CN106319757A - Electrospun polyvinyl alcohol-based tannic acid anti-oxidation nanofiber membrane - Google Patents
Electrospun polyvinyl alcohol-based tannic acid anti-oxidation nanofiber membrane Download PDFInfo
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- CN106319757A CN106319757A CN201611021161.4A CN201611021161A CN106319757A CN 106319757 A CN106319757 A CN 106319757A CN 201611021161 A CN201611021161 A CN 201611021161A CN 106319757 A CN106319757 A CN 106319757A
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- Prior art keywords
- tannic acid
- pva
- electrospinning
- polyvinyl alcohol
- fibrous membrane
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Links
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 75
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 75
- 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 title claims abstract description 67
- 239000001263 FEMA 3042 Substances 0.000 title claims abstract description 67
- 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 title claims abstract description 67
- 229940033123 tannic acid Drugs 0.000 title claims abstract description 67
- 235000015523 tannic acid Nutrition 0.000 title claims abstract description 67
- 229920002258 tannic acid Polymers 0.000 title claims abstract description 67
- 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 title claims abstract description 66
- 239000012528 membrane Substances 0.000 title claims abstract description 42
- 230000003064 anti-oxidating effect Effects 0.000 title claims abstract description 34
- 239000002121 nanofiber Substances 0.000 title abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 37
- 238000001523 electrospinning Methods 0.000 claims abstract description 23
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000011159 matrix material Substances 0.000 claims abstract description 10
- 238000001338 self-assembly Methods 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 9
- 230000009977 dual effect Effects 0.000 claims abstract description 8
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 70
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 57
- 238000010041 electrostatic spinning Methods 0.000 claims description 29
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 16
- -1 polyethylene Polymers 0.000 claims description 11
- 239000000523 sample Substances 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 210000002950 fibroblast Anatomy 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 9
- 239000005030 aluminium foil Substances 0.000 claims description 7
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 238000002474 experimental method Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 5
- 229940020452 neupro Drugs 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- KFQYTPMOWPVWEJ-INIZCTEOSA-N rotigotine Chemical compound CCCN([C@@H]1CC2=CC=CC(O)=C2CC1)CCC1=CC=CS1 KFQYTPMOWPVWEJ-INIZCTEOSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000013068 control sample Substances 0.000 claims description 3
- 230000005684 electric field Effects 0.000 claims description 3
- 229910001447 ferric ion Inorganic materials 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 150000002085 enols Chemical class 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 11
- 239000000835 fiber Substances 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 8
- 235000013824 polyphenols Nutrition 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 4
- 150000008442 polyphenolic compounds Chemical class 0.000 abstract description 4
- 230000009920 chelation Effects 0.000 abstract description 3
- LRBQNJMCXXYXIU-YIILYMKVSA-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(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-YIILYMKVSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 230000003078 antioxidant effect Effects 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000010408 film Substances 0.000 description 8
- 235000013305 food Nutrition 0.000 description 8
- 230000006870 function Effects 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- 238000010668 complexation reaction Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 235000014593 oils and fats Nutrition 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- JVJFIQYAHPMBBX-UHFFFAOYSA-N 4-hydroxynonenal Chemical compound CCCCCC(O)C=CC=O JVJFIQYAHPMBBX-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- OHDRQQURAXLVGJ-HLVWOLMTSA-N azane;(2e)-3-ethyl-2-[(e)-(3-ethyl-6-sulfo-1,3-benzothiazol-2-ylidene)hydrazinylidene]-1,3-benzothiazole-6-sulfonic acid Chemical compound [NH4+].[NH4+].S/1C2=CC(S([O-])(=O)=O)=CC=C2N(CC)C\1=N/N=C1/SC2=CC(S([O-])(=O)=O)=CC=C2N1CC OHDRQQURAXLVGJ-HLVWOLMTSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 239000002657 fibrous material Substances 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 235000013373 food additive Nutrition 0.000 description 2
