CN112300299A - Preparation method and application of zinc and calcium polysaccharide complex - Google Patents
Preparation method and application of zinc and calcium polysaccharide complex Download PDFInfo
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- CN112300299A CN112300299A CN202011264839.8A CN202011264839A CN112300299A CN 112300299 A CN112300299 A CN 112300299A CN 202011264839 A CN202011264839 A CN 202011264839A CN 112300299 A CN112300299 A CN 112300299A
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- polysaccharide complex
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- 239000011575 calcium Substances 0.000 title claims abstract description 65
- 239000011701 zinc Substances 0.000 title claims abstract description 60
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 60
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 54
- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 25
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 25
- -1 calcium polysaccharide Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000047 product Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920001218 Pullulan Polymers 0.000 claims abstract description 18
- 239000004373 Pullulan Substances 0.000 claims abstract description 18
- 235000019423 pullulan Nutrition 0.000 claims abstract description 18
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- 239000006228 supernatant Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000008213 purified water Substances 0.000 claims abstract description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000004108 freeze drying Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000012043 crude product Substances 0.000 claims description 12
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 11
- 238000000502 dialysis Methods 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 235000015872 dietary supplement Nutrition 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 60
- 229960005069 calcium Drugs 0.000 description 43
- 238000011068 loading method Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 14
- 230000001965 increasing effect Effects 0.000 description 11
- 150000004676 glycans Chemical class 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 208000001132 Osteoporosis Diseases 0.000 description 6
- 150000001413 amino acids Chemical class 0.000 description 6
- 210000000988 bone and bone Anatomy 0.000 description 6
- 241000699670 Mus sp. Species 0.000 description 5
- 206010048259 Zinc deficiency Diseases 0.000 description 5
- 159000000007 calcium salts Chemical class 0.000 description 5
- 241000699666 Mus <mouse, genus> Species 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
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- 239000012153 distilled water Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
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- 238000011160 research Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
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- 229940038879 chelated zinc Drugs 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000011573 trace mineral Substances 0.000 description 3
- 235000013619 trace mineral Nutrition 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 206010006956 Calcium deficiency Diseases 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
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- 230000007423 decrease Effects 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 210000001035 gastrointestinal tract Anatomy 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 210000000689 upper leg Anatomy 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 239000011670 zinc gluconate Substances 0.000 description 2
- 235000011478 zinc gluconate Nutrition 0.000 description 2
- 229960000306 zinc gluconate Drugs 0.000 description 2
- 208000002310 Achlorhydria Diseases 0.000 description 1
- 208000032170 Congenital Abnormalities Diseases 0.000 description 1
- 235000002722 Dioscorea batatas Nutrition 0.000 description 1
- 235000006536 Dioscorea esculenta Nutrition 0.000 description 1
- 240000001811 Dioscorea oppositifolia Species 0.000 description 1
- 235000003416 Dioscorea oppositifolia Nutrition 0.000 description 1
- 206010013883 Dwarfism Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 206010070840 Gastrointestinal tract irritation Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 208000037147 Hypercalcaemia Diseases 0.000 description 1
- 206010022971 Iron Deficiencies Diseases 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 206010024642 Listless Diseases 0.000 description 1
- 206010025476 Malabsorption Diseases 0.000 description 1
- 208000004155 Malabsorption Syndromes Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 206010034203 Pectus Carinatum Diseases 0.000 description 1
- 244000179560 Prunella vulgaris Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 206010043183 Teething Diseases 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- SHGAZHPCJJPHSC-YCNIQYBTSA-N all-trans-retinoic acid Chemical compound OC(=O)\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C SHGAZHPCJJPHSC-YCNIQYBTSA-N 0.000 description 1
- 208000022531 anorexia Diseases 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 208000027499 body ache Diseases 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004227 calcium gluconate Substances 0.000 description 1
