CN116925257B - Method for preparing low-methoxy orange peel pectin by regional temperature control and electrochemical cathode and anode co-operation - Google Patents
Method for preparing low-methoxy orange peel pectin by regional temperature control and electrochemical cathode and anode co-operation Download PDFInfo
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- 229920001277 pectin Polymers 0.000 title claims abstract description 143
- 239000001814 pectin Substances 0.000 title claims abstract description 142
- 235000010987 pectin Nutrition 0.000 title claims abstract description 142
- 238000000034 method Methods 0.000 title claims abstract description 67
- 239000003792 electrolyte Substances 0.000 claims abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 230000008569 process Effects 0.000 claims abstract description 24
- 238000005886 esterification reaction Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 230000001105 regulatory effect Effects 0.000 claims abstract description 13
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 8
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 30
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000012528 membrane Substances 0.000 claims description 22
- 230000009471 action Effects 0.000 claims description 19
- 239000000498 cooling water Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 230000000694 effects Effects 0.000 claims description 17
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 239000011780 sodium chloride Substances 0.000 claims description 14
- 238000003487 electrochemical reaction Methods 0.000 claims description 12
- 239000004627 regenerated cellulose Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 238000000502 dialysis Methods 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 230000005684 electric field Effects 0.000 claims description 9
- 239000010410 layer Substances 0.000 claims description 8
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- 238000007068 beta-elimination reaction Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 230000002195 synergetic effect Effects 0.000 claims description 6
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- 239000011229 interlayer Substances 0.000 claims description 4
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- 229910052751 metal Inorganic materials 0.000 claims description 3
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- 238000002156 mixing Methods 0.000 claims description 2
- 235000013305 food Nutrition 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 11
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 abstract description 10
- 230000032050 esterification Effects 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 5
- PYMYPHUHKUWMLA-UHFFFAOYSA-N 2,3,4,5-tetrahydroxypentanal Chemical compound OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- AEMOLEFTQBMNLQ-YMDCURPLSA-N D-galactopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-YMDCURPLSA-N 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 17
- IAJILQKETJEXLJ-RSJOWCBRSA-N aldehydo-D-galacturonic acid Chemical compound O=C[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)C(O)=O IAJILQKETJEXLJ-RSJOWCBRSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000000499 gel Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
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- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 235000012209 glucono delta-lactone Nutrition 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000010318 polygalacturonic acid Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920002230 Pectic acid Polymers 0.000 description 2
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
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- 239000003153 chemical reaction reagent Substances 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000002255 enzymatic effect Effects 0.000 description 2
- 238000006911 enzymatic reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- -1 gelators Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- LCLHHZYHLXDRQG-ZNKJPWOQSA-N pectic acid Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)O[C@H](C(O)=O)[C@@H]1OC1[C@H](O)[C@@H](O)[C@@H](OC2[C@@H]([C@@H](O)[C@@H](O)[C@H](O2)C(O)=O)O)[C@@H](C(O)=O)O1 LCLHHZYHLXDRQG-ZNKJPWOQSA-N 0.000 description 2
- 238000011027 product recovery Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000009754 rhamnogalacturonan I Substances 0.000 description 2
- 239000008914 rhamnogalacturonan II Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 241000207199 Citrus Species 0.000 description 1
- AEMOLEFTQBMNLQ-DTEWXJGMSA-N D-Galacturonic acid Natural products O[C@@H]1O[C@H](C(O)=O)[C@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-DTEWXJGMSA-N 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 101000615488 Homo sapiens Methyl-CpG-binding domain protein 2 Proteins 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 208000031226 Hyperlipidaemia Diseases 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 102100021299 Methyl-CpG-binding domain protein 2 Human genes 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- AEMOLEFTQBMNLQ-BKBMJHBISA-N alpha-D-galacturonic acid Chemical class O[C@H]1O[C@H](C(O)=O)[C@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-BKBMJHBISA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- ZXVOCOLRQJZVBW-UHFFFAOYSA-N azane;ethanol Chemical compound N.CCO ZXVOCOLRQJZVBW-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- AEMOLEFTQBMNLQ-UHFFFAOYSA-N beta-D-galactopyranuronic acid Natural products OC1OC(C(O)=O)C(O)C(O)C1O AEMOLEFTQBMNLQ-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- UBXYXCRCOKCZIT-UHFFFAOYSA-N biphenyl-3-ol Chemical compound OC1=CC=CC(C=2C=CC=CC=2)=C1 UBXYXCRCOKCZIT-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000001335 demethylating effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013325 dietary fiber Nutrition 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229960003681 gluconolactone Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004192 high performance gel permeation chromatography Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000007365 immunoregulation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010829 isocratic elution Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000006198 methoxylation reaction Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 108020004410 pectinesterase Proteins 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- 235000009048 phenolic acids Nutrition 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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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
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0045—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Galacturonans, e.g. methyl ester of (alpha-1,4)-linked D-galacturonic acid units, i.e. pectin, or hydrolysis product of methyl ester of alpha-1,4-linked D-galacturonic acid units, i.e. pectinic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
- C25B15/021—Process control or regulation of heating or cooling
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Automation & Control Theory (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention belongs to the technical field of food processing, and discloses a method for preparing low-methoxy orange peel pectin by combining regional temperature control with electrochemical cathode and anode. The method comprises the following steps: pouring the pectin electrolyte of the orange peel into an electrochemical cell, regulating the temperature to a proper level, turning on a power supply, regulating the pectin electrolyte of the anode chamber and the cathode chamber to a proper pH value after the reaction is finished, and obtaining the pectin of the low methoxyl orange peel through alcohol precipitation, washing and drying of the pectin electrolyte. The method provided by the invention can simultaneously prepare the low methoxy orange Pi Guojiao with different molecular weights and methyl esterification degrees, and the prepared pectin has high galacturonic acid content and good gel property, so that the application potential of the pectin in the fields of food, medicine, environmental protection and the like is improved; compared with the existing technology for preparing low methoxy pectin, the method has the characteristics of simplified process, high efficiency, high quality, safety, environmental friendliness and the like.