- 239000002778 food additive Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000040710 Chela Species 0.000 description 1
- 101000891579 Homo sapiens Microtubule-associated protein tau Proteins 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
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- 235000021474 generally recognized As safe (food) Nutrition 0.000 description 1
- 235000021473 generally recognized as safe (food ingredients) Nutrition 0.000 description 1
- 102000057063 human MAPT Human genes 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 239000002574 poison Substances 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
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Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/4309—Polyvinyl alcohol
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The invention relates to an electrospun polyvinyl alcohol-based tannic acid anti-oxidation nanofiber membrane. A prepration method includes the steps of tannic acid-metal ion self-assembly complex solution preparation, polyvinyl alcohol fiber-forming matrix preparation, polyvinyl alcohol-based tannic acid-metal ion complex electrospinning solution preparation and anti-oxidation nanofiber membrane preparation through electrospinning. By the utilization of the dual effects of polyphenol efficient anti-oxidation activity of tannic acid molecular structures and self-assembly chelation crosslinking between the tannic acid molecular structures and metal ions, with polyvinyl alcohol being a membrane-forming matrix, a chelated net structure of tannic acid and the metal ions is constructed by the utilization of the electrospinning technology to enhance fiber mechanical properties, a nanfiber porous microstructure is used for efficiently exerting anti-oxidation activity of tannic acid, a high mechanical property and anti-oxidation function integrated forming technology for preparing the nanofiber membrane in a one-step mode is created, and the polymer nanofiber membrane is endowed with the dual functional characteristics of anti-oxidation and mechanical property enhancement.
Description
Technical field
The present invention relates to electrostatic spinning and prepare the preparation method of hydrophilic antioxidation nano fibrous membrane, can be as oils and fats antioxygen
Formed material be applied to fats and oils processing and oils and fats fresh-keeping in.
Background technology
Oxidation of Fat and Oils causes the quality deteriorations such as spoiled by rancid oil or fat, abnormal flavour, and even producing acrylic aldehyde or 4-Hydroxynonenal etc. has
Poison harmful substance.The Natural antioxidant has the features such as efficient, safe and nontoxic or low toxicity, is the important directions of antioxidation research and development
One of.But, Natural antioxidant dissolubility is poor, and most of Natural antioxidants such as tea polyphenols mostly is colour generation taste compound, adds
Dosage crosses organoleptic attributes such as affecting the original local flavor of food, mouthfeel at most.At present, the research of antioxidant only rests on natural antioxygen
The screening of agent antioxidative and non-oxidizability functional evaluation.Develop the generalization anti-oxidation function of novel " little consumption, high efficiency "
Property product, become antioxidant development a disruptive technology difficult problem.
Nanofiber is that collection multi-crossed disciplines, fundamental research and novel product develop forward position, the world skill being closely connected
Art, compared with normal film material, has unrivaled superior function: the diameter of (1) every fiber is about human tau hair
One thousandth, can reach 10-300nm so that it is possess great specific surface, and nanoparticle surface atomic number increases, this type of atom
Easily adsorb bond with foreign atom, therefore there is the highest chemism, it is possible to make functional component effectively penetrate into, protect and expand
Dissipate, give full play to its dimensional effect.(2) high molecular functional, by functional (conduction/heat conduction, antibacterial etc. performance) inorganic nano
Uniform particle is scattered in polymer fiber matrix, gives polymer nanofiber functional characteristic, it is achieved high-performance is with multi-functional
Integration.(3) loaded down with trivial details time-consuming preparation technology is to a certain degree simplified, with low cost, realize the controlled diameter of fiber, pattern various
Change.Electrostatic spinning technique is currently the only a kind of effective ways that can directly and continuously prepare nanofiber.Therefore by quiet
It is a kind of new and innovative ways solving long-standing problem antioxidant technology bottleneck that Electrospinning is applied to oxidation-resistant material.
