JPS59190226A - Bivalent and trivalent iron salt and their preparation - Google Patents

Abstract

PURPOSE:To prepare a bivalent and a trivalent iron salts having physiological actions such as an inhibitory action on various kinds of ions, antiviral action, carcinostatic action, immunizing action, etc., by adding a trivalent iron salt to a large amount of an aqueous solution of a strong acid. CONSTITUTION:For example, a trivalent iron salt such as FeCl3, etc. is added to a large amount of aqueous solution of strong alkali, dissolved in it by stirring, and allowed to stand. The formed insoluble substances are filtered off, the filtrate is neutralized with an acid, concentrated under reduced pressure, dried and crystallized. An aqueous solution of alcohol is added to the crystal, the soluble component is collected, concentrated under reduced pressure to remove the solvent, and dried. These operations of extraction-concentration-drying are repeated several times, to prepare high-purity bivalent and trivalent iron salts. The bivalent and trivalent salts are inorganic or organic acid salts of iron showing properties between those of bivalent and trivalent iron salts.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a divalent and trivalent iron salt having an inhibitory effect on various ion reactions and also has physiological effects such as an antiviral effect, an anticancer effect, and an immunological effect.

A known existing divalent and trivalent iron compound is triiron tetroxide, but a divalent and trivalent iron salt is newly provided by the present invention. The divalent and trivalent iron salts dissolve in water, converting the water into a nonionic reaction system, suppressing various ionic reactions, and leading to reactions that are significantly different from those caused by ionic reactions in ordinary aqueous systems. It turned out to be a guide. It is clear that all normal in-vivo reactions take place in the same type of nonionic reaction system formed by the above-mentioned divalent and trivalent iron salts. Therefore, if divalent and trivalent iron salts are introduced into an abnormal living body, the nonionic reaction system within the living body will be restored, and the living body will be able to return to normal. Thus, the divalent and trivalent iron salt of the present invention has physiological effects such as antiseptic action, antiviral action, anticancer action, and immunological action in addition to metal corrosion inhibiting action, salt damage removal action, and soil damage removal action based on ionic reaction inhibition action. It also has a function.

The divalent and trivalent iron salts of the present invention are inorganic salts such as hydrochlorides, sulfates, phosphates, and nitrates, formates, acetates, and propionates of iron, which exhibit intermediate properties between divalent iron and trivalent iron. Organic salts such as
Large amounts of trivalent iron salts, caseinida, potassium hydroxide,
When placed in a strong alkali aqueous solution such as lithium hydroxide or calcium hydroxide to cause valence conversion to divalent iron,
It is obtained as a transition form when salts of divalent iron are added to a large amount of an aqueous solution of a strong acid such as hydrochloric acid or sulfuric acid to cause valence conversion to trivalent iron. Specific examples of the method for producing divalent and trivalent iron salts are shown below.

■, 1.0 ferric chloride (FeCl 3.6H20) from divalent iron salt
The mixture was poured into 0.00ml of 0.5N caustic soda aqueous solution, stirred for 7 hours to dissolve, and then set aside overnight. The resulting insoluble substances are classified into tears.
- Neutralize the Oki liquid with hydrochloric acid, then concentrate under reduced pressure and place in a desiccator.
The chloride of divalent and trivalent iron (hereinafter referred to as iron chloride (n, ITJ)) is thus supported on sodium chloride.
Iron chloride (IL)' is obtained from the support.
To separate iT), 50 m7 of an 80% aqueous Improvil alcohol solution is added, the eluted components are collected, concentrated under reduced pressure to remove the solvent, and dried. By repeating the above extraction-m and condensation-drying operations several times, 0.25Fl of iron chloride (T
i, m) are obtained ○2, 1.0# ferrous sulfate (FeSO47"/H20) from trivalent iron salt 10
0 yt of 0.5N aqueous hydrochloric acid solution, stirred and dissolved, and then set up overnight. The resulting insoluble substances are separated in a furnace, and the P solution is concentrated under reduced pressure and dried in a desiccator. To the obtained dry powder is added 10 d of an aqueous solution of isopropanol, the eluted components are collected, concentrated under reduced pressure to remove the solvent, and dried. By repeating the above extraction-concentration-drying operation several times, the fl
Iron chloride (I[, ITI) of p is obtained.

The divalent and trivalent iron salts of the present invention include inorganic compounds such as sodium chloride, sodium sulfate, ammonium chloride, ammonium sulfate, diatomaceous earth, bentonite, silica, alumina, etc.
It may also be supported on organic compounds such as vitamins, hormones, proteins, and lipids, and even in that case, the action of the divalent and trivalent iron salt does not change.

Examples of the present invention are shown below.

Example 1 (Corrosion protection of metal) This example shows the corrosion protection effect of divalent and trivalent iron according to the present invention. Corrosion of metals occurs due to the generation of corrosion current between similar or dissimilar metals on the metal surface. Therefore, corrosion protection can be achieved by surface treating metals with a solution containing divalent and trivalent iron.

After precaulking an iron piece of 0.2cMX5σX5ox and washing and drying it with dilute hydrochloric acid and distilled water,
) (2,5X 1.0-5g/lit), hydrofluoric acid (1,2X10'f/ml) and glucose
(10g/nl) (Pour into 200g of D mixed solution, 8g/nl)
It was treated at 0°C for 30 minutes.

When the treated iron piece was subjected to a corrosion test in an HCI air stream, the untreated iron piece already showed significant corrosion after one hour, but the treated iron piece showed no corrosion even after a 6-day corrosion test.

Example 2 (Removal of salt damage) This example shows the salt damage removal effect of divalent and trivalent iron of the present invention. Electrolyte solutions, especially seawater, are harmful to ships, seas, and coastal areas due to the metal ions they contain. These obstacles can be removed by the application of divalent and trivalent iron.0 Iron chloride (n
When , I [ It didn't happen.

Example 3 (Improvement of continuous cropping impaired soil) This example shows the effect of improving continuous cropping impaired soil with divalent and trivalent iron of the present invention. If the same crop is continuously cultivated, pathogenic bacteria may proliferate in the soil depending on the crop, making it almost impossible to harvest. The root cause is ionic reactions between inorganic and organic substances that accumulate in the soil. Therefore, these obstacles can be removed by introducing divalent and trivalent iron compounds.

Iron chloride (Il, IIr) with NaCl as a carrier was diluted with water to a concentration of 10 1j/lxl in soil with severe continuous cropping damage accompanied by the proliferation of 7salium that occurred in a radish cultivation area (under Gifu Prefecture). The diluted solution was applied to the soil to moisten it, and radish was planted as usual. As a result, all the crops in the treated soil grew healthy, and a yield index of 240 was obtained, compared to 11QO in the control plot.

Example 4 (Biological Tissue Preservation) This example shows the biological tissue preservation effect of divalent and trivalent iron of the present invention.

Once a biological tissue is separated from a living individual, biological components such as proteins and carbohydrates immediately begin to decompose because the biological system is destroyed and tissue functions are lost. Since divalent and trivalent iron compounds are basic substances that establish biological systems,
Even after the living tissue is cut out from the living body, tissue disintegration does not occur in a solution containing a divalent and trivalent iron compound.

α-t in 10d of iron chloride (1, lit) lo M solution
ocopherol and Ubiquinone (C
After adding and suspending a mixture of 0.11 each of o-enz7meQy), the above lipid portion was collected with ethanal.

In this way, the above-mentioned lipid carrying iron chloride (l, li) is obtained.This lipid is treated with Tween-2 as a surfactant.
00,1f/ was added and dispersed in water, and successively diluted with distilled water to prepare an adjusted solution with a lipid concentration of 2 x 10 M/L.

Immediately after killing the white rat, the muscle tissue was placed in a bottle, the above treatment solution was added, the bottle was tightly capped leaving some air space, and the bottle was allowed to stand at room temperature. At the same time, as a control, distilled water was added to the muscle tissue and the tissue was sealed and left standing.

As a result, the tissue in the control plot collapsed after one week, microorganisms multiplied, and water rapidly dried up. However, the tissue of the samples from the treatment area remained intact, no microbial growth occurred, and the liquid remained clear for more than 12 years.

Example 5 Regeneration of plant tissue) This example shows the regeneration effect of divalent and trivalent iron of the present invention on plant tissue.

Divalent and trivalent iron compounds are added to lipids (α-tocopherol).
+Ubiquinone) was synthesized as a carrier and adjusted with a solution with a lipid concentration of 7 10 M/L. Cut branches of Japanese black pine were immersed in the adjusted solution for 30 minutes, and then the cuttings were placed in a pot containing quartz sand. All of the control plots died, but the treated black pines took root and took root.

Example 6 (Abiotic synthesis of biological components) This example shows the effect of the divalent and trivalent iron of the present invention in abiotic synthesis of the main component.

In vivo, divalent and trivalent iron compounds are involved in the biosynthesis of body proteins, which is generally known as a genetic phenomenon. By using divalent and trivalent iron compounds, any protein can be synthesized in an abiotic system.

Iron chloride (II, m) was re-extracted from 100 g of a 1% iron chloride (n, III) aqueous solution containing 1 q of incirin, washed with ethanol, and then dried and purified. A new aqueous solution (10-6 M) containing this crystal as a solute was prepared, 0.1 g of cystine was dissolved therein, and the solution was subjected to dialysis through a cellulose membrane using distilled water as an external liquid.

1 oy of product in dialysis tube! When the Ig was collected, crystallized, and subjected to various analyses, it was confirmed that it was insulin with the same composition as before.

Example 7 (Preservative and anti-mold effect) This example shows the anti-septic and anti-mold effect of divalent and trivalent iron of the present invention. When divalent and trivalent iron compounds come into contact with microorganisms, they acquire new protein synthesis functions based on the information possessed by the microorganisms. This phenomenon has conventionally been understood as an antigen-antibody reaction.