Description
Technical Field
The invention relates to the technical field of food processing, in particular to a method for preparing low-methoxy orange peel pectin by combining regional temperature control with electrochemical cathode and anode.
Background
Natural pectic substances are widely present in the fruits, roots, stems, leaves of plants in the form of protopectin, pectin, pectic acid, are a constituent of the cell wall, constitute a gelatinous matrix in the plant cell wall, and are often used as thickeners, colloidal stabilizers, gelators, emulsifiers and drug delivery vehicles in the food industry. Pectin main domains include Homogalacturonan (HG), rhamnogalacturonan I (RG-I), rhamnogalacturonan II (RG-II), and small amounts of substituted galacturonan. Commercial pectins, such as citrus peel and apple pomace pectins, must reach galacturonic acid (GalA) levels above 65%. Generally, pectin is classified into High-methyl pectin (HMP, DM) according to the degree of methyl esterification (Degree of methoxylation, DM) of pectin>50%) and Low methyl ester pectin (LMP, DM)<50%) DM also determines the gel mode of the pectin. Since most of the carboxyl groups in HMP are methoxy esterified and therefore cannot interact, gelation of HMP requires acidic conditions (e.g., pH 3.5) and high concentration of sucrose as a co-solvent (typically 65% sucrose), whereas gelation of LMP depends on divalent cations (e.g., ca) 2+ 、Zn 2+ And Mg (magnesium) 2+ Etc.) to form a gel of the so-called "egg box" model.
With the improvement of the living standard of people, the number of patients with diabetes, hyperlipidemia, hypertension and complications thereof tends to increase year by year. With the low sugar and low calorie health care food, people are more and more favored. LMP is increasingly in demand because it has a broader range of applications in terms of pH and solids content and can be used to produce low sugar, low calorie, low sweetness, and other nutritionally rich foods. In addition, pectin is also an excellent natural water-soluble dietary fiber, has certain physiological function and biological activity, such as antioxidant activity, immunoregulation, anti-inflammatory effect, cholesterol regulation, bowel relaxing, blood lipid reducing, heavy metal in human body removing, anticancer and the like, and can be applied to health-care food.
Most of the natural pectins currently on the market are HMP, and the LMP occupies a small proportion and has higher price. The commercial LMP is currently produced by the de-esterification of HMP using acid, base and enzymatic methods. The ammonia process de-esterification of HMP is mainly an ammonia-ethanol de-methyl ester system, and hydroxylamine and other ammonia derivatives are also used for the de-methyl esterification of HMP; the acid-process de-esterification of HMP is mainly realized by strong acid such as HCI, and the alkali-process de-esterification is mainly realized by strong alkali such as NaOH. However, both of the above methods have respective drawbacks. The acid process de-esterification reaction is not only pH dependent, but also very inefficient, and at lower pH pectin molecules undergo hydrolysis reactions. The subject of pectic acid hydrolysis is mainly the neutral sugar side chains of pectin, and secondly some proteins and phenolic acids. And the pectin is de-esterified under alkaline conditions, so that the molecular chain of the pectin is subjected to beta-elimination reaction, and the pectin quality is affected. In addition to acid and alkaline processes, enzymatic de-esterification of HMP is popular because of its high efficiency and environmental protection characteristics. The use of enzymatic methods is advantageous for HMP demethylating to produce random or regionally distributed unesterified GalA units due to the relative specificity of their action. The most commonly used HMP demethylase at present is pectin methylesterase. However, enzymatic de-esterification is difficult to produce commercially on a large scale due to its high cost.
Disclosure of Invention
The purpose of the invention is that: in order to provide a method for preparing low-methoxy orange peel pectin by combining regional temperature control with electrochemical cathode and anode with better effect, the specific purpose is to achieve a plurality of substantial technical effects in the specific implementation part.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the method for preparing the low-methoxy orange peel pectin by combining regional temperature control with electrochemical cathode and anode is characterized by comprising the following steps of:
dispersing orange peel pectin and electrolyte in distilled water to make it fully hydrated, uniformly stirring to obtain electrolyte;
pouring the prepared electrolyte into an electrochemical cell, regulating the electrolyte in the anode chamber and the cathode chamber to a required temperature, and then opening a circulating pump in the cathode chamber; then, the power supply is turned on to enable the anode and the cathode to start working; the electrochemical reaction is carried out by adopting the regional temperature control, the anode chamber and the cathode chamber are divided into different temperature regions, the de-esterification efficiency of pectin in the anode chamber under the high temperature condition is ensured, meanwhile, the problem that pectin in the cathode chamber is possibly decomposed and lost due to beta-elimination reaction is also inhibited under the low temperature condition, the co-preparation effect is achieved, and the quality and the activity of products are ensured; taking out products in the anode chamber and the cathode chamber after continuous reaction in the temperature control and electrode environment;
and mixing products in the anode chamber and the cathode chamber or respectively adjusting the pH value of the products, and carrying out alcohol precipitation, washing and drying to obtain the low-methoxy orange peel pectin.
The invention has the further technical scheme that an electrochemical cell is divided into an anode chamber and a cathode chamber by a regenerated cellulose membrane, the anode chamber and the cathode chamber are respectively connected with a cooling water circulator, an anode electrode is arranged in the anode chamber, a cathode electrode is arranged in the cathode chamber, and a circulating pump is arranged in the cathode chamber; two pipes are connected outside the cathode chamber through a circulating pump; inside the cathode chamber, one tube near the bottom of the electrochemical cell is used as a liquid inlet tube, and the other tube near the dialysis membrane is used as a liquid outlet tube for dispersing pectin enriched by the action of an electric field in the modification process.
The invention has the further technical proposal that the temperature in the electrolysis process is 0-15 ℃ of the cathode chamber and 5-50 ℃ of the anode chamber.
The invention has the further technical proposal that the voltage of the electrolysis power supply is 50-5000V, and the reaction time is 0.5-5 h.
The invention further adopts the technical scheme that the orange peel pectin is commercial orange peel pectin.
The invention further adopts the technical scheme that the electrolyte is sodium chloride or potassium chloride; the mass of pectin is sodium chloride or potassium chloride=500:1-10:1; the concentration of the pectin solution is 0.5-5 w/w%, and the dispersion time is 5-15 h; the molecular weight cut-off of the regenerated cellulose membrane is 500 Da-200 kDa; the anode electrode and the cathode electrode are made of metal platinum sheets.
The invention further adopts the technical scheme that the anode chamber and the cathode chamber respectively comprise a magnetic stirrer for rotation.
The further technical scheme of the invention is that the products in the anode chamber and/or the cathode chamber are respectively adjusted to pH=3-5 by NaOH/HCl of 1-3M, then 95% v/v ethanol with 3 times of the volume of the products is respectively added, and the products are centrifuged for 10-20 min under the condition of 10000-12000 rpm; followed by two washes with 75% v/v and 95% v/v ethanol; drying pectin at 40-45 deg.c.
The invention further adopts the technical scheme that the anode chamber and the cathode chamber respectively comprise an outer interlayer, and the outer interlayer is connected with a cold water circulator; the structure of the electrochemical cell is an H-shaped double-layer water bath sealing electrochemical cell.
The method for preparing the low-methoxy orange peel pectin by combining regional temperature control with electrochemical cathode and anode is characterized by comprising any one of the following steps:
A. (1) Dispersing 4g of pectin and 0.2g of sodium chloride into 400g of distilled water under the action of a magnetic stirrer, and stirring for 12 hours to fully hydrate the pectin to obtain uniform electrolyte;
(2) Dividing the H-type double-layer water bath sealed electrochemical cell into an anode chamber and a cathode chamber by using a 500Da regenerated cellulose membrane, wherein the anode chamber and the cathode chamber are 300mL respectively; the anode chamber and the cathode chamber are respectively connected with a cooling water circulator, an anode platinum sheet electrode is arranged in the anode chamber, a cathode platinum sheet electrode is arranged in the cathode chamber, and a circulating pump with adjustable flow is arranged in the cathode chamber; two transparent PVC pipes are connected through a circulating pump; inside the cathode chamber, one PVC pipe near the bottom of the electrochemical cell is used as a liquid inlet pipe, and the other PVC pipe near the dialysis membrane is used as a liquid outlet pipe for dispersing pectin enriched due to the action of an electric field in the modification process;
(3) Adding 175mL of the electrolyte in the step (1) into the anode chamber and the cathode chamber in the step (2), wherein the rotating speed of the magnetic stirrer is 800rpm; the flow of the cooling water circulator is regulated to be 10L/min, so that the temperatures of electrolyte in the cathode chamber and the anode chamber respectively reach 0-5 ℃ and 15-20 ℃;
(4) After the electrolyte in the step (3) is determined to reach the set temperature by an electronic thermometer, a circulating pump of a cathode chamber is opened, and the flow is 3L/min;
(5) Turning on a power supply connected with the anode and the cathode, adjusting the voltage to 180V, and reacting for 3 hours;
(6) After the reaction, pouring the products of the anode chamber and the cathode chamber in the step (5) into beakers respectively, and then adjusting the pH to be 3.8 by using 1M NaOH/HCl;
(7) Adding 3 times of 95% v/v ethanol to the product in the step (6), and centrifuging at 25 ℃ and 10000rpm for 10min; the precipitated pectin was then removed and washed twice with 75% v/v and 95% v/v ethanol;
(8) Finally, placing the pectin washed in the step (7) in an electrothermal blowing drying oven, setting the temperature to 40 ℃ and the drying time to 12 hours;
B.
(1) Dispersing 5g of pectin and 0.2g of sodium chloride into 400g of distilled water under the action of a magnetic stirrer, and stirring for 12 hours to fully hydrate the pectin to obtain uniform electrolyte;
(2) An H-type double-layer water bath sealed electrochemical cell (300 mL+300 mL) is divided into an anode chamber and a cathode chamber by a 5kDa regenerated cellulose membrane, the anode chamber and the cathode chamber are respectively connected with a cooling water circulating machine, an anode platinum sheet electrode (length multiplied by width=10 mm multiplied by 10 mm) is arranged in the anode chamber, a cathode platinum sheet electrode (length multiplied by width=10 mm multiplied by 10 mm) is arranged in the cathode chamber, and a circulating pump with adjustable flow is arranged in the cathode chamber; two transparent PVC pipes (outer diameter: 6mm, inner diameter: 4 mm) are connected by a circulating pump; inside the cathode chamber, one PVC pipe near the bottom of the electrochemical cell is used as a liquid inlet pipe, and the other PVC pipe near the dialysis membrane is used as a liquid outlet pipe for dispersing pectin enriched due to the action of an electric field in the modification process;
(3) Adding 200mL of the electrolyte in the step (1) into the anode chamber and the cathode chamber in the step (2), wherein the rotating speed of the magnetic stirrer is 500-1000 rpm; the flow of the cooling water circulator is regulated to be 12L/min, so that the temperatures of the electrolyte in the cathode chamber and the anode chamber respectively reach 5-10 ℃ and 25-30 ℃;
(4) After the electrolyte in the step (3) is determined to reach the set temperature by an electronic thermometer, a circulating pump of a cathode chamber is opened, and the flow is 4L/min;
(5) Turning on a power supply connected with the anode and the cathode, adjusting the voltage to 200V, and reacting for 0.5h, 1.5h, 2.5h and 3h;
(6) After the reaction, pouring the products of the anode chamber and the cathode chamber in the step (5) into beakers respectively, and then adjusting the pH to be 3.8 by using 1M NaOH/HCl;
(7) Adding 3 times of 95% v/v ethanol to the product in the step (6), and centrifuging at 25 ℃ and 10000rpm for 12min; the precipitated pectin was then removed and washed twice with 75% v/v and 95% v/v ethanol;
(8) And finally, placing the pectin washed in the step (7) in an electrothermal blowing drying oven, setting the temperature to 40 ℃ and drying for 15 hours.
Compared with the prior art, the invention adopting the technical scheme has the following beneficial effects: during electrolysis, sodium chloride or potassium chloride solutions undergo a series of electrochemical reactions: acidic oxidation water is generated in the anode chamber, and alkaline reduction water is generated in the cathode chamber.
At a higher temperature, the de-esterification efficiency of the pectin solution in the anode chamber under the acidic condition can be improved, and the efficiency of oxidizing methoxy groups in high-ester pectin by free radicals in oxidation water can be accelerated, so that the efficiency of preparing low-methoxy pectin under the acidic condition is improved together.
At lower temperature, the beta-elimination reaction of pectin molecular chain under alkaline condition can be inhibited, and the reduced water can also play a role in protecting functional groups in pectin molecules. The method has the advantages of wide applicability, low cost, convenience, environmental protection and the like.
Regional temperature control: the electrochemical reaction is carried out by adopting the regional temperature control, the anode chamber and the cathode chamber are divided into different temperature regions, the de-esterification efficiency of pectin in the anode chamber under the high temperature condition is ensured, meanwhile, the problem that pectin in the cathode chamber is possibly decomposed and lost due to beta-elimination reaction is also inhibited under the low temperature condition, the co-preparation effect is achieved, and the quality and activity of the product are ensured.
High efficiency: electrochemical reactions can increase reaction rates and product recovery. The invention can achieve the de-esterification effect which can be achieved only in 0.5h by the traditional acid method and can be achieved in 3h, thereby obviously shortening the time, improving the efficiency and realizing the recovery rate of 83.15 to 90.28 percent. Meanwhile, the efficiency is further improved due to the co-preparation effect.
The simplified process comprises the following steps: compared with the traditional complex process for preparing pectin by an enzyme method, an acid method or an alkali method, the invention adopts electrochemical reaction, has simple steps and convenient operation, and reduces the process flow and equipment requirements.
The product quality is excellent: the low-methoxy orange peel pectin prepared under the low-temperature synergistic electrochemical reaction condition has higher purity and activity, and can meet the requirements of different fields on pectin, such as foods, medicines, cosmetics and the like.
Environmental protection: the invention adopts the electrochemical method to prepare the low methoxyl pectin without using harmful chemical reagents, reduces the pollution to the environment, improves the edible safety, and accords with the concepts of sustainable development and green chemistry.
In conclusion, the method for preparing the low-methoxy orange peel pectin by using the regional temperature control synergistic electrochemical cathode and anode has the advantages of high efficiency, simplified process, high product quality, environmental friendliness and the like, and is suitable for industrial production and wide application.
Drawings
For further explanation of the invention, reference is made to the following further description, taken in conjunction with the accompanying drawings:
FIG. 1 is a schematic flow chart of the method for preparing low methoxyl orange Pi Guojiao by combining temperature control with electrochemical anode and cathode;
FIG. 2 shows the molecular weight distribution diagrams of example 1, example 2 and comparative example 1;
FIG. 3 is a scanning electron microscope topography of the pectin aerogels of example 1, example 2 and comparative example 1;
fig. 4 shows the physicochemical parameters of the pectin of the invention and those of the comparative example.
Description of the embodiments
The present invention is further illustrated in the following drawings and detailed description, which are to be understood as being merely illustrative of the invention and not limiting the scope of the invention.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The patent provides a plurality of parallel schemes, and the different expressions belong to an improved scheme based on a basic scheme or a parallel scheme. Each scheme has its own unique features.
The invention aims to provide a method for preparing low-methoxy orange peel pectin by combining regional temperature control with electrochemical cathode and anode.
During electrolysis, sodium chloride or potassium chloride solutions undergo a series of electrochemical reactions: acidic oxidation water is generated in the anode chamber, and alkaline reduction water is generated in the cathode chamber.
At a higher temperature, the de-esterification efficiency of the pectin solution in the anode chamber under the acidic condition can be improved, and the efficiency of oxidizing methoxy groups in high-ester pectin by free radicals in oxidation water can be accelerated, so that the efficiency of preparing low-methoxy pectin under the acidic condition is improved together.
At lower temperature, the beta-elimination reaction of pectin molecular chain under alkaline condition can be inhibited, and the reduced water can also play a role in protecting functional groups in pectin molecules. The method has the advantages of wide applicability, low cost, convenience, environmental protection and the like.
In order to achieve the above purpose, the invention provides a method for preparing low methoxy orange peel pectin by regional temperature control and electrochemical cathode and anode co-preparation, which comprises the following steps:
(1) Dispersing a proper amount of commercial orange peel pectin (P9135, sigma-Aldrich) and electrolyte in a certain proportion in distilled water, fully hydrating the mixture, and uniformly stirring to obtain electrolyte;
(2) Dividing an electrochemical cell into an anode chamber and a cathode chamber by using a regenerated cellulose membrane, wherein the anode chamber and the cathode chamber are respectively connected with a cooling water circulator, an anode electrode is arranged in the anode chamber, a cathode electrode is arranged in the cathode chamber, and a circulating pump is arranged in the cathode chamber;
(3) Pouring the prepared electrolyte into an electrochemical cell, opening a magnetic stirrer, adjusting the electrolyte in the anode chamber and the electrolyte in the cathode chamber to the required temperature by using a cooling water circulator, and opening a circulating pump in the cathode chamber. Then, a power supply is started, and the voltage is regulated to be a proper value, so that the anode and the cathode start to work;
(4) After a certain time of reaction, the power supply, the cooling water circulation, the circulating pump and the magnetic stirrer are turned off, and products in the anode chamber and the cathode chamber are taken out. And after adjusting the pH to a proper value, obtaining the low-methoxy orange peel pectin after alcohol precipitation, washing and drying.
Further, the electrolyte in the step (1) is sodium chloride or potassium chloride.
Further, the pectin in the step (1) has the mass of sodium chloride or potassium chloride=500:1-10:1.
Further, the concentration of the pectin solution in the step (1) is 0.5-5 w/w%, and the dispersion time is 5-15 h.
Further, the molecular weight cut-off of the regenerated cellulose membrane in the step (2) is 500 Da-200 kDa.
Further, the anode electrode and the cathode electrode in the step (2) are made of metal platinum sheets.
Further, the step (2) is outside the cathode chamber, and two transparent PVC pipes (the outer diameter is 5-20mm, and the inner diameter is 3-18 mm) are connected through a circulating pump; inside the cathode chamber, one PVC pipe near the bottom of the electrochemical cell is used as a liquid inlet pipe, and the other PVC pipe near the dialysis membrane is used as a liquid outlet pipe for dispersing pectin enriched due to the action of an electric field in the modification process.
Further, the volume of electrolyte in the anode chamber and the cathode chamber in the step (3) is 100-1000 mL, and the rotating speed of the magnetic stirrer is 500-1000 rpm.
Further, the temperature of the cathode chamber in the step (3) is 0-15 ℃, the temperature of the anode chamber is 5-50 ℃, the flow rate of the cooling water circulating machine is 6-20L/min, and the flow rate of the circulating pump is 1-8L/min.
Further, the power supply voltage in the step (3) is 50-5000V, and the reaction time is 0.5-5 h.
Further, in the step (3), the products in the anode chamber and the cathode chamber after being taken out are respectively adjusted to pH=3-5 by using NaOH/HCl of 1-3M, then 95% v/v ethanol of 3 times volume is respectively added, and the products are centrifuged for 10-20 min at room temperature and 10000-12000 rpm. Thereafter, the mixture was washed twice with 75% v/v and 95% v/v ethanol.
Further, the pectin is dried at 40-45 ℃ until the moisture content reaches the national standard.
The beneficial effects of the invention are as follows:
regional temperature control: the electrochemical reaction is carried out by adopting the regional temperature control, the anode chamber and the cathode chamber are divided into different temperature regions, the de-esterification efficiency of pectin in the anode chamber under the high temperature condition is ensured, meanwhile, the problem that pectin in the cathode chamber is possibly decomposed and lost due to beta-elimination reaction is also inhibited under the low temperature condition, the co-preparation effect is achieved, and the quality and activity of the product are ensured.
High efficiency: electrochemical reactions can increase reaction rates and product recovery. The invention can achieve the de-esterification effect which can be achieved only in 0.5h by the traditional acid method and can be achieved in 3h, thereby obviously shortening the time, improving the efficiency and realizing the recovery rate of 83.15 to 90.28 percent. Meanwhile, the efficiency is further improved due to the co-preparation effect.
The simplified process comprises the following steps: compared with the traditional complex process for preparing pectin by an enzyme method, an acid method or an alkali method, the invention adopts electrochemical reaction, has simple steps and convenient operation, and reduces the process flow and equipment requirements.
The product quality is excellent: the low-methoxy orange peel pectin prepared under the low-temperature synergistic electrochemical reaction condition has higher purity and activity, and can meet the requirements of different fields on pectin, such as foods, medicines, cosmetics and the like.
Environmental protection: the invention adopts the electrochemical method to prepare the low methoxyl pectin without using harmful chemical reagents, reduces the pollution to the environment, improves the edible safety, and accords with the concepts of sustainable development and green chemistry.
In conclusion, the method for preparing the low-methoxy orange peel pectin by using the regional temperature control synergistic electrochemical cathode and anode has the advantages of high efficiency, simplified process, high product quality, environmental friendliness and the like, and is suitable for industrial production and wide application.
Examples
(1) 4g of pectin and 0.2g of sodium chloride are dispersed into 400g of distilled water under the action of a magnetic stirrer, and the pectin is fully hydrated by stirring for 12 hours, so that a uniform electrolyte is obtained.
(2) An H-type double-layer water-bath sealed electrochemical cell (300 ml+300 ml) was partitioned into an anode chamber and a cathode chamber by a 500Da regenerated cellulose membrane, the anode chamber and the cathode chamber were connected to a cooling water circulator, respectively, an anode platinum sheet electrode (length×width=10 mm×10 mm) was placed in the anode chamber, a cathode platinum sheet electrode (length×width=10 mm×10 mm) was placed in the cathode chamber, and a circulation pump with adjustable flow rate was provided. Two transparent PVC pipes (outer diameter: 6mm, inner diameter: 4 mm) are connected by a circulating pump; inside the cathode chamber, one PVC pipe near the bottom of the electrochemical cell is used as a liquid inlet pipe, and the other PVC pipe near the dialysis membrane is used as a liquid outlet pipe for dispersing pectin enriched due to the action of an electric field in the modification process.
(3) 175mL of the electrolyte in step (1) was added to the anode and cathode chambers in step (2), respectively, and the magnetic stirrer was rotated at 800rpm. The flow rate of the cooling water circulator is regulated to be 10L/min, so that the temperatures of the electrolyte in the cathode chamber and the anode chamber respectively reach 0-5 ℃ and 15-20 ℃.
(4) And (3) after the electrolyte in the step (3) reaches the set temperature by using an electronic thermometer, opening a circulating pump of the cathode chamber, wherein the flow is 3L/min.
(5) And (3) turning on a power supply connected with the anode and the cathode, adjusting the voltage to 180V, and reacting for 3 hours.
(6) After the reaction was completed, the products of the anode and cathode compartments described in step (5) were poured into beakers, respectively, and then adjusted to ph=3.8 with 1M NaOH/HCl.
(7) 3 volumes of 95% v/v ethanol were added to the product of step (6), and the mixture was centrifuged at 25℃and 10000rpm for 10 minutes. The precipitated pectin was then removed and washed twice with 75% v/v and 95% v/v ethanol.
(8) And finally, placing the pectin washed in the step (7) in an electrothermal blowing drying oven, wherein the set temperature is 40 ℃, and the drying time is 12 hours.
Examples
(1) 5g of pectin and 0.2g of sodium chloride are dispersed into 400g of distilled water under the action of a magnetic stirrer, and the pectin is fully hydrated by stirring for 12 hours, so that a uniform electrolyte is obtained.
(2) An H-type double-layer water-bath sealed electrochemical cell (300 ml+300 ml) was partitioned into an anode chamber and a cathode chamber by a 5kDa regenerated cellulose membrane, the anode chamber and the cathode chamber were connected to a cooling water circulator, respectively, an anode platinum sheet electrode (length×width=10 mm×10 mm) was placed in the anode chamber, a cathode platinum sheet electrode (length×width=10 mm×10 mm) was placed in the cathode chamber, and a circulation pump with adjustable flow rate was provided. Two transparent PVC pipes (outer diameter: 6mm, inner diameter: 4 mm) are connected by a circulating pump; inside the cathode chamber, one PVC pipe near the bottom of the electrochemical cell is used as a liquid inlet pipe, and the other PVC pipe near the dialysis membrane is used as a liquid outlet pipe for dispersing pectin enriched due to the action of an electric field in the modification process.
(3) 200mL of the electrolyte in the step (1) is added into the anode chamber and the cathode chamber in the step (2), and the rotating speed of the magnetic stirrer is 500-1000 rpm. The flow rate of the cooling water circulator is regulated to be 12L/min, so that the temperatures of the electrolyte in the cathode chamber and the anode chamber respectively reach 5-10 ℃ and 25-30 ℃.
(4) And (3) after the electrolyte in the step (3) reaches the set temperature by using an electronic thermometer, opening a circulating pump of the cathode chamber, wherein the flow rate is 4L/min.
(5) And (3) turning on a power supply connected with the anode and the cathode, adjusting the voltage to 200V, and reacting for 3 hours.
(6) After the reaction was completed, the products of the anode and cathode compartments described in step (5) were poured into beakers, respectively, and then adjusted to ph=3.8 with 1M NaOH/HCl.
(7) 3 volumes of 95% v/v ethanol were added to the product of step (6), and the mixture was centrifuged at 25℃and 10000rpm for 12min. The precipitated pectin was then removed and washed twice with 75% v/v and 95% v/v ethanol.
(8) And finally, placing the pectin washed in the step (7) in an electrothermal blowing drying oven, setting the temperature to 40 ℃ and drying for 15 hours.
Examples
The same as in example 2, except that the reaction time was 0.5h.
Examples
The same as in example 2, except that the reaction time was 1.5h.
Examples
The same as in example 2, except that the reaction time was 2.5h.
Comparative example 1
The same as in example 1, except that the temperature of the electrolyte in the anode and cathode chambers was controlled without using a cooling water circulator, the reaction was performed at room temperature (25.+ -. 2 ℃).
Test example 1 measurement of weight average molecular weight (Mw) and distribution
The Mw of the pectin was analyzed and calculated by HPGPC system. The mobile phase was 100mmol/L sodium nitrate (0.04% sodium azide contained) at a flow rate of 0.6mL/min and column temperature of 35℃for isocratic elution. Pectin samples are prepared into 1mg/mL solution by using a mobile phase, the samples are separated by adopting a protective column Ultrahydrogel Guard and an UltraHydrogel 2000 chromatographic column and a 1000 chromatographic column which are connected in series, and the samples are detected by using a 2414 differential refraction detector. 8 dextran standards (Mw: 1X 10) 3 ～1×10 7 Da) is dissolved in a solution of which the flow rate is matched to 2mg/mL, the solution is filtered by a filter membrane of 0.45 mu m and then is detected by a liquid phase system, and the obtained data is processed by Breeze data processing software to establish standard curve. The differential elution profile of the resulting pectin samples is then integrated according to the standard curve to obtain the molecular weight of the corresponding pectin.
Test example 2-galacturonic acid GalA) content determination the galacturonic acid content of pectin was determined colorimetrically using 3-phenylphenol as the color developing agent. After the solution is developed, the maximum absorbance at 520nm is measured by an ultraviolet-visible spectrophotometer. D-galacturonic acid is used as a standard substance to establish standard yeast, and the content of GalA in pectin is calculated by using the standard yeast.
Test example 3 measurement of degree of methyl esterification (DM) and Degree of Acetylation (DA)
The degree of methyl esterification and the degree of acetylation of the pectin were determined by HPLC. 30mg pectin samples were saponified with 1mL of a saponification solution containing 0.4M NaOH (isopropanol: water 1:1, V/v) at 25℃for 2h. Subsequently, the resulting saponified solution was filtered through a 0.45 μm filter and analyzed by HPLC. The chromatographic system uses 5mmol/L H 2 SO 4 The flow rate was 0.6mL/min as a flow equality elution. The column temperature was 45℃and the sample volume was 25. Mu.L. Samples were tested using a 2414 differential refractive detector. DM and DA values for this experiment were obtained by calculating the molar ratio of methanol to acetic acid to GalA after saponification.
Test example 4 preparation and characterization of pectin gel
Adding a certain amount of Gluconolactone (GDL) into the fully hydrated pectin solution, stirring, adding a certain amount of calcium carbonate (CaCO) 3 ) So that pectin, GDL and CaCO 3 The final concentrations of (C) were 1.25wt%,45mM and 37.5mM, respectively. Then placing in a refrigerator at 4 ℃ for 24 hours to form uniform pectin gel. The freeze-dried pectin aerogel phase pattern was photographed using a scanning electron microscope.
TABLE 1 physicochemical parameters of pectin
Physicochemical parameters of apparent pectin
In summary, as shown in table 1, the method for preparing low-methoxy orange peel pectin disclosed by the invention not only can improve the content of galacturonic acid, but also can furthest reduce damage to pectin molecules while achieving the de-esterification effect, and can keep the structural integrity of pectin, thereby realizing the controllable preparation of low-methoxy orange peel pectin; as can be seen from FIG. 2, the low methoxyl orange peel pectin prepared by the method has good uniformity and high purity; as can be seen from fig. 3, the low methoxy orange Pi Guojiao-based hydrogel prepared by the method has a uniform and stable structure, which is helpful for improving the application potential of pectin in the fields of food, medicine and the like.
Overall, the following is true: the invention belongs to the technical field of food processing, and discloses a method for preparing low-methoxy orange peel pectin by combining regional temperature control with electrochemical cathode and anode. The method comprises the following steps: pouring the pectin electrolyte of the orange peel into an electrochemical cell, regulating the temperature to a proper level, turning on a power supply, regulating the pectin electrolyte of the anode chamber and the cathode chamber to a proper pH value after the reaction is finished, and obtaining the pectin of the low methoxyl orange peel through alcohol precipitation, washing and drying of the pectin electrolyte. The method provided by the invention can simultaneously prepare the low methoxy orange Pi Guojiao with different molecular weights and methyl esterification degrees, and the prepared pectin has high galacturonic acid content and good gel property, so that the application potential of the pectin in the fields of food, medicine, environmental protection and the like is improved; compared with the existing technology for preparing low methoxy pectin, the method has the characteristics of simplified process, high efficiency, high quality, safety, environmental friendliness and the like.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the foregoing embodiments, which have been described in the foregoing description merely illustrates the principles of the invention, and that various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (6)
1. The method for preparing the low-methoxy orange peel pectin by combining regional temperature control with electrochemical cathode and anode is characterized by comprising the following steps of: dispersing orange peel pectin and electrolyte in distilled water to make it fully hydrated, uniformly stirring to obtain electrolyte; pouring the prepared electrolyte into an electrochemical cell, regulating the electrolyte in the anode chamber and the cathode chamber to a required temperature, and then opening a circulating pump in the cathode chamber; then, the power supply is turned on to enable the anode and the cathode to start working; the electrochemical reaction is carried out by adopting the regional temperature control, the anode chamber and the cathode chamber are divided into different temperature regions, the de-esterification efficiency of pectin in the anode chamber under the high temperature condition is ensured, meanwhile, the problem that pectin in the cathode chamber is possibly decomposed and lost due to beta-elimination reaction is also inhibited under the low temperature condition, the co-preparation effect is achieved, and the quality and the activity of products are ensured; taking out products in the anode chamber and the cathode chamber after continuous reaction in the temperature control and electrode environment; then mixing the products in the anode chamber and the cathode chamber or respectively adjusting the pH value of the products, and obtaining low methoxy orange Pi Guojiao after alcohol precipitation, washing and drying;
dividing an electrochemical cell into an anode chamber and a cathode chamber by using a regenerated cellulose membrane, wherein the anode chamber and the cathode chamber are respectively connected with a cooling water circulator, an anode electrode is arranged in the anode chamber, a cathode electrode is arranged in the cathode chamber, and a circulating pump is arranged in the cathode chamber; two pipes are connected outside the cathode chamber through a circulating pump; inside the cathode chamber, one pipe close to the bottom of the electrochemical cell is used as a liquid inlet pipe, and the other pipe close to the dialysis membrane is used as a liquid outlet pipe for dispersing pectin enriched due to the action of an electric field in the modification process;
the temperature in the electrolysis process is 0-10 ℃ of the temperature of the cathode chamber, and the temperature of the anode chamber is 15-30 ℃;
the electrolysis power supply voltage is 180-200V, and the reaction time is 0.5-5 h;
the electrolyte is sodium chloride or potassium chloride; the mass of pectin is sodium chloride or potassium chloride=20:1-25:1; the concentration of the pectin solution is 0.5-5 w/w%, and the dispersion time is 5-15 h; the molecular weight cut-off of the regenerated cellulose membrane is 500 Da-200 kDa; the anode electrode and the cathode electrode are made of metal platinum sheets.
2. The method for preparing low-methoxy orange peel pectin by using the regional temperature control synergistic electrochemical cathode and anode co-preparation method as claimed in claim 1, wherein the orange peel pectin is commercial orange peel pectin.
3. The method for preparing pectin with low methoxyl content by combining regional temperature control with electrochemical cathode and anode as claimed in claim 1, wherein each of the anode chamber and the cathode chamber comprises a magnetic stirrer for stirring.
4. The method for preparing low-methoxy orange peel pectin by using regional temperature control and co-electrochemistry cathode and anode co-preparation according to claim 1, wherein products in an anode chamber and/or a cathode chamber are respectively adjusted to pH=3-5 by using NaOH/HCl of 1-3M, then 95% v/v ethanol of 3 times of the volume of the products is respectively added, and the products are centrifuged for 10-20 min under the condition of 10000-12000 rpm; followed by two washes with 75% v/v and 95% v/v ethanol; pectin is 40-45% ° And C, drying the mixture to obtain the product.
5. The method for preparing low-methoxy orange peel pectin by using the regional temperature control synergistic electrochemical cathode and anode as claimed in claim 1, wherein the anode chamber and the cathode chamber respectively comprise an outer interlayer, and the outer interlayer is connected with a cold water circulator; the structure of the electrochemical cell is an H-shaped double-layer water bath sealing electrochemical cell.
6. The method for preparing the low-methoxy orange peel pectin by combining regional temperature control with electrochemical cathode and anode is characterized by comprising any one of the following steps:
A. (1) Dispersing 4g of pectin and 0.2g of sodium chloride into 400g of distilled water under the action of a magnetic stirrer, and stirring for 12 hours to fully hydrate the pectin to obtain uniform electrolyte;
(2) The H-shaped double-layer water bath sealing electrochemical cell is divided into an anode chamber and a cathode chamber by a 500Da regenerated cellulose membrane, wherein the anode chamber and the cathode chamber are 300mL respectively; the anode chamber and the cathode chamber are respectively connected with a cooling water circulator, an anode platinum sheet electrode is arranged in the anode chamber, a cathode platinum sheet electrode is arranged in the cathode chamber, and a circulating pump with adjustable flow is arranged in the cathode chamber; two transparent PVC pipes are connected through a circulating pump; inside the cathode chamber, one PVC pipe near the bottom of the electrochemical cell is used as a liquid inlet pipe, and the other PVC pipe near the dialysis membrane is used as a liquid outlet pipe for dispersing pectin enriched due to the action of an electric field in the modification process;
(3) Adding 175 and mL of the electrolyte in the step (1) respectivelyIn the anode chamber and the cathode chamber described in (2), the rotation speed of the magnetic stirrer was 800rpm; the flow rate of the cooling water circulating machine is regulated to be 10L/min, so that the temperatures of the electrolyte in the cathode chamber and the electrolyte in the anode chamber respectively reach 0-5 ° C and 15 to 20 ° C；
(4) After the electrolyte in the step (3) is determined to reach the set temperature by an electronic thermometer, a circulating pump of a cathode chamber is opened, and the flow is 3L/min;
(5) Turning on a power supply connected with the anode and the cathode, adjusting the voltage to 180V and the reaction time to 3h;
(6) After the reaction, pouring the products of the anode chamber and the cathode chamber in the step (5) into beakers respectively, and then adjusting the pH to be 3.8 by using 1M NaOH/HCl;
(7) Adding 3 times of 95% v/v ethanol to the product in the step (6) respectively at 25 ° Centrifuging for 10min under the conditions of C and 10000 rpm; the precipitated pectin was then removed and washed twice with 75% v/v and 95% v/v ethanol; (8) Finally, the pectin washed in the step (7) is placed in an electrothermal blowing drying oven, and the temperature is set to be 40 ° C, drying time is 12h;
B. (1) Dispersing 5g of pectin and 0.2g of sodium chloride into 400g of distilled water under the action of a magnetic stirrer, and stirring for 12 hours to fully hydrate the pectin to obtain uniform electrolyte;
(2) Dividing an H-type double-layer water bath sealed electrochemical cell into an anode chamber and a cathode chamber by using a 5kDa regenerated cellulose membrane, wherein the anode chamber and the cathode chamber are respectively connected with a cooling water circulator, an anode platinum sheet electrode is arranged in the anode chamber, a cathode platinum sheet electrode is arranged in the cathode chamber, and a circulating pump with adjustable flow is arranged in the cathode chamber; two transparent PVC pipes are connected through a circulating pump; inside the cathode chamber, one PVC pipe near the bottom of the electrochemical cell is used as a liquid inlet pipe, and the other PVC pipe near the dialysis membrane is used as a liquid outlet pipe for dispersing pectin enriched due to the action of an electric field in the modification process;
(3) Adding 200 parts of the electrolyte in the step (1) and 200 parts of the electrolyte in each of the step mL into the anode chamber and the cathode chamber in the step (2), wherein the rotating speed of the magnetic stirrer is 500-1000 rpm; regulating cooling water circulationThe flow rate of the ring machine is 12L/min, so that the temperatures of the electrolyte in the cathode chamber and the anode chamber respectively reach 5-10 ° C and 25 to 30 ° C；
(4) After the electrolyte in the step (3) is determined to reach the set temperature by an electronic thermometer, a circulating pump of a cathode chamber is opened, and the flow is 4L/min;
(5) Turning on a power supply connected with the anode and the cathode, adjusting the voltage to be 200V, and reacting for 0.5h, 1.5h, 2.5h and 3h;
(6) After the reaction, pouring the products of the anode chamber and the cathode chamber in the step (5) into beakers respectively, and then adjusting the pH to be 3.8 by using 1M NaOH/HCl;
(7) Adding 3 times of 95% v/v ethanol to the product in the step (6) respectively at 25 ° Centrifuging at 10000rpm for 12min; the precipitated pectin was then removed and washed twice with 75% v/v and 95% v/v ethanol; (8) Finally, the pectin washed in the step (7) is placed in an electrothermal blowing drying oven, and the temperature is set to be 40 ° C, drying time 15h.
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|---|---|---|---|---|
| RU2070890C1 (en) * | 1993-09-29 | 1996-12-27 | Владимир Петрович Вислов | Method of pectin preparing |
| RU2116075C1 (en) * | 1996-02-16 | 1998-07-27 | Пятигорская государственная фармацевтическая академия | Method of medicinal purified pectin preparing |
| RU2261868C1 (en) * | 2004-07-14 | 2005-10-10 | Государственное образовательное учреждение высшего профессионального образования Воронежская государственная технологическая академия | Method for producing pectin and food fibers from sugar beet |
| CN109232769A (en) * | 2018-08-17 | 2019-01-18 | 河北科技大学 | A method of extracting pectin from persimmon slag |
| CN109898096A (en) * | 2018-05-28 | 2019-06-18 | 湖北省农业科学院农产品加工与核农技术研究所 | The method of citrus pectin oligosaccharide is prepared under the conditions of light current solution |
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| RU2070890C1 (en) * | 1993-09-29 | 1996-12-27 | Владимир Петрович Вислов | Method of pectin preparing |
| RU2116075C1 (en) * | 1996-02-16 | 1998-07-27 | Пятигорская государственная фармацевтическая академия | Method of medicinal purified pectin preparing |
| RU2261868C1 (en) * | 2004-07-14 | 2005-10-10 | Государственное образовательное учреждение высшего профессионального образования Воронежская государственная технологическая академия | Method for producing pectin and food fibers from sugar beet |
| CN109898096A (en) * | 2018-05-28 | 2019-06-18 | 湖北省农业科学院农产品加工与核农技术研究所 | The method of citrus pectin oligosaccharide is prepared under the conditions of light current solution |
| CN109232769A (en) * | 2018-08-17 | 2019-01-18 | 河北科技大学 | A method of extracting pectin from persimmon slag |
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| Effect of different NaCl concentrations on the structure-function relationship of citrus peel pectins modified by electrochemistry;Zhanwei Yang et al.;International Journal of Biological Macromolecules;20230527(第244期);125147 * |
| Effect of electrochemistry modification on the macromolecular, structural, and rheological characteristics of citrus peel pectin;Zhanwei Yang et al.;Food Hydrocolloids;20221016(第136期);108246 * |
| Effect of localized electrochemical pH and temperature synergistic modification on the structural and antibacterial properties of pectin/ polyvinyl alcohol/zinc oxide nanorod films;Zhanwei Yang et al.;International Journal of Biological Macromolecules;20230904(第253期);126703 * |
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