Polyvinyl alcohol is widely used in pharmacy, medical science, tissue because having biodegradability and characteristic nontoxic, environmental protection
The field such as engineering material, food, is fibroblast matrix good in nanofiber preparation.But the receiving of the random alignment of at present application
Rice fibre strength is relatively low, and poor mechanical property the most seriously limits the application of nano fibrous membrane.Many researchs change
The mechanical strength of kind fibrous material, as compounding in polymer, additive embedding, crosslinking, spun orientation technology have been used for improving its machine
Tool performance.But great majority operation needs fiber carries out time-consuming complicated postprocessing working procedures, preparation process toxic in addition
The use learning organic solvent more limits the development of the field of food having strict control to safety, although solvent volatilization, but solvent
Residue problem can not be ignored, and therefore the preparation of Electrospun nano-fibers material rarely has report in food applications.
Summary of the invention
The present invention be overcome the deficiencies in the prior art in place of, it is provided that a kind of simple, efficient, safe electrospinning is PVA-based
Tannic acid antioxidation nano fibrous membrane.
The technical scheme that the present invention realizes purpose is as follows:
A kind of electrospinning PVA-based tannic acid antioxidation nano fibrous membrane, preparation process is as follows:
(1) tannic acid and the preparation of metal ion self assembly complex
Tannic acid is 4-5:1 with the mass concentration ratio of metal ion, ultra-pure water preparation TA and metallic solution, fully mixes
After, regulation system pH to 7.4；The concentration of tannic acid is 12-16mg/mL, and metallic solution is 3-4mg/mL；
(2) polyvinyl alcohol fibroblast matrix preparation
The mean molecule quantity of polyvinyl alcohol is 85,000-124,000, and degree of hydrolysis is 84-89%, uses ultra-pure water preparation
PVA solution 16-24wt%, removes bubble；
The preparation of the most PVA-based tannic acid-iron ion complexation electrostatic spinning solution
Under room temperature condition, poly-vinyl alcohol solution is mixed with tannic acid and metal ion self assembly complex equal-volume, use
Propeller stirrer carries out rotating 0.5-1 hour with 700 turns/min rotating speed, the final prepared PVA electrospinning containing TA-metal complex
Solution；
(4) electrostatic spinning technique prepares antioxidation nano fibrous membrane
Use electrostatic spinning apparatus continuous electrostatic spinning, obtain electrospinning PVA-based tannic acid antioxidation nanofiber
Film.
And, described step detailed process (4) is: electrostatic spinning apparatus is NaBond NEU-PRO, and 5mL syringe is pacified
It is contained at electrostatic spinning apparatus draw-in groove, solenoid and air pump dual regulation and control sample introduction flow velocity, control accurate sample rate.Select not
Viscous type aluminium-foil paper can reach more preferably to separate fibrous membrane the effect of aluminium foil, and experiment intermediate roll formula catcher controls at 41rpm, sample introduction
Flow velocity is 0.5mL/h, voltage 15kv, and sample introduction needle to catcher vertical dimension is 15cm, connects outside the rustless steel syringe needle of syringe
See a size of 0.7mm × 32mm, diameter 0.390mm to be connected with syringe, at rustless steel syringe needle, connect high voltage electric field for experiment
High voltage power supply, continuous electrostatic spinning 6h are provided.
And, the step of the preparation of described poly-vinyl alcohol solution is as follows:
Under the conditions of 85 DEG C, polyvinyl alcohol is slowly dissolved in ultra-pure water preparation PVA solution, uses propeller stirrer
Carry out rotating 0.5-2 hour with 700 turns/min rotating speed, it should be noted that need to add a small amount of every time during polyethylene dissolving alcohol granule
Granule of polyvinyl alcohol, it is ensured that granule of polyvinyl alcohol is fully suspended in water, after whole polyvinyl alcohol dissolve, sealed membrane seals and puts
Put 4 DEG C of fridge overnight cold preservations, to promote bubble all to dissolve.
And, described bivalence Ca ion is 5-1 with the molar ratio of TA.
And, described ferric ion ion is 4-1 with the molar ratio of TA.
Advantage and the good effect of the application are as follows:
The present invention only uses tannic acid (Tannic acid, TA), trichlorine from raw material pre-treatment to nanofiber product molding
Change ferrum, polyvinyl alcohol, four kinds of materials of ultra-pure water, be the safety non-toxic composition of FDA certification, can be directly added in food
Food additive.Preparation process uses electrostatic spinning preparation technology whole process to reach food stage preparation flow, Product Green from raw material
Pollution-free.