- 235000013927 calcium gluconate Nutrition 0.000 description 1
- 229960004494 calcium gluconate Drugs 0.000 description 1
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 1
- 239000001527 calcium lactate Substances 0.000 description 1
- 235000011086 calcium lactate Nutrition 0.000 description 1
- 229960002401 calcium lactate Drugs 0.000 description 1
- IMYZCYXTVFOXAQ-LJUKVTEVSA-N calcium;(2r,3s)-2,3,4-trihydroxybutanoic acid Chemical compound [Ca].OC[C@H](O)[C@@H](O)C(O)=O IMYZCYXTVFOXAQ-LJUKVTEVSA-N 0.000 description 1
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- RQFQJYYMBWVMQG-IXDPLRRUSA-N chitotriose Chemical compound O[C@@H]1[C@@H](N)[C@H](O)O[C@H](CO)[C@H]1O[C@H]1[C@H](N)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)[C@@H](CO)O1 RQFQJYYMBWVMQG-IXDPLRRUSA-N 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 206010061428 decreased appetite Diseases 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- 230000007661 gastrointestinal function Effects 0.000 description 1
- 238000003304 gavage Methods 0.000 description 1
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- 230000000148 hypercalcaemia Effects 0.000 description 1
- 208000030915 hypercalcemia disease Diseases 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940001447 lactate Drugs 0.000 description 1
- 210000002414 leg Anatomy 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 208000017971 listlessness Diseases 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 208000005368 osteomalacia Diseases 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 150000004804 polysaccharides Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 229930002330 retinoic acid Natural products 0.000 description 1
- 208000007442 rickets Diseases 0.000 description 1
- 235000008113 selfheal Nutrition 0.000 description 1
- 210000000813 small intestine Anatomy 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
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- 230000001502 supplementing effect Effects 0.000 description 1
- 230000036346 tooth eruption Effects 0.000 description 1
- 229960001727 tretinoin Drugs 0.000 description 1
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
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- 235000016804 zinc Nutrition 0.000 description 1
- 239000011746 zinc citrate Substances 0.000 description 1
- 235000006076 zinc citrate Nutrition 0.000 description 1
- 229940068475 zinc citrate Drugs 0.000 description 1
- 239000011576 zinc lactate Substances 0.000 description 1
- 235000000193 zinc lactate Nutrition 0.000 description 1
- 229940050168 zinc lactate Drugs 0.000 description 1
- 229940091251 zinc supplement Drugs 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/125—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives containing carbohydrate syrups; containing sugars; containing sugar alcohols; containing starch hydrolysates
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/16—Inorganic salts, minerals or trace elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0018—Pullulan, i.e. (alpha-1,4)(alpha-1,6)-D-glucan; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
Abstract
The invention discloses a preparation method and application of a zinc and calcium polysaccharide complex. The method comprises the following steps: (a) dissolving carboxymethyl pullulan in purified water to obtain a CMP solution with the concentration of 0.5-5 wt%, and heating the solution to 30-60 ℃; (b) dropwise adding a zinc solution into a CMP solution, and dropwise adding an alkali liquor to control the pH value of the reaction solution to be 6-8; or dropwise adding the calcium solution into the CMP solution, and simultaneously dropwise adding alkali liquor to control the pH value of the reaction solution to be 9-11; (c) stirring while adding until the solution is saturated, then continuously stirring at constant temperature for reaction for 0.5-1.5 h, and then centrifuging the reaction solution to remove precipitates; (d) and treating the centrifuged supernatant to obtain a finished product. The invention has simple and convenient process, low cost and easy large-scale production, and the prepared product has good bioavailability.
Description
Technical Field
The invention belongs to the technical field of complex preparation, and particularly relates to a preparation method and application of a zinc and calcium polysaccharide complex.
Background
The most prominent phenomenon of calcium, iron and zinc deficiency of children. The calcium, iron and zinc are essential elements for human body, and are very important for growth and development and intelligence development of children; from the third nutrition survey in China, the zinc deficiency or zinc deficiency of children accounts for 60 percent. The lack of calcium, iron and zinc elements in children can cause various diseases. The calcium deficiency can cause rickets of children, such as osteomalacia, late teething, loose teeth, chicken breast, short and small body, X-shaped legs, deformity, and the like. The zinc deficiency is manifested by growth and development retardation, intelligence decline, listlessness, anorexia, etc., and in severe cases, zinc deficiency dwarfism is caused.
The trace element zinc reinforcer is developed, the first generation is inorganic zinc salt, zinc sulfate is a representative, but the zinc absorption rate of a human body is only 7%, so that severe gastrointestinal mucosa stimulation can be caused, and the trace element zinc reinforcer is mainly used for clinical vomiting promotion. The second generation is organic acid zinc salt, mainly including zinc gluconate, zinc citrate, zinc glycyrrhetate and zinc lactate, etc., which can increase the zinc absorption rate of human body to 14% and reduce gastrointestinal tract irritation, but the introduced organic acid produces side effect (Yaodejia. research of pharmacokinetics and bioavailability of oral zinc gluconate and zinc sulfate. microelement and health research, 1995(2): 11-12.). The third generation is amino acid chelated zinc, which was first developed successfully by the american "ai bi wang" biological laboratory. The product is formed by amino acid and zinc through chelation reaction under fixed process condition. Compared with inorganic zinc, the amino acid chelated zinc has the advantages that after zinc elements in the inorganic zinc salt such as zinc sulfate enter intestinal tracts in an ionic state, the pH value is changed, insoluble substances are generated and cannot be absorbed, the amino acid chelated zinc is a stable six-membered ring generated by coordination combination of lone-pair electrons of carboxyl and amino in amino acid molecules and zinc ions, the molecules tend to be neutral, the solubility in the pH environment of a human digestive system is good, free zinc ions can be continuously released, and the zinc is easy to be absorbed by a human body.
The physiological activity and action effect of the calcium nutrition enhancer mainly depend on the source of calcium element and the property of carrier. According to the record of the sanitary standards for the use of nutrition enhancers, the currently used calcium supplement preparations are classified into four main categories of inorganic calcium salts, organic acid calcium salts, organic calcium and natural bioactive calcium, and have different characteristics. The typical representative of inorganic calcium is calcium carbonate, the most common preparation form of the inorganic calcium is calcium tablets, and the inorganic calcium has the characteristics of high content, low price and the like and is widely used. However, the inorganic calcium salt has relatively low absorption rate, is easy to generate precipitate, has side effects of causing calculus and the like, and can cause serious malabsorption after being taken by people with achlorhydria, thereby affecting the normal gastrointestinal function. The presence of organic calcium salts has a great improvement over the above disadvantages of inorganic calcium salts, but it is not negligible that individual organic calcium salts also have problems, such as: the calcium gluconate has low calcium content and high sugar content, and is not suitable for the daily administration of diabetics; calcium lactate is decomposed to generate lactate after entering the digestive tract of a human body, and the side effect of body ache and fatigue is brought; calcium acetate competitively antagonizes the absorption of other trace elements such as zinc by the small intestine and is at risk of inducing hypercalcemia. The organic calcium is a general name of amino acid represented by L-threonic acid calcium and compound amino acid chelated calcium, the calcium supplement product has a levorotatory structure and better lipid solubility, and the stable combination effect of calcium ions and acid radicals ensures that the calcium supplement product has good biological activity.
Saccharides are important constituent substances of organisms and play a wide role in living organisms. The significant structural characteristics of saccharides are that they contain a large number of hydroxyl groups, and the oxygen atoms on the groups can be regarded as proton donors and can be combined with metal cations. The sugar-metal complex is difficult to form for sugar molecules with single structures in aqueous solution or other organic solvents due to the competitive action of solvent molecules, but after the molecules are connected with certain Lewis basic functional groups, the competitive ability is obviously enhanced to have the condition of being matched with metal ions, and the research on the matching action of the metal ions and carbohydrates has important significance in the fields of biochemistry and coordination chemistry.
At present, although some reports about polysaccharide chelated metal ion preparations exist, such as chitosan oligosaccharide zinc chelate for plant disease control, selfheal polysaccharide zinc chelate for cancer resistance, Chinese yam polysaccharide zinc complex for blood sugar reduction and the like, the wide application of the products is limited due to the problems of undefined raw material components, high price, complex preparation process and the like, so that the research on a conventional zinc-calcium nutrition supplement product which is simple and convenient in process, low in cost, safe and good in effect has important market value and wide application prospect.
Disclosure of Invention
The invention aims to provide a preparation method and application of a zinc and calcium polysaccharide complex. The problems of irrational zinc and calcium supplementing effect, high cost and difficult wide application in the prior art are solved.
