CN100355918C - Preparation method and use of single, compound arsenic with bio-effect - Google Patents
Preparation method and use of single, compound arsenic with bio-effect Download PDFInfo
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- CN100355918C CN100355918C CNB2006100531152A CN200610053115A CN100355918C CN 100355918 C CN100355918 C CN 100355918C CN B2006100531152 A CNB2006100531152 A CN B2006100531152A CN 200610053115 A CN200610053115 A CN 200610053115A CN 100355918 C CN100355918 C CN 100355918C
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- arsenic
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- elemental
- arsenide
- elemental arsenic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a method for simple substance arsenic with biology effect and the application. It generates simple substance arsenic by reduction reaction in the colloid system with the existence of protection agent that plays a role of bi-template, dispersing and stabilizing simple substance. The mineral used as carrier supplies large scale surface for the dispersing of simple substance to make it has small diameter, narrow distribution and good stability. The invention has the advantages of low toxicity, high efficiency. It could be used as feed additive or pesticide, and also could be used to make health products and medication for cure tumor.
Description
Technical field
The present invention relates to a kind of elemental arsenic preparation method and purposes with biological effect.
Background technology
Arsenic belongs to metalloid element, has the character of amphoteric element, and nonmetallic property is stronger.Arsenic is a kind of very dispersive element, seldom sees the arsenic of native state at nature, mainly exists with the sulphide ores form.The toxicity of arsenic compound is relevant with its dissolving poison in water, and element arsenic is water insoluble, thus nontoxic, yellow arsenic, arsenic trisulfide is water-soluble very little, and toxicity is lower, and white arsenic is soluble in water, and toxicity is very big.The toxicity of arsenic compound reduces according to following order: hydrogen arsenide＞As
2O
3The compound of＞arsenus acid＞arsenic acid＞arsenic (four arsenic that organic group is positively charged)＞elemental arsenic.The toxicity of trivalent arsenic compound is greater than the pentavalent arsenic compound.
Arsenical has antitumor spectra widely, and studying more at present is white arsenic (As
2O
3), yellow arsenic (As
2S
2, the main component of realgar) and organoarsenic U.S.A draw arsenic alcohol (melarsoprol), phenylarsine oxide (PAO) etc.In the arsenical with As
2O
3The toxicity maximum, As is adopted in the antitumor research of carrying out both at home and abroad at present of arsenical more
2O
3(major ingredient is As to arsenic
2O
3) and realgar (major ingredient As
2S
2) as drug use in the traditional Chinese medical science history of existing nearly one thousand years.The traditional Chinese medical science thinks that both are all arduous, poisonous, and Chang Weiliang is used for eliminating dampness, dispels the wind, desinsection and detoxifcation.In western countries, the therapeutic treatment effect of arsenic starts from the 15th century.To 18th century, Thomas doctor Fowler has developed the As that is dissolved in saleratus
2O
3Preparation, Here it is well-known FowlerShi liquid, it mainly is to be used for the treatment of various infectivity and malignant disease by rule of thumb.Chinese scholar adopts injection As in recent years
2O
3Treatment acute promyelocytic leukemia (APL) has been obtained the progress that attracts people's attention, and " science " magazine claims " this is another thrilling discovery after all-trans-retinoic acid (ATRA) ".Thereby the arsenide that always is considered to severe toxicity caused people again, particularly studies the scholars' of tumour pass both at home and abroad, extensively carried out the research of arsenide treatment neoplastic hematologic disorder and solid tumor.But still there are many problems at present in the clinical application of traditional arsenic preparation, and is big as toxic side effect, particle is bigger than normal, bioavailability is lower etc., thus we see contain arsenic class Chinese medicine clinical value in.If can be by improving conventional formulation technology.Adopt modern technologies to prepare and novelly contain arsenic Chinese medicine, will have the important clinical meaning thereby improve bioavailability, reduce drug dose, reduce toxic side effect and improve curative effect.
