CN112106975B - 甲壳素单宁酸复合胶体颗粒乳化剂及其制备方法和应用 - Google Patents
甲壳素单宁酸复合胶体颗粒乳化剂及其制备方法和应用 Download PDFInfo
- Publication number
- CN112106975B CN112106975B CN202011058750.6A CN202011058750A CN112106975B CN 112106975 B CN112106975 B CN 112106975B CN 202011058750 A CN202011058750 A CN 202011058750A CN 112106975 B CN112106975 B CN 112106975B
- Authority
- CN
- China
- Prior art keywords
- chitin
- emulsifier
- tannic acid
- colloidal particle
- tannin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920002101 Chitin Polymers 0.000 title claims abstract description 151
- 239000002245 particle Substances 0.000 title claims abstract description 67
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 229920001864 tannin Polymers 0.000 title claims abstract description 39
- 239000001648 tannin Substances 0.000 title claims abstract description 39
- 235000018553 tannin Nutrition 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000839 emulsion Substances 0.000 claims abstract description 48
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 41
- 229920002258 tannic acid Polymers 0.000 claims abstract description 41
- 229940033123 tannic acid Drugs 0.000 claims abstract description 41
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 40
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 38
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 38
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 31
- 239000006185 dispersion Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 17
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 14
- 235000013824 polyphenols Nutrition 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 239000004202 carbamide Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000010257 thawing Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 238000000265 homogenisation Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 230000003993 interaction Effects 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 241001122767 Theaceae Species 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 12
- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- 230000001804 emulsifying effect Effects 0.000 abstract description 5
- 102000011632 Caseins Human genes 0.000 abstract description 4
- 108010076119 Caseins Proteins 0.000 abstract description 4
- 150000004676 glycans Chemical class 0.000 abstract description 4
- 229920001282 polysaccharide Polymers 0.000 abstract description 4