The purpose of the invention is realized by the following technical scheme: the invention provides a preparation method of a zinc and calcium polysaccharide complex, which comprises the following steps:
(a) dissolving carboxymethyl pullulan in purified water to obtain a CMP solution with the concentration of 0.5-5 wt%, and heating the solution to 30-60 ℃;
(b) dropwise adding a zinc solution into a CMP solution, and dropwise adding an alkali liquor to control the pH value of the reaction solution to be 6-8; or
Dropwise adding a calcium solution into a CMP solution, and dropwise adding an alkali liquor to control the pH value of the reaction solution to be 9-11;
(c) stirring while adding until the solution is saturated, then continuously stirring at constant temperature for reaction for 1-2 h, and then centrifuging the reaction solution to remove precipitates;
(d) concentrating the centrifuged supernatant, precipitating with ethanol, standing, and vacuum filtering to obtain CMP-Zn2+A crude product; adding CMP-Zn2+Dissolving the crude product, dialyzing to remove salt, and freeze-drying to obtain the CMP-Zn2+Pure products; or
Adding Na into the supernatant after centrifugation2CO3Generating white precipitate in the solution, centrifuging to remove the precipitate, concentrating the supernatant, precipitating with ethanol, standing, and vacuum filtering to obtain CMP-Ca2+Crude product, CMP-Ca2+Dissolving the crude product, dialyzing to remove salt, and freeze-drying to obtain CMP-Ca2+And (5) purifying.
In the step (a), the carboxymethyl pullulan has a molecular weight of 5-2000KDa, and the carboxyl source is X-RCOOH, wherein X represents pullulan, and R represents a hydrocarbon chain.
In the step (a), the carboxymethyl pullulan has a carboxymethyl substitution degree of 40-60% per pullulan unit.
In the step (a), the temperature of the solution is raised to 45-55 ℃.
In the step (b), the zinc solution is a zinc sulfate solution, the calcium solution is a calcium chloride solution, and the alkali liquor is a NaOH solution of 1.5-2.5 mol/L.
In the step (c), the final addition amount of the zinc solution is CMP and Zn2+The mass ratio is 4-6; the calcium solution is added with Ca2+The mass ratio of the chemical component to the CMP is 1-4.
And (d) dialyzing for 48-60 hours by using deionized water.
In the step (d), the freeze drying process of the dialysate comprises the following steps: pre-freezing the obtained dialysate at-60 ℃ for 20-28 h, and freeze-drying the obtained pre-frozen product at-60 ℃ under the vacuum degree condition of 0.1Pa for 20-28 h.
The zinc and calcium polysaccharide complex prepared by the method is applied to a nutritional supplement.
The application of the zinc and calcium polysaccharide complex prepared by the method in the calcium-zinc composite nutritional supplement is characterized in that the ratio of the calcium polysaccharide complex to the zinc polysaccharide complex in the nutritional supplement is 5-20: 1.
The invention has the beneficial effects that: the invention utilizes free hydroxyl and carboxyl of CMP polysaccharide chain to carry out complex reaction with zinc and calcium ions under the conditions of controlling specific temperature, pH, reactant feed ratio and reaction time, excessive ions can be removed by a dialysis method, and the granular polysaccharide chelating granules are obtained after freeze-drying of dialysate.
The successful synthesis of the CMP chelating zinc and calcium preparation is proved by ultraviolet and infrared of the polysaccharide chelating zinc or calcium, experiments prove that the CMP chelating zinc and calcium preparation has the effect of improving the bone of an osteoporosis mouse, and the calcium and zinc with proper dosage are supplemented to be more beneficial to the bone improvement of the osteoporosis mouse, thereby indicating the specific good bioavailability of the invention.
The preparation method provided by the invention has the advantages of wide source of main raw materials, low cost, mild synthesis conditions, simple production process, strong operability and easier control of production quality, and most importantly, the product prepared by the method has price advantage and clinical use value compared with the existing similar products.
Drawings
FIG. 1 shows CMP and CMP-Zn2+、CMP-Ca2+Ultraviolet spectrum of the product.
FIG. 2 shows CMP and CMP-Zn2+、CMP-Ca2+Infrared spectra of the product.
FIG. 3 shows CMP and CMP-Zn2+、CMP-Ca2+Electron micrograph of the product. Wherein, a, CMP, b, CMP-Zn2+、c.CMP-Ca2+。
Detailed Description
The following examples are intended to illustrate the present invention in further detail, but the present invention is not limited thereto in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. But are not intended to limit the invention in any manner.
The invention is further illustrated by the following examples.
Example 1: CMP-Zn2+Preparation of
(1) Weighing 10g of carboxymethyl pullulan CMP with the carboxymethyl substitution degree of 40 percent and the molecular weight of 240KDa, dissolving the carboxymethyl pullulan in distilled water to obtain 1 percent (w/v, g/mL) of CMP solution, and adding 0.5mol/L of ZnSO under the condition of a constant-temperature water bath at 50 DEG C4Slowly dripping the solution into the CMP solution, simultaneously dripping 2mol/L NaOH solution, controlling the dripping speed and the dripping amount of the solution and the CMP solution to adjust the pH value of the reaction solution to 7, and carrying out complex reaction.
(2) Stirring while adding until the solution is saturated, wherein the amount of the added zinc solution is CMP and Zn2+The mass ratio is 5, the mixture is stirred and reacts for 1 hour under the constant temperature water bath to generate CMP-Zn2+The complex is prepared by centrifuging reaction solution at 4000r/min for 5min to remove precipitate, concentrating supernatant under reduced pressure, adding 3 times of anhydrous ethanol for precipitating, standing for 24h, and vacuum filtering to obtain precipitate which is CMP-Zn2+And (5) crude product.
(3) Adding CMP-Zn2+Dissolving the crude product, adding the solution into a dialysis bag, dialyzing with deionized water for 48h, and freeze-drying the obtained dialysate: pre-freezing the obtained dialysate at-60 deg.C for 24h, freeze-drying the obtained pre-frozen product at-60 deg.C under vacuum degree of 0.1Pa for 24h, and freeze-drying to obtain granular CMP-Zn2+And (5) purifying. The zinc loading of the obtained product (EDTA titration method) was determined to be 11.5%, and the obtained product was characterized, with the results shown in FIGS. 1-3.
Wherein, the carboxymethyl pullulan is prepared by the following method:
3.0g of pullulan particles are accurately weighed into a 250mL three-necked bottle, 25mL of distilled water is added, and ultrasonic dissolution is carried out. The pullulan solution was transferred to a 70 ℃ water bath and isopropanol was slowly added to the clear solution in a volume fraction of 30% (v/v, mL/mL). 1.5g of sodium hydroxide (sodium hydroxide/saccharide unit 2.0, mmol/mmol) was dissolved in 20mL of distilled water, and the solution was slowly dropped into a 70 ℃ pullulan solution to react for 4 hours. 0.75g (1.0 mmol/mmol sodium hydroxide/sugar unit) solution and 1.8g (1.0 mmol/mmol chloroacetic acid) solution were added dropwise to the reaction solution, and the reaction was continued for 3 hours in 70 ℃ oil bath. Naturally cooling the reaction solution to room temperature, pouring into 500mL of absolute ethyl alcohol to obtain a dark yellow-brown viscous product, and pouring out the upper clear alcohol solution. And completely dissolving the product in a proper amount of deionized water, performing suction filtration, transferring all the filtrate to a dialysis bag (with the molecular weight cutoff of Mw 8000-10000Da), continuously dialyzing the sample in the dialysis bag for 48 hours by using 5000mL of dilute hydrochloric acid solution with the pH value of 4-5, and changing water once every 12 hours. And dialyzing with 5000mL of deionized water for 24h, changing water every 12h, and freeze-drying after dialysis to obtain a white film-shaped solid, namely the product CMP. And (5) characterizing the obtained product, wherein the result is shown in figures 1-3.
Examples 2 to 7: effect of different pH on Zinc Loading
The pH of the reaction solution was changed (see Table 1), and the amount of the zinc solution added was CMP and Zn2+The mass ratio was 3, and the other raw materials and operations were the same as in example 1, and the amount of zinc carried in the product was measured, and the results are shown in Table 1.
Table 1:
| examples | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 |
| pH | 4 | 5 | 6 | 7 | 8 | 9 |
| The zinc loading capacity% | 2.86 | 3.97 | 4.74 | 6.04 | 5.72 | 4.23 |
As can be seen from Table 1, the pH affected the zinc loading of the CMP-Zn (II) complex, which increased with increasing pH and reached the highest level at pH 7, and decreased the zinc content as the pH increased, and the solution became cloudy and pale yellow at pH 9.
