turn, US Patent Application No. 2009 148 540 describes a method of producing an aqueous solution of copper citrate which has excellent bactericidal properties against Gram positive bacteria such as Staphylococcus aureus (MRSA), Streptococcus, Clostridium difficile and Listeria monocytogenes.

The authors of RU patent No. 2,352,147 have developed a dietary supplement that improves overall health, in which one of the ingredients is copper citrate.

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There are more and more reports in medical publications about the positive results of research on copper chelates as anticancer drugs. It has long been known that copper is one of the body's essential transition metals, involved in biological processes such as embryo development, tissue formation, and the control of temperature and nerve cell function. The anti-cancer activity of copper complexes was noted several decades ago, but modern research methods and the development of science allow for more detailed analyzes. They showed that many new copper complexes showed enormous anti-cancer potential. Additionally, copper complexes have been shown to have relatively fewer side effects than cis-platinum based drugs.

On the other hand, zinc citrate is quite commonly used, mainly as one of the ingredients of pharmaceutical and biocidal preparations for various applications.

The authors of GB Patent No. 2,479,712 have disclosed the composition of an aqueous composition for suppressing and even deodorizing, which may be in the form of an aerosol, in which one of the desired ingredients is zinc citrate.

A method for the production of pure zinc citrate for pharmaceutical applications is disclosed in CN Patent No. 101,935,274.

The authors of the patent application WO 2011 027 363 supported the evidence of the positive effect of zinc citrate on the prevention of the formation of kidney stones, and the authors of the description of US 2010 210 728 presented an improved formulation of a composition used in the treatment of gastric ulcer, containing, among others, zinc citrate.

In turn, CN patent No. 101 513 442 and KR No. 100 827 350 presents the composition of capsules used in the treatment of diabetes, which are characterized by the content of zinc citrate in the amount of approx. 0.4%.

Zinc citrate is a fairly popular ingredient in dietary supplements. This has been proved by the authors in their patents: RU No. 2 419 362, which presents the composition of a nutritional supplement for athletes and people leading an active lifestyle, and RU No. 2 352 147 and US description No. 2008 268 095, which describes the composition of the supplement positively influencing general health, and in CN patent No. 101 554 231 and CN No. 101 181 631, a prepared supplement containing calcium carbonate, collagen and zinc citrate as the main ingredients prevents! and alleviated the effects of osteoporosis.

CN patent No. 101 803 633 and JP No. 2008 189 677 describe the composition of an eye wash pharmaceutical composition to relieve fatigue and irritation, with a high anti-inflammatory and antipruritic effect, containing, inter alia, zinc citrate.

The healing properties of zinc have been known since ancient times: zinc ointment was used by the ancient Egyptians more than five thousand years ago. Zinc is the second most abundant micronutrient in the human body. It is found in all cells of the body, including the cells of the eyes, liver, thymus, brain, muscles and reproductive organs. It is essential for the synthesis of DNA and RNA, proteins, insulin and semen. It is involved in the metabolism of carbohydrates, fats, proteins and alcohol. Zinc is an active center in about 200 enzymes, including it forms part of the enzyme that regulates the secretion of insulin by the pancreas, and also regulates the work of the thymus. It is found in virtually all body fluids and is necessary for the synthesis of genetic material. Zinc supports immune immunity, accelerates wound healing, supports the treatment of heart and brain ischemia, and is beneficial in peripheral vascular diseases.

The latest research by scientists from the Princeton Psychiatric Institute has proven the effect of zinc content on the work of the brain. An irrefutable relationship has been shown between the concentration of zinc and the occurrence of dyslexia, some form of schizophrenia and epilepsy. Taking zinc improves short-term memory and sharpens the senses of taste and smell.

Zinc has practically always been a trace element associated with beauty: it affects the appearance of skin, hair and nails. It is irreplaceable in the treatment of AE (Acrodermatitis Enteropathica), a disease resistant to pharmacological treatment, manifested by hair loss, wounds on the skin and diarrhea. Zinc therapy is also recommended for people suffering from acne and psoriasis.