The present invention carries functional antioxidant content TA using PVA as fibroblast matrix association, successfully prepares size diameter and is distributed as
100-300nm nano-fiber material, gives full play to the high efficient expression of the anti-oxidation function factor with the small-size effect of fibre structure,
Antioxidant activity improves more than 40%.
The present invention prepares nano fibrous membrane, airtight 48h under 53% relative moisture damp condition room temperature, stretches according to thin film
Test ASTM (D 882-02) acquired results, pure polyethylene glycol fiber films hot strength is 18.6 ± 4.2Mpa, elongation at break
It is 11.5 ± 4.1%, compared with pure PVA fibrous membrane, TA-Fe+++The addition of complex makes hot strength reach 31.4 ± 2.5MPa,
Hot strength improves 70%, and elongation at break increases by 2 times.The present invention utilize TA molecular structure have concurrently polyphenol strong antioxidant action with
Chelation of metal ion dual function nature, creates one-step method and prepares nano fibrous membrane strong mechanical performance and anti-oxidation function one
Body forming technique, verifies the critical technical parameter indexs such as filmogen modification, optimum formula, moulding process, performance evaluation, prominent
Broken new polymers/inorganic matter composite nano fiber technology of preparing bottleneck, builds the chelating network structure of tannic acid and iron ion
Reinforcing fiber mechanical property, fills the domestic gaps.
Accompanying drawing explanation
Fig. 1 is the PVA-based tannic acid of electron-microscope scanning (SEM)-iron ion complexation nanofiber microstructure and diameter divides
Butut, wherein nanofiber component is respectively: Fig. 1-1 is 8%PVA/TA-Fe+++, Fig. 1-2 is 10%PVA/TA-Fe+++, Fig. 1-
3 is 12%PVA/TA-Fe+++。
Fig. 2 is electrospun fibers film photo；
Fig. 3 is fibrous membrane sample strip submergence oils and fats photo；
Fig. 4 is tannic acid and iron ion chelation structure schematic diagram.
Detailed description of the invention
Below by specific embodiment, the invention will be further described, and following example are illustrative, is not limit
Qualitatively, it is impossible to limit protection scope of the present invention with this.
The present invention utilize tannic acid molecular structure have concurrently polyphenol high-efficiency antioxidant activity and with metal ion self assembly chela
Close crosslinking dual function, using polyvinyl alcohol as fibroblast matrix, utilize electrostatic spinning technique to build tannic acid and chelate with iron ion
Network structure reinforcing fiber mechanical property, efficiently plays tannic acid antioxidant activity with the many empty micro structures of nanofiber, creates one
Footwork prepares nano fibrous membrane strong mechanical performance and anti-oxidation function integrated molding technology, gives polymer nanofiber antioxygen
Change and strengthen dual function nature with mechanics, fill the domestic gaps.
Raw material only TA, Fe in the present invention+++, water, PVA, wherein TA, Fe+++Can be directly added in food by GRAS certification
Food additive；Biodegradable material PVAC polyvinylalcohol is food supplement, from preparing raw material to preparation technology safety nothing
Poison, environmental protection.
The present invention utilizes the polyhydroxy structure of tannic acid to have antioxidation and complexing of metal ion double grading concurrently, specify TA with
Fe+++Use threshold value, it is achieved TA and Fe+++Reversible/dynamically the complexation of crosslinking, reaction is quickly carried out automatically, it is not necessary to any special
Equipment or reaction.
It is spun into fiber material using PVAC polyvinylalcohol high polymer as quiet, utilizes electrostatic spinning technique to prepare nanometer agent undulation degree
Material, breaks through new polymers/inorganic matter and is combined spinnability technology, it is achieved PVA high polymer and tannic acid-Fe+++Spinning of complex
Property.
Spinning nanofiber diameter reaches 100-200nm, and high-specific surface area improves tannic acid antioxidation height efficient expression.
A kind of electrospinning PVA-based tannic acid antioxidation nano fibrous membrane, preparation process is as follows:
(1) tannic acid (TA) and iron ion (Fe+++) preparation of self assembly complex
Tannic acid is the macromolecular substances in Secondary metabolites, the phenolic hydroxyl group at multiple ortho positions in molecule, belongs to many
Unit's phenol.TA and Fe+++The reaction of solution complex mechanism is divided into two steps: be first that phenolic hydroxyl group is first dissociated into negative oxygen ion, subsequently
Negative oxygen ion and metallic ion coordination.PH value is by the equilibrium constant of regulation reaction system thus affects TA and Fe+++In conjunction with making
With.
In complexation chemism, the coordination constant of part is closely related with its protonation constants, along with the rising TA of pH
H will occur+Dissociate, pH value is the highest, TA and Fe+++Equilibrium constant the highest, i.e. Stability of Metal Complexes strengthen.As TA and Fe+++
When system pH is respectively 2,5 and 8, TA and Fe+++The complex coefficient of stability is respectively 1.5 × 105、3.4×109With 2.8 × 1017。
For realizing Fe+++Three ions coordination saturated with TA polyphenol hydroxyl can form stable state complexation, TA and Fe+++Quality
Concentration ratio for 4:1, ultra-pure water preparation TA and FeCl3Solution.For avoiding free Fe+++Quickly consume and the most first add title
Measured TA reagent, adds FeCl afterwards3, fully after mixing, use 3-4 to drip 1mol/L NaOH regulation system pH to 7.4, wherein
The concentration of tannic acid is 12-16mg/mL, FeCl3Concentration is 3-4mg/mL.
Iron ion in the present embodiment can use bivalence Ca ion to replace, wherein bivalence Ca ion and the molar ratio of TA
It is 5-1；
(2) polyvinyl alcohol fibroblast matrix preparation
It is 85,000-124,000 that polyvinyl alcohol (PVA) is chosen to be mean molecule quantity, and degree of hydrolysis is the PVA examination of 84-89%
Agent, this reagent is capable of PVA and adds and dissolve under hydrothermal solution effect, it is not necessary to the interpolation of organic solvent and ensure electrostatic spinning mistake
The abundant fibroblast of journey solidifies.As fibroblast matrix, PVA solution needs to control finite concentration, on the one hand, when solution concentration is the lowest,
The entanglement of molecules in solution chain is insufficient, it is impossible to maintain the seriality of jet, and causing can not fibroblast or formation bead string defect fibre
Dimension.Otherwise, when solute concentration is too high, solution easily forms gel at nozzle at nozzle owing to quantity of solvent is easily few, blocks pin
Head.Use ultra-pure water preparation PVA solution 16-24wt%, removes bubble in the present invention, solves discontinuous or blocks spout really
Fixed；
The step of the preparation of PVA solution is as follows:
Under the conditions of 85 DEG C, a certain amount of PVA is slowly dissolved in ultra-pure water preparation PVA solution, uses rotary propeller type stirring
Device carries out rotating 0.5-2 hour, it should be noted that need to add a small amount of PVA every time during dissolving PVA granule with 700 turns/min rotating speed
Granule, it is ensured that PVA granule is fully suspended in water, after whole PVA dissolve, sealed membrane seals and is placed on 4 DEG C of fridge overnight
Cold preservation, to promote bubble all to dissolve.
The preparation of the most PVA-based tannic acid-iron ion complexation electrostatic spinning solution
PVA solution is high viscoelastic solution, for realizing PVA solution and TA and Fe+++Self assembly complex is sufficiently mixed, room
By PVA solution and TA and Fe under the conditions of temperature+++Self assembly complex equal-volume mixes, and uses propeller stirrer with 700 turns/min
Rotating speed carries out rotating 0.5-1 hour, and aluminium-foil paper sealing prevents steam volatilization from affecting system concentration, final prepared containing TA-Fe+++The PVA electrospun solution of complexation；
(4) electrostatic spinning technique prepares antioxidation nano fibrous membrane
Use electrostatic spinning apparatus continuous electrostatic spinning, obtain electrospinning PVA-based tannic acid antioxidation nanofiber
Film.Particularly as follows: electrostatic spinning apparatus is NaBond NEU-PRO, 5mL syringe is arranged at electrostatic spinning apparatus draw-in groove, electromagnetism
Coil and air pump dual regulation and control sample introduction flow velocity, control accurate sample rate.Select non-stick aluminium-foil paper can reach by fibrous membrane more
Separating well the effect of aluminium foil, experiment intermediate roll formula catcher controls at 41rpm, and sample introduction flow velocity is 0.5mL/h, and voltage 15kv enters
Sample pin to catcher vertical dimension is 15cm, and the rustless steel syringe needle apparent size connecting syringe is 0.7mm × 32mm, diameter
0.390mm is connected with syringe, and connecting high voltage electric field at rustless steel syringe needle provides high voltage power supply, continuous electrostatic spinning for experiment
6h。
The application is enclosed with solenoid at syringe outer rim interval, and magnetic line of force direction flows to identical in liquid.
The application increases air pump at syringe piston boom end, and air pump can increase the propulsive force of piston rod, it is ensured that liquid
Body jet velocity, blocks after preventing piston, it is ensured that flow rate of liquid is uniform.
(5) nanofiber Microstructure characterization
Use Quanta 200FEG scanning transmission electron microscope for measuring the microscopic appearance of nano fibrous membrane, fibre diameter divides
Cloth (FDS).First a small pieces nano fibrous membrane is fixed on double-faced adhesive tape, sprays colloid elargol after the oil gidling of surface, use
Quanta 200FEG scanning electron microscope observes its pattern under fine vacuum/secondary electron imaging pattern.Scanning transmission electron microscope runs work
Make condition as follows: accelerating potential selects 10kV, and operating distance is 10.1-11.4mm.FDS measures and uses XT Document (FEI
Corp, Hillsboro, OR) analyze software sample microscopic appearance is measured, the data obtained is in order to build distribution of sizes Nogata
Figure.
Antioxygenic property:
When the 0.01g superfine fibre film containing 2%TA is with oxidant ABTS+reaction, nano fibrous membrane ABTS+removing
Rate is equivalent to the antioxidation clearance rate of 1.761g/L TA, and its antioxidant activity improves about 43 times, and nano fibrous membrane can play work
The model of action of property composition " little consumption, high efficiency ".
The interpolation of Fe+++ can significantly improve fibrous membrane mechanical property, overcomes the not good enough defect of fibrous membrane mechanical performance.Work as TA-
When Fe+++ addition is 2%, the hot strength of fibrous membrane (thickness 0.06mm) is 5.34MPa, improves than comparison (2.45MPa)
117%.
Using method is recommended, and the film directly present invention prepared can be used for milk, fish as packaging material or deposited pad
The fresh food such as meat are fresh-keeping.Can also electrospinning on other biological membrane material surface, be used in combination with other breathable moisture permeability films.Can
With electrospinning different-thickness according to demand from 0.08 millimeter to 0.1 millimeter.
Claims (8)
1. an electrospinning PVA-based tannic acid antioxidation nano fibrous membrane, it is characterised in that: preparation process is as follows:
(1) tannic acid and the preparation of metal ion self assembly complex
Tannic acid is 4-5:1 with the mass concentration ratio of metal ion, after ultra-pure water preparation TA and metallic solution, fully mixing, adjusts
Joint system pH is to 7.4；The concentration of tannic acid is 12-16mg/mL, and metallic solution is 3-4mg/mL；
(2) polyvinyl alcohol fibroblast matrix preparation
The mean molecule quantity of polyvinyl alcohol is 85,000-124,000, and degree of hydrolysis is 84-89%, uses ultra-pure water preparation PVA molten
Liquid 16-24wt%, removes bubble；
The preparation of the most PVA-based tannic acid-complexing of metal ion electrostatic spinning solution
Under room temperature condition, poly-vinyl alcohol solution is mixed with tannic acid and metal ion self assembly complex equal-volume, use rotating plasma
Formula agitator carries out rotating 0.5-1 hour with 700 turns/min rotating speed, and the final PVA electrospinning prepared containing TA-metal complex is molten
Liquid；
(4) electrostatic spinning technique prepares antioxidation nano fibrous membrane
Use electrostatic spinning apparatus continuous electrostatic spinning, obtain electrospinning PVA-based tannic acid antioxidation nano fibrous membrane.
Electrospinning the most according to claim 1 PVA-based tannic acid antioxidation nano fibrous membrane, it is characterised in that: described
Step detailed process (4) is: electrostatic spinning apparatus is NaBond NEU-PRO, and 5mL syringe is arranged on electrostatic spinning apparatus card
At groove, solenoid and air pump dual regulation and control sample introduction flow velocity, control accurate sample rate.Select non-stick aluminium-foil paper can reach by
Fibrous membrane more preferably separates the effect of aluminium foil, and experiment intermediate roll formula catcher controls at 41rpm, and sample introduction flow velocity is 0.5mL/h, voltage
15kv, sample introduction needle to catcher vertical dimension is 15cm, connect syringe rustless steel syringe needle apparent size be 0.7mm ×
32mm, diameter 0.390mm are connected with syringe, and connecting high voltage electric field at rustless steel syringe needle provides high voltage power supply for experiment, even
Continuous electrostatic spinning 6h.
Electrospinning the most according to claim 1 PVA-based tannic acid antioxidation nano fibrous membrane, it is characterised in that: described
The step of the preparation of poly-vinyl alcohol solution is as follows:
Under the conditions of 85 DEG C, polyvinyl alcohol is slowly dissolved in ultra-pure water preparation PVA solution, uses propeller stirrer with 700
Turn/min rotating speed carry out rotate 0.5-2 hour, it should be noted that a small amount of poly-second need to be added every time during polyethylene dissolving alcohol granule
Enol granule, it is ensured that granule of polyvinyl alcohol is fully suspended in water, after whole polyvinyl alcohol dissolve, sealed membrane seals and is placed on
4 DEG C of fridge overnight cold preservations, to promote bubble all to dissolve.
Electrospinning the most according to claim 1 PVA-based tannic acid antioxidation nano fibrous membrane, it is characterised in that: described
Electrostatic spinning apparatus is NaBond NEU-PRO, and 5mL syringe is arranged at electrostatic spinning apparatus draw-in groove, outer intermarginal at syringe
Every being enclosed with solenoid, magnetic line of force direction flows to identical in liquid.
Electrospinning the most according to claim 1 PVA-based tannic acid antioxidation nano fibrous membrane, it is characterised in that: at note
Emitter piston rod end increases air pump.
Electrospinning the most according to claim 1 PVA-based tannic acid antioxidation nano fibrous membrane, it is characterised in that: described
Metal ion is ferric ion or the replacement of bivalence Ca ion.
Electrospinning the most according to claim 6 PVA-based tannic acid antioxidation nano fibrous membrane, it is characterised in that: described
Bivalence Ca ion is 5-1 with the molar ratio of TA.
Electrospinning the most according to claim 6 PVA-based tannic acid antioxidation nano fibrous membrane, it is characterised in that: described
Ferric ion ion is 4-1 with the molar ratio of TA.
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Denomination of invention: Electrospun PVA-based tannic acid antioxidant nanofiber membrane Effective date of registration: 20230117 Granted publication date: 20190507 Pledgee: Tianjin Zhongguancun Science and Technology Financing Guarantee Co.,Ltd. Pledgor: TIANJIN GASIN-DH FRESH TECHNOLOGY CO.,LTD. Registration number: Y2023120000003 |
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Denomination of invention: Electrospun polyvinyl alcohol based tannic acid antioxidant nanofiber membrane Effective date of registration: 20230712 Granted publication date: 20190507 Pledgee: Tianjin Zhongguancun Science and Technology Financing Guarantee Co.,Ltd. Pledgor: TIANJIN GASIN-DH FRESH TECHNOLOGY CO.,LTD. Registration number: Y2023120000063 |