Examples 8 to 13: different CMP and Zn2+Influence of Mass ratio on Zinc Loading
Changing CMP and Zn2+The mass ratio (controlled by the amount of zinc solution added) and the reaction pH were 6, and the other raw materials and operations were the same as in example 1The zinc loading of the resulting product was measured and the results are shown in Table 2.
Table 2:
| examples | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 |
| CMP：Zn2+ | 1:1 | 2:1 | 3:1 | 4:1 | 5:1 | 6:1 |
| The zinc loading capacity% | 5.03 | 6.15 | 6.68 | 7.04 | 5.97 | 4.63 |
As shown in Table 2, CMP and Zn2+The mass ratio of the two influences the coordination reaction, and the mass ratio of the two influences the coordination reaction along with mCMP to mZn2+The quantity of the zinc carried by the CMP-Zn (II) complex is increased firstly and then decreased.
Examples 14 to 18: influence of different temperatures on the amount of zinc loaded
Changing the reaction temperature, adding the zinc solution in the amount of CMP and Zn2+The mass ratio was 3, the reaction pH was 9, other raw materials and operations were the same as in example 1, and the zinc-carrying amount of the obtained product was measured, and the results are shown in Table 3.
Table 3:
| examples | Example 14 | Example 15 | Example 16 | Example 17 | Example 18 |
| Temperature of | 30 | 40 | 50 | 60 | 70 |
| The zinc loading capacity% | 4.12 | 5.77 | 6.53 | 6.35 | 5.98 |
As can be seen from Table 3, when the reaction temperature is increased, the zinc content of the complex is rapidly increased and reaches a maximum value at 50 ℃, and then the zinc content is gradually decreased when the reaction temperature is increased, and possibly when the temperature is less than 50 ℃, the complex is suitable for the forward progress of the chemical reaction, and the reaction rate is gradually increased; when the temperature is more than 60 ℃, it is presumed that too high temperature causes a change in the activity of the polysaccharide to inhibit the formation of a coordinate bond.
Example 19: CMP-Ca2+Preparation of
(1) Weighing carboxymethyl pullulan CMP 10g with carboxymethyl substitution degree of 40% and molecular weight of 240KDa, dissolving in distilled water to obtain 1% (w/v, g/mL) CMP solution, and adding 2mol/L CaCl under the condition of 50 deg.C constant temperature water bath2Slowly dripping the solution into the CMP solution, simultaneously dripping 2mol/L NaOH solution, controlling the dripping speed and the dripping amount of the solution and the CMP solution to adjust the pH value of the reaction solution to 10.0, and carrying out complex reaction.
(2) Stirring while adding until the solution is saturated, wherein the amount of the added calcium solution is Ca2+The mass ratio of the mixed solution to the CMP is 2, the mixture is stirred and reacts for 1 hour under the constant-temperature water bath to generate the CMP-Ca2+The complex is obtained by centrifuging the reaction solution at 4000r/min for 5min to remove the precipitate, and adding 2mol/L Na into the supernatant2CO3The solution, with a large amount of white precipitate, was centrifuged until no precipitate was formed, i.e., free calcium ions were removed. Then decompressing and concentrating the supernatant, adding 3 times volume of absolute ethyl alcohol for alcohol precipitation, standing for 24h, and filtering to obtain a precipitate, namely CMP-Ca2+And (5) crude product.
(3) CMP-Ca2+Dissolving the crude product, adding the solution into a dialysis bag, dialyzing with deionized water for 48h, and freeze-drying the obtained dialysate: pre-freezing the obtained dialysate at-60 deg.C for 24h, freeze-drying the obtained pre-frozen product at-60 deg.C under vacuum degree of 0.1Pa for 24h, and freeze-drying to obtain granular CMP-Ca2+And (5) purifying. The zinc loading of the resulting product (EDTA titration) was determined to be 10.4%, andand (5) characterizing the obtained finished product, wherein the result is shown in figures 1-3. Of these, carboxymethyl pullulan was prepared in the same manner as in example 1.
Examples 20 to 25: effect of different pH on calcium Loading
The pH of the reaction solution was changed (see Table 4), and the amount of the calcium solution added was Ca2+The mass ratio to CMP was 1:1, and the other raw materials and the operation conditions were the same as in example 16, and the calcium-carrying amount of the product was measured, and the results are shown in Table 4.
Table 4:
| examples | Example 20 | Example 21 | Example 22 | Example 23 | Example 24 | Example 25 |
| pH | 7 | 8 | 9 | 10 | 11 | 12 |
| The calcium-carrying amount% | 5.57 | 7.51 | 9.36 | 10.24 | 9.68 | 4.74 |
As can be seen from Table 4, the synthetic CMP-Ca (II) complex is affected by pH, and the synthetic CMP-Ca (II) ability increases first and then decreases with increasing pH. The pH value is low, the dissociation degree of carboxyl in CMP molecules is low, and the coordination of the carboxyl and calcium ions in CMP is not facilitated. The highest calcium content in the CMP-ca (ii) complex was determined when the pH was 10.
Examples 26 to 31: different CMP and Ca2+Effect of Mass ratio on calcium Loading
Changing CMP and Ca2+The mass ratio (controlled by the amount of calcium solution added) and the reaction pH were 9, the other raw materials and the operation were the same as in example 16, and the calcium-carrying amount of the obtained product was measured, and the results are shown in Table 5.
Table 5:
| examples | Example 26 | Example 27 | Example 28 | Example 29 | Example 30 | Example 31 |
| CMP：Ca2+ | 1:4 | 1:3 | 1:2 | 1:1 | 2:1 | 3:1 |
| The calcium-carrying amount% | 8.95 | 10.0 | 10.07 | 8.24 | 6.93 | 4.26 |
As shown in Table 5, CMP and Ca2+The mass ratio of the two influences the coordination reaction, and the mass ratio of the two influences the coordination reaction along with mCMP: mCa2+Increasing the calcium loading of the CMP-Ca (II) complex, increasing the calcium loading first and then decreasing the calcium loading, and the optimum mCMP: mCa2+The feeding ratio is 1:2, and the optimal calcium loading of the CMP-Ca (II) complex is achieved.
Examples 32 to 36: effect of different temperatures on the amount of calcium loaded
The reaction temperature was changed to give a reaction pH of 9, and the amount of the calcium solution added was Ca2+The calcium loading of the resulting product was measured in the same manner as in example 16 except that the mass ratio to CMP was 1:1, and the results are shown in Table 6.
Table 6:
| examples | Example 32 | Example 33 | Example 34 | Example 35 | Example 36 |
| Temperature of | 30 | 40 | 50 | 60 | 70 |
| The calcium-carrying amount% | 5.54 | 6.87 | 9.90 | 8.72 | 7.23 |
As shown in Table 6, the reaction temperature affects the calcium loading of the CMP-Ca (II) complex, and the reaction temperature is properly raised to accelerate CMP and Ca2+The frequency of collisions between reactant molecules promotes CMP and Ca2+The coordination reaction is completed. The calcium-carrying amount of the CMP-Ca (II) complex is optimal at 50 ℃. However, too high a temperature causes CMP molecules and Ca2+The too fast movement limits the coordination groups and Ca on the CMP molecule2+In combination with (1).
Example 37CMP-Zn2+、CMP-Ca2+Experiment for improving osteoporosis of mice
A clean-grade three-week-old Balb/C mouse is half male and half female, and the body mass is 15-20 g. The mice are divided into a control group and a model group, the model group is subjected to retinoic acid intragastric administration to make the osteoporosis model, the control group is subjected to intragastric administration by using normal saline as a control, and the molding effect is verified after intragastric administration for 14 days. Setting the rest mice in the control group as a blank control group; the model groups were randomly divided into model control group, CMP-Ca (II) dosage group and CMP-Ca (II)/CMP-Zn (II) dosage group, and the gavage was continued for 28d, the specific dosage is shown in Table 7, and the components were raised in cages, fed with standard feed and allowed to drink water freely during the experiment.
Table 7:
the femur of the mouse treated as described above was examined, and the results are shown in tables 8 and 9.
Table 8:
table 9:
| group of | Bone Density (g/cm)3) | Bone hardness (N) |
| Blank control group | 1.17±0.07 | 27.85±2.49 |
| Model control group | 1.03±0.02* | 18.89±3.55* |
| Supplement calcium alone | 1.06±0.03 | 21.91±6.73# |
| Calcium and zinc supplement | 1.15±0.04# | 24.86±5.34# |
Table denotes P <0.05vs control group; # denotes a P <0.05vs model group.
As shown in tables 8 and 9, the combination of CMP-Ca (II) and CMP-Zn (II) prepared by the invention with proper dosage can prevent the bone mass loss of mice in osteoporosis models to a certain extent, increase the transverse diameter and the weight of the femur bone of the mice, increase the bone density and improve the bone biomechanical property, show good effect of resisting osteoporosis and simultaneously show that the product has good bioavailability.
The above examples are intended to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. In addition, various modifications of the methods and compositions set forth herein, as well as variations of the methods and compositions of the present invention, will be apparent to those skilled in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the above-described embodiments which are obvious to those skilled in the art to which the invention pertains are intended to be covered by the scope of the present invention.
Claims (10)
1. A preparation method of a zinc and calcium polysaccharide complex is characterized by comprising the following steps:
(a) dissolving carboxymethyl pullulan in purified water to obtain a CMP solution with the concentration of 0.5-5 wt%, and heating the solution to 30-60 ℃;
(b) dropwise adding a zinc solution into a CMP solution, and dropwise adding an alkali liquor to control the pH value of the reaction solution to be 6-8; or
Dropwise adding a calcium solution into a CMP solution, and dropwise adding an alkali liquor to control the pH value of the reaction solution to be 9-11;
(c) stirring while adding until the solution is saturated, then continuously stirring at constant temperature for reaction for 1-2 h, and then centrifuging the reaction solution to remove precipitates;
(d) concentrating the centrifuged supernatant, precipitating with ethanol, standing, and vacuum filtering to obtain CMP-Zn2+A crude product; adding CMP-Zn2+Dissolving the crude product, dialyzing to remove salt, and freeze-drying to obtain the CMP-Zn2+Pure products; or
Adding Na into the supernatant after centrifugation2CO3Generating white precipitate in the solution, centrifuging to remove the precipitate, concentrating the supernatant, precipitating with ethanol, standing, and vacuum filtering to obtain CMP-Ca2+Crude product, CMP-Ca2+Dissolving the crude product, dialyzing to remove salt, and freeze-drying to obtain CMP-Ca 2+And (5) purifying.
2. The process according to claim 1, wherein in step (a), the carboxymethyl pullulan has a molecular weight of 5 to 2000kDa and the carboxyl group source is X-RCOOH, wherein X represents pullulan and R represents a hydrocarbon chain.
3. The method according to claim 1, wherein the carboxymethyl pullulan has a degree of substitution of carboxymethyl group of 40 to 60% per pullulanose unit in the step (a).
4. The method for preparing zinc-calcium polysaccharide complex according to claim 1, wherein in the step (a), the temperature of the solution is raised to 45-55 ℃.
5. The method for preparing zinc-calcium polysaccharide complex as claimed in claim 1, wherein in step (b), the zinc solution is zinc sulfate solution, the calcium solution is calcium chloride solution, and the alkali solution is NaOH solution with a concentration of 1.5-2.5 mol/L.
6. The process according to claim 1, wherein the final amount of zinc solution added in step (c) is CMP plus Zn2+The mass ratio is 4-6; the calcium solution is added with Ca2+The mass ratio of the chemical component to the CMP is 1-4.
7. The method for preparing zinc-calcium polysaccharide complex according to claim 1, wherein in the step (d), deionized water is adopted for dialysis for 48-60 h.
8. The method for preparing zinc-calcium polysaccharide complex according to claim 1, wherein the freeze-drying process of the dialysate in step (d) comprises: pre-freezing the obtained dialysate at-60 ℃ for 20-28 h, and freeze-drying the obtained pre-frozen product at-60 ℃ under the vacuum degree condition of 0.1Pa for 20-28 h.
9. Use of a zinc, calcium polysaccharide complex prepared by the process of any one of claims 1 to 8 in a nutritional supplement.
10. The application of the zinc and calcium polysaccharide complex prepared by the method of any one of claims 1 to 8 in a calcium-zinc composite nutritional supplement, wherein the mass ratio of the calcium polysaccharide complex to the zinc polysaccharide complex in the nutritional supplement is 5-20: 1.
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