HK1081521B - Aqueous solution of non-colloidal silicic acid and boric acid - Google Patents

Description

Aqueous solution of non-colloidal silicic acid and boric acid

Technical Field

The present invention relates to an aqueous solution containing bioavailable silicon and boron, which can be used to fortify plants or trees, or as a dietary and feed additive for humans and animals. The invention also relates to the preparation of stable solutions containing bioavailable silicon and boron.

Background

Silicon is a plantAn essential nutrient, silicon, low-concentration ortho-silicic acid (H)₂SiO₄) Present in soil, minerals and seawater. In modern agricultural systems, the nutrient solution is most deficient in ortho-silicic acid, and the added silicate cannot compensate for this deficiency. Silicic acid is sometimes added to nutrient formulations, but it does not have sufficient bioavailability because silicates are poorly soluble in water.

Silicates are not readily absorbed by living organisms. Preferably, for diatoms (diatoms), plants, animals and humans, ortho silicic acid is the most bioavailable silicon compound. In water, silicates and silica gel are slowly hydrolyzed to orthosilicic acid, which is difficult to dissolve and rapidly polymerizes into small particles (non-colloidal matter (non-opalescent, non-cloudy)). These polymeric structures aggregate directly into long chains (still non-colloidal), resulting in the appearance of true networks (colloidal; milky, cloudy). This process results in the formation of a soft gel (soft gel), which has a low bioavailability. The formation of these colloids and gels depends on the pH. The longest gel time occurs at pH 2. At lower and more basic pH conditions, the time to colloid formation and ultimately gel formation is reduced (Iler RK. the Chemistry of silica. Wiley: New York, 1979). According to these references, the process of polymerization from monomers into sol-gels can be summarized as follows:

1. monomeric ortho-silicic acid in an acidic medium;

2. the orthosilicate monomers polymerize into small oligomers (mainly dimers, trimers and tetramers, linear or cyclic);

3. further condensation into linear or randomly branched polymers (mini-clones, +/-2 nm) (sol precursors (pre-sol));

4. particle growth (sol, colloidal, particle size of about 5-100 nm);

5. the particles are linked into chains (aggregated, colloidal);

6. linked into a network and extended in a liquid (aggregation, gel precursor);

7. the gel is concentrated (gel).

According to literature reports, silicon helps to thrive the roots of plants, while being essential for maintaining good growth of the plants and for combating diseases. The silicic acid is formed as a mechanical barrier, strengthening the blade. The silicon also links various plant substances, such as sugars, proteins or those phenolic compounds present in various plant fibers. The mycelium of the fungus can no longer penetrate the plant. It can increase yield, enhance stress resistance, control plant diseases and insect pests, reduce toxicity of certain minerals such as manganese and aluminum, improve tolerance to low temperature disasters, regulate water consumption, and enhance leaf firmness, resulting in enhanced photosynthesis. Silicon is reported to be taken up by roots in the form of ortho silicic acid. Silicates, silica gel (Kieselgel), metasilicates, zeolites and other silicon compounds are also commonly used, but have low bioavailability.

Novel compounds that induce the polymerization and aggregation of orthosilicic acid into colloids (such as fluoride, nitrogen and chlorine compounds, pesticides (insecticides), antibiotics, fungicides, and the like) are also used in agriculture. But ignores or attenuates the synergistic activity between the root and the micro-organism, which improves the bioavailability of the mineral and the solubility of the silicate, thus producing a weakened plant with low mineral content. To overcome this problem, more unnecessary fertilizers are required for plants, and more unnecessary insecticides, fungicides, and the like are required for plants as protection. This is particularly a problem for aquatically cultured plants.

In addition to the importance of silicon to plants, there is also evidence that silicon is also an essential element for animals and humans (DE 19530882). A question has thus arisen as to whether silicon is equally capable of protecting and strengthening animals and humans against attack by pathogenic microorganisms (bacteria, fungi) and may be directly related to certain physiological conditions. The human body contains very abundant silicon, far higher than most of the essential trace elements such as Mn, Fe, Cu or Zn. In particular, the internal organs, connective tissue, cartilage and bone contain large amounts of silicon. Some studies have shown that the silicon content decreases with age. Pregnant women have a reduced serum silicon concentration and they use a silicon supplement to treat the skin and reduce the aluminum toxicity (Reffitt DM, Jugdaohsingh R, Thompson RPH, Powell J.J.: silicon: organic acidic uptake and yield evolution in man and efficiencies on aluminum evolution J.Inorg Biochem 1999; 76: 141-6; and Van Dyck K., Van Cauwenbergh R.R., Robberecht H., Destrella H.: biological availability of silicon from and benefits J.Anal. chem.199; 363: 541-4). The use of silicon supplements may also reduce the toxicity of aluminum. Aluminum inhibits bone formation and is associated with neurological diseases such as Parkinson's disease and Alzheimer's disease. Silicon is associated with the elasticity of arteries and vessel walls and can enhance the immune system.

Clinical reports have shown that the use of silica gel can improve skin diseases, heart diseases, asthma, rheumatic diseases, psoriasis, bone diseases, and the like. Silica gel is widely used throughout the world. However, these gels have low bioavailability due to the difficulty of dissolving the colloidal silicic acid.

Therefore, in order to enable silicon to be effectively bioavailable, it is necessary to use a non-colloidal ortho silicic acid solution, and to prevent the formation of colloids and gels. However, at high concentrations (> 10)^-4mol Si), it is difficult to prevent the formation of colloids and gels at all pH. Colloids and gels are not bioavailable, but colloids can slowly disaggregate into smaller particles and orthosilicic acid. This depolymerization is very limited and irreversible because these colloids are relatively unstable and the polymerization is dependent on the water content, pH and salt concentration. This produces very low concentrations of orthosilicic acid in the gastrointestinal system, which adheres to all biological materials, and leaves behind colloidal substances.

In addition to silicon, boron is also considered an important trace element. Boron is a recognized essential element for plants. The lack of boron can cause growth inhibition (Ishii T, Matsuna T, Hayashi N.Format of rhamnogalacturonan II-promoter in peptides derivatives cell wall thickness of pumkin tissue. in: Plant Physiology; 126 (4)1698 1705Aug 2001), boric acid delays senescence of carnations (borano M, Amonos A, Pretel MT, Martinez-Madrid MC, Romojaro F.previtans regulation nucleic acid sensitivity of flowering plants. Postveable Biology and Technology; 23 (2) 133. Nov. 2001). High concentrations of boron in water can reduce crop yield. Boric acid in various concentrations (except high concentrations) can be used as fungicides, insecticides, and herbicides. As a herbicide, it has strong toxicity. It can be used as a drying compound, or can inhibit photosynthesis or inhibit algae in swimming pools and sewage systems. As a fungicide, it can be used as a wood preservative. Boric acid is therefore used in agricultural and non-agricultural fields, in particular in the field of food and feed treatment.

Boron is also used in human wound healing, vaginal infections, eye drops, cosmetics, as a food preservative or as an antimicrobial compound, mild preservative. It may also have antiviral activity. Its high toxicity limits its use as an antibacterial compound in animals and humans. Boron was considered a non-essential element in human nutrition before 1980. Recently, experiments in a number of animals and humans have shown that it is also essential for normal growth, similar to that in plants, and that it is important for hormones (testosterone and estrogen) that are involved in growth and skeletal metabolism. It is also involved in bone mineralization.

In nature, boron (similar to silicon) is found in volcanoes and other natural water sources (spas), and also in minerals as borates.

The use of silicon and boron in combination for food additives or as a medicament is well documented, for example in DE19530882 a medicament is used which comprises 21.43 wt.% silicon (from silica) and 2.14 wt.% boron (from borax). The medicament is solid or liquid. One obvious disadvantage is that this form of silicon is not bioavailable. Another document, WO 00/27221, describes a solution for concentrating metals in plants comprising at least 100mg/kg silicon and at least 100mg/kg boron. Also, a disadvantage of silicon in this respect is that it is not or hardly bioavailable. The range of silicon and boron that can be added also produces some combinations that have a negative impact on bioavailability. For example, in humans, high intakes of silicon can cause lithiasis, immunological effects, or silicon accumulation. These two elements also interfere with the absorption of other minerals. High intake of boron can increase testosterone and estrogen levels and, thus, can interfere with parathyroid hormone function.

Boric acid and silicic acid are weakly acidic and poorly soluble in water. They are widely present in uncontaminated water on earth and are critical to mineral balance in plants, animals and humans. In contaminated systems, these acids are gradually depleted and their bioavailability is reduced.

Other combinations referred to in the literature also do not take advantage of the bioavailable form of silicon and do not exploit the synergistic effect of boron on the bioavailability of non-colloidal silicon. In addition, there is a need for a highly concentrated silicic acid solution that can be used as a stock solution, wherein the silicic acid is present in a non-colloidal form despite its high concentration and also contains boron.

The aim of the invention is to produce a solution containing highly bioavailable and highly active silicon (in the form of silicic acid) and boron (in the form of boric acid). It is another object of the present invention to prepare a highly concentrated silicic acid solution which does not undergo polymerization and/or gelation, and which can be stored as a stock solution for a long period of time without the solution undergoing gelation polymerization with boric acid.

Disclosure of Invention

The invention includes an aqueous solution comprising boric acid and a non-colloidal silicic acid. The solution may also contain a water-absorbing additive. The solution contains bioavailable non-colloidal silicic acid and can remain stable for more than one year.

The invention also includes a process for preparing a solution in which one or more silicon and boron compounds are hydrolyzed in an acidic solution containing one or more dissolved (strongly) water-absorbing additives (humectants).

The invention also includes the use of the solution, wherein the solution is diluted and added to plants or trees to increase their resistance to one or more of microbial infections, insects (insects), pests (pests), fungi, weeds or extreme physiological conditions, or the diluted solution is fed to fish. The invention also includes the use of the solution for strengthening connective tissue, bone, skin, nails, arteries, cartilage and joints in animals and humans.

Detailed Description

The present inventors have now surprisingly found that the bioavailability of a combination of non-colloidal silicic acid and boric acid may lead to an increased bioavailability of silicic acid.

These effects are found not to be present in one of these weak acids, but only when they are used in combination. When boric acid is added, the biological effect of adding silicic acid is greater. Accordingly, the present invention comprises an aqueous solution comprising boric acid and non-colloidal silicic acid. Thus, rather than the sole effect of boron, the presence of boron enhances the effect of silicic acid. However, these effects only occur when these weak acids are used together and the silicic acid does not aggregate into large particles.

The effect of boron in solution as a synergistic element for non-colloidal silicic acid only occurs if the ratio of boron to silicon is not too high. The silicon to boron ratio of the solution of the invention is between 1 and 1000.

Since the silicic acid should be present in a non-colloidal form in order to be bioavailable, the formation of colloidal silicic acid should be avoided. This can be achieved by selecting a suitable concentration, for example, below about 10^-4And (4) mol of Si. The solution of the invention should be filterable at 0.1 micronMembrane filtration, for example a membrane filtration membrane. Filterable means that 90% or more of the solution can pass through the filter. When the concentration is too high and colloidal silicic acid is formed, part of the solution will not pass through the filter membrane.

The concentration of silicon in the form of silicic acid and boron in the form of boric acid in the solution should be between about 0.0001 to 0.005 wt.% and 0.000001 to 0.005 wt.%, respectively, preferably between about 0.0001 to 0.01 wt.% and 0.000001 to 0.01 wt.%, respectively.

The concentration of silicic acid in the solution as described above should not be very high, which is a disadvantage for the use or storage of the solution, which means that a large volume is required. The present inventors have surprisingly found that the combined use of silicic acid, boric acid and a strongly water-absorbing additive (a humectant capable of absorbing water to maintain its water-absorbing state and prevent evaporation of water) can solve this problem. In this embodiment, when the solution also contains a water absorbing additive, the solution may contain a high concentration of non-colloidal silicic acid (e.g., up to 2 wt.% Si) and maintain the synergistic effect of boric acid. The solution should have a low pH, below pH2, and preferably below pH1, such as 0.5. By addition of an acid such as HCl or H₃PO₄To achieve such a low pH. Due to such low pH (e.g., < 1), water and particles can be highly protonated.