- 239000005017 polysaccharide Substances 0.000 abstract description 4
- 229940080237 sodium caseinate Drugs 0.000 abstract description 4
- 235000010469 Glycine max Nutrition 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000004519 grease Substances 0.000 abstract description 3
- 244000068988 Glycine max Species 0.000 abstract description 2
- 238000011160 research Methods 0.000 abstract description 2
- JLPULHDHAOZNQI-ZTIMHPMXSA-N 1-hexadecanoyl-2-(9Z,12Z-octadecadienoyl)-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCC\C=C/C\C=C/CCCCC JLPULHDHAOZNQI-ZTIMHPMXSA-N 0.000 abstract 1
- 229940083466 soybean lecithin Drugs 0.000 abstract 1
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- 239000007764 o/w emulsion Substances 0.000 description 15
- 235000013305 food Nutrition 0.000 description 13
- 239000013256 coordination polymer Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 235000019198 oils Nutrition 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 244000269722 Thea sinensis Species 0.000 description 6
- 239000011246 composite particle Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 150000003904 phospholipids Chemical class 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 235000012424 soybean oil Nutrition 0.000 description 4
- 239000003549 soybean oil Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 235000010489 acacia gum Nutrition 0.000 description 2
- 239000001785 acacia senegal l. willd gum Substances 0.000 description 2
- 235000003084 food emulsifier Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002749 Bacterial cellulose Polymers 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000005016 bacterial cellulose Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- -1 fish oil Chemical class 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 235000020124 milk-based beverage Nutrition 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000010909 process residue Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
Images
Classifications
-
- 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
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/10—Foods or foodstuffs containing additives; Preparation or treatment thereof containing emulsifiers
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
- A23C9/00—Milk preparations; Milk powder or milk powder preparations
