CN1014522B

CN1014522B - Preparation of selenide of carragheen

Info

Publication number: CN1014522B
Application number: CN 88103347
Authority: CN
Inventors: 唐家骏; 芮海凤
Original assignee: Research Center for Eco Environmental Sciences of CAS
Current assignee: Research Center for Eco Environmental Sciences of CAS
Priority date: 1988-06-10
Filing date: 1988-06-10
Publication date: 1991-10-30
Also published as: CN1038454A

Abstract

The present invention relates to a method for preparing selenized carragheen which is carrageenin in a hydrosol state. Part of sulfur is substituted by selenium to form ester selenate under the strong acidic condition, and 3, 6-inner ether-D-galactose at the terminal unit forms a C-Se-H structure through ring opening at C-1. Animal tests prove that the selenized Kappa-carragheen has toxicity which is a plurality of hundred times lower than that of the best selenide-sodium selenite available at present and has better biologic usability and physiological gaining effect. The selenized carragheen has wide application prospects in the aspects of health care and clinical treatment.

Description

Preparation of selenide of carragheen

The invention belongs to the preparation method of organic selenide.Selenium is the essential trace element of humans and animals.At present the most noticeable is the anti-oxidant of selenium, suppresses effects such as chemical substance mutagenesis and enhancing body immunological competence, and in the application of mankind's anti-cancer, anti-ageing, prevention and treatment cardiovascular patient, Keshan disease, Kaschin-Beck disease and domestic animal white muscle disease etc.

Use Sodium Selenite to the Keshan disease acute attack, prevention Kaschin-Beck disease and reduction onset of liver cancer rate have all obtained good result, but the toxicity of inorganic selenium is higher than organoselenium.In recent years, take to be sprayed on plant strain or to the soil application inorganic selenium increasing the source of organoselenium as human body and livestock, but its biological effect is when remaining further to be explained (Xu Huibi writes " biologic trace element-selenium " Huazhong Institute of Technology press, 1983).A kind of organic selenium compounds-selenium yeast has preparation (" trace element " 1985, No.4P.28) but product is formed unstable, selenium content is lower, bioavailability also undesirable (Liu Manxi etc. " research of selenium yeast composition " " Huazhong Institute of Technology journal " No.3 in 1985).Therefore people just are being devoted to seek low toxicity and other good organic selenide of bioavailability.

The objective of the invention is to prepare organic selenide that a class low toxicity mask has the good biological availability, for the Secure Application of health care.

The preparation process of selenocarrageenan of the present invention is as follows:

(1) with behind the concentrated nitric acid dissolving selenium powder, is mixed with the selenium liquid that concentration is the 0.5-1.0 mg/ml with deionized water.

(2) carrageenin (referring to Kappa-carrageenin or Lambda-carrageenin) is joined in the sodium chloride aqueous solution of 0.5 molconcentration by the proportional quantity (weight/volume) of 0.5-5% and be controlled at heated and stirred under the 75-100 ℃ of temperature, make into the carrageenin sol solutions of homogeneous.

(3) the even sol solutions of above-mentioned carrageenin after 2-4 hour, is being continued at 25-30 ℃ of reaction 12-24 hour in 50-80 ℃ of reaction under the pH0.5-2.5 condition.

(4) doubly measure (volume) by reaction solution 1-2 and add 95% ethanol precipitating selenizing product, filter the back and use 95% ethanol, absolute ethanol washing successively leaching thing.In air seasoning below 75 ℃, through pulverizing, Φ 0.2mm sieves, and obtains the product selenocarrageenan.

The infrared spectra of product, ¹³C-nucleus magnetic resonance, x-photoelectron spectrum, laser Raman spectroscopy and ultraviolet absorption characteristic are measured and are shown that the selenizing product still keeps the basic configuration of polysaccharide sulfate.Wherein selenium exists with two different valence state, and promptly the part sulphur in the carrageenin is that selenium replaces formation selenic acid ester; And the 3.6-of its terminal units inner ether-D-semi-lactosi forms the C-Se-H structure in the C-1 open loop.

Kappa-selenocarrageenan end structure

Lambda-selenocarrageenan end structure

The selenium content of product is 2500-15000ppm.

Molecular weight of product classification and demarcation: selenocarrageenan to be fractionated is made into 5% solution with deionized water, and 4000 commentaries on classics/per minutes are got supernatant liquid Seharose after centrifugal 20 minutes ^RSeparate on the 4B gel column, 25 ℃ of column temperatures, elutriant are 5 millimole sodium phosphates, and 0.2 mol sodium-chlor is measured behind the pH7.0 fraction collection [α] ¹⁰ ₀Molecular weight is demarcated with 0.2%Dextran.

The method of producing organic selenide-selenocarrageenan of the present invention, because raw materials used-carrageenin derives from two kinds of husky dish red algaes can taking in a large number in China Hainan Island, raw material is easy to get, and the preparation technology of selenocarrageenan is simple, so production cost is low.Especially the selenocarrageenan that is made by the inventive method proves than the selenide-Sodium Selenite of current application the best to have better bioavailability and physiology enhancement effect through animal experiment; As contain the selenizing Kappa-carrageenin of selenium 1100ppm, the oral LD of mouse ₅₀The 95% credible 4.98-2.66 gram/kilogram that is limited to, toxicity only is hundreds of/one of Sodium Selenite, than existing organic selenium compounds toxicity also low (three international symposiums of J.A.Vinson, the selenium effect-Di in biology and medical science, 1984, Beijing).Prove that through animal experiment feeding selenizing Kappa-carrageenin increases 23% than the Sodium Selenite blood selenium level, red corpuscle is crossed stability of peroxide and is increased 50%, and oxyphorase increases 22%, and red corpuscle suppresses the free radical ability and increases 55%(such as table 1, table 2).

Animal experiment also proves, drinking-water adds raises selenizing Kappa-carrageenin, and significant anti-gamma-radiation ionization radiation effect and the toxic effect of antagonism mycotoxins are arranged, and long-term low dose is added and raised selenizing Kappa-carrageenin mouse is had remarkable function in delaying senility.

Therefore, selenocarrageenan is expected to replace Sodium Selenite at aspects such as health care and clinical treatments wide application prospect to be arranged.

Example 1:

First, selenium powder 20 restrains, adds 100 milliliters of concentrated nitric acids, adds 1800 milliliters of deionized waters after selenium powder dissolves fully, and 50%NaOH transfers pH to 1.0, is settled to 2000 milliliters; Second, 40 gram Kappa-carrageenins are in 2000 milliliter of 0.5 mol sodium chloride aqueous solution after the solation.Add first liquid, behind the thorough mixing in 50 ℃ the reaction 2 hours after, continue at 30 ℃ of reactions 24 hours, after the cooling, add doubly 95% ethanol precipitating selenizing product of 1-2, after the filtration, leach thing with 95% ethanol, absolute ethanol washing successively,, pulverize then in air seasoning below 75 ℃, 0.2 millimeter order of Φ sieves, and gets the product selenocarrageenan.

Example 2

First, selenium powder 2.5 grams add 12.5 milliliters of concentrated nitric acids, after selenium powder dissolves fully, add 1500 milliliters of deionized waters; Second, 50 gram Kappa-carrageenins, after adding the water-soluble gel of 1000ml0.5 mol sodium-chlor, add first liquid, behind the thorough mixing, after 4 hours, continue at 30 ℃ of reactions after 12 hours in 70 ℃ of reactions, add doubly 95% ethanol precipitating selenizing product of 1-2, by example 1, method washing, dry, pulverize, sieve product.

Example 3

400 milligrams of first, selenium powders add 50 milliliters of concentrated nitric acids, after selenium powder dissolves fully, add 1800 milliliters of deionized waters, transfer pH to 2.0 quantitatively to 2000 milliliters with 50%NaOH; Second, 40 gram Kappa-carrageenins after the solation, add first liquid in 2000 milliliter of 0.5 mol sodium chloride aqueous solution, behind the thorough mixing,, continue 25 ℃ of reactions after 20 hours in 60 ℃ of reactions 3 hours, by example 1, method handle product.

Example 4

First, selenium powder 2.5 grams add 62.5 milliliters of concentrated nitric acids, after selenium powder dissolves fully, add deionized water and are settled to 1500 milliliters, transfer pH to 1.0 with 50%NaOH; Second, 25 gram Lambda-carrageenins after 1000 milliliter of 0.5 water-soluble gel of mol sodium-chlor, add first liquid, behind the thorough mixing, in 60 ℃ of reactions 2 hours, continue at 25 ℃ of reactions and make selenizing Lambda-carrageenin by the processing of example 1 method after 22 hours.

Example 5:

First, selenium powder 10 grams add 50 milliliters of concentrated nitric acids, and selenium powder dissolves the back fully and is settled to 6000 milliliters with deionized water; Second, 100 gram Kappa-carrageenins after the solation, add first liquid in 4000 milliliter of 0.5 mol sodium chloride aqueous solution, behind the thorough mixing,, continue 25 ℃ of reactions after 12 hours after 4 hours in 50 ℃ of reactions, make selenizing Kappa-carrageenin by the method for example 1.

Example 6:

Second, get Kappa-carrageenin 200 and restrain solation in 4000 milliliters of sodium chloride aqueous solutions, other conditions are with example 5.

The bioavailability of table 1, selenide of carragheen

Blood selenium liver selenium serum SOD as a result_pm

The relative % of the relative % ppm of test group ppm P value p value relative % u/ml p value

Normal diet group 0.46 100 0.798 100 36.0 100

Add and raise selenizing Kappa-

0.72 ＜0.01 157 1.419 178 44.4 ＜0.01 123

The carragheen group

Add and raise selenizing Lambda

0.62 ＜0.01 135 1.407 ＜0.01 176 31.2 ＜0.01 87

The carragheen group

Add and raise sodium selenite group 0.56＜0.01 122 1.152＜0.01 144 39.4＜0.01 109

Table 2, add and raise selenide of carragheen to the impact of mouse red blood cell

Processing red blood cell oozes the suspension red blood cell and oozes suspension red blood cell inhibition freedom waiting waiting

Among the result, 37 ℃, 60 add 0.1mMH₂O ₂(hemoglobin was relative in 5 minutes for the ability of base

37 ℃, 60 minutes haemolysis % of test group minute haemolysis % are average, relatively % % content

Normal diet group 10.0 32.4 25.4 100

Add and raise selenizing Kappa-

7.8 20.6 100 117.9

The carrageenin group

Add and raise selenizing Lambda-

10.6 33.0 36.1 90.9

The carrageenin group

Add and raise Sodium Selenite group 10.7 30.3 64.3 96.9

Claims

A kind of method for preparing selenocarrageenan is characterized in that adopting the following step:

(1) with behind the concentrated nitric acid dissolving selenium powder, be mixed with the selenium liquid that concentration is the 0.5-1.0 mg/ml with deionized water,

(2) carrageenin (referring to Kappa-carrageenin or Lambda-carrageenin) is joined in the sodium chloride aqueous solution of 0.5 molconcentration by the proportional quantity (weight/volume) of 0.5-5% and is controlled at heated and stirred under the 75-100 ℃ of temperature, make into the carrageenin sol solutions of homogeneous,

(3) the even sol solutions of above-mentioned carrageenin after 2-4 hour, is being continued at 25-30 ℃ of reaction 12-24 hour in 50-80 ℃ of reaction under the pH0.5-2.5 condition,

(4) doubly measure (volume) by reaction solution 1-2 and add 95% ethanol precipitating selenizing product, filter the back and use 95% ethanol successively leaching thing, absolute ethanol washing, in air seasoning below 75 ℃, through pulverizing, Φ 0.2mm sieves, and obtains the product selenocarrageenan.