CN1264521C - Nano selenium of chitin and its preparation method - Google Patents
Nano selenium of chitin and its preparation method Download PDFInfo
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- CN1264521C CN1264521C CN 02138643 CN02138643A CN1264521C CN 1264521 C CN1264521 C CN 1264521C CN 02138643 CN02138643 CN 02138643 CN 02138643 A CN02138643 A CN 02138643A CN 1264521 C CN1264521 C CN 1264521C
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Abstract
The present invention relates to a nanometer selenium of chitin, which is a compound comprising chitin and red nanometer selenium. The compound is prepared by the reaction of the chitin comprising chitosan, water-soluble chitosan and chitosan oligosaccharide and a selenium compound. The structure, the composition, the property of the nanometer selenium of chitin are comparatively researched by an infrared spectrometer, an ultraviolet spectrometer, a mass spectrometer, a transmission electron microscope, etc. The red nanometer selenium is absorbed and wrapped by the chitin to form a stable particle, and the microstructure is in a spherical or fractal structure. The structure and the property of the chitin are unchanged. The nanometer selenium of chitin has the efficacy of immunological regulation, ageing resistance of the nanometer selenium and the chitin, face beautification, cancer prevention, cardiovascular disease prevention, etc. The nanometer selenium of chitin has wide application prospects in the fields of medicine, health protection, food, etc. The preparation method is simple and practical at normal temperature and pressure, and the nanometer selenium of chitin is operated and controlled conveniently, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of nutritional health food and preparation method thereof, say it is chitin nanometer selenium and preparation method thereof definitely.
Background technology
Chitin (Chitin) has another name called chitin, chitin, and chitin, poly-acylamino-glucoses etc. are a kind of linear aminopolysaccharides of keeping and protecting crustacean and microorganism body.Chitin extensively is present in the cell of rudimentary plant mushroom, algae, the shell of arthropod shrimp, Eriocheir sinensis, fly larvae and insecticide, the shell and the cartilage of shellfish, Mollusca (as squid, sepiellae seu sepiae), the cell wall of higher plant etc., its annual biosynthetic stock number is up to 10,000,000,000 tons, be the second largest living resources that are only second to the Plant fiber on the earth, wherein halobiontic growing amount is more than 1,000,000,000 tons, can be described as a kind of nexhaustible natural resources, be called as the third-largest living resources except that starch, cellulose.French scientist Bu Lakenuo (Braconmo) at first extracted a kind of Plant fiber's of being similar to hexose polymer in 1811 from mushroom, its called after Fungine (gill fungus element).1823, French scientist Ou Jieer (Odier) also extracted this material in the crustacean shell, and called after Chitin (chitin), and the meaning of " shell ", " envelope " be willing to mean in the Chitin Greek.The mankind utilize carapace resource source to start from China the earliest, are just putting down in writing the function that carapace has broken silt removing food stagnancy in the famous Compendium of Materia Medica, and " Eriocheir sinensis " word itself promptly refers to: the antidotal insects.
Chitin belongs to the straight chain aminopolysaccharide, and formal name used at school is [(1,4)-2-is acylamino--2-deoxy-D-glucose], and molecular formula is (C
8H
13NO
5) n, connecting with (1 → 4) key between the monomer, molecular weight is generally 10
6About, theoretical nitrogen content 6.9%.Its molecular structure characteristics are: oxygen atom is connected to the sugar ring of each carbon atom on the next sugar ring, and pendant groups " extension " is on these rings.The cellulose that extensively exists in chitin molecule chemical constitution and the plant is closely similar, and different is that if the hydroxyl of forming on second carbon atom of cellulosic single glucose molecule is changed into hexanamido, such cellulose has just become chitin.Carapace have α, β, three kinds of crystal formations of γ, and wherein α-chitin exists the abundantest, also the most stable.Because extremely strong hydrogen bond action between the macromole causes it generally not allow and water, chemical property is highly stable, thereby uses limitedly, is called chitin usually.The chitin of occurring in nature is to be closely linked with each water-fast inorganic salt and protein mostly.People are in order to obtain chitin, and the shell that often first is restrained animal is sloughed calcium salt, protein by acid-alkali treatment, can obtain chitosan, then, and then, just can be translated into water-soluble chitosan, oligochitosan etc. with methods such as alkaline hydrolysis, acidolysis, oxidation, enzymolysis, structural modifications.Chitin is the unique positively charged natural polymers of nature, it is the edibility animal fiber of unique cation, also be necessary the 6th vital principle of human health after protein, sugar, fat, cellulose, mineral, enjoy the good reputation of " soft gold " abroad.
The molecular weight of chitin own surpasses 1,000,000, neither is dissolved in water, also is not dissolved in general soda acid, can not utilize for human body decomposes, and is used in the adsorption treatment of waste water, radiocontamination more.After chemistry or biochemical treatment, chitin can generate the chitose that is dissolved in diluted acid, can be applied in industrial circle, agriculture field, cosmetics, medicine, material and other environmental protection, health field.Various water-soluble chitosans, the water-soluble chitosan oligosaccharide developed of people has better physiologically active in recent years, both can suppress cancer, hepatopathy, diabetes, and cholesterol has the enhancing body immunity again, and a series of spirited effects such as prevent to wear out.For example, oligochitosan is in human body internal absorption factor nearly 100%, has the immunity of raising, suppress the growth of cancerous protuberance cell, promote liver spleen antibody to form, promote the absorption of calcium and mineral, the propagation bifidus bacillus, human body beneficial's floras such as lactobacillus, blood fat reducing, blood pressure lowering, blood sugar lowering, cholesterol regulating, fat-reducing, functions such as prevention adult disease also can obviously be eliminated human body negative oxygen ion free radical, the activation equipment somatic cell, slow down aging, suppress the harmful bacterium of skin surface and grow, and have performance of keeping humidity, antiseptic property is widely used in medicine with it both at home and abroad, food, fields such as health care.
From the sixties in 20th century, the research of relevant chitin becomes very active, and many countries all very pay close attention to these research.Special formula started one chitin research and development upsurge in nearly 10 years at home, had set up many chitins research institution, and the Ministry of Science and Technology is listed it in " 95 ", " 15 " key research projects.The enterprise that the chitin exploitation is engaged in the whole world has reached thousands of families.The research and development of chitin are to become the sciemtifec and technical sphere that catches people's attention and rich new industry of making a profit.Some developed countries competitively drop into substantial contribution and research and develop.Japanese government transfers to 5,000,000,000 dollars of startup funds to entrust 13 universities in the whole nation that chitin is carried out system development, is obtaining great achievement aspect basic research and the application and development so far.Chitin is the unique functional food of being permitted to propagate curative effect of Japanese government at present.Japanese health ministry in 1993 has been accepted the application that chitin acts on cancer cell metastasis inhibitor intravenous injection medicine.Chitin in 1996 has passed through united states drug, food control office (FDA) and the European Community (EC) again to be appraised and decided, and checks and approves the European market in the U.S..Global competition trend has appearred in the research and development of chitin and commercial product thereof, and will continue the stable high speed development of maintenance.Someone says: " 21 century STUDY ON POLYSACHAROSE most promising be chitin." also the someone say: " 20th century were centuries of plastics, and 21 century is the century of chitin.”
1973, The World Health Organization (WHO) announced to the whole world: selenium is trace element essential in human and animal's life, and selenium supplement can effectively prevent multiple disease.
Selenium is the component of GPx in the organism (glutathion peroxidase), PHGPx (phospholipid hydrogen glutathion peroxidase), ID (5 '-take off iodine enzyme) active center key, participate in the metabolism of body endoperoxide and iodine, regulate the level and the free radical level of iodine in the organism, but enhancing body diseases prevention, resistance against diseases.Selenium has the effect of aspects such as removing free radical, prophylaxis of cancer, face nourishing antidebilitation, the liver protecting, opposing harmful heavy metal, radioprotective, immunomodulating; selenium has remarkable effect to treatment hepatitis, arthritis, cataract, cardiovascular disease, lupus erythematosus, hemorrhagic fever, and selenium also has tangible auxiliary treatment effect to the chemicotherapy of tumour patient.
A large amount of clinical researches, Epidemiological study prove: selenium is the anticancer factor that body weight for humans is wanted.In hepatocarcinoma district occurred frequently, Qidong, Jiangsu, esophageal carcinoma district occurred frequently, Lin County, Henan, the crowd has significantly reduced cancer morbidity after strengthening selenium supplement.In the U.S., 8000 people are carried out decade-long selenium supplement research, the result shows that selenium can significantly reduce the sickness rate of cancers such as pulmonary carcinoma, intestinal cancer, gastric cancer, leukemia, so selenium is confirmed to be " trophism anticarcinogen ".Finland has carried out follow-up study in 23 years, finds that low selenium state smoking population patients with lung cancer crowd blood Se content is lower than healthy population.The U.S. just went out a monograph about AIDS and nutrition before 5 years, it is all relevant with patient's Se content from infecting to life cycle to mention AIDS in the book.Studies show that if lack selenium, lymphocyte is broken through by virus especially easily, so ubiquity lacks the selenium situation in the Susceptible population.In addition, virus will consume selenium in a large number in reproduction process, also can cause to lack selenium in the human body.So, in the AIDS treatment, can continue its life cycle for patient's selenium supplement.China scientist proves, scarce selenium is the main cause of keshan disease, and Keshan disease area all is in and lacks the selenium area, and this disease shows that the heart of human body is subjected to major injury, through pathological anatomy, disease patient's heart generally is the part of normal person's heart.Result of the test shows that selenium supplement can make prevalence and case fatality rate descend 80%.Along with the age increases, the ability that human body produces antioxidant reduces gradually, and the defence capability decline to free radical damage causes old and feeble the acceleration.A large amount of clinical researches show, selenium is as antioxidant, can remove intravital free radical rapidly after entering human body, thereby can defend the infringement of radical pair cell effectively, reduce the formation of lipofuscin, have anti-ageing effect of lengthening the life.
Disclose according to World Health Organization (WHO), the whole world has 2,000,000,000 populations (in state-owned 200,000,000 populations) to survive in scarce selenium environment approximately at present.Selenium supplement can effectively prevent and treat multiple disease, but a selenic marked feature be exactly between its nutrition dosage and the toxicity dose scope narrow, and selenic useful physiological action such as anticancer often depends on higher intake, so its effective use amount is difficult to control.For many years, people are studying the efficient selenium product of low toxicity always.Compare with inorganic selenium, it is higher that the absorbing of organic selenium is worth, and acute toxicity is less, is considered to selenium product preferably.Experimental study shows that nanometer selenium more is better than organic selenium in many aspects, demonstrates the efficient feature of low toxicity: aspect acute toxicity (LD50), inorganic selenium are 15mg/kg, and organic selenium is 35mg/kg, and nanometer selenium then is 113mg/kg.Aspect the slow toxicity in Asia, the content of inorganic selenium or organic selenium can cause rat body weight to descend and liver cirrhosis when 4～5ppm in the feedstuff, and above-mentioned phenomenon does not take place when 6ppm nanometer selenium content yet.Aspect biological effect, the external removing hydroxy radical of nanometer selenium efficient is 5 times of inorganic selenium, is 2.5 times of organic selenium.In addition, the nanometer selenium sensitive characteristics that also shows abnormality aspect health-care effect, nanometer selenium are promptly demonstrating under low dosage very and are suppressing tumor and immunomodulating health-care effect, and the inorganic selenium of corresponding low dosage there is no effect.In a word, nanometer selenium has the characteristics of high security and high bioactivity, is a kind of good immunomodulator and antioxidant, has effectiveness such as disease resistance, slow down aging.
The biological effectiveness of nanometer selenium is approved that health ministry approved nanometer selenium capsule is health food (No. the 134th, a hygienic food and health number 1998).
CN1184776A discloses a kind of preparation method of red elemental selenium, reduction selenium compound or grey black simple substance selenium obtain protein attitude red elemental selenium or polypeptide attitude red elemental selenium in protein or polypeptide system (solution), obtain the red elemental selenium of biologically active again through separation.
Summary of the invention
The present invention will have the nanometer selenium of biological significance and the catabolite of chitin comprises that chitosan, water-soluble chitosan and water miscible oligochitosan etc. combine, and are used for people's nourishing healthy or disease treatment or auxiliary treatment.Problem to be solved is at first to prepare stabilized nano selenium and chitin complex, and take on a red color nanomorphic and be rolled into stable particle by chitin absorption of selenium is referred to as the chitin nanometer selenium in the complex.
Technical scheme of the present invention is directly to prepare the chitin nanometer selenium with selenium compound and chitin.
Described selenium compound can be selenite or acid selenite, such as sodium selenite (Na
2SeO
3), hydrogen selenite is received (NaHSeo
3) etc., also can be selenium dioxide (SeO
2), it reacts under the Reducing agent existence condition to redness with chitin or its solution and no longer changes.Can also use the initiation material selenium dioxide, water and sodium hydroxide prepare selenite or acid selenite earlier, and product needn't separate, and directly react to redness with chitin or its solution no longer to change under the Reducing agent existence condition.
Described selenium compound can also be a seleno sulfate, as sodium thiosulfate (Na
2SeSo
3) etc., it mixes the back with chitin or its solution and transfers PH to 4.5～6.5 with organic acid.
Described chitin comprises chitosan, water-soluble chitosan and water-soluble chitosan oligosaccharide etc.
The first-selected vitamin C of described Reducing agent.
Described organic acid can be an ascorbic acid, other edible organic acid such as citric acid.
The relative quantity of two kinds of main component selenium compounds and chitin can the proper proportion adjustment during preparation.But should note selenic intake when using the chitin nanometer selenium to be processed into health-care products or when adding in other health product or the medicine as auxiliary agent.
Chinese scholar Yang Guangqi professor and professor Chen Xiaoshu etc. are through result of study is as follows for many years: selenic physiological need amount 40 micrograms (ug)/day, boundary toxic dose 800ug/ day, suggestion meal supplement amount 50～250ug/ day, the highest safe intake 400ug/ day.These data are adopted by three international organizations of FPA/WHO/IAEA.
The chitin nanometer selenium is through infrared spectrometer, ultraviolet spectrometer, velocitron, transmission electron microscope etc. are to its structure, many-sided comparative study of composition and character shows, it is spherical or fractal structure that red nano selenium is rolled into stable particle microstructure by chitin absorption, the structure of chitin, character does not change.Product has nanometer selenium and chitin immunomodulating concurrently, face nourishing antidebilitation, and effects such as prophylaxis of cancer and cardiovascular disease, at medicine, health care, fields such as food have wide practical use.
Preparation method is simple, normal temperature and pressure,, operation, control is convenient, if also do not relate to the separation of product, suitability for industrialized production with initiation material.
The specific embodiment
1. it is soluble in water to get 0.05g sodium selenite or sodium hydroselenite, evenly spray then in 5g chitosan powder or the oligochitosan powder and make it moistening, spray vitamin c solution at last while stirring, no longer change to the mixture redness, vacuum drying is sloughed moisture and is promptly got product.
2. get the 0.05g sodium selenite or inferior selenium hydrogen sodium is soluble in water, stir and add the aqueous solution that contains 5g chitosan or oligochitosan down, add vitamin C or its solution to reactant liquor redness more no longer to change, the product that moisture is is sloughed in distilling under reduced pressure.
3. in embodiment 1 and 2, can use initiation material to prepare sodium selenite or hydrogen selenite sodium solution earlier, product needn't be separated, and directly is used for preparing the chitin nanometer selenium.Here it is uses earlier selenium dioxide, water and sodium hydroxide prepare sodium selenite or hydrogen selenite sodium solution, directly prepare chitin nanometer selenium (as embodiment 1) with chitosan powder or oligochitosan powder, vitamin c solution then with this reactant liquor, perhaps with chitosan or oligochitosan aqueous solution, vitamin C or its formulations prepared from solutions chitin nanometer selenium (as embodiment 2).
4. get 0.05g sodium selenite or sodium hydroselenite or selenium dioxide and grind with 5g chitosan powder or the oligochitosan powder even back that is mixed, adding vitamin C or its aqueous solution while grinding, the mixture color reddens gradually, no longer changes until redness promptly to get product.If added is the vitamin C aqueous solution.Then need the vacuum drying dehydration.
5. getting 0.05g sodium selenite or sodium hydroselenite or selenium dioxide under agitation drops into and adds vitamin C or its aqueous solution in the aqueous solution that contains 5g chitosan or oligochitosan again, the reactant liquor color reddens gradually and no longer changes until redness, and the product that moisture is is sloughed in distilling under reduced pressure.
6. getting the sodium thiosulfate solution that contains 0.05g grinds after with 5g chitosan powder or oligochitosan powder mix homogeneously, add ascorbic acid or its aqueous solution while grinding, perhaps add other edible organic acid solns such as citric acid, the color of mixture reddens gradually and no longer changes until redness, the PH of this moment 4.5～6.5 stops to add acid, ground 3 minutes, vacuum drying is sloughed the product that moisture is again.
7. get the sodium thiosulfate solution that contains 0.05g, under agitation drop into and contain in the aqueous solution of 5g chitosan or oligochitosan, add other edible organic acid solns such as ascorbic acid or citric acid again, the reactant liquor color reddens gradually, no longer change until redness, stop to add acid, the PH of this moment is 4.5～6.5, and distilling under reduced pressure is sloughed moisture and promptly got product.
8. in embodiment 6 and 7, can use initiation material preparation sodium thiosulfate solution earlier, product needn't be separated, and directly is used for preparing the chitin nanometer selenium.Here it is earlier with sodium thiosulfate or sodium sulfite with simple substance selenium prepared in reaction sodium thiosulfate solution; Perhaps with sodium selenite with elemental sulfur prepared in reaction sodium thiosulfate solution.Directly use this sodium thiosulfate solution with chitosan powder or oligochitosan powder (as embodiment 6) then, perhaps chitosan or oligochitosan solution (as embodiment 7) prepare the chitin nanometer selenium.
Claims (3)
1, a kind of chitin nanometer selenium, it is characterized in that: sodium selenite or sodium hydroselenite or selenium dioxide react the complex that no longer changes red nano selenium that the back drying obtains and chitin composition to red in Reducing agent or sodium thiosulfate under the organic acid existence condition in chitin, and described chitin is meant chitosan, water-soluble chitosan and oligochitosan.
2, the preparation method of the described chitin nanometer selenium of a kind of claim 1, comprise and mixing and dehydration, it is characterized in that: sodium selenite or sodium hydroselenite or selenium dioxide or its aqueous solution are mixed with chitosan or water-soluble chitosan or oligochitosan aqueous solution and Reducing agent vitamin C, by grinding or stirring reaction to redness no longer changes the back dehydrate.
3, the preparation method of the described chitin nanometer selenium of a kind of claim 1, comprise and mixing and dehydration, it is characterized in that: transfer reactant pH to 4.5～6.5 with ascorbic acid or citric acid by sodium thiosulfate solution after with chitosan or water-soluble chitosan or oligochitosan aqueous solution, by grinding or stirring reaction to redness no longer changes the back dehydrate.
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| CN101721435B (en) * | 2009-12-10 | 2012-02-22 | 安徽省康美来大别山生物科技有限公司 | Ganoderma lucidum spore and nano selenium compound and preparation method thereof |
| CN103876158A (en) * | 2013-11-18 | 2014-06-25 | 国家海洋局第三海洋研究所 | Elemental selenium and sugar compound and preparation method thereof |
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-
2002
- 2002-11-18 CN CN 02138643 patent/CN1264521C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101721435B (en) * | 2009-12-10 | 2012-02-22 | 安徽省康美来大别山生物科技有限公司 | Ganoderma lucidum spore and nano selenium compound and preparation method thereof |
| CN103876158A (en) * | 2013-11-18 | 2014-06-25 | 国家海洋局第三海洋研究所 | Elemental selenium and sugar compound and preparation method thereof |
| CN103876158B (en) * | 2013-11-18 | 2016-09-28 | 国家海洋局第三海洋研究所 | A kind of elemental selenium and sugared complex and preparation method thereof |
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| CN1415310A (en) | 2003-05-07 |
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