- A23C9/12—Fermented milk preparations; Treatment using microorganisms or enzymes
- A23C9/13—Fermented milk preparations; Treatment using microorganisms or enzymes using additives
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
- A23C9/00—Milk preparations; Milk powder or milk powder preparations
- A23C9/12—Fermented milk preparations; Treatment using microorganisms or enzymes
- A23C9/13—Fermented milk preparations; Treatment using microorganisms or enzymes using additives
- A23C9/1307—Milk products or derivatives; Fruit or vegetable juices; Sugars, sugar alcohols, sweeteners; Oligosaccharides; Organic acids or salts thereof or acidifying agents; Flavours, dyes or pigments; Inert or aerosol gases; Carbonation methods
-
- 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
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3472—Compounds of undetermined constitution obtained from animals or plants
-
- 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
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3481—Organic compounds containing oxygen
- A23L3/3508—Organic compounds containing oxygen containing carboxyl groups
-
- 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
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3562—Sugars; 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Microbiology (AREA)
- Nutrition Science (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Botany (AREA)
- General Preparation And Processing Of Foods (AREA)
- Colloid Chemistry (AREA)
Abstract
本发明提供了一种甲壳素单宁酸复合胶体颗粒乳化剂及其制备方法和应用,该乳化剂是将甲壳素胶体粒子与单宁酸溶液混合,搅拌均匀即得甲壳素单宁酸复合颗粒乳化剂。研究发现在同等浓度下,相比单独使用甲壳素与单宁酸,甲壳素与单宁酸复合使用时所稳定乳液具有最小的粒径,且室温条件下放置半年不发生破乳,长期储存后保持稳定,所稳定乳液中油脂的氧化产物含量最低,表明复合乳化剂所稳定乳液具有最好的物理及氧化稳定性。且在稳定油水界面方面,甲壳素单宁酸复合乳化剂的乳化性能优于常见商业乳化剂如大豆卵磷脂、酪蛋白酸钠、大豆多糖。本发明的甲壳素复合乳化剂可以较低含量乳化剂制备粒径更小、稳定性更强以及抗氧化性能更强的皮克林乳液。
Description
技术领域
本发明涉及乳化剂技术领域,特别涉及一种一种甲壳素单宁酸复合胶体颗粒乳化剂及其制备方法和应用。
背景技术
食品乳状液是一类常见的食品体系,只有在稳定的状态下,乳状液在食品体系中的其它功能才能得以正常发挥。但是食品乳状液体系不稳定是食品生产和贮藏过程中十分常见的问题,突出表现在产品发生油水分离以及油相发生氧化。
目前,食品中采用的乳化剂以小分子(如磷脂)、高分子(如蛋白、阿拉伯胶等)为主,然而,这些乳化剂的尺寸较小,界面吸附能低,吸附到油水界面后很容易从界面脱落下来,另一方面,这些乳化剂在油水界面提供的空间位阻效应较弱,会导致乳液易上浮和析油,因此,现有天然乳化剂的乳状液容易出现分散相液滴聚集和聚并、从而引起乳状液失稳或相分离并最终出现乳状液油水分离。
相比传统小分子乳化剂稳定的乳液,固体颗粒稳定的乳液,即Pickering乳液,因其强界面稳定性而受到研究者广泛关注。而生物大分子基有机颗粒因其生物可降解性、环境友好特性而受青睐。甲壳素是世界上储量仅次于纤维素的第二大多糖,广泛来源于虾蟹壳等食品加工废弃物,前期研究发现甲壳素经碱尿素溶解再生并在适当条件下超声处理后能稳定水包油乳液。且甲壳素颗粒能在较广范围pH内稳定水包油乳液,所稳定乳液能耐高温等极端条件,因此甲壳素颗粒是一种具有较好潜力的新型颗粒乳化剂。然而短时间超声处理所得甲壳素颗粒具有有限乳化性,所稳定乳液粒径较大,稳定性差。而乳液的粒径及稳定性与相关产品的稳定性密切相关,制备粒径更小稳定性更强的乳液需长时间超声处理甲壳素或使用大量甲壳素。另外,对于含不饱和脂肪酸如鱼油等油相乳液,抑制油相的氧化也是乳液的重要性质之一,也与产品的稳定性货架期息息相关。因此制备一种新型高乳化性能且具有较强界面抗氧化性能的甲壳素固体颗粒乳化剂将具有广阔的应用前景。