Zinc deficiency may indicate diseases such as hypothyroidism, cirrhosis, Crohn's disease, colitis, and sickle cell anemia. Low levels of zinc have been found in people suffering from bulimia, alcoholism, arteriosclerosis and other heart ailments. The latest scientific reports clearly show the relationship between the lower amount of zinc in the body and the occurrence of oncological diseases, including Hodgkin's disease, bronchial cancer, various types of leukemia, prostatic hyperplasia and others.

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In the patent and specialist literature, combinations of silver (I) and copper (II) are known as strong biocides with various applications.

A quite popular combination is the mixing of silver ions and copper ions with powdered bentonite, the use of which in agriculture, construction, medicine, pharmacy, the textile and paper industries is described in patents RU No. 2 407 289, RU No. 2 416 435, RU No. 2 408 755 and in WO patent specification 2011 035 988.

US Patent Nos. 2011 129 545 and WO 2009 151 146 disclose the composition of a disinfectant and antimicrobial multifunctional use agent consisting of copper and silver compounds.

The authors of US Patent No. 2011,123,597 incorporated silver and copper compounds into gas, starch and cellulose dressings, thus ensuring excellent antibacterial properties, and the patent number UA No. 32,814 describes a method of producing animal wound dressings containing silver and copper nanoparticles.

In RU patent No. 2,414,912, silver ions (in the amount of 0.01-1.5 g / l) and copper (in the amount of 0.04-4.0 g / l) obtained electrolytically were mixed with lactic acid (1-50 g / l), 33% hydrogen peroxide (0.1-3 g / l) and distilled water, and then this mixture was used to disinfect swimming pool water and drinking water, similarly to patent No. WO 98 22 397, where the same for the purpose, a mixture of water peroxide, cyanuric acid, phosphoric acid and soluble silver and copper salts was used.

The authors of the CN patent No. 101 863 581 described a device for the treatment of industrial wastewater in which a silver and copper ion generator was installed after a series of filters. This apparatus removes solids, kills algae, bacteria and viruses in water, and GB Patent No. 487,675 describes a method of purifying drinking and industrial water by filtration through dolomite saturated with copper and / or silver solutions.

US Patent No. 2,010,266,990 describes an antimicrobial preparation for dental use containing colloidal silver in an amount of 0.01-2 percent by weight and colloidal copper in an amount of 0.05-10 percent by weight, which act as antibiotics in monotherapy or in combination with a lacquer. dental. It has also been proven that this preparation prevents tooth decay.

An invention relating to a mosquito bite prevention fabric and a method of its production in which the yarn is added with 1-5 percent by weight of silver and copper compounds is described in WO 2010 044 628.

KR patent specification No. 2000 0 025 171 describes methods of preventing and treating skin diseases with preparations containing silver and copper compounds, which additionally reduce skin unpleasant odors.

The authors of the UA patent No. 25,023 describe the bactericidal properties of paints and varnishes containing copper nanoparticles, silver nanoparticles or a mixture of copper and silver nanoparticles.

It turns out that an equally popular combination in biocides is the combination of silver (I), copper (II) and zinc (II) ions in one solution.

RU Patent No. 2,414,902 describes a bactericidal composition for veterinary use, e.g. for the treatment of infectious diseases of animal hooves, consisting of stabilized copper and zinc compounds and silver nanoparticles.

In turn, US Patent No. 7,942,958 discloses the composition of a general purpose biocidal preparation, the main components of which are zinc, copper, silver, bismuth and zirconium compounds.

The authors of WO 2011 035 988 disclosed their invention relating to an antiseptic ointment for external use containing as a base petroleum jelly or a combination of petroleum jelly with lanolin with an admixture of silver, copper and zinc ions.

JP Patent No. 2010 280 577 and MX No. 2010 008 389 describe a biocidal composition consisting of silver, copper and zinc compounds, used as bactericides, fungicides and antibacterials.