Arsenic preparation has also obtained using widely in livestock industry.Arsenide as fodder additives mainly is the little organoarsenic of toxicity, and at present commonly used have atoxylic acid (Pro-gen 90), 3-nitro-4-phenol-arsonic acid (Luo Keshasheng), an Arsanilic acid sodium salt etc.Arsenic mainly comprises the biological function of livestock and poultry: 1. participate in protein metabolism; 2. the activator of some enzyme and inhibitor; 3. directly or by the erythrocytic degradation production in the blood come the hemopoietic organ; Can quicken bone growth when low dose of, make the bone hematopoietic function active, impel red corpuscle and hemochrome new life, improve skin-nourishing, the excitor nerve system improves a poor appetite, and improves digestibility; Then suppress hemocytopoietic organ when heavy dose of; 4. prevent arseniasis, arsenic and arsenic all have the anti-toxic unique effect of multiple metal, and each toxic toxinicide each other again, arsenic still are stupid dose of arsenic, mercury, plumbous a word used in person's names; 5. relevant with the breeding of animal; 6. make the attenuation of intestines wall, thereby help the absorption of nutritive substance; 7. reduce intestinal bacteria quantity, have anti-microbial effect, so once once controlled the pig dysentery characterized by blood in the stool with arsenide; 8. can effectively suppress Enterozoa, have outstanding performance aspect the anticoccidial of chicken especially.
Summary of the invention
The purpose of this invention is to provide a kind of elemental arsenic preparation method and purposes with biological effect.
A kind of preparation method with elemental arsenic of biological effect may further comprise the steps:
1) with white arsenic (As
2O
3), arsenic trisulfide (As
2S
3), yellow arsenic (As
2S
2) or the arsenide of their combinations, being dissolved in the aqueous sodium hydroxide solution of 0.1～10moL/L, the solid-to-liquid ratio of arsenide and sodium hydroxide solution is (1～100) g: 1L;
2) with weight be the protective material of 10～1000 times of arsenides, be mixed with the protective material aqueous solution of bulking value concentration for (0.1～100) g: 1L, slowly add in the arsenide aqueous solution of step 1), slowly add the reductive agent that molar ratio is 3～10 times of arsenides down again in stirring, the pH=4 of conditioned reaction system～9, room temperature reaction 1～10 hour;
3) reaction solution step 2) is a kind of elemental arsenic colloidal sol with biological effect, perhaps with step 2) reaction solution that obtains carries out centrifugal or filtering separation under nitrogen or argon gas atmosphere, centrifugal or the filter dehydration in washing back, the filter cake of gained obtains having the elemental arsenic of biological effect being lower than vacuum-drying under 80 ℃ of temperature, being crushed to greater than 300 orders.
The said protective material of the present invention is Xylo-Mucine, glucomannan, chitosan, polyvinyl alcohol, polyoxyethylene glycol or polyvinylpyrrolidone.Said reductive agent is vitamins C, mercaptoethanol, POTASSIUM BOROHYDRIDE, sodium borohydride, Na
2S
2O
3, Na
2S
2O
4, S-WAT, sodium bisulfite, Sodium Pyrosulfite or hydrazine hydrate.
A kind of have the elemental arsenic of biological effect as ox, sheep, livestock and poultry, aquatic animal feed additive.
A kind of elemental arsenic used as pesticides with biological effect.
A kind of elemental arsenic with biological effect is used to prepare by antineoplastic healthcare products of the arsenic of drug treatment and medicine.
Advantage of the present invention is:
(1) the present invention is in the colloidal dispersion that protective material exists, and arsenic compound is added the reductive agent reduction form elemental arsenic.Because protective material absorption is wrapped in the elemental arsenic surface and protective material forms the colloidal dissemination, protective material plays a part template, dispersion and stable elemental arsenic, and the elemental arsenic particle diameter that makes is little, narrowly distributing, good stability.