单宁酸是一种常见的水溶性多酚,价廉、可生物降解,是一种在食品中允许使用的食品添加剂,因此本发明尝试利用甲壳素与单宁酸制备复合颗粒乳化剂。
发明内容
为解决传统天然食品乳化剂如磷脂、酪蛋白酸钠、阿拉伯胶等所分子乳化剂所稳定食品乳状液易分层,导致油水分离的问题,以及所稳定乳液中油相易氧化酸败等问题,本发明利用一种简单的分子组装的方法制备了一种甲壳素单宁酸复合胶体颗粒乳化剂,所制备颗粒乳化剂相比原始甲壳素颗粒乳化剂,乳化活性及稳定性显著增强,制备相同粒径乳状液,所用乳化剂质量分数大幅度降低。
未解决上述技术问题,本发明采用以下技术方案:
一种甲壳素单宁酸复合胶体颗粒乳化剂,所述复合颗粒乳化剂中单宁酸与甲壳素的质量比为1: 1~1: 50。
进一步,所述甲壳素单宁酸复合颗粒乳化剂的pH为2~4。
本发明所述的甲壳素单宁酸复合胶体颗粒乳化剂的制备方法如下:通过向含有甲壳素胶体颗粒或甲壳素纤维的甲壳素分散液中添加单宁酸溶液,搅拌均匀制得。
进一步,所述甲壳素分散液的pH为2~5。
进一步,所述复合胶体颗粒乳化剂在室温以下温度条件下制备。
本发明利用甲壳素与单宁酸之间强烈的分子间氢键以及疏水相互作用制备得到甲壳素单宁酸复合胶体颗粒乳化剂。
进一步,所述的甲壳素单宁酸复合胶体颗粒乳化剂的制备方法,包括以下步骤:
(1)配置质量分数为0.5%-1.5%的再生甲壳素溶液,调节pH至2-5,经高强度超声波或高压均质处理后,得到甲壳素胶体粒子分散液;
(2)配置单宁酸溶液,将单宁酸溶液与甲壳素分散液按照单宁酸与甲壳素的质量比为1: 1~1: 50混合,然后磁力或机械搅拌30分钟,得到甲壳素单宁酸复合胶体颗粒乳化剂。
进一步,所述再生甲壳素溶液的制备方法如下:甲壳素经含有11wt%NaOH、4% wt尿素的水溶液,在-30℃条件下通过冻融循环得到透明甲壳素溶液,通过加酸中和NaOH得到再生甲壳素,然后水洗除去NaOH以及尿素得到再生甲壳素溶液。
进一步,所述单宁酸溶液可以用茶多酚等其它水溶性多酚溶液代替。
作为本发明的一个实施方案,甲壳素单宁酸复合胶体颗粒乳化剂的制备方法,包括以下步骤:
(1)甲壳素在11wt%NaOH、4 wt %尿素溶剂中在-30℃条件下通过冻融循环得到透明甲壳素溶液,通过加酸中和NaOH得到再生甲壳素,后水洗除去NaCl以及尿素。后配置一定质量分数再生甲壳素(0.5%-1.5%),调节pH至2-5,经超声波(300w, 超声5分钟) 处理后,得到甲壳素胶体粒子分散液。
(2) 配置一定质量分数的单宁酸溶液,将单宁酸溶液与甲壳素分散液按一定比例混合,单宁酸与甲壳素的质量比为1:1至1:50,后磁力或机械搅拌一定时间,得到甲壳素单宁酸复合胶体颗粒乳化剂。
在该实施方案中,甲壳素单宁酸复合胶体颗粒乳化剂的pH值为2-4之间。
在另一个实施方案中,配置一定质量分数再生甲壳素(0.5%-1.5%),调节pH至2-5,经高压均质(50 MPa, 5次)处理后,得到甲壳素胶体粒子分散液或甲壳素纳米纤维。将单宁酸溶液与甲壳素分散液按一定比例混合,单宁酸与甲壳素的质量比为1:1至1:50,后磁力或机械搅拌一定时间,得到甲壳素单宁酸复合胶体颗粒乳化剂。
在该实施方案中,甲壳素单宁酸复合胶体颗粒乳化剂的pH值为2-4之间。
本发明中所描述胶体粒子还可扩大范围至纤维素胶体粒子,纤维素纳米纤维,细菌纤维素,以及蛋白质类胶体粒子,多酚还可扩大至茶多酚以及其它水溶性多酚。
在另一个实施方案中,甲壳素通过以上超声或高压均质方法制备得到甲壳素粒子分散液或甲壳素纳米纤维,将茶多酚溶液与甲壳素分散液按一定比例混合,茶多酚与甲壳素的质量比为1:1至1:50,后磁力或机械搅拌一定时间,得到甲壳素茶多酚复合乳化剂。
本发明所制备甲壳素单宁酸复合胶体颗粒乳化剂在制备水包油型乳状液类食品尤其在酸性乳饮料以及其它乳状液中的用途。
在另一个实施方案中,水包油型乳状液的制备方法是:将甲壳素胶体颗粒与单宁酸混合搅拌均匀后,得到甲壳素单宁酸复合乳化剂,将复合乳化剂与油混合,用均质设备进行乳化,制得水包油型乳状液。
所述均质设备可为超声设备、高压均质设备或者高速剪切设备。
与现有技术相比,本发明具有以下有益效果:
(1)本发明采用了一种绿色简单的食品分子组装技术制备了一种新型甲壳素复合乳化剂,组装后复合乳化剂的界面性质发生改变,从而更易于吸附于油水界面,且所稳定乳液具有更好的物理稳定性。
(2)该复合乳化剂稳定乳液具有乳化剂用量低的突出特点,使得乳液制备所用的乳化剂的用量更小,制备相同平均粒径的乳液时,该复合乳化剂用量仅为原始甲壳素乳化剂用量的10-20%。所制得的乳液粒径更小,更稳定,具有十分优良的稳定性,室温条件下放置半年不发生破乳。此外,制备的乳液粒径小,复合乳化剂高效,大大降低了制备水包油乳液的成本。
(3)本发明制备的乳化剂具有较强的界面抗氧化性能,能显著抑制油相的氧化。
(4)本发明复合颗粒乳化剂可高效稳定食用油如大豆油、葵花籽油、中链脂肪酸甘油酯等甘油三酯类油性物质以及烷烃、芳烃等油性物质。
总之,采用多酚对甲壳素进行修饰,制备甲壳素多酚复合乳化剂,能够长时间稳定乳液,充分发挥甲壳素作为食品乳化剂的作用,扩大甲壳素在食品工业中的应用范围。
附图说明
以下图标题中CP= chitin particles (甲壳素胶体粒子)TA=tannic acid (单宁酸)CP-TA (4:1) complex = CP-TA (4/5) complex:甲壳素单宁酸(4:1)复合胶体颗粒CP-TA (3:2) complex = CP-TA (3/5) complex:甲壳素单宁酸(3:2)复合胶体颗粒;
