CN1207300C - Combined holoside as well as preparation method and application - Google Patents
Combined holoside as well as preparation method and application Download PDFInfo
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- CN1207300C CN1207300C CNB031391907A CN03139190A CN1207300C CN 1207300 C CN1207300 C CN 1207300C CN B031391907 A CNB031391907 A CN B031391907A CN 03139190 A CN03139190 A CN 03139190A CN 1207300 C CN1207300 C CN 1207300C
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- acid
- chitosan
- oligomeric
- oligose
- heavy metal
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Abstract
The present invention relates to combined oligosaccharide which is characterized in that the oligosaccharide is prepared from any two or all of the components of 1 portion of low molecule carboxymethyl chitosan, 0.1 to 10 portions of oligogalacturonic acid and 0.1 to 10 portions of oligoguluronic acid through dissolution, filtration, alcohol precipitation, drying, mixing and grinding at a normal temperature. The raw materials used by the product of the present invention all come from natural polysaccharide or derivatives thereof, and thus, the product has the advantages of favorable selective elimination of heavy metal ion, no toxic or side effect, no obvious effect on human body required elements of sodium, potassium, calcium, magnesium, iron, etc. and long-term use. The product of the present invention can be used as a food additive with the function of selective elimination of heavy metal ions to be conveniently applied to various foods popular with children, such as jelly, soft candy, QQ candy, dairy products of yoghurt, milk powder, sour milk beverages, ice-creams, etc., and can be used for being made into tablets, pulvis, granules, capsules and various other oral health-care foods.
Description
Technical field
The present invention relates to a kind of protective foods, specifically relate to a kind ofly have that selectivity is got rid of combination oligose and preparation method thereof of heavy metal ion effect and in Application in Food.
Background technology
Along with the continuous quickening of industrialization development and urbanization process, the pollution of heavy metal ion has become one of Hazard Factor of serious harm human life health in the modern civilization society, and is wherein serious to the threat of human life's health with Lead contamination.Industrial gaseous waste, vehicle exhaust, leaded articles for use, food and bad habits such as dust and long-term smoking all are the important sources of Lead contamination.Lead is absorbed into after the human body, because it can be accumulated in each histoorgan of human body, particularly easily accumulates (85-90% that accounts for body accumulation lead) in bone, thereby marrow, hemopoietic system and the neural system of human body caused serious harm.Simultaneously, plumbous also have than macrolesion digestion, endocrine system, immunity system and reproductive system etc.Plumbous neural infringement is mainly shown as causes peripheral neuritis, motion and paresthesia occur.Enter cerebral tissue if invade intravital lead with blood circulation, just can cause the damage of cerebellum and brain cortex cell, and the normal Metabolic activity of interference brain, thereby symptoms such as headache, dizzy, tired, hypomnesis, insomnia appear, and often with gastrointestinal symptoms such as poor appetite, gastro-enteritis, diarrhoea, constipation, stomachache, severe patient can develop into mentally deranged, even shock and dead.The World Health Organization (WHO) thinks in the environmental poisonous substance that it is plumbous threatening maximum to children.Because the height that the lead in the atmosphere is everlasting below 1 meter is assembled, consistent with children's breathing zone height, and children since grow fast, metabolism is vigorous, make children's digestive tube exceed adult's several times to the specific absorption of lead, and the excretion rate of children's lead only is adult's 2/3 on the other hand.Therefore infant and children are strong to the susceptibility of lead, specific absorption and the property accumulated height, the approach that enters body through the life contact is many, thus lead to infant and children's harm far above the adult.Plumbous all can cause serious damage to the growing of infant, intelligence and brain functions such as cognitive function, neurobehavioral and learning and memory.At present, the Chinese children blood lead problem that exceeds standard is extremely serious, and national blood lead content surpasses children's ratio of the comparatively safe standard of 100ug/L more than 61%, part city even reach 85%.In the control lead poisoning, particularly in getting rid of body aspect the lead ion, that use at present mainly is some medicines such as EDTA, CaNa
2Sequestrants such as EDTA, dimercaprol dimercaptopropanol (BAL), sodium dimercaptosuccinate (DMSA), Trolovol (D-USP), dimercaprol dimercaptopropanol propane sulfonic acid sodium (DMPS), thiamine disulfide manthanoate.In addition, also have lead discharging preparations such as some Chinese medicine classes and nutrient substance class.But EDTA, CaNa
2EDTA class medicine since they can cause the loss of calcium ion in the body and disturb the metabolism of other metallic element, and cause plumbous redistribution in brain, also need adopt intravenous injection etc. former thereby limited its application simultaneously; Poor, the easily oxidation of dimercapto such as BAL, DMSA class medicine stability, and use is inconvenient, medical expense is higher; Other lead discharging preparation has certain side effect mostly, and poor selectivity in lead discharging, is also obviously discharged the more intravital essential elements of people such as calcium, zinc, iron etc.Though lead discharging preparation toxic side effect such as some Chinese medicines and nutrient substance are less, the lead discharging effect is not good enough.
Summary of the invention
The purpose of this invention is to provide a kind of combination oligose and its production and application, can overcome the above-mentioned shortcoming and defect of prior art with the product of its preparation.
A kind of combination oligose, it is characterized in that it contains low molecule cm-chitosan, in oligomeric galactose aldehydic acid and the oligomeric guluronic acid any two kinds or all, their mass ratio is followed successively by 1: 0.1-10: 0.1-10, described low molecule cm-chitosan is meant the daltonian N-cm-chitosan in molecular weight＜100000, O-cm-chitosan and N, the O-cm-chitosan, described oligomeric galactose aldehydic acid is meant from beet pectin, apple pectin, the oligomeric galactose aldehydic acid that orange peel pectin or wolfberry fruit extract obtain through hydrolysis, described oligomeric guluronic acid are meant through alginic acid is degraded and comprise acid degradation, enzyme liberating, oxidative degradation, the oligomeric guluronic acid that ultrasonic degradation and pH classification obtain.
The preparation method of aforesaid combination oligose, it is characterized in that hanging down any two kinds or all successively by 1 in molecule cm-chitosan, oligomeric galactose aldehydic acid and the oligomeric guluronic acid: the mass ratio of 0.1-10: 0.1-10 is prepared through dissolving, filtration, alcohol precipitation, oven dry, mixing and pulverizing under normal temperature condition.
The aforesaid combination oligose is as a kind of foodstuff additive with selectivity eliminating heavy metal ion.
Product of the present invention has following advantage: (1) the present invention is a raw material with complete water-soluble low molecule cm-chitosan, oligomeric galactose aldehydic acid and oligomeric guluronic acid, and carries out the composite back dissolved state that all is according to their constructional feature and physico-chemical property in simulated gastric fluid and simulated intestinal fluid; (2) product of the present invention can form the spacial framework with suitable space and molecular conformation, can offer an explanation metal ion by the ionic radius size, its binding ability to lead, cadmium, barium, mercury and strontium will be higher than far away calcium, the binding ability of magnesium, thus the effect that good selectivity is got rid of heavy metal ion had; (3) product of the present invention is raw materials used all is to derive from natural polysaccharide or derivatives thereof, and human body is had no side effect, and human essential elements such as sodium, potassium, calcium, magnesium, iron etc. are not had obviously influence, but life-time service.(4) because product of the present invention is a kind of combination oligose, has good water-solubility, and viscosity is low, can be used as a kind of foodstuff additive, be conveniently used in various food that children like such as jelly, soft sweets, QQ sugar, milk-product comprise sour milk, milk powder, lactobacillus drink and ice-creams etc., also can make various protective foodss such as tablet, powder, granule, capsule, thereby can be widely used in the pollution of heavy metal ion such as lead and the control of poisoning, especially prevention and the treatment to children ' s lead poisoning has important and practical meanings.
Embodiment
The present invention is described further below by some specific embodiments.
Embodiment 1
Take by weighing low molecule cm-chitosan 5.0g respectively, oligomeric galactose aldehydic acid 2.0g and oligomeric guluronic acid 3.0g, be added in the 1000mL water, stirring and dissolving under normal temperature condition, filter with 300 mesh sieve thin,tough silk, remove insoluble impurities, use 95% ethanol sedimentation again, in 40 ℃ of following vacuum-dryings, pulverizing is that 80 orders promptly get combination oligose of the present invention after dewatering.
Embodiment 2
Taking by weighing low molecule cm-chitosan 3.5g and oligomeric guluronic acid 6.5g respectively is added in the 1000mL water by embodiment 1 operation promptly.
Embodiment 3
Take by weighing oligomeric galactose aldehydic acid 7.0g and oligomeric guluronic acid 3.0g respectively, be added in the 1000mL water and operate promptly by embodiment 1.
Embodiment 4
Taking by weighing low molecule cm-chitosan 4.5g, oligomeric galactose aldehydic acid 5.5g respectively is added in the 1000mL water by embodiment 1 operation promptly.
Embodiment 5
Take by weighing combination oligose 1.5g of the present invention, after the 1.0g carrageenin mixes, under agitation condition, slowly be added in the 70mL water and dissolve, add the 0.2g secondary calcium phosphate, and heated and boiled 5min.The 15g white sugar is added in the 20g Sucus Mali pumilae, be added in the above-mentioned glue after the heating for dissolving while hot, filter with 200 mesh sieve thin,tough silk, this rubber cement liquid is carried out homogeneous with the pressure of 40MPa in clarifixator, the processing that outgases of rubber cement liquid after adopting vacuum degassing machine to homogeneous again, add auxiliary materials such as the solution contain 0.15g citric acid, 0.08g potassium sorbate and 0.2g Repone K and an amount of essence in the time of 70 ℃, stir rapidly, injection molding immediately, after 85 ℃ of sterilizations, leaving standstill to become the jelly with heavy metal ion effects such as selectivity eliminating lead then.
Embodiment 6
Take by weighing combination oligose 1.0g of the present invention, whole milk powder 14g, sweetened condensed milk 6g, cream 8g and white sugar 6.5g, add water and mix back adding 0.3g mono-glycerides emulsifying agent, post-heating to 65 ℃ stirs, homogeneous under 40MPa pressure, descend sterilization 25min in 80 ℃ after making the abundant miniaturization of particle, be cooled to 2-4 ℃ rapidly, put into the aging 12h of aging tank, be cooled to-2 ℃ then, after forcing to stir the 20min that congeals, pour in the shaping mould, promptly get ice-creams with heavy metal ion effects such as selectivity eliminating lead in-20 ℃ of 8h that harden down.
Embodiment 7
Take by weighing combination oligose 3.0g of the present invention and 0.5g starch, adding behind the water slowly, heated and stirred becomes mashed prod.After getting 9g white sugar and 7g Liquid Glucose again and mixing, be heated to 160 ℃, constantly stir down and slowly pour in the above-mentioned mashed prod, pour in the mould after slowly being heated to 116 ℃, the section of cooling back promptly gets has the soft sweets that selectivity is got rid of heavy metal ion effect such as lead.
Embodiment 8
Take by weighing combination oligose 2.0g of the present invention and starch 2.5g, Icing Sugar 3.0g, behind thorough mixing with 75% ethanol system softwood, cross then 12 order stainless steel sifts granulate, in 50-60 ℃ of dry down back by the whole grain of 14 order stainless steel sifts.Add 1% Magnesium Stearate and talcum powder again, thorough mixing evenly back carries out compressing tablet by general compressed cores requirement, makes label have suitable hardness.The plain sheet that compacting is obtained carries out alternating packets sub-coat 15-18 layer with syrup and talcum powder, sugar coating layer 10-15 layer, and last polishing promptly gets the tablet with heavy metal ion effects such as selectivity eliminating lead.
Cm-chitosan of the present invention is meant the daltonian N-cm-chitosan in molecular weight＜100000, O-cm-chitosan and N, O-cm-chitosan; Oligomeric galactose aldehydic acid of the present invention is meant the oligomeric galactose aldehydic acid that obtains through hydrolysis from the pectin in various sources such as beet pectin, apple pectin, orange peel pectin etc. or wolfberry fruit extract; Oligomeric guluronic acid of the present invention is meant and comprises the oligomeric guluronic acid that acid degradation, enzyme liberating, oxidative degradation, ultrasonic degradation and other degraded mode and pH classification obtain through alginic acid is degraded.
Because oligomeric guluronic acid molecular chain is the twofold spirrillum, have suitable space between molecular chain, and because of the interaction of molecule intrachain hydrogen bond, the binding ability that it compares calcium, zinc to the binding ability of lead, cadmium, barium, mercury and strontium is much higher.The present invention adopts degraded and pH stage division that oligomeric guluronic acid is extracted from natural alginic acid, compares it with alginic acid and selects complex ability further to strengthen to harmful heavy metal ionic such as lead; The derivative that has polygalacturonic acid in pectin and the wolfberry fruit extract, the polygalacturonic acid that the present invention will wherein play main heavy metal ion eliminating effect extracts, make its elimination ability significantly be better than pectin and wolfberry fruit extract to heavy metal ion, and oligomeric galactose aldehydic acid has no side effect to human body, and human essential elements is not had obvious influence.Chitosan is a large amount of class glycosaminoglycans that exist of nature, has preferred metal ion complexation ability, but has limited its widespread use owing to its water-insoluble.Chitosan is through carboxymethylation and the low molecule cm-chitosan made through degraded, because the introducing of carboxyl and the reduction of molecular weight make it have good water-solubility, the complex ability of metal ion is also further strengthened, and should use also more convenient.
Product of the present invention is to the eliminating effect and the safety evaluation test of heavy metal ion
The lead-eliminating effect test-results of the plumbous mouse of the 1 pair of lotus: will make up the oligose water and be mixed with 3% colloidal sol, according to dosage be converted to volume during administration after, directly irritate stomach with colloidal sol.Get 60 healthy mices, male and female half and half, 19-22g is divided into 5 groups at random, i.e. normal control group, model control group and the basic, normal, high dosage group of combination oligose, every group of equal ad lib standard feed, drink ordinary tap water.Every day normal control group abdominal injection equivalent physiological saline, all the other 4 groups of abdominal injection plumbic acetate double distilled water solution 10mg/Kgd, the 7d that contaminates continuously, mouse recovers to begin administration behind the 3d.Continuous 15d, irritate stomach every day once: normal control group, model control group are given double distilled water, and the basic, normal, high dosage of combination oligose is respectively 200,400,800mg/Kg/d.15d gets femur, liver and whole blood after mouse is put to death, and uses the content of atomic absorption measuring lead after blood and the tissue usefulness nitric acid-Perchloric Acid Digestion.The every 5d record of duration of test mouse body weight once.Each is organized the testing data measured value and represents with X ± S that all mean relatively adopts the t method of inspection between each group.Test-results shows: mouse is taken behind the combination oligose 15d plumbous content and model control group comparison, low dose group P＜0.05, high dose group P＜0.01 in the blood; Content and model control group plumbous in the mouse liver compare low dose group P＜0.01, middle dosage group P＜0.005; Content and model control group plumbous in the mouse kidney compare low, middle dosage group P＜0.05, high dose group P＜0.01; Content and model control group plumbous in the mouse femur compare middle dosage group P＜0.005.The mouse body weight there was no significant difference of test normal control group and model control group when finishing, combination basic, normal, high three dosage groups of oligose and model control group be there was no significant difference more also, shows that making up oligose does not have influence to the body weight of mouse.
2 external complexing test-results to lead: that gets the 4ml different concns makes up oligose with simulated intestinal fluid (pH=6.8) dissolved, slowly add 1ml lead nitrate standardized solution (20mg/ml) then, be added in the centrifuge tube, after vortex oscillation, be put in 37 ℃ of shaking tables jolting 4 hours.The centrifugal 10min of 8000rpm gets the 2ml supernatant liquor and measures lead content by dithizone method then.Test-results shows: the combination oligose can be up to 3.76mmol/g to the binding capacity of lead ion.
3 couples of different metal ionic adsorption test results: get 50mg combination oligose respectively and join in Tris-HCl (pH=7.4) damping fluid, after vortex oscillation is fully dissolved, the different metal ion standardized solution of volumetric molar concentrations such as quantitative adding, room temperature jolting 24 hours is got supernatant liquor after centrifugal and is carried out metal ion content and measure.Pb wherein
2+, Ba
2+, Cd
2+, Cu
2+And Mn
2+Adopt atomic absorption method (Tianjin, island AA-670) to measure; Hg
2+Adopt Cold Atomic Fluorescent Mercury method (YYG-2 type mercury vapor analyzer) to measure; Fe
2+Adopt adjacent coffee sieve quinoline colorimetric method for determining; Ca
2+, Mg
2+Adopt the EDTA complexometric titration; Concentration * 100 before adsorption rate (%)=(concentration before the absorption-absorption back concentration)/absorption.Test-results shows: the combination oligose has good selective adsorption effect to harmful heavy metal ions such as lead, to Ca
2+, Mg
2+And Fe
2+Lower Deng the human essential elements adsorption rate.The combination oligose is to Pb
2+, Ba
2+, Hg
2+, Cd
2+, Cu
2+, Mn
2+, Fe
2+, Ca
2+And Mg
2+Adsorption rate be respectively 82.41%, 89.75%, 84.72%, 76.45%, 67.73%, 14.34%, 12.26%, 6.76% and 8.03%.
4 The acute toxicity tests: get 20 of mouse, the combination oligose colloidal sol that every mouse divided three minor tick 8h to give maximum concentration of ordinary dissolution that can be by irritating the stomach syringe needle in one day is equivalent to the 15.0g/Kg body weight altogether, observed for two weeks, the body weight of mouse, outward appearance, behavioral activity do not occur any unusual, death condition do not occur yet.The LD that mouse is oral
50Fail to measure.
Claims (3)
1 one kinds of combination oligose, it is characterized in that it contains low molecule cm-chitosan, in oligomeric galactose aldehydic acid and the oligomeric guluronic acid any two kinds or all, their mass ratio is followed successively by 1: 0.1-10: 0.1-10, described low molecule cm-chitosan is meant the daltonian N-cm-chitosan in molecular weight＜100000, O-cm-chitosan and N, the O-cm-chitosan, described oligomeric galactose aldehydic acid is meant from beet pectin, apple pectin, the oligomeric galactose aldehydic acid that orange peel pectin or wolfberry fruit extract obtain through hydrolysis, described oligomeric guluronic acid are meant through alginic acid is degraded and comprise acid degradation, enzyme liberating, oxidative degradation, the oligomeric guluronic acid that ultrasonic degradation and pH classification obtain.
The preparation method of the described combination oligose of 2 claims 1, it is characterized in that hanging down any two kinds or all successively by 1 in molecule cm-chitosan, oligomeric galactose aldehydic acid and the oligomeric guluronic acid: the mass ratio of 0.1-10: 0.1-10 is prepared through dissolving, filtration, alcohol precipitation, oven dry, mixing and pulverizing under normal temperature condition.
The described combination oligose of 3 claims 1 is as a kind of foodstuff additive with selectivity eliminating heavy metal ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031391907A CN1207300C (en) | 2003-09-01 | 2003-09-01 | Combined holoside as well as preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031391907A CN1207300C (en) | 2003-09-01 | 2003-09-01 | Combined holoside as well as preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1518897A CN1518897A (en) | 2004-08-11 |
| CN1207300C true CN1207300C (en) | 2005-06-22 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031391907A Expired - Fee Related CN1207300C (en) | 2003-09-01 | 2003-09-01 | Combined holoside as well as preparation method and application |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100364420C (en) * | 2005-02-01 | 2008-01-30 | 黄恒燊 | Sour milk powder containing chitosan |
| CN101857642B (en) * | 2009-04-10 | 2012-08-29 | 烟台海岸带可持续发展研究所 | Polysaccharide derivative and vanadium complex application thereof |
| CN102190688A (en) * | 2010-03-01 | 2011-09-21 | 西北大学 | Oligogalacturonide preparation method |
| CN102415526A (en) * | 2011-12-09 | 2012-04-18 | 苏州先阔生物科技有限公司 | Xylo-oligosaccharide-containing health food |
| CN104083395B (en) * | 2014-06-05 | 2016-07-06 | 深圳大学 | The application of marine source Oligoguluronic Acids |
| FR3022738B1 (en) * | 2014-06-30 | 2019-02-08 | Roquette Freres | NEW CONFECTIONERY WITHOUT FAT |
| CN111214441B (en) * | 2020-03-16 | 2021-06-08 | 深圳大学 | Guluronic acid oligosaccharide liposome and preparation method thereof |
| CN115005447B (en) * | 2022-06-16 | 2024-02-06 | 青岛海关技术中心 | Application of oligoguluronic acid in preparation of anti-fatigue product |
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2003
- 2003-09-01 CN CNB031391907A patent/CN1207300C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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