(2) elemental arsenic of the present invention has low toxicity, characteristics of high efficiency, and use range is extensive, can be used as fodder additives or agricultural chemicals; The arsenic that also can be used for preparing by drug treatment comes antineoplastic healthcare products and medicine.
Embodiment
The present invention is further described in conjunction with following example.
Embodiment 1
1) with white arsenic (As
2O
3) be dissolved in the aqueous sodium hydroxide solution of 0.1moL/L, As
2O
3With the solid-to-liquid ratio of sodium hydroxide solution be 1g: 1L;
2) be As with weight
2O
310 times Xylo-Mucine is mixed with the sodium carboxymethyl cellulose solution that bulking value concentration is 0.1g: 1L, slowly adds the As of step 1)
2O
3In the aqueous solution, slowly adding molar ratio again under stirring is As
2O
33 times vitamins C, the pH=4 of conditioned reaction system, room temperature reaction 1 hour;
3) reaction solution step 2) is a kind of elemental arsenic colloidal sol with biological effect.
Embodiment 2
1) with arsenic trisulfide (As
2S
3) being dissolved in the aqueous sodium hydroxide solution of 10moL/L, the solid-to-liquid ratio of arsenide and sodium hydroxide solution is 100g: 1L;
2) be As with weight
2S
31000 times polyvinylpyrrolidone, being mixed with bulking value concentration is the polyvinylpyrrolidone aqueous solution of 100g: 1L, slowly adds the As of step 1)
2S
3In the aqueous solution, slowly adding molar ratio again under stirring is As
2S
310 times POTASSIUM BOROHYDRIDE, the pH=9 of conditioned reaction system, room temperature reaction 10 hours;
3) with step 2) reaction solution that obtains carries out centrifugation under nitrogen atmosphere, washing back centrifuge dehydration, the filter cake of gained obtains having the elemental arsenic of biological effect being lower than vacuum-drying under 80 ℃ of temperature, being crushed to 400 orders.
Embodiment 3
1) with yellow arsenic (As
2S
2) be dissolved in the aqueous sodium hydroxide solution of 5moL/L, As
2S
2With the solid-to-liquid ratio of sodium hydroxide solution be 50g: 1L;
2) be As with weight
2S
2100 times chitosan, being mixed with bulking value concentration is the chitosan aqueous acetic acid of 10g: 1L, slowly adds the As of step 1)
2S
2In the aqueous solution, slowly adding molar ratio again under stirring is As
2S
27 times hydrazine hydrate, the pH=8.5 of conditioned reaction system, room temperature reaction 5 hours;
3) with step 2) reaction solution that obtains carries out filtering separation under argon gas atmosphere, the dehydration of washing after-filtration, the filter cake of gained obtains having the elemental arsenic of biological effect being lower than vacuum-drying under 80 ℃ of temperature, being crushed to 500 orders.
Embodiment 4
1) with 1 gram white arsenic (As
2O
3) and 1 gram arsenic trisulfide (As
2S
3) arsenide that combines is dissolved in the aqueous sodium hydroxide solution of 200 milliliters of 1moL/L;
2) 100 gram polyvinyl alcohol are dissolved in 10 premium on currency, slowly add again in the arsenide aqueous solution of step 1), slowly add the Na that molar ratio is 10 times of arsenides down again in stirring
2S
2O
3, the pH=6.0 of conditioned reaction system, room temperature reaction 5 hours;
3) reaction solution step 2) is a kind of elemental arsenic colloidal sol with biological effect.