附图1:A. CP,B.CP-TA (4:1) complex (4g/L CP+1 g/L TA),C .CP-TA (3:2)complex (3 g/L CP+2 g/L TA) 所稳定乳液的微观显微镜图;
附图2:A. CP,B.CP-TA (4:1) complex (4g/L CP+1 g/L TA),C .CP-TA (3:2)complex (3 g/L CP+2 g/L TA) 所稳定乳液储存24h, 7d后乳液的粒径变化图;
附图3:A. CP,B.CP-TA (4:1) complex (4g/L CP+1 g/L TA),C .CP-TA (3:2)complex (3 g/L CP+2 g/L TA) 所稳定乳液的样品不稳定指数(TSI)图;
附图4:A. CP,B.CP-TA (4/5) complex (4g/L CP+1 g/L TA),C .CP-TA (3/5)complex (3 g/L CP+2 g/L TA) 所稳定乳液16天内油脂氧化的初级产物(LH) 以及次级产物 (MDA) 变化趋势图;
附图5:四种同等浓度(5g/L)乳化剂(甲壳素单宁酸(3:2)复合乳化剂、磷脂、酪蛋白酸钠、大豆多糖)所稳定水包油乳液在储藏一周内的粒径变化情况。
具体实施方式
下面结合具体实施例,对本发明做进一步说明。应理解,以下实施例仅用于说明本发明而非用于限制本发明的范围,该领域的技术熟练人员可以根据上述发明的内容作出一些非本质的改进和调整。
以下实验所用甲壳素购置于浙江金壳药业有限公司
实施例1
本实施例甲壳素单宁酸复合胶体颗粒乳化剂的制备方法如下:
(1)4g甲壳素与100g (11g NaOH, 4g 尿素,85g 水) 溶剂混合,并在-30℃下冷冻3小时,后采用机械搅拌桨在搅拌状态下解冻甲壳素,冻融循环重复3次,采用高速离心机在1000 g条件下离心20分钟,取上清液部分得到透明甲壳素溶液。
(2)在搅拌状态(200rpm)缓慢加入20倍体积的去离子水,直至甲壳素全部析出,并在搅拌状态下加入一定量HCl中和NaOH至pH=7, 并采用过滤、水洗等步骤除去再生甲壳素中的NaCl以及尿素,浓缩得到再生甲壳素并测定含水再生甲壳素中甲壳素的质量分数。
(5)配置质量分数为0.5%的再生甲壳素100ml, 调节pH至4,并用高强度超声波(450w, 2s on, 2s off)处理甲壳素5分钟,得到再生甲壳素分散液。
(6)配置质量分数为0.5%的单宁酸溶液100ml,将再生甲壳素分散液与单宁酸以体积比3:2或4:1混合,并磁力或机械搅拌30分钟,得到不同的甲壳素单宁酸复合颗粒乳化剂。
本实施例水包油乳状液的制备方法,步骤包括:
取40ml甲壳素单宁酸复合颗粒乳化剂,加入10ml大豆油,用高速剪切设备(8000rpm, 2min)剪切制备得到水包油乳状液。
实施例2
本实施例甲壳素单宁酸复合胶体颗粒乳化剂的制备方法如下:
(1)3g甲壳素与100g (11g NaOH, 4g尿素,85g水) 溶剂混合,并在-30℃下冷冻3小时,后采用机械搅拌桨在搅拌状态下解冻甲壳素,冻融循环重复3次,采用高速离心机在8000 g条件下离心15分钟,取上清液部分得到透明甲壳素溶液。
(2)在搅拌状态(150 rpm)缓慢加入20倍体积的去离子水,直至甲壳素全部析出,并在搅拌状态下加入一定量盐酸中和NaOH至pH=7, 并采用过滤、水洗等步骤除去再生甲壳素中的NaCl以及尿素,浓缩得到再生甲壳素并测定含水再生甲壳素中甲壳素的质量分数。
(7)配置质量分数为1 %的再生甲壳素100ml, 调节pH至3,并用高强度超声波(450w, 2s on, 2s off)处理甲壳素10分钟,得到再生甲壳素分散液。
(8)配置质量分数为1 %的单宁酸溶液100ml,将再生甲壳素分散液与单宁酸以体积比3:2或4:1混合,并磁力或机械搅拌30分钟,得到不同的甲壳素单宁酸复合颗粒乳化剂。
本实施例水包油乳状液的制备方法,步骤包括:
取30ml甲壳素单宁酸复合颗粒乳化剂,加入10ml大豆油,用高速剪切设备(10000rpm, 2min)剪切制备得到水包油乳状液
实施例3
本实施例甲壳素单宁酸复合胶体颗粒乳化剂的制备方法如下:
(1)4g甲壳素与100g (11g NaOH, 4g 尿素,85g 水) 溶剂混合,并在-30℃下冷冻3小时,后采用机械搅拌桨在搅拌状态下解冻甲壳素,冻融循环重复3次,采用高速离心机在8000 g条件下离心15分钟,取上清液部分得到透明甲壳素溶液。
(2)在搅拌状态(150rpm)缓慢加入20倍体积的去离子水,直至甲壳素全部析出,并在搅拌状态下加入一定量盐酸中和NaOH至pH=7, 并采用过滤、水洗等步骤除去再生甲壳素中的NaCl以及尿素,浓缩得到再生甲壳素并测定含水再生甲壳素中甲壳素的质量分数。
(9)配置质量分数为0.5%的再生甲壳素100ml,调节pH至3,并用高压均质(50 MPa)处理甲壳素5次,得到再生甲壳素分散液。
(10)配置质量分数为0.5%的单宁酸溶液100ml,将再生甲壳素分散液与单宁酸以体积比3:2或4:1混合,并磁力或机械搅拌30分钟,得到不同的甲壳素单宁酸复合颗粒乳化剂。
本实施例的水包油乳状液的制备方法,步骤包括:
取30ml甲壳素单宁酸复合颗粒乳化剂,加入10ml大豆油,用高压均质设备(10000rpm, 2min)乳化得到水包油乳状液。
实施例4
本实施例中再生甲壳素分散液与单宁酸以体积比1:1混合,其他步骤同实施例1。
实施例5