The authors of US 2010 119 669 disclose a method of growing sweet potatoes while preventing or at least inhibiting the deterioration of the edible parts by contacting the plant with an aqueous composition containing silver, copper and zinc ions in an amount from 1 to 1000 ppm, among others.

The invention described in CN patent No. 101 757 246 relates to traditional Chinese drugs modified with the addition of zinc, copper and nanosilver compounds, which significantly improve the therapeutic effect of the preparations.

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JP Patent No. 2010 270 079 describes a disinfectant and refreshing agent for human and animal applications, which, apart from antibacterial activity, also has antiviral and anti-allergic properties, and contains titanium oxide enriched with compounds of silver, copper, zinc, tin, cobalt, nickel and manganese in an amount of 1 to 20% by weight. A similar use of copper, zinc and silver compounds is described in JP Patent No. 3,032,672.

U.S. Patent No. 4,859,240 describes an invention relating to a dental amalgam containing by weight: 30-70% silver, 20-35% tin, 10-30% copper, 0-5% indium and 0-1% zinc, and the patent no. JP 11 049 625 shows a solution for stomatitis resulting from the insertion of an artificial tooth by making the tooth material with the addition of silver, copper or zinc.

UA Patent No. 32,813 describes a method of treating infected wounds in animals using a preparation containing silver, copper and zinc nanoparticles.

In turn, US Patent No. 6,495,052 describes a system and method for decontaminating water by removing the slurry, disinfecting bacteria and viruses, improving color, taste and smell to obtain drinking water. Bacterial static water is obtained by electrochemical introduction of silver and / or copper and zinc ions.

In contrast, in US Patent No. 2010 172,948, the authors disclosed a recipe for an anti-bacterial coating of the surface of the walls of a building, which includes silver, copper, zinc, boom, platinum, gold or palladium ions.

In turn, the combination of silver, copper, zinc, boom or antimony compounds was used in GB patent No. 2 470 088 for dental filling of dental canals.

The authors of US Patent No. 2009 130,161 disclose the composition of an antimicrobial composition used either as a finished solution or as an additive to a variety of construction materials, coatings, fabrics, membranes, and other materials. This composition includes parabens, oxides, salicylates, acetates, citrates, benzoates and phosphates of silver, copper, zinc and possibly platinum.

EA Patent No. 012,467 discloses the composition of a fruit dessert for infant nutrition. To homogenized fruits, including cherries, plums, apples, cranberries, cowberry, apricots, black currants and vegetables such as carrots, pumpkin, tomatoes, calcium phosphate and citrate, potassium iodate, iron citrate, vitamins C, E, A, D, vitamins from the group B and silver ions and zinc sulfate.

Boron compounds and their healing properties are also widely described in the patent literature.

U.S. Patent No. 7,767,657 describes organic, bicyclic boron compounds with substituents as detailed in the claims. These compounds proved to be very effective in the treatment of fungal infections, in particular in the topical treatment of onychomycosis and skin fungus. The structure of the new bom compound promotes rapid penetration into the nail plate.

The authors of US Patent No. 7,816,344 have described new bom compounds used in the treatment of bacterial infections as well as pharmaceutical compositions containing these patented compounds.

The inventors of U.S. Patent No. 5,312,816 have described methods of preventing and treating cystic fibrosis, psoriasis, rheumatoid arthritis, gout, osteoporosis, and other diseases by administering to patients organic boron compounds, including chemical groups such as adducts of bom to Lewis acids, amide derivatives, esters , amino acids and more.

From US Patent No. 2009 214,500, it is possible to learn about methods of preventing and treating osteochondrosis in humans and animals by administering organic boron compounds to them.

The authors of U.S. Patent No. 2009 291,917 presented new organic boron compounds and methods of treating chronic inflammations of the body with them, which lead to diseases such as arthritis, kidney failure, lupus, asthma, psoriasis, pancreatitis, allergy, muscle fibrosis, anemia, postoperative complications and many more.

The invention disclosed in US Patent No. 2010,034,901 relates to novel bom compounds and their use in the treatment of osteochondrosis (OC).

A supplement with boron and vitamin C has been proven to prevent and treat leg weakness and lameness.

The subject of the invention described in the patent description WO 2008 058 490 are new, complex, organic compounds of boric acid, salicylic acid or its derivatives and silver, the method of their preparation and their use as components of a preparation for the destruction of mold, fungi and insects from the Ligniperdous family.

With regard to citrate-borate complexes of silver (I) and / or copper (II), no solutions have been found.

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Reviewing the existing patent and specialist literature in the field of the above combinations, only US Patent No. 4,766,102 was found describing a method for the preparation of new borate-aluminum silver compositions of the general formula x (Ag2O) y (Al2O3) with (B ₂ O3), acting as a catalyst for oxidation by ammonolysis reaction.

In turn, US Patent No. 4,168,166 describes a novel composition for use in photography containing borate and silver compounds known in the art.

In addition, GB Patent No. 1,377,520 teaches the improvement of the phototropic properties of alkaline borate glass by adding silver halides to its composition.

It is noteworthy that the compounds cited in the above three examples are water-insoluble compounds.

For some time now, in Poland and around the world, there has been a cult of antibiotics, which are too often recommended and used to treat people, animals and birds. Bacteria and other microbes become resistant to them fairly quickly, mutating and creating new resistant species.

The World Health Organization (WHO) is developing a global strategy to reduce the use of antibiotics in agriculture, veterinary medicine and human medicine. Instead, it proposes the use of preparations to which pathogenic organisms do not become resistant.

Such preparations include silver, preferably as finely divided as possible and stable during transport, storage and dosing.

In the United States, the Food and Drug Administration (FDA) registers and recommends the use of all forms of silver, except for nitrates, which are reduced by bacteria to poisonous nitrites, which, when combined with amines and amino acids, form carcinogenic compounds - nitro and nitrosamines.

The aim of the invention is to develop an aqueous solution of ionic silver, ionic copper and ionic zinc (silver ion radius 0.126 nm, copper ion radius 0.73 nm, zinc ion radius 0.74 nm) bound in a time-stable and non-toxic to humans, animals and birds and plants, an organic complex.

As a result of long-term trials and tests, it was possible to find an organic chelate of silver, copper and zinc that practically meets all the goals.

This biochelate is boron citrate in the form of a white powder with the molecular formula C ₁₈ H ₁₅ BO ₂₁ and molecular weight 578.1 g / mol, which is a well-known chemical and is currently produced by many companies. Boron citrate 5%, a powder that contains 5% boron calculated as an element, is non-toxic to humans, only over 500 mg / person / day can cause digestive problems such as nausea, diarrhea, decreased appetite and others.

Boron citrate in doses of 3 to 9 mg / day offers many benefits, for example by activating vitamin D and calcitonin, it prevents or alleviates the effects of osteoporosis and arthritis, especially in postmenopausal women. It is also very important for men because it helps to maintain an adequate level of estradiol in the blood.

According to experts' assessments, over 80% of Polish soils do not contain boron compounds or contain them in minimal amounts. Therefore plants, birds and mammals, especially humans, are deficient in boron.

Boron and its compounds have been used for thousands of years as food preservatives to prevent rotting and decay. In addition, they were used in various dressings for wounds, ulcers, sunburn, thermal burns, and various skin diseases.

Boron compounds are used to this day because they have a number of positive advantages, such as antiseptic, antifungal, anti-inflammatory, antiperspirant, astringent and other properties.

The most popular boron compounds are: boric acid (H ₃ BO ₃ ) and borax (Na ₂ B ₄ O ₇ x 10 H ₂ O). These compounds are used to prepare boron preparations that are used in medicine, cosmetics and dietary supplements.

The latest comprehensive research proves that boron in the human body is responsible for the metabolism of calcium and magnesium, the proper production of estrogens, progesterone, testosterone and vitamin D ₃ . The lack of an adequate amount of boron in the body leads to many dangerous diseases: degeneration of joints and articular cartilage, and other bone diseases such as osteoporosis, arthritis and osteochondrosis. Experts also suggest that the deficiency of this micronutrient weakens the functioning of the brain and cognitive abilities, slows down thought processes, causes problems with short-term memory and causes impaired coordination of hands and eyes.

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The boron supplement recently available on the American market under the name Fructo Borate is a complex of boron with large-molecule compounds from the oligosaccharide group. Supplementation with this product reduces joint swelling and pain, re-mineralizes bones by increasing the absorption of calcium and magnesium, reduces PSA markers of the prostate, affects the regulation of the immune system and the production of vitamin D ₃ .

In medical scientific publications, boron is more and more often mentioned as a chemotherapeutic agent used in the prevention and treatment of various forms of cancer. Recent scientific reports prove the relationship between the lack of boron in the body and the occurrence of diseases such as prostate cancer, cervical cancer, and lung cancer.

In addition, it is said in the scientific and medical community that boron ensures proper embryonic development, helps maintain the proper functioning of cell membranes, prevents blood clots, reduces the risk of fungal infections, improves libido, and regulates metabolism.

An extremely important finding is the fact that thanks to boron compounds, a number of parasites and fungi can be defeated, including Candida albicans and lupus erythematosus.

It turns out that this bioelement, which until recently was somewhat "censored", is safe to use. The author of the book "Encyclopedia of Natural Medicine", and also the doctor Michael T. Murray, states that the safe daily dose of boron ranges from 3 to 9 mg.

In practice, ingesting inorganic boron (in the form of boric acid or its salt) has many undesirable side effects. The most common ones are: nausea, diarrhea, dermatitis, growth inhibition, somnolence, water retention, congestive jaundice, headaches, testicular degeneration, thromboembolism, bile duct cancer and others. On the other hand, those skilled in the art, and at the same time the authors of the patents No. US 5,312,816, US 5,962,049, US 5,985,842, US 6,080,425 and US 6,669,419, argue that organic boron compounds do not have these negative properties.

New aqueous solutions of silver (I), copper (II) and zinc (II) complexes are very stable over time, resistant to reduction and sunlight, because boron citrate has a blocked effect of the hydroxyl group - by combining this group with boric acid.

In addition, boron, which has antiseptic, antifungal, anti-inflammatory, antiperspirant and astringent properties, increases the biocidal activity of the new aqueous silver, copper and zinc borate citrate complexes.

The aqueous solutions of the citrate-borate complexes of silver (I), copper (II) and zinc (II) according to the invention are represented by the general formula:

^[Ag] m * ^[C 18 ^H 15 - (p + r) ^BO 21 ^] n ^P + ^{r Me}

[Cu] s ² · [C1eH15- (p + r) BO21] n ^P + r Me ^[Zn] w ² * ^[C 18 ^H 15- (p + r) ^BO 21 ^] n ^P + ^{r Me} or

[Ag] m + · [Cu] s ² + · [Zn] w ² + · [C18H15- (p + r) BO21] n ^p- + r Me + where min independently assume a value from 1 to 5, s and s irrespective of themselves take a value from 1 to 10, p is an integer from 1 to 9, r is an integer from 0 to 9, and Me is a monovalent cation from Group I of the periodic table.

The method of obtaining aqueous solutions of citrate-borate complexes of silver (I), copper (II) and zinc (II) is characterized by the fact that to water is added continuously or in portions, in any order, boron citrate or its salts, compounds introducing cations of the group I of the periodic table and water-soluble and / or water-insoluble silver (I) compounds, copper (II) compounds and zinc (II) compounds in a molar ratio from 1: 1: 1: 1 to 5: 1: 10: 10 in various combinations , at a temperature of 0 to 100 ° C.

It is preferable to use the following organic and inorganic silver (I) compounds to obtain aqueous solutions of citrate-borate complexes of silver (I), copper (II) and zinc (II): nitrate, bromide, chloride, diammonium chloride, iodide, oxide, phosphate, iodate, sulfate, cyanide, permanganate, dichromate, thiocyanate, tetrafluoroborate, lactate, citrate, oxalate, acetate, benzoate, butyrate, cinnamate, picrate, salicylate, tartrate, valerate and others.

It is preferable to use the following organic and inorganic compounds of copper (II) to obtain aqueous solutions of citrate-borate complexes of silver (I), copper (II) and zinc (II): chloride, nitrate, sulfate, acetate, phosphate , gluconate, glycinate, edetate, oxalate, oleate, melate, citrate, sorbate, benzoate and others.

It is preferable to use the following organic and inorganic zinc (II) compounds to obtain aqueous solutions of citrate-borate complexes of silver (I), copper (II) and zinc (II): chloride, selenate, sulfate, oxide, hydroxide, gluconate, borate , phosphate, lactate, acetate, salicylate, aspartate and more.

Supplementary substances may be added to the compound thus obtained, depending on the application of the compound obtained, without affecting its stability and properties, it is advantageous to add calcium, magnesium and calcium complexing compounds to the new aqueous solutions of citrate-borate complexes of silver, copper and zinc according to the invention. other metals in the water. As complexing compounds for the above metals, there are used amino carboxylic acids and / or salts, amino succinic, amino hydroxysuccinic, amino phosphonate, phosphonate, phosphonocarboxylic, polycarboxylic, alkylhydroxycarboxylic, hydroxycarboxylic and others.

It is also advantageous to add natural and / or artificial macromolecular compounds such as gelatin, peptone, various animal or vegetable protein hydrolysates, starch to the aqueous citrate-borate solutions of silver (I), copper (II) and zinc (II) complexes according to the invention. , cellulose and its derivatives, chitosan and its derivatives, polyvinyl alcohol, polyvinylpyrrolidone, copolymers and homopolymers of acrylic and / or methacrylic acid or other unsaturated compounds, polyaspartates, polyglutamates and others.

It is preferable to add anionic, non-ionic, cationic and / or amphoteric surfactants to the aqueous citrate borate solutions of the silver (I), copper (II) and zinc (II) complexes according to the invention in order to lower the surface tension of the aqueous solutions, disperse poorly soluble in water silver compounds, ingredients of ointments, creams, shampoos and other insoluble or poorly soluble ingredients in water and most importantly in order to better penetrate deep into human tissues.

It is preferable to add known biocidal compounds, preferably sulfonamides, antibiotics, dithiocarbamates, isothiazolones, phenol and its derivatives, thiopyridines and their derivatives to the aqueous citrate borate solutions of silver (I), copper (II) and zinc (II) complexes according to the invention. , benzoic acid and its derivatives.

It is preferable to add inorganic sulfur compounds such as thiosulphates, sulphites and metabisulphates to the aqueous citrate borate solutions of silver (I), copper (II) and zinc (II) complexes according to the invention.

It is preferred that flavors are added to the aqueous citrate borate solutions of silver (I), copper (II) and zinc (II) complexes according to the invention in an amount of up to 1% by weight.

It is preferable to add organic dyes up to 0.1% by weight to the aqueous citrate borate solutions of the silver (I), copper (II) and zinc (II) complexes according to the invention.

The aqueous solutions of citrate-borate complexes of silver (I), copper (II) and zinc (II) obtained according to the invention are non-toxic and additionally contain organic boron necessary for living organisms. They will be used in virtually every area of the economy, but also as valuable silver supplements and booms for humans, animals, birds and plants.

The aqueous solutions of citrate-borate complexes of silver (I), copper (II) and zinc (II) obtained according to the invention will find application in the treatment of various skin diseases, wounds, bedsores and in the treatment of various infections of bacterial, fungal and viral origin.

The aqueous solutions of citrate-borate complexes of silver (I), copper (II) and zinc (II) obtained according to the invention will be used in cosmetics as a component of tonics, creams, ointments, shampoos, hair and nail conditioners and other skin, hair and hair care products. nails.

The aqueous solutions of citrate-borate complexes of silver (I), copper (II) and zinc (II) obtained according to the invention will be used for the disinfection of soft and hard surfaces made of natural and artificial materials.

The aqueous solutions of the citrate-borate complexes of silver (I), copper (II) and zinc (II) obtained according to the invention will be used for the disinfection of various types of water, including drinking water.

The subject matter of the invention will be explained in more detail in the following examples without limiting its scope.

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P r z k ł a d 1

650 ml of distilled water at 30 ° C was poured into a glass reactor equipped with a high-speed stirrer, followed by 12.50 g of boron citrate in the form of a white powder with a boron content of 5% by weight. Thereafter, 9.64 g of silver acetate, 7.14 g of copper carbonate and 4.70 g of zinc oxide are poured in and mixed until all components are completely dissolved.

The content of individual microelements in the above synthesized sample is: organic boron - 0.625 g, which is 0.0578 mol, complexed silver - 6.23 g, which is 0.0578 mol, complexed copper - 3.67 g, which is 0.0578 mol, complexed zinc - 3.78 g, which is 0.0578 mol. The molar ratio of boron to silver to copper to zinc is therefore 1: 1: 1: 1. The obtained clear solution of the novel silver-copper-zinc complex according to the invention was exposed to daylight for 21 days. No blackening or even turbidity of the solution was observed, which proves the high stability of the obtained citrate-borate complex of silver, copper and zinc.

P r z k ł a d 2

750 ml of distilled water at 50 ° C was poured into the reactor as in example 1 and 16.0 g of boron citrate were poured as in example 1, and then 7.28 g of silver lactate, 9.14 g of copper carbonate and 8 were added to the solution. 12 g of zinc acetate, then basified with 8% sodium hydroxide solution to pH 6.6.

0.3 g of 5-chloro-2-methyl-3 (2H) -isothiazolone was added to the thus obtained new citrate-borate complex of silver, copper and zinc, and then it was subjected to repeated freezing. After each defrosting, the sample was clear, without turbidity and sediment, it did not change color, which proves the high stability of the new complex.

The content of individual microelements in the sample obtained above is: organic boron - 0.80 g, which is 0.074 moles, complexed silver - 3.99 g, which corresponds to 0.037 moles, complexed copper - 4.70 g, i.e. 0.074 moles, complex zinc - 2.42 g which is 0.037 mol. The molar ratio of boron to silver to copper to zinc is therefore 2: 1: 2: 1.

P r z k ł a d 3

850 ml of distilled water at a temperature of 35 ° C were poured into the reactor as in example 1 and 18.75 g of boron citrate was poured as in example 1, and then 3.35 g of silver oxide, 65.56 g of copper gluconate and 36.24 g of carbonate were added. zinc and the pH was adjusted to 5.8 with a 2% lithium hydroxide solution.

3 ml of a 40% solution of ethylenediaminetetraacetic acid tetrasodium salt was added to the thus obtained new citrate-borate complex of silver, copper and zinc, and then it was subjected to several freezing conditions. After each defrosting, the sample was clear, without turbidity and sediment, it did not change color, which proves the high stability of the new complex.

The content of individual microelements in the sample obtained above is: organic boron 0.9375 g - which is 0.0867 moles, complexed silver - 3.12 g which corresponds to 0.0289 moles, complexed copper - 9.18 g, i.e. 0.1445 moles, complexed zinc - 18.90 g which is 0.289 mol. The molar ratio of boron to silver to copper to zinc is therefore 3: 1: 5: 10.

P r z k ł a d 4

450 ml of distilled water at a temperature of 5 ° C were poured into the reactor as in example 1 and 2.16 g of boron citrate were poured as in example 1, then silver carbonate was added in the amount of 0.28 g, 2.12 g of copper glycinate and 0, 99 g of zinc hydroxide and basified to pH 6.0 with 0.5% cesium hydroxide. 2.5 ml of the sulfobetaine surfactant was added to the clear solution.

The content of individual microelements in the above-synthesized sample is: organic boron - 0.108 g, which is 0.01 mole, complexed silver - 0.2157 g, which corresponds to 0.002 mole, complexed copper - 0.635 g, which is equivalent to 0.01 mole, and complexed zinc - 0.654 g which corresponds to 0.01 mole. The molar ratio of boron to silver, to copper and to zinc is therefore 5: 1: 5: 5. The solution of the new silver complex according to the invention obtained in this way was repeatedly frozen and thawed. After each cycle, the sample was clear. No turbidity, precipitation or color change was found, which proves the high stability of the obtained complex.

P r z k ł a d 5

850 ml of distilled water at a temperature of 90 ° C were poured into the reactor as in example 1 and 33.80 g of boron citrate, 3.90 g of silver hydroxide and 75.42 g of copper lactate and 68.49 g of zinc acetate were poured in, and then the solution was made alkaline. to pH 6.5 using 2% sodium hydroxide.

PL 223 968 B1

2 g of polyvinylpyrrolidone were added to the thus obtained new citrate-borate complex of silver, copper and zinc, and then exposed to daylight for 7 days. After this period, the sample was subjected to several freezes. After each defrosting, the sample was clear, without turbidity and sediment, it did not change color, which proves the high stability of the new complex.

The content of individual microelements in the above-synthesized sample is: organic boron - 1.69 g, which is 0.156 moles, complexed silver - 3.365 g, which corresponds to 0.0312 moles, complexed copper - 19.83 g, i.e. 0.312 moles, complexed zinc - 20.41 g, 0.312 moles. The molar ratio of boron to silver to copper to zinc is therefore 5: 1: 10: 10.

P r z k ł a d 6

800 ml of distilled water at 15 ° C were poured into the reactor as in example 1 and 4.34 g of silver citrate were poured into the reactor. After stirring for a few minutes, 11.00 g of boron citrate as in example 1, 15.41 g of copper oxalate and 22.30 g of zinc carbonate were added to the solution in a single manner, and then it was made alkaline to pH 5.7 with 0.5% hydroxide. lithium.

0.05 g of tartrazine was added to the thus obtained new citrate-borate copper silver complex, and then it was subjected to multiple freezing. After each defrosting, the sample was clear, without turbidity and sediment, which proves the high stability of the new complex.

The content of individual microelements in the sample obtained above is: organic boron - 0.55 g, which is 0.0508 moles, complexed silver - 2.74 g, which corresponds to 0.0254 moles, complexed copper - 6.46 g, i.e. 0.1016 moles, complexed zinc - 11.63 g corresponding to 0.1778 mol. The molar ratio of boron to silver to copper to zinc is therefore 2: 1: 4: 7.

Claims (2)

1. Aqueous solutions of silver (I), copper (II) and zinc (II) citrate borate complexes according to the present invention are represented by the general formula: ^[Ag] m * ^[C 18 ^H 15- (p + r) ^BO 21 ^] n ^P + ^{r Me} [Cu] s ² · [C1 ₈ H15- (p _{+ r} ) BO21] n ^P + r Me ^[Zn] w ² · ^[C 18 ^H 15- (p + r) ^BO 21 ^] n ^P + ^{r Me} or [Ag] m + · [Cu] s ² + · [Zn] w ² + · [C1 ₈ H15- ( _P + _r ) BO ₂ 1] n ^p- + r Me + where min independently assume a value from 1 to 5, s and s and independently from each other take a value from 1 to 10, p is an integer from 1 to 9, r is an integer from 0 to 9, and Me is a monovalent cation from Group I of the Periodic Table. Method for the preparation of aqueous solutions of citrate-borate complexes of silver (I), copper (II) and zinc (II), characterized in that to the water is added continuously or in portions, in any order, boron citrate or its salts, compounds introducing cations of group I of the periodic table and water-soluble and / or water-insoluble silver (I) compounds, copper (II) compounds and zinc (II) compounds in a molar ratio from 1: 1: 1: 1 to 5: 1: 10: 10 in various combinations, at a temperature from 0 to 100 ° C.