The main oligomers (small particles) are: dimers, linear trimers, linear tetramers, up to heptamers, cyclic trimers, cyclic tetramers, cyclic pentamers and small derivatives of these cyclic and linear compounds. These small compounds (+/-a few nanometers or less) do not continue to grow due to the action of the strong moisturizers, thus preventing their aggregation and precipitation. Boric acid is adsorbed to these small particles. These particles can easily pass through 100 nm filters, but are difficult to pass through molecular filters of less than 10,000MW (Da), such as Amicon filters.

Sol particles larger than 4 nm become inhomogeneous and colloidal and fail to pass through a 0.1 micron filter or, for example, a 20,000Mw filter. Since small "particles" in solution are easy to pass through a 0.1 micron filter, the formulation cannot be sol or gel in nature (non-colloidal, and therefore non-sol, non-gel). Furthermore, virtually no "particles" remain on the MW20,000 filter or filters with higher cut-off values (cut-off), such filters only allowing passage of very small particles such as small oligomers and small polymers of grades 2 and 3 (see above). On the other hand, the oligomers (after dilution) usually reach equilibrium with the ortho silicic acid by dissolution. The solubility of orthosilicic acid is limited to concentrations of Si below 50 ppm. In view of these circumstances, it can be concluded that the synthesis of non-colloidal silicic acid enables silicic acid oligomers with low molecular weight to remain stable, while the oligomer remaining stable prevents further sol and gel formation. The concentration of orthosilicic acid (monomer) in the concentrated stock solution can be determined by the known silicon-molybdic acid reaction (silicon-molybdic acid reaction) (R.K. Ill. 1979 p.95-105). No positive reaction was confirmed by this method. This indicates that the stock solution of the invention is a solution containing stable silicic acid oligomers (oligomeric particles) which are smaller than 4 nm and which do not contain detectable free orthosilicic acid. These stable silicic acid oligomers do not polymerize further to form colloids (sols, aggregates) or gels and can be filtered through a 0.1 micron filter or, for example, a 20,000Mw filter. This form of silicic acid, grade 2 and 3, is bioavailable.

The solution according to the invention thus comprises, in addition to B, non-colloidal silicas, namely mainly silicas of grade 2 (silicic acid polymerized to small oligomers (mainly dimers, trimers and tetramers, linear or cyclic)) and grades 3 (linear randomly branched polymers (+/-2 nm small particles) (sol precursors)), and small amounts of monomeric silicic acid which cannot be detected. The solution was passed through a 0.1 micron filter. Preferably, free orthosilicate is not detectable (silicon-molybdic acid reaction), although monomers may be present (due to the presence of an equilibrium effect). The present invention does not relate to colloidal silica or sol silica. The colloid comprises particles of about 5 to 100 nanometers (Kirk-Othmer, "colloid"), and R ö mpp is described in its Chemie Lexikon as colloidal amorphous SiO₂Of the anionic aqueous solutionSilica sol having an average particle size of 5 to 150 nm. It cannot be excluded that small amounts of this component will be present in the solutions of the invention, but the solutions of the invention essentially comprise non-colloidal silica (mainly orthosilicic acid of grade 2 and 3, i.e. bioavailable silicon as described above).

Surprisingly, the biological activity of the solutions of the invention is due to these particles: small silicic acids and boric acid oligomers. Pure silicic acid is less active. The humectant allows the silicic acid to reach high concentrations (non-colloidal silica) and prevents it from aggregating. Aggregation of these particles can lead to opalescence, turbidity, light reflection, colloid and gel formation, and thus loss of biological activity.

The additives are preferably selected from food additives (columns E and a). The solution of the invention is thus a solution wherein the water absorbing additive (humectant) may be a polysorbate, gum, substituted cellulose, polyglycerol fatty acid ester, polyethylene glycol, polydextrose, propylene glycol alginate, polyoxyethylene glycerol ester, pectin or amidated pectin, sucrose fatty acid ester, acetylated or hydroxypropyl starch, starch phosphate, urea, sorbitol, maltitol, vitamins or various mixtures thereof. Strong moisturizers absorb moisture and inhibit silicic acid from aggregating to form a gel. Silicic acid adsorbed to the humectant-water complex will not aggregate.

To obtain a high concentration of non-colloidal silicic acid, a high concentration of water-absorbing additive is required. The concentration of the water-absorbing additive in the solution according to the invention is at least 30% (W/V for powders and V/V for liquids), preferably 40%. Surprisingly, such solutions can be stored at room temperature for long periods (> 1 year) in the form of stock solutions and then diluted for application to plants, animals and humans. Thus, a solution containing a high concentration of silicic acid can be prepared which can be used as a stock solution, wherein the silicic acid is in a non-colloidal, bioavailable form despite its high concentration and the presence of boron. The solution has a pH below 2, and preferably below 1, a silicon to boron ratio between 0.1 and 1000, and can be filtered through a 0.1 micron filter, such as a membrane filter, and can be filtered through a 20,000MW (Da) filter, such as an Amicon filter.

For such concentrated solutions containing a water-absorbing additive (or combination of water-absorbing additives), the concentrations of these two elements in acid form may be between about 0.01 and 2 wt.% (Si) and between 0.0001 and 4 wt.% (B) (1% refers to 10mg/ml), respectively.

B is also known to stabilize non-colloidal silica. However, this stabilization lasts only for a short time, about 1 day. Furthermore, this stabilization occurs only when the amount of B is much higher than in the solution according to the invention (e.g. at least 10 times higher than Si).

Boric acid, silicic acid, and fulvic acid (an extract of a griseofulvin raw material and miscellaneous raw materials, including organic weak acids and minerals) are weak acids and are hardly soluble in water. They are widely present in low concentrations in uncontaminated water worldwide. They are of vital importance for the mineral health of plants, animals and humans. In contaminated systems, all of these acids are depleted and thus their bioavailability is reduced. We have found that selected mixtures of these acids in low concentration liquid formulations can stimulate normal health conditions and can be used as nutritional agents for the prevention of some diseases and as anti-ageing agents. Thus, in a particular embodiment, the solution of the invention may also comprise fulvic acid. The final concentration of fulvic acid in the solution is between 0.1 and 10% (V/V).

Concentrated solutions like these, comprising non-colloidal silicic acid, boric acid (and optionally fulvic acid) and a water-absorbing additive, can be prepared by a process in which one or more silicon and boron compounds are hydrolyzed in a solution containing one or more dissolved water-absorbing additives. In this method, a water-absorbing additive (humectant) is dissolved in water, and a strong acid is added. The temperature of the water-absorbing additive (e.g., PEG400 or PEG 600, polyethylene glycol with an average MW of 400 or 600, respectively) needs to be brought to or maintained at about 20 ℃ prior to the addition of the acid. The solution is then allowed to stabilize above about 20 c but below about 40 c, e.g. 25 c, and this temperature is maintained for several hours, e.g. 5h, to facilitate hydration. Boric acid may be added in the form of a crystalline material or a borate of an alkali metal or alkaline earth metal. Preferably, the water-absorbing additive (liquid humectant or powder mixed with water) is acidified and fully hydrated for a period of time at a temperature of about above 20 ℃ before the silicate is added. Then, silicon (e.g., an alkali metal or alkaline earth metal silicate solution) is added. An equal volume of 5 or 10 fold diluted aqueous alkaline potassium silicate solution (12-18% Si) (the temperature of the water must be above about 22 ℃) was slowly added to the concentrated PEG-boric acid solution and stirred, whereby good results were obtained. The solution was heated to 25 ℃ to fully hydrate the humectant (to prevent precipitation of silicic acid). This means that the humectant concentration is initially at least 60%, preferably at least 80%, and after addition of the silicon containing solution, the humectant concentration is at least 30%, preferably at least 40%.

The invention also includes aqueous solutions containing only acidified water-absorbing additives and boric acid, which may be used after mixing with the silicic acid solution. The solution obtained after mixing can be used after dilution. For example, the humectant-boron solution may be mixed with the silicic acid solution prior to use, then diluted, for example, and sprayed onto the plant. Several solution combinations may be employed to obtain the solutions of the present invention.

The resulting solution contains a high concentration of silicon and can be stored (stock solution) for more than 1 year without forming or substantially without forming colloids. Because of the low pH, the solution needs to be diluted before use to achieve the appropriate pH. The pH depends on the application. The concentrated solution of the present invention may be added to plants or trees upon dilution. The solution is diluted with water about 200 to 20,000 times, preferably 300 to 10,000 times, and more preferably 500 to 3000 times before being added to the plant or tree. The diluted solutions of the present invention may be used to fortify plants or trees to enhance their resistance to microbial infections, insects, pests, fungi, or extreme physiological conditions such as cold.

Obviously, the (concentrated) solution to be added to the plants or trees may also contain other additives. These additives may be added, for example, after dilution of the concentrated solution, or they may be added to the concentrated stock solution. The skilled person will be able to select a suitable route. The additive can be, for example, minerals, nutrients, antimicrobial agents, insecticides (insecticides), pesticides (pesticides), fungicides, herbicides, and the like, or combinations thereof. Preferably, these additives do not substantially reduce the solubility of the silicic acid in the solution or promote colloid formation. However, if sprayed with the solution of the invention (after dilution) on e.g. fruit, usually only less fungicide etc. is needed due to the improved quality of the fruit.

The concentrated solution of the invention may be added after dilution by spraying on the plants or trees and/or their leaves, or by adding the solution to the culture medium in which the roots of the plants or trees are located. As described above, this may enhance the health of the plant or tree. This is also a way to concentrate boron and silicon in, for example, vegetables and fruits. Such vegetables and fruits are then used for human consumption.

Good results have been obtained on fruits like bananas, apples, grapes, pears or on rice, onions (unions), potatoes, tomatoes, etc. using a solution containing Si in a concentration of about 0.1 to 1 wt.%, preferably about 0.2 to 0.6 wt.%, a B in a concentration of about 0.01 to 0.5 wt.%, preferably about 0.05 to 0.2 wt.%, and a humectant PEG400 in an amount of about 30 to 60 wt.%, preferably about 35 to 50 wt.%. The pH of the solution is about 0.3 to 0.7, preferably about 0.4 to 0.6.

The (concentrated) solutions of the invention can also be used after saturation of the superabsorbers (superabsorbers), such as polyacrylates (sodium polyacrylates) or homopolymeric amino acid compounds, such as polyaspartic acid, or natural materials, such as clays or zeolites, etc., the mixtures of these compounds with soil matrices can be used as slow-release preparations for plants, for example slow-release Si and B.

The (concentrated) of the present invention may also be used to fortify fish, including crustaceans, after dilution to increase their resistance to microbial infection. The solution is typically diluted approximately 1000 to 30000 times and then added to the fish. For example, it may be added to the aquarium after dilution in order to achieve the appropriate acid concentration. The solution can also be used to concentrate boron and silicon in seaweed.

The solution can also be used in combination with minerals, nutrients, antimicrobial agents, or combinations thereof. These additives may be added, for example, after dilution of the concentrate, or they may be added to the stock solution. The skilled person will be able to select a suitable route.

The (concentrated) solutions of the invention can also be used after dilution in humans and animals to strengthen, for example, connective tissue, bone, skin, nails, arteries, cartilage and joints. Humans and animals may benefit from both bioavailable silicon and boron, and in particular from this synergistic effect of boron in its ability to increase the bioavailability of silicon. The solution can be diluted for treating diseases related to bone, skin, artery, connective tissue, cartilage, joint, osteoporosis, rheumatic diseases, arteriosclerosis, hair, nail and skin diseases, cardiovascular diseases, allergic diseases, arthritis, degenerative diseases, etc. The solution should be applied in therapeutic form, which means that possible physiologically acceptable additives are included. This can be achieved, for example, by adding drops of undiluted or diluted solution to the beverage, using the undiluted or diluted solution as a food additive or supplement for preparing a food product, and other methods known to those skilled in the art. The solution can be used in cosmetics, therapeutic creams and ointments, shampoos, gels, etc., and in their preparation.

The final dilution can achieve an acceptable pH, depending on the particular application. Typically, the range of dilution with water (or water-based liquid) prior to ingestion is about 10 to 500-fold, and may be lower or higher if desired. When diluting the solution or raising the pH of the solution, as during application, it is preferred that the pH is not higher than 4-6. If the pH is higher than about 6, the advantageous effect is reduced. Thus, the solution will be used primarily at acidic pH (below about 6). Less dilute (e.g., about < 20 fold) solutions have less stability, while higher dilute solutions (e.g., greater than about 500 or 1000 fold) have greater stability in use.

The frequency of taking in the (diluted) solution of the invention and/or using the cosmetic comprising the (diluted) solution of the invention depends on the specific application. The total daily intake in humans may be about 0.5 to 10mg Si per 50kg body weight (animals and humans); for cosmetic purposes, the concentration in the cosmetic may be from about 0.5mg/ml to 0.0001mg/ml Si.

Depending on the particular application, the (concentrated) solutions of the invention may contain additives such as flavourings, sweeteners, toners, preservatives, stabilisers and the like. These additives may be added, for example, after dilution of the concentrate and prior to use. But these additives may also be added to the concentrated stock solution. The skilled person will be able to select a suitable route. Preferably, these additives do not substantially reduce the solubility of the non-colloidal silicic acid in solution and do not promote the formation of colloids or gels. The person skilled in the art is likewise able to select a suitable dilution before use.

Examples

Experiment 1: effect of boron on the toxicity of silicon:

in our experiments, leaves of salad plants (lettuce nodosa (cobble lette)) were sprayed daily for two weeks with a fresh formulation of soluble orthosilicic acid containing 0.01% (W/V)) Si dissolved in propylene glycol 5% (V/V) and a non-colloidal silica solution. Potassium silicate was used as the Si source. The solution is prepared fresh; without filtration. The plant growth stops completely and the plant becomes very rigid. The addition of boron in the form of 0.001% boric acid to the silicic acid reduced the above toxicity (growth), but the plants remained very rigid. The control experiment used only 0.001% boron dissolved in 5% propylene glycol and showed no effect (control). This indicates that boric acid is involved in the metabolism of silicic acid and that the Si/B ratio is important.

Experiment 2: antimicrobial activity of boric acid with or without silicon

Preparation of aqueous boric acid solutions containing different boric acid concentrations: 1%, 0.1%, 0.03%, 0.01%, 0.005%, 0.0003% and 0.0001% (W/V).

Sodium silicate (10% Si) was diluted 10 times with water and further diluted 1000 times in this solution or water, with a pH of 4.5 after dilution and a final concentration of 0.0010 wt.% (or 10g/ml Si) of silicon.

All solutions were filtered through 0.1 μmembrane filters to give clear solutions and used immediately. These compounds were tested against phytophthora infestans in a potato garden: by 20m²Is tested per m²There were 6 2-month-old potato plants (Bintje strain). In various solutions (approximately 10 liters/100 m)²) Spraying plant leaves twice a week at 4m²The plants of (4) were used as controls.

As a result:

after about 2 months, phytophthora infection begins to spread on the leaves of potato plants. All control plants showed dark spots on the leaves and gradually necrosed. Surprisingly, all boron-treated plants were also infected, except for those treated with silicon (10. mu.g/ml) and a low concentration of boric acid, wherein the concentration of boron did not exceed the concentration of silicon.

Treatment of plants with high concentration boron solutions (1%, 0.1% and 0.03% boric acid) for 1 week showed stronger toxic reactions (necrosis of leaves, e.g. black spots, cavities, etc.), but did not show antifungal effect. The use of silicon alone can only retard fungal infections to a certain extent. All plants treated with silicon (even in the absence of boron) were stronger. Starting from 0.003% boric acid, all made the plant leaves stronger and reduced fungal infections. The best results indicate that diseased plants can be reduced by about 70%.

Experiment 3:

the solutions were prepared as described in experiment 2:

boric acid 0.0003%, silicon 10 μ g/ml (1)

Boric acid 0.0001%, silicon 10 μ g/ml (2)

Silicon 10 ug/ml (3)

These solutions were stored at room temperature for 2 months and then filtered through a 0.1 μ filter (Millipore, type 0.1 μm). In further experiments, the filtrate was sprayed onto the leaves of potato plants (3 months old) twice a week.

As a result:

almost all plants show a necrotic effect common to phytophthora infections. At the same time, a blade strengthening effect similar to that of experiment 2 was also observed. Solution 2 alone was shown to reduce the number of spots at the initial stage of infection to some extent and to delay infection to some extent.

These results demonstrate that the active compound in the solution is deactivated by the formation of a colloid in 2 months after the preparation of the solution (since no moisturizer is used which makes the solution more stable). The low concentrations of boron and silicon have a synergistic effect in enhancing the resistance of plants to fungal infections. Boron is a cofactor for the antifungal infection activity of silicon. The two acids mixed in a weakly acidic medium can be effectively absorbed by the leaves of the plant.

Experiment 4: active particles capable of being filtered by a molecular filter (≠ silicic acid)

The aqueous solution of experiment 2 containing 0.0003% + silicon 10. mu.g/ml boric acid and only silicon 10. mu.g/ml (after filtration through a 0.1 μm membrane) was filtered through a membrane filter with a cut-off of 5000 Dalton (Amicon filter 5000 Dalton). After preparation of the above solution, experiment 2 was repeated. The activity of both solutions was significantly reduced compared to the similar solution of experiment 1 without molecular filtration, indicating that the synergy produced by both compounds was not due to orthosilicic acid (silicic acid is not retained by the filter membrane).

Molecular filtration must allow the loss of small molecules that produce the above-mentioned biological activities. While the ortho-silicic acid is still present in the solution, the activity of the solution is reduced. This indicates that the non-colloidal silica in the solution of the invention that is capable of passing through a 0.1 micron filter but not a membrane filter with a cut-off of 5000 daltons should be in the form of non-colloidal silica (together with boron).

Experiment 5: preparation of stock solutions, testing their stability over time

Concentrated sodium and potassium silicate liquids were used as starting materials (13% W/V Si in silicate form; see experiment 7). The concentrated solutions were first diluted 5 to 10 times in different concentrated humectants (acidified to ph0.5) and these stock solutions contained up to 1% silicon and up to 0.1% boron. Only the addition of highly concentrated humectants such as non-toxic food additives, e.g., polysorbate, polyethylene glycol, propylene glycol, urea, polydextrose, sorbitol, etc., results in a stable solution of the two weak acids.

All of these humectants are miscible with water and can be mixed with various silicates or silanols. Only strong humectants (such as those with a water absorption 0.5 times or more higher than that of glycerin) can inhibit silicic acid from forming colloids and gels for a long time: at room temperature for more than 6 months, filtration through a 0.1 micron filter (gel-free) was still possible. The stability of over 100 strong moisturizers and combinations thereof was observed over a period of 3 weeks at 50 ℃ (10 strong moisturizers were selected and used at different concentrations and combinations thereof). It was concluded that the humectant concentration in the final acidified stock solution must be at least 30%, preferably 40%, to inhibit colloid formation. Only with the selected humectant was a solution obtained which after 3 weeks was still filterable by a 0.1 μmembrane filter without a reduction in the flow rate through the filter.

Examples of such strongly water absorbing additives are PEG 200, PEG400, PEG 600, PEG 800, propylene glycol, urea, glucose, polysorbate, sorbitol, galactose, cellulose, dextran, gums and combinations thereof. Concentrations below 30% W/V will produce colloids and gels after 3 months and even more quickly.

Biological testing of typical moisturizers:

experiment 6: two acid stocks were prepared: a stable method was sought that effectively maintained both the active particles (non-colloidal) and the biological activity.

To make more economic use of this synergistic effect, two plants were selected as antifungal models: lollo Bionda (a lettuce) and White Lisbon (an onion). Strong antifungal compounds were used in both cultures to inhibit the fungal infection causing leaf blight (Botrytis). The plant is cultivated outdoors between 3 months and 8 months, and is completely free of saprolegniasis after being treated by antifungal drugs. Untreated results in serious infections. We now replaced the antifungal treatment with several diluted stock solutions (sprayed once a week).

PEG400 and propylene glycol (Merck) at a final concentration of 40% (V/V) were used as typical humectants, and silicic acid-boric acid formulations at various concentrations, Si 6mg/ml, were prepared; Si/B is 1/1 to 1/300 for both plants. Stock solution was diluted 1000-fold before use. The best antifungal activity and preventive results for enhanced plant growth were silicon/boron > 1, 5. Even when the ratio is as high as 300, the biological activity is not significantly reduced. It is a novel finding that very low concentrations of boric acid enhance the activity of silicic acid and can act as a cofactor.

Experiment 7: preparation of stock solution (diluted before use)

To 5 l of PEG 600(Merck) at 20 ℃ 300ml of concentrated HCl (first diluted with 300ml of distilled water (aqua dest.)) are added. The solution was warmed to 25 ℃ and held stable for 5 h. 2 g of boric acid (crystals) are added and dissolved. Then, 500ml of a concentrated potassium silicate solution diluted in 4.5 liters of distilled water was slowly added and stirred. The resulting solution contained 0.6% Si and 0.2% boric acid (Si/B: 18) and a final pH of +/-0.4.

Quality control: non-colloidal solutions of silicic acid and boric acid

The solution must be stable at room temperature for more than one year after formulation. To achieve this, the solution must be completely clear (transparent), not opalescent or coloured, not reactive to the turbidimeter (light reflection), and capable of being filtered through a 0.1 micron filter at 50 ℃ after 3 months storage without a drop in flow rate.

Dilution of this stock solution 5-fold in phosphate buffer at pH6.5 completely formed a gel after 10 minutes, indicating that too high a pH immediately resulted in gel formation. This solution, after dilution with PEG400 or propylene glycol according to 1/10, was only partially retained by the molecular filter with a cut-off of 5000.

Experiment 8: patient testing

10 volunteers (2 men and 8 women) were selected, who were generally in good health, had no hair, skin or nail disease, and had normal hair and nail growth. Some elderly (30%) patients have rheumatic diseases. They received a preparation of PEG400 (see above) (placed in 50ml plastic vials)

Stock solution a containing boron (0.03% W/V B) and silicon (0.5% W/VSi)

Boron-free stock solution b

Boron and silicon free stock solution c

Silicon-free stock solution d

All patients received the 4 stock solutions orally in a blinded fashion in different sequential orders. One drop (60 μ l) was taken daily for 3 days per patient to evaluate the rapid biological effect of each solution. Between the sequential application of the two solutions, a one week "wash-out period" is performed. The biological effect was evaluated on day 5 after the start of a particular treatment.

Conclusion 3 months after using different solutions. A significant effect on nail and hair growth was observed:

no effect was seen in 70% of patients after intake of solution d (only boron).

80% of the patients showed no effect after intake of solution b (silicon only).

80% of the patients did not show an effect after intake of solution c (placebo).

A significant effect was seen in 90% of patients after intake of solution a.

Surprisingly, in our experiments the vast majority (90%) of patients receiving the synergistic formulation claimed significant effects after 5 days. The effects mentioned are: firmer nails (90%), neck pain relief (10%), and knee pain relief (10%). Pain relief in 2 patients with rheumatic disease continued even up to 5 and 3 days. 40% of patients claim to have strong hair and nail growth after the completion of the entire experiment, and 50% of patients claim to have reduced natural hair loss after the completion of the entire experiment.

Since silicon is ingested daily from food and water at about 40-60 mg/day and boron at about 3-10 mg/day, according to literature, such low concentrations of silicic acid or boric acid (1 drop containing only 0.5% W/V Si) do not produce rapid biological effects, respectively. Some effect is only produced after several weeks of treatment at higher concentrations.

These results demonstrate that only short-term oral treatment with synergistic formulations produces direct biological effects in patients (pain relief, nail stiffness) and that the non-colloidal silicic-boric acid formulation has a high bioavailability in humans.

Experiment 9: improvement of brittle nail

Two patients with fragile nails received 2 drops (0.12ml diluted in a glass of mineral water) per day for a period of 1 week (solution a, experiment 8). Two patients claimed that the nails became significantly stiffer at least 2 weeks after treatment.

Experiment 9: hair loss reduction

Two patients with hair loss were selected (48 and 57 years old, male). Both people received 2 drops of solution per day (solution a, experiment 8). After one week, both patients claimed a 50% reduction in hair loss within the first week after treatment.

Experiment 10: increasing hair growth

3 female patients who had just been dyed were asked to measure their hair growth (new hair) within 2 months before the experiment was performed as a control. After a second professional dyeing, the treatment was started with the oral administration of a different solution. Each patient began treatment on the day of hair coloring. The patient took 2 drops of solution a per day (experiment 8). New hair growth was evaluated after 60 days. All patients were measured and found to have longer hairs after 2 months. The average growth ratio of treated to untreated hair for 3 patients was 1.3. They were colored with hair every 2 months for 6 months and measured growth values (mean of growth values (cm) at 5 different sites) to evaluate their hair growth. They claimed the nail to be harder and the nail to grow faster. One patient with tennis elbow claimed pain relief, while one patient with (chronic) inflammation of the shoulder tendons also claimed pain substantial relief.

Experiment 11: low dose effects on fungal infection resistance and immune system of cultured rainbow trout

Fungi often cause secondary infections in fish and occur most easily when there are other wounds such as injuries (wounds) or diseases that create opportunities for fungal infections. A typical example is the genus Saprolegnia (Saprolegnia), a widespread fungus and common in fresh water. Fungal attack occurs when there is malnutrition, stress, shock, parasitosis, hypoxia, and a wound (lesion) where bacterial infection occurs. The fish started to appear white cotting clusters from both sides of the mouth and spread throughout the body. Rainbow trout is sensitive to saprolegniasis or similar fungi. It has a serious influence on lake water and fish farming and causes deterioration in fish meat quality. White and grey patches rapidly appeared on the skin of fish, with a cotting fibrous appearance.

It is generally believed that this infection can lead to fish death and that the infected fish meat cannot be consumed. The immune status of fish appears to have a major impact on the development of disease. It is almost impossible to treat infected fish unless highly toxic compounds are used.

Rainbow trout were bred in 8X 4X 2 meter pots. 300 fishes with the average weight of 350 g are cultured in spring and summer. The water temperature was +/-16 deg.C, the water was mobile, the silicon content was < 1 mg/liter, and the boron content was < 1 mg/liter.

Fish are often infected with this fungus in summer, beginning with white to gray spots appearing in the corners of the mouth and in the infected open wounds due to typical movement of the fish. Without antifungal treatment, the fish will be totally infected and die within 2 months. After the first appearance of symptoms, we turned off the water source and added 20,000 fold diluted solution a (solution of experiment 7, but formulated with PEG 400). The final concentrations of Si and boron are extremely low and preclude direct antifungal effects. After two days, the water source was re-opened after treatment. The treatment was repeated every 3 elbows. All fish survived and infection gradually and completely resolved 3 months after treatment. The dishes made from these fish have good taste.

The experiment was repeated. 10 control fish were removed from the pot and cultured in a small pot. Unlike treated fish, untreated fish become infected and die.

These experiments demonstrate that highly diluted solutions of the invention containing boron and silicon are able to protect fish against fungal infection and that such treatment allows the immune status of the fish to be restored. Silicate or other mineral compounds alone do not provide the same protective effect.

Experiment 12: applying the solution to fruits of Mona (Gala) and Huangjia Fruit of Mona (Royal Gala Fruit, south Africa)

The solution contained about 0.4 wt.% Si, about 0.1 wt.% B and about 45 wt.% PEG400, pH about 0.5, diluted 800-fold before use, and applied to henna and royal pina fruits (apples) after dilution. 350ml of this solution are sprayed per hectare per week over a period of 6 weeks.

3 samples of each of the two fruits were taken and the results are shown in the following table:

date of sampling	Sample ID	Fruit size	Weight (D)	Degree of solidity	Color	Seed color	Red colour	％TSS	% acid	Starch
											Fruit of Monacoa
	25970	62,2	108,3	12,1	1,0	1,0	4,9	11,7	0,39	0,1
											1 month and 15 days	Control	61,1	107,1	11,1	1,3	1,2	3,3	11,5	0,37	0,0
	Rise up	1,1	1,2	1,0	-0,3	-0,2	1,6	0,2	0,0	0,1
												26076	65,5	140,3	12,4	1,1	1,0	5,7	11,9	0,42	5,9
Day 1, 21	Control	62,6	118,5	9,5	1,6	1,3	3,5	11,6	0,38	33,1
												Rise up	2,9	21,8	2,9	-0,5	-0,3	2,2	0,4	0,0	-27,2
Day 1, 28	26362	68,8	151,7	12,8	1,2	1,1	8,6	12,1	0,37	41,5
											Control	64,1	138,3	9,6	1,9	2,2	4,3	11,9	0,39	38,9
	Rise up	4,7	13,4	3,2	-0,7	-1,1	4,3	0,2	-0,0	2,6
1 month and 14 days	25832	60,6	107,7	10,9	1,0	1,0	7,5	10,1	0,44	1,0
											Control	58,4	103,6	9,4	1,2	1,2	4,3	12,1	0,38	0,4
	Rise up	2,2	4,1	1,5	-0,2	-0,2	3,2	-2,0	0,1	0,6
											Day 1, 21	26074	64,5	138,2	11,2	1,1	1,0	8,6	9,8	0,39	2,5
Control	59,9	130,4	9,5	1,3	1,3	4,4	12,3	0,37	0,8
										Rise up		4,6	7,8	1,7	-0,2	09,3	4,2	-2,5	0,0	1,7
Day 1, 28	26361	69,8	156,3	11,9	1,1	1,1	8,9	10,1	0,38												41,5
										Control	60,1	131,8	9,6	1,6	1,4	4,5	12,5	0,39	40,8
	Rise up	9,7	24,5	2,3	-0,5	-0,3	4,4	-2,4	0,0											0,7

It can be seen that after 6 weeks the fruit size, weight, firmness (firmness), colour, TSS value (TSS ═ total soluble solids, which represents sugar content) and starch content of each group were higher than those of the untreated fruit.

Experiment 13: improving fruit quality (Jonagold apple and Conference pear)

Jonagold apples and Conference pears were treated in the same manner as experiment 12 at the RSF research center of Gorsem, Belgium. Comparing the treated and untreated fruits, it can be seen that the treated apples are much purer in pulp and have a significantly better green background colour. Further, it was found that it has no effect on the mineral composition of the fruit.

In the case of pears, the treated fruit has a significantly higher refractive index (indicating that the fruit has a higher sugar content) as viewed from the back light side of the fruit. Further, both the average fruit weight as well as the fruit diameter of the treated fruit tend to be greater. Further, it was also found that it has no effect on the mineral composition of the fruit.

Experiment 14: intensified chrysanthemum "Vesuvio Green"

The pedicel of some flowers develops coloration (padded), which can lead to a reduction in flowering time (from about 40 days (uncolored) to 27 days (colored)). Secondly, the leaves of the colored flowers are more oxidized (leaveburning).

A solution (stock solution) containing about 0.5 wt.% Si, about 0.1 wt.% B, and about 45 wt.% PEG400, pH0.5, was diluted 500-fold with tap water. The pH was about 6 and the solution temperature was about 17 ℃. About 1 liter was used to spray 20m²(50 ml of diluted solution/m²) So that the flowers (shoots) are covered with a film visible to the naked eye. No longer watering (with water or herbicide/insecticide, etc.) within 24 hours after spraying. Spray 7 times per week for 4 hours at regular intervals over 7 weeks. Each time, a fresh solution prepared by diluting the concentrated solution (stock solution) was used.

Flowers treated with the solution of the invention (diluted and sprayed with the diluted solution) showed the ability to absorb more water and dye (compared to flowers treated with tap water only). This indicates that the vascular bundle system has a more regular structure, resulting in reduced intake obstruction. Further, this treatment results in an extended flowering period.

Claims (21)

1. An aqueous solution comprising boric acid, non-colloidal silicic acid and a water absorbing additive, wherein the silicic acid form of silicon is between 0.01 and 2 wt% and the boric acid form of boron is between 0.0001 and 4 wt%, wherein the pH of the solution is below 2, the solution comprising stable silicic acid oligomers, the oligomers being less than 4 nanometers, wherein the solution can be filtered through a 0.1 micron filter membrane, and wherein the water absorbing additive is a polysorbate, a gum, a substituted cellulose, a polyglycerol fatty acid ester, a polyethylene glycol, a polydextrose, propylene glycol alginate, a glycerol polyethylene oxide ester, pectin or amidated pectin, sucrose fatty acid ester, acetylated or hydroxypropyl starch, starch phosphate, urea, sorbitol, maltitol, vitamins or mixtures thereof.

2. The solution of claim 1, which is filterable through a 20,000mw (da) filter.

3. The solution of claim 1 wherein the silicon to boron ratio is between 0.1 and 1000.

4. The solution according to any one of claims 1 to 3, wherein the concentration of the water-absorbing additive is at least 30% W/V for powders and V/V for liquids.

5. The solution of any one of claims 1-3, further comprising fulvic acid.

6. The solution of claim 5, wherein the final concentration of fulvic acid is between 0.1% (V/V) and 10% (V/V).

7. A process for preparing a solution according to any one of claims 1 to 6, wherein one or more silicon and boron compounds are subjected to hydrolysis in an acidic solution containing one or more dissolved water-absorbing additives.

8. Use of the solution according to any one of claims 1 to 6 or the solution obtained by the method according to claim 7, wherein the solution is diluted and added to plants or trees.

9. The use of claim 8, wherein the solution is diluted 200 to 20,000 times with water prior to addition to the plant or tree.

10. Use according to claim 8 or 9 for strengthening a plant or tree to increase its resistance against one or more of an microbial infection, an insect, a pest, a fungus or an extreme physiological condition.

11. The use of claim 8 or 9, wherein the solution is used in combination with a mineral, a nutrient, an antimicrobial formulation, an insecticide, a pesticide, a fungicide, a herbicide, or a combination thereof.

12. Use according to claim 8 or 9 for concentrating boron and silicon in vegetables and fruits.

13. Use according to claim 8 or 9, wherein the solution is added by spraying on the plant or tree and/or its leaves, or by adding the solution to a medium in which the roots of the plant or tree are located.

14. Use of a solution according to any one of claims 1 to 6 in the manufacture of a medicament for addition to fish.

15. The use according to claim 14, wherein the solution is diluted 1000 to 30000 times in the medicament.

16. The use of claim 14 or 15, wherein the medicament is for fortifying fish to increase their resistance against microbial infection.

17. The use of claim 14 or 15, wherein the solution is used in combination with minerals, nutrients, antimicrobial agents, or combinations thereof.

18. Use of a solution according to any one of claims 1 to 6 in the manufacture of a medicament for strengthening one or more of connective tissue, bone, skin, nails, arteries, cartilage and joints.

19. Use of a solution according to any one of claims 1 to 6 in the manufacture of a medicament for the treatment of a disease associated with one or more of bone, skin, arteries, connective tissue, cartilage, joints, osteoporosis, rheumatic diseases, arteriosclerosis, hair, nail and skin diseases, cardiovascular diseases, allergic diseases, arthritis and degenerative diseases.

20. Use of a solution according to any one of claims 1 to 6 in the manufacture of a food additive or supplement for the treatment of a disease associated with one or more of bone, skin, arteries, connective tissue, cartilage, joints, osteoporosis, rheumatic diseases, arteriosclerosis, hair, nail and skin diseases, cardiovascular diseases, allergic diseases, arthritis and degenerative diseases.

21. Use of a solution according to any one of claims 1 to 6 for the preparation of cosmetics, therapeutic creams and ointments, shampoos or gels.