本实施例中再生甲壳素分散液与单宁酸以体积比10:1混合,其他步骤同实施例1。
实施例6
本实施例中再生甲壳素分散液与单宁酸以体积比20:1混合,其他步骤同实施例1。
实施例7
本实施例中再生甲壳素分散液与单宁酸以体积比30:1混合,其他步骤同实施例1。
实施例8
本实施例中再生甲壳素分散液与单宁酸以体积比40:1混合,其他步骤同实施例1。
实施例9
本实施例中再生甲壳素分散液与单宁酸以体积比50:1混合,其他步骤同实施例1。
实施例10
本实施例中将茶多酚溶液替换单宁酸溶液,其他步骤同实施例1。
本发明还采用激光粒度仪测定了实施例1制得的水包油型乳状液,比较了三种胶体颗粒所稳定乳液的粒径。通常乳液粒径越小,其稳定性越强,从图1中可以看出,相比甲壳素颗粒,甲壳素单宁酸 (3:2) 复合物稳定的乳液的粒径最小(图1,图2),且储存一星期后粒径变化较小(图2),表明所制备乳液具有较好的物理稳定性。
另外,本发明还采用了Turbiscan稳定性分析仪(Formulaction公司,法国生产)对实施例1中乳液的物理稳定性进行了评价。实验过程包括:采用上述制备甲壳素胶体颗粒以及甲壳素单宁酸复合物分别取实施例1制得的水包油型乳状液20ml作为测试样品,摇匀样品;将样品加入到样品透明玻璃样品池中,液面与样品支架平齐,设置测试时间为10min,利用仪器自带的软件获得稳定性指数,背散射光强等数据。TSI为样品不稳定指数,由仪器自动计算得出,TSI值越大,表明样品越不稳定。由图3可以看出,三种乳化剂定的乳液的TSI值随着时间的延长都在增大,表明样品的稳定性随着时间的延长而降低,但是甲壳素单宁酸(3:2)复合物稳定的乳液的TSI值均小于其他两种乳化剂定的乳液,表明甲壳素单宁酸 (3:2)复合物稳定的乳液的稳定性是最高的。
此外,本发明还测定了三种胶体粒子所稳定乳液中油脂氧化的初级氧化产物以及次级氧化产物,结果如图4所示,相比甲壳素胶体粒子以及甲壳素单宁酸(4:1)复合物胶体粒子,甲壳素单宁酸(3:2)复合物所稳定乳液的初级氧化产物以及次级氧化产物含量最低,表明甲壳素单宁酸 (3:2)复合物所稳定乳液具有最好的氧化稳定性。
同时,本发明还对比了甲壳素单宁酸(3:2)复合物与GB2760中规定允许在食品中使用的几种天然食品乳化剂(磷脂,酪蛋白酸钠,大豆多糖)在同等条件下稳定水包油乳液的能力。结果发现如图5所示,在4℃条件下储存7天后,甲壳素单宁酸(3:2)复合物、磷脂、酪蛋白酸钠、大豆多糖所稳定水包油乳液粒径分别为16.7μm、20.8μm、 37.8μm、51.9μm,甲壳素单宁酸(3:2)复合物所稳定乳液粒径显著小于其它3组乳化剂所稳定乳液。通常乳液粒径越小,表明乳化剂的乳化能力越强。同时,甲壳素单宁酸(3:2)复合物所稳定乳液在7天内乳液粒径没有显著变化,而大豆卵磷脂所稳定乳液粒径由第一天的8.2 μm增加到了第七天的20.8 μm,酪蛋白酸钠所稳定乳液粒径由第一天的27.85 μm增加到了第七天的37.8 μm,大豆多糖多稳定乳液粒径由第一天的32.8μm增加到第七天的51.9 μm。表明甲壳素单宁酸复合物所稳定乳液具有更好的稳定性,进一步突出了甲壳素单宁酸复合物所稳定乳液的优势。
以上显示和描述了本发明的基本原理和主要特征以及本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (4)
1.一种甲壳素单宁酸复合胶体颗粒乳化剂的制备方法,其特征在于:在室温以下温度条件下,通过向含有甲壳素胶体颗粒或甲壳素纤维的甲壳素分散液中添加单宁酸溶液,搅拌均匀,利用甲壳素与单宁酸之间强烈的分子间氢键以及疏水相互作用制备得到甲壳素单宁酸复合胶体颗粒乳化剂,具体包括以下步骤:
(1)配置质量分数为0.5%-1.5%的再生甲壳素溶液,调节pH至2-5,经高强度超声波或高压均质处理后,得到甲壳素胶体粒子或纤维状分散液;
(2)配置单宁酸溶液,将单宁酸溶液与甲壳素分散液按照单宁酸与甲壳素的质量比为1: 1~1: 50混合,然后磁力或机械搅拌30分钟,得到甲壳素单宁酸复合胶体颗粒乳化剂,所述甲壳素单宁酸复合颗粒乳化剂的pH为2~4。
2.根据权利要求1所述的甲壳素单宁酸复合胶体颗粒乳化剂的制备方法,其特征在于:所述再生甲壳素溶液的制备方法如下:甲壳素经含有11wt%NaOH、4% wt尿素的水溶液,在-30℃条件下通过冻融循环得到透明甲壳素溶液,通过加酸中和NaOH得到再生甲壳素,然后水洗除去NaOH以及尿素得到再生甲壳素溶液。
3.根据权利要求1所述的甲壳素单宁酸复合胶体颗粒乳化剂的制备方法,其特征在于:所述单宁酸溶液可以用茶多酚及其它多酚溶液代替。
4.权利要求1所述的制备方法制得的甲壳素单宁酸复合胶体颗粒乳化剂在制备水包油型乳状液中的用途。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011058750.6A CN112106975B (zh) | 2020-09-30 | 2020-09-30 | 甲壳素单宁酸复合胶体颗粒乳化剂及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011058750.6A CN112106975B (zh) | 2020-09-30 | 2020-09-30 | 甲壳素单宁酸复合胶体颗粒乳化剂及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112106975A CN112106975A (zh) | 2020-12-22 |
CN112106975B true CN112106975B (zh) | 2023-03-31 |
Family