This antibody can be used to prevent food from becoming preservative and moldy.

Iron chloride (n, l1lr) was synthesized using magnesium chloride as a carrier, and a solution with a magnesium chloride concentration of 1O-6f/xl was prepared and used as a treatment liquid.

The pre-caulked clams and mochi pieces were left standing at 32°C in an open system for 3 days to allow microorganisms to propagate. The resulting microorganisms were placed in a test tube containing 10ml of the above treatment solution, and 0.0% each of starch and peptone were added.
5g and left at 32°C for 5 days. 0.1 ptl of the resulting suspension was added to 100 grams of water, and this solution was poured over fresh clams and rice cakes, sealed and stored at room temperature.

In all control plots, rotting and mold growth was observed, but no growth of microorganisms occurred in the treated samples for more than 3 weeks.

Example 8 (Antiviral action) This example shows the antiviral action of divalent and trivalent iron of the present invention.

When a substance or factor that alters the biological system maintained by divalent and trivalent iron compounds invades from outside, the biological function deteriorates and appears as a so-called lesion. Viral infection disorders are caused by the introduction of nucleic acids from the outside and destruction of biological systems.

Therefore, infectious disorders can be eliminated by effectively introducing divalent and trivalent iron compounds.

TM and V were inoculated onto tomato leaves using a pre-caulked tomato as a host plant, and the sap was grown biologically. Just before the test, the sap was collected from the tomato leaves and diluted 500 times with water to prepare a test TMV suspension.

After about 1 month, carborundum was applied to leaves of cultivated tobacco plants, and half of the test leaves were treated with TMV suspension diluted 2 times with water as a control, and the other half of the test leaves were treated with TMV suspension. The solution was diluted 2 times with a testable solution and then soaked in cotton and applied. Testable liquids include iron chloride (II, III JIOM
A solution containing Mg Cl 2-6H20 added to a concentration of 1% was used. When the leaves are dry after application (approximately 3
0 minutes later] The remaining carborundum was washed with water, and the plants were cultured in a coitotron at 26°C.

After 3 days of culture, the number of spots that appeared on each test leaf and the inhibition rate of detectable substances were determined, and the results are shown in Table 1.

Table 1 Inhibition of virus infection by iron (II, In) chloride solution Example 9 (Anticancer effect) This example shows the anticancer effect of divalent and trivalent iron of the present invention. Malignant tumors are caused when biological systems are severely destroyed by viruses or various carcinogenic substances from the outside, and normal cells migrate to abnormal cells. By introducing divalent and trivalent ferrous compounds here, a biological system is established and the proliferation of abnormal cells can be inhibited.

Iron chloride (n, IIT) 10-6M solution 1. α-tocopherol and Ubiquinone in Otgl
(Co-enzVmeQ7) After adding and suspending 1.0 g of each mixture, the lipid portion was collected with ethanol. The above-mentioned lipid carrying iron chloride (T'J, m) is thus obtained. This lipid was dispersed in water with Tween-200.
A culture solution of c medium 858 was prepared. Try culturing healthy parts of the human stomach and cancerous tissues using culture media with various lipid concentrations.
The cells obtained by sim digestion were cultured for 24 hours from 1 to 1, and the number of cells was expressed as an index of 100 when cultured in a culture medium that did not contain lipids, as shown in Figure 1. . Clear inhibition of abnormal cell proliferation was observed at 2×10 M, where normal cell proliferation occurs.

Example 10 (Anticancer effect) This example also shows the anticancer effect of divalent and trivalent iron according to the present invention.
m) The complex was synthesized and orally administered to a terminal stage gastric cancer patient at 60 doses per day, resulting in complete recovery with the following progress.

Symptoms before application: 6cI in the pyloric region of the stomach of a patient (♀, 42 years old)
An R x 12a tumor had formed and removal surgery was not possible, so the tumor was left as is and only surgery was performed to connect the stomach and intestines with a tube.

Symptoms after application: Recovery of physical strength was observed from the first week, and from the third week the patient was able to go out, increased food intake, and gained weight.

One month later, the patient was able to lead a normal daily life. Since application, liver functions have remained normal.

[Brief explanation of the drawing]

FIG. 1 shows the proliferation index in a culture solution containing divalent and trivalent iron salts. In the figure, lines indicate normal cells, lines indicate abnormal cells, patent applicant Shoji Yamashita

Claims (1)

[Scope of Claims] 1. Divalent and trivalent iron salt 2. A method for producing a divalent and trivalent iron salt, which is characterized by adding the trivalent iron salt to a large amount of a strong alkali aqueous solution 3. Divalent iron salt Method 4 for producing a divalent and trivalent iron salt, characterized in that it is added to a large amount of an aqueous solution of a strong acid, Claim 1
An inorganic compound 5 carrying divalent and trivalent iron, and an organic compound carrying divalent and trivalent iron according to claim 1.