Claims (5)
1. preparation method with elemental arsenic of biological effect is characterized in that the step of method is as follows:
1) with white arsenic (As
2O
3), arsenic trisulfide (As
2S
3), yellow arsenic (As
2S
2) or the arsenide of their combinations, being dissolved in the aqueous sodium hydroxide solution of 0.1～10moL/L, the solid-to-liquid ratio of arsenide and sodium hydroxide solution is (1～100) g: 1L;
2) with weight be the protective material of 10～1000 times of arsenides, be mixed with the protective material aqueous solution of bulking value concentration for (0.1～100) g: 1L, slowly add in the arsenide aqueous solution of step 1), slowly add the reductive agent that molar ratio is 3～10 times of arsenides down again in stirring, the pH=4 of conditioned reaction system～9, room temperature reaction 1～10 hour;
3) reaction solution step 2) is a kind of elemental arsenic colloidal sol with biological effect, perhaps with step 2) reaction solution that obtains carries out centrifugal or filtering separation under nitrogen or argon gas atmosphere, centrifugal or the filter dehydration in washing back, the filter cake of gained is being lower than vacuum-drying under 80 ℃ of temperature, is being crushed to greater than 300 orders, obtain having the elemental arsenic of biological effect
Said protective material is Xylo-Mucine, glucomannan, chitosan, polyvinyl alcohol, polyoxyethylene glycol or polyvinylpyrrolidone.
2. the preparation method with elemental arsenic of biological effect according to claim 1 is characterized in that, said reductive agent is vitamins C, mercaptoethanol, POTASSIUM BOROHYDRIDE, sodium borohydride, Na
2S
2O
3, Na
2S
2O
4, S-WAT, sodium bisulfite, Sodium Pyrosulfite or hydrazine hydrate.
3. the purposes with elemental arsenic of biological effect as claimed in claim 1 is characterized in that it is used as ox, sheep, livestock and poultry, aquatic animal feed additive.
4. purposes with elemental arsenic of biological effect as claimed in claim 1 is characterized in that it uses used as pesticides.
5. the purposes with elemental arsenic of biological effect as claimed in claim 1 is characterized in that being used to prepare by antineoplastic healthcare products of the arsenic of drug treatment and medicine.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100531152A CN100355918C (en) | 2006-08-24 | 2006-08-24 | Preparation method and use of single, compound arsenic with bio-effect |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100531152A CN100355918C (en) | 2006-08-24 | 2006-08-24 | Preparation method and use of single, compound arsenic with bio-effect |
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| Publication Number | Publication Date |
|---|---|
| CN1912158A CN1912158A (en) | 2007-02-14 |
| CN100355918C true CN100355918C (en) | 2007-12-19 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111519044A (en) * | 2020-05-19 | 2020-08-11 | 福州大学 | Method for preparing simple substance arsenic by chemical reduction of sodium arsenate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB248975A (en) * | 1925-06-10 | 1926-03-18 | Basf Ag | Improvements in the manufacture and production of arsenic preparations |
| US4244927A (en) * | 1979-07-27 | 1981-01-13 | Hazen Research, Inc. | Process for recovering arsenic compounds by sodium hydroxide leaching |
| CN1120018A (en) * | 1994-05-07 | 1996-04-10 | 湖南大学 | Method of wet-extraction for arsenic |
| CN1042919C (en) * | 1994-05-07 | 1999-04-14 | 湖南大学 | Method of wet-extraction for arsenic |
-
2006
- 2006-08-24 CN CNB2006100531152A patent/CN100355918C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB248975A (en) * | 1925-06-10 | 1926-03-18 | Basf Ag | Improvements in the manufacture and production of arsenic preparations |
| US4244927A (en) * | 1979-07-27 | 1981-01-13 | Hazen Research, Inc. | Process for recovering arsenic compounds by sodium hydroxide leaching |
| CN1120018A (en) * | 1994-05-07 | 1996-04-10 | 湖南大学 | Method of wet-extraction for arsenic |
| CN1042919C (en) * | 1994-05-07 | 1999-04-14 | 湖南大学 | Method of wet-extraction for arsenic |
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|---|---|
| CN1912158A (en) | 2007-02-14 |
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Granted publication date: 20071219 Termination date: 20100824 |