ID=73797909
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011058750.6A Active CN112106975B (zh) | 2020-09-30 | 2020-09-30 | 甲壳素单宁酸复合胶体颗粒乳化剂及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112106975B (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114276560B (zh) * | 2021-12-29 | 2023-11-14 | 佛山市中医院 | 一种β-甲壳素纳米纤维悬浮液的浓缩方法及自支撑材料 |
CN115430306B (zh) * | 2022-07-26 | 2023-12-15 | 渤海大学 | 大豆种皮多糖与二氧化硅颗粒协同制备Pickering乳液的方法 |
CN117820652B (zh) * | 2024-03-01 | 2024-05-10 | 上海希森材料科技有限公司 | 一种生物降解改性松香树脂及其制备方法和应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109603786A (zh) * | 2018-12-26 | 2019-04-12 | 东北林业大学 | 基于壳聚糖的单宁微球缓释型甲醛捕捉剂及其制备方法 |
CN110511408A (zh) * | 2019-09-04 | 2019-11-29 | 合肥工业大学 | Lm/ta-壳聚糖盐酸盐复合纳米颗粒、其制备方法和应用 |
CN110547442A (zh) * | 2019-09-20 | 2019-12-10 | 武汉轻工大学 | 一种乳清分离蛋白-单宁酸纳米颗粒稳定剂及其制备方法和油相Pickering乳液 |
CN111518291A (zh) * | 2019-02-01 | 2020-08-11 | 武汉大学 | 一种壳聚糖微球材料的制备方法 |
-
2020
- 2020-09-30 CN CN202011058750.6A patent/CN112106975B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109603786A (zh) * | 2018-12-26 | 2019-04-12 | 东北林业大学 | 基于壳聚糖的单宁微球缓释型甲醛捕捉剂及其制备方法 |
CN111518291A (zh) * | 2019-02-01 | 2020-08-11 | 武汉大学 | 一种壳聚糖微球材料的制备方法 |
CN110511408A (zh) * | 2019-09-04 | 2019-11-29 | 合肥工业大学 | Lm/ta-壳聚糖盐酸盐复合纳米颗粒、其制备方法和应用 |
CN110547442A (zh) * | 2019-09-20 | 2019-12-10 | 武汉轻工大学 | 一种乳清分离蛋白-单宁酸纳米颗粒稳定剂及其制备方法和油相Pickering乳液 |
Non-Patent Citations (3)
Title |
---|
壳聚糖/单宁酸复合胶体粒子的制备及功能涂层研究;石甜甜等;《功能材料》;20171231;第48卷(第5期);05042-05047 * |
甲壳素在食品领域的最新研究进展;望运滔等;《食品与机械》;20200731;第36卷(第7期);221-226 * |
石甜甜等.壳聚糖/单宁酸复合胶体粒子的制备及功能涂层研究.《功能材料》.2017,第48卷(第5期), * |
Also Published As
Publication number | Publication date |
---|---|
CN112106975A (zh) | 2020-12-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112106975B (zh) | 甲壳素单宁酸复合胶体颗粒乳化剂及其制备方法和应用 | |
Ma et al. | Formation of soy protein isolate (SPI)-citrus pectin (CP) electrostatic complexes under a high-intensity ultrasonic field: Linking the enhanced emulsifying properties to physicochemical and structural properties | |
Zhang et al. | Emulsion gels stabilized by soybean protein isolate and pectin: Effects of high intensity ultrasound on the gel properties, stability and β-carotene digestive characteristics | |
Wang et al. | Microwave technology as a new strategy to induce structural transition and foaming properties improvement of egg white powder | |
Agi et al. | Application of polymeric nanofluid in enhancing oil recovery at reservoir condition | |
Zhou et al. | High internal phase Pickering emulsion by Spanish mackerel proteins-procyanidins: Application for stabilizing astaxanthin and surimi | |
Klinkesorn | The role of chitosan in emulsion formation and stabilization | |
Chen et al. | Development of anti-photo and anti-thermal high internal phase emulsions stabilized by biomass lignin as a nutraceutical delivery system | |
Zhang et al. | Investigation of the formation mechanism and β-carotene encapsulation stability of emulsion gels based on egg yolk granules and sodium alginate | |
KR20130091663A (ko) | 키토산 조성물 | |
CN113397156B (zh) | 一种双重Pickering乳液及其制备方法 | |
Safian et al. | Utilization of lignocellulosic biomass: A practical journey towards the development of emulsifying agent | |
Jiang et al. | Comparative study of high‐intensity ultrasound and high‐pressure homogenization on physicochemical properties of peanut protein‐stabilized emulsions and emulsion gels | |
CN106937737A (zh) | 一种酪蛋白凝胶颗粒乳化剂及其制备方法和用途 | |
Zhao et al. | Structure and stability characterization of pea protein isolate-xylan conjugate-stabilized nanoemulsions prepared using ultrasound homogenization | |
Zhong et al. | Oxidized chitin nanocrystals greatly strengthen the stability of resveratrol-loaded gliadin nanoparticles | |
Liu et al. | Pickering emulsion stabilized by Haematococcus pluvialis protein particles and its application in dumpling stuffing | |
Wang et al. | Nanocapsules formed by interactions between chondroitin sulfate and egg white protein for encapsulating hydrophilic ingredients | |
Zhang et al. | The droplet breakup model and characteristics of pH-shifted peanut protein isolate-high methoxyl pectin stabilised emulsions under ultrasound | |
Duan et al. | Effect of konjac oligo‐glucomannan on emulsifying properties of myofibrillar protein | |
Morales et al. | Blend of renewable bio-based polymers for oil encapsulation: Control of the emulsion stability and scaffolds of the microcapsule by the gummy exudate of Prosopis nigra | |
CN114246326A (zh) | 一种改性蛋清蛋白的制备方法及其应用 | |
Yan et al. | Construction and characterization of egg white protein-gallic acid-xanthan gum-based emulsion and oleogel | |
WO2024045791A1 (zh) | 莲藕淀粉皮克林乳液的超声波制备及作为功能食品应用 | |
Lin et al. | Effect of cellulose nanofibrils on stability and digestive properties of legume protein-based emulsions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |