CN114575153B - Intelligent fiber material capable of rapidly adhering cells and preparation method and application thereof - Google Patents
Intelligent fiber material capable of rapidly adhering cells and preparation method and application thereof Download PDFInfo
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- CN114575153B CN114575153B CN202210219794.5A CN202210219794A CN114575153B CN 114575153 B CN114575153 B CN 114575153B CN 202210219794 A CN202210219794 A CN 202210219794A CN 114575153 B CN114575153 B CN 114575153B
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- 239000002657 fibrous material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 238000000855 fermentation Methods 0.000 claims description 59
- 230000004151 fermentation Effects 0.000 claims description 59
- 229920000742 Cotton Polymers 0.000 claims description 37
- 239000000835 fiber Substances 0.000 claims description 29
- 210000004027 cell Anatomy 0.000 claims description 25
- 210000001822 immobilized cell Anatomy 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 14
- 239000008103 glucose Substances 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 238000010526 radical polymerization reaction Methods 0.000 claims description 6
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 102000008186 Collagen Human genes 0.000 claims description 2
- 108010035532 Collagen Proteins 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 229920006221 acetate fiber Polymers 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 229920001436 collagen Polymers 0.000 claims description 2
- 235000001727 glucose Nutrition 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 abstract description 20
- 229920000642 polymer Polymers 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 230000003100 immobilizing effect Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 231100000683 possible toxicity Toxicity 0.000 abstract description 2
- 230000003313 weakening effect Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- -1 transition metal salt Chemical class 0.000 description 8
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 6
- 235000014680 Saccharomyces cerevisiae Nutrition 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 150000001879 copper Chemical class 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920002246 poly[2-(dimethylamino)ethyl methacrylate] polymer Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUUBCHWRXWPFFH-UHFFFAOYSA-N Hydroxytyrosol Chemical compound OCCC1=CC=C(O)C(O)=C1 JUUBCHWRXWPFFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 231100000135 cytotoxicity Toxicity 0.000 description 2
- 230000003013 cytotoxicity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002054 inoculum Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 1
- SYHVBRQKMHIAJQ-UHFFFAOYSA-N 3-(2-aminoethyl)benzene-1,2-diol Chemical compound NCCC1=CC=CC(O)=C1O SYHVBRQKMHIAJQ-UHFFFAOYSA-N 0.000 description 1
- HYUIDAKMNFQPTI-UHFFFAOYSA-N 4-(ethylamino)benzene-1,2-diol Chemical compound CCNC1=CC=C(O)C(O)=C1 HYUIDAKMNFQPTI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000193401 Clostridium acetobutylicum Species 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 238000007126 N-alkylation reaction Methods 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- ULVXDHIJOKEBMW-UHFFFAOYSA-N [3-(prop-2-enoylamino)phenyl]boronic acid Chemical compound OB(O)C1=CC=CC(NC(=O)C=C)=C1 ULVXDHIJOKEBMW-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000007444 cell Immobilization Methods 0.000 description 1
- 230000004663 cell proliferation Effects 0.000 description 1
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- DAKIDYQCFJQMDF-UHFFFAOYSA-N dichloromethane;pyridine Chemical compound ClCCl.C1=CC=NC=C1 DAKIDYQCFJQMDF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000002900 effect on cell Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000011068 loading method Methods 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
- 150000002739 metals Chemical class 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DWFKOMDBEKIATP-UHFFFAOYSA-N n'-[2-[2-(dimethylamino)ethyl-methylamino]ethyl]-n,n,n'-trimethylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN(C)CCN(C)C DWFKOMDBEKIATP-UHFFFAOYSA-N 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
- D06M14/04—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
- C12N11/082—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
- C12N11/12—Cellulose or derivatives thereof
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Organic Chemistry (AREA)
- Zoology (AREA)
- Genetics & Genomics (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Textile Engineering (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Abstract
The invention discloses an intelligent fiber material for rapidly adhering cells, a preparation method and application thereof. The invention combines the characteristics of SI-ATRP, utilizes a green nontoxic reducer, and carries out SI-ATRP by weakening the oxidation rate of a catalyst, so that the degree of controllable polymerization degree of the polymer on the surface of the obtained carrier is effectively improved, and the potential toxicity of residual organic chemical reagent to cells in the process of immobilizing the cells is further weakened.
Description
Technical Field
The invention relates to a surface initiation-atom transfer radical polymerization (SI-ATRP) method, in particular to an intelligent fiber material for rapidly adhering cells, a preparation method and application thereof.
Background
In 1995, the atom transfer radical polymerization was found and named Atom Transfer Radical Polymerization (ATRP) by the Japanese student Wang Jinshan, university of Carnegie-Mellon, boston. ATRP uses simple organic halide as initiator, transition metal complex as halogen atom carrier, and establishes reversible dynamic balance between active species and dormant species through oxidation-reduction reaction, thus realizing control of polymerization reaction. Through more than ten years of research by scholars of various countries, a plurality of ATRP reaction systems have been developed, and the research field of ATRP is greatly widened, wherein surface-initiated atom transfer radical polymerization (SI-ATRP) is an effective method for obtaining a controllable polymer brush on the surface of a material.
Zhang et al (Industrial & Engineering Chemistry research.2019,58, 7107-7119) grafted poly (ethyl polyethylene glycol) dimethacrylate as a cross-linking agent onto the stainless steel surface by SI-ATRP to obtain a poly (2- (dimethylamino) ethyl methacrylate) (PDMAEMA) layer, followed by N-alkylation of the PDMAEMA chain to introduce a high surface density positively charged quaternary ammonium salt to enhance the anti-fouling and anti-corrosion properties of the stainless steel surface. Deng et al (microchip acta.2018,185, 189) grafted poly-3-acrylamidophenylboronic acid onto polydopamine coated magnetic graphene oxide using SI-ATRP to obtain a novel boronic acid affinity material that can selectively capture cis-diol under non-cis-diol interference. Ma et al (Langmuir.2013, 29, 5631-5637) prepared capsules with dual temperature and pH response using SI-ATRP, which showed controlled loading and release, and adsorbed the anionic dye methyl orange in addition to the better adsorption of the cationic dye rhodamine 6G. In addition, ma et al (Journal of Agricultural and Food chemistry.2013,61, 12232-12237) further expand SI-ATRP to applications for preparing thermosensitive release type multi-element compound fertilizers, and have high controllability of release rate of coating elements and high permeability according to ambient temperature.
Compared with other active polymerization, the SI-ATRP has the advantages of mild polymerization conditions, simple process, wider applicable monomer range, stronger molecular design capability and the like, but in the practical application process, the low-valence transition metal salt catalyst is easily oxidized and difficult to preserve, meanwhile, the use amount of the transition metal complex is large, the transition metal complex is not consumed in the polymerization process, and the problems of polymer aging and the like caused by the fact that the transition metal complex is remained in the polymer are easy to cause the SI-ATRP to be unfavorable for industrial production. To solve the above problems, CN 101508745A uses an optimized Cu (i) and Cu (ii) compatible catalyst during the polymerization reaction to obtain polymers with a conversion up to 90% and a molecular weight distribution in the range of 1.05-1.3. In addition, in the SI-ATRP polymerization process, the reaction system has higher requirement on oxygen content, and the atomic transfer radical polymerization (ARGET ATRP) reaction system of the electron transfer generation catalyst is generated, so that the whole reaction system can realize efficient and convenient ATRP by means of an activating agent regeneration electron transfer mechanism only by adding a proper amount of reducing agent. CN 101768227B increases the polymerization rate of the reaction by adding a catalyst amount of a base to the polymerization system, and increases the controllability of the polymerization reaction by adding a base. Meanwhile, CN 101775090B combines the respective characteristics of AGET ATRP catalyzed by copper salt and ferric salt, adopts stable high-valence ferric salt in air as a main catalyst, adopts a small amount of copper (salt) with high catalytic activity as a reducing agent, and carries out AGET ATRP polymerization by generating an iron and copper bimetallic catalyst in situ through oxidation-reduction reaction between metals.
Currently, catalysts used for SI-ATRP are mainly copper salts (e.g., cuCl, cuBr) and iron salts (FeCl) 2 ，FeBr 2 ) Copper salt catalyzed SI-ATRP tends to have higher reactivity, but copper salts have some cytotoxicity to microorganisms; in contrast, ferric salts are less toxic and have better biocompatibility, but ferric salts have lower SI-ATRP activity, which limits the application of SI-ATRP in material modification and subsequent immobilization of cells to some extent. Accordingly, the present invention proposes an improved SI-ATRP method for the preparation of smart fiber materials for fast adherent cells and the subsequent multi-batch fermentation process of immobilized cells.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the invention provides an intelligent fiber material for rapidly adhering cells and a preparation method thereof.
The invention also solves the technical problem of providing the application of the intelligent fiber material for rapidly adhering cells in immobilized cells.
In order to solve the first technical problem, the invention discloses a preparation method of an intelligent fiber material for rapidly adhering cells, which comprises the steps of placing functionalized fibers with hydroxyl groups and amino groups on the surfaces into a polymerization solution containing a monomer capable of free radical polymerization, an initiator, a complexing agent, a catalyst, a reducing agent and a solvent for surface initiation-atom transfer radical polymerization (SI-ATRP) reaction to obtain the intelligent fiber material; in some embodiments, the preparation method comprises the steps of firstly reacting functionalized fiber with hydroxyl and amino on the surface with an initiator to obtain functionalized cotton fiber with a surface grafted with the initiator; and then placing the functionalized cotton fiber with the surface grafted with the initiator into a polymerization solution containing a monomer capable of free radical polymerization, a complexing agent, a catalyst, a reducing agent and a solvent to perform surface initiation-atom transfer radical polymerization (SI-ATRP) reaction, thus obtaining the intelligent fiber material.
The method comprises the steps of cutting the functionalized fiber into the size of 3cm or 3cm, and preprocessing the fiber to obtain the functionalized fiber; pretreatment modes of the functionalized fiber include, but are not limited to, 3-hydroxytyrosol, catecholethylamine, 4- (2-ethylamino) benzene-1, 2-diphenol and silane coupling agents.
Wherein the fiber is any one or a combination of a plurality of natural cotton fiber, polyester fiber, polyvinyl alcohol fiber, polyamide fiber, boron fiber, collagen fiber, ceramic fiber and acetate fiber.
Wherein the dosage of the free radical polymerizable monomer is 0.5-2 g/g of functionalized fiber, and the dosage ratio of the functionalized fiber to the polymerization solution is 0.5-10 g/100mL.
Wherein the free radical polymerizable monomer is any one or a combination of a plurality of methyl methacrylate, acrylonitrile, glycidyl methacrylate, N-isopropyl acrylamide, isobutene, styrene, sodium styrene sulfonate and N-methylol acrylamide.
Wherein the molar ratio of the monomer, the initiator, the complexing agent, the catalyst and the reducing agent for free radical polymerization is (100-1000): 1: (0.5-2): (0.5-2): (0.1-10).
Wherein the initiator includes, but is not limited to, 2-bromoisobutyryl bromide and/or 2-bromoisobutyryl ethyl ester.
Wherein the complexing agent includes, but is not limited to, hexamethyltriethylenetetramine and/or tris- (N, N-dimethylaminoethyl) amine.
Wherein the catalyst is CuX or FeX 2 Any one or a combination of a plurality of the above, wherein X=Cl or Br.
Wherein the reducing agent is any one or a combination of more of citric acid, sodium citrate, ascorbic acid, sodium sulfite, sodium bisulphite and glucose.
Wherein the solvent includes but is not limited to toluene, methanol.
Wherein the reaction is carried out by magnetic stirring at 50-110 ℃ for more than 6 hours.
Wherein the reaction is carried out under anhydrous and anaerobic conditions.
In order to solve the second technical problem, the invention discloses application of the intelligent fiber material in adherent cells and immobilized cell fermentation.
Wherein the immobilized cell fermentation is multi-batch continuous fermentation.
Wherein the cells include, but are not limited to, saccharomyces cerevisiae cells, E.coli cells, clostridium acetobutylicum.
Wherein, the cell seed liquid is inoculated into a fermentation culture medium containing intelligent fiber materials for culture in a volume ratio of 1-10 percent of the inoculation amount.
Wherein the dosage of the intelligent fiber material is 30-80 g/L of fermentation medium.
Wherein the immobilized cells can be adhered to the surface of the intelligent fiber material within 2-6 hours.
Wherein, the fermentation liquid OD is in 2-6 h 600 The temperature is reduced to 1-10% of the original system, and is close to 0.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
(1) The improved surface-initiated atom transfer radical polymerization method provided by the invention improves the polymerization stability of the whole reaction, and simultaneously maintains the grafting rate and the polymerization efficiency of the whole reaction.
(2) On one hand, due to the limitations of instruments and materials and high requirements of SI-ATRP on oxygen content, strict oxygen-free can not be achieved in the polymerization process, so that even if a trace amount of oxygen exists in a reaction system, the addition of the reducing agent can also play a role in improving the stability and efficiency of the processes such as monomer polymerization, polymer grafting and the like; on the other hand, the addition of the reducing agent effectively weakens cytotoxicity caused by residual chemical agents to a certain extent, so that the immobilized cells can still keep higher cell activity in multi-batch fermentation.
(3) The mild reducing agent provided by the invention can avoid the use of simple substances corresponding to transition metal salts, and can effectively improve the controllable degree of the whole polymerization process.
(4) The improved surface-initiated atom transfer radical polymerization method provided by the invention has higher applicability to both rough-surface and smooth-surface fibers, and does not influence the immobilized cell effect of the fibers besides endowing the surfaces of the fibers with various polymer structures.
(5) The intelligent fiber material prepared by the invention has good biocompatibility, higher adhesion rate to cells and no adverse effect on cell growth and proliferation.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings and detailed description.
FIG. 1 is an XPS spectrum of an unmodified cotton fiber and a functionalized cotton fiber after modification.
FIG. 2 is an SEM image of fibers before and after SI-ATRP reaction.
FIG. 3 shows the results of a multi-batch continuous fermentation.
FIG. 4 shows the effect of SI-ATRP modification on fermentation before and after modification.
Detailed Description
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
Example 1: the pretreatment and functionalization of the fiber are carried out according to the following method:
(1) The commercial cotton fiber is taken and cut into blocks with the size of 3cm by 3cm, and is dried at 60 ℃ for standby after being alternately washed for 3 times by ethanol and water.
(2) A50 mM Tris-HCl solution was prepared, the pH was adjusted to about 8.5 with hydrochloric acid, and a certain amount of 4- (2-ethylamino) benzene-1, 2-diol and polyethyleneimine having a relative molecular mass of 600 were added to give concentrations of 1g/L, respectively.
(3) Weighing 20g of the dry cotton fiber obtained in the step (1), soaking the dry cotton fiber in the solution prepared in the step (2), mechanically stirring the dry cotton fiber for more than 12 hours, washing the dry cotton fiber with water for 3 to 5 times to remove 4- (2-ethylamino) benzene-1, 2-diphenol and polyethyleneimine sticky substances with unreacted surfaces completely, and drying the dry cotton fiber at 60 ℃ for standby, thus obtaining the functional cotton fiber with hydroxyl groups and amino groups on the surfaces. XPS spectra before and after functionalization of cotton fibers are shown in fig. 1.
Example 2: the preparation process of the intelligent fiber material comprises the following steps:
(1) 4g of the functionalized cotton fiber with hydroxyl groups and amino groups on the surface, prepared in example 1, was weighed, added into 100mL of a 2% (v/v) dry pyridine dichloromethane solution, 200. Mu.L of 2-bromoisobutyryl bromide was dropwise added under ice bath conditions, and after 1h of reaction, the mixture was transferred to room temperature and then the magnetic stirring reaction was continued for 12h.
(2) And (3) after the reaction is finished, taking out the cotton fiber in the step (1), washing the cotton fiber once by using acetone and toluene respectively, and drying the cotton fiber in vacuum at 25 ℃ to obtain the functionalized cotton fiber with the surface grafted with the initiator.
(3) Immersing the functionalized cotton fiber with the surface grafting initiator prepared in the step (2) in a methanol aqueous solution (the volume ratio of methanol to water is 1:1, and the total volume is 100 mL), taking N-isopropyl acrylamide (NIPAM) as a monomer, cuprous bromide as a catalyst, pentamethyl diethylenetriamine as a complexing agent, ascorbic acid as a reducing agent, and carrying out surface initiated atom transfer radical polymerization reaction with the corresponding addition amount of 4g,0.32g,1.6mL and 0.1g, and carrying out continuous magnetic stirring reaction at 60 ℃ for 14h under anhydrous and anaerobic conditions to graft poly-N-isopropyl acrylamide (PNIPAM), washing for 3-5 times after the reaction is finished, and drying at 55 ℃ for standby, thus obtaining the intelligent cotton fiber with the surface grafted PNIPAM, which is marked as the modified SI-ATRP. SEM images of cotton fiber modified PNIPAM front and back are shown in fig. 2.
Example 3: the application of intelligent fiber materials in immobilized cell fermentation:
(1) The cells selected in the experiment were Saccharomyces cerevisiae cells, and the fermentation medium was (g/L): glucose 60, peptone 4, (NH) 4 ) 2 SO 4 4 Yeast extract 3, KH 2 PO 4 3，MgSO 4 0.5，ZnSO 4 ·7H 2 O 0.05，FeSO 4 ·7H 2 O0.05。
(2) Free cell fermentation: the activated Saccharomyces cerevisiae CICC1308 seed solution is transferred into a fermentation medium with an inoculum size of 10vt percent, and free cell fermentation is carried out for 16 hours under the conditions of 35 ℃ and 200 rpm.
During free cell fermentation, at fermentation time of 6h, fermentation broth OD 600 2.917 the fermentation period was 12 hours, the glucose consumption rate was 5g/L/h, the ethanol yield was 20.51g/L, and the ethanol yield was 1.71g/L/h.
(3) Immobilized cell fermentation: the activated seed solution of Saccharomyces cerevisiae CICC1308 was transferred to a fermentation medium containing the smart cotton fiber with PNIPAM grafted on the surface, prepared in example 2, in an inoculum size of 10vt%, and cell immobilization was performed, wherein the addition amount of the smart cotton fiber was 50g/L, and immobilized cell fermentation was performed at 35℃and 200rpm for 16 hours.
In the immobilized cell fermentation process, saccharomyces cerevisiae adheres to the surface of intelligent cotton fiber within 6 hours, and fermentation liquid OD 600 The fermentation period was 14h, the glucose consumption rate was 4.29g/L/h, the ethanol yield was 21.85g/L, and the ethanol yield was 1.56g/L/h, respectively, at 0.054.
(4) Continuous fermentation of multiple batches: setting the glucose concentration lower than 1g/L as the end of fermentation, after the fermentation of the first batch is finished, leaving 10vt% fermentation liquor as seed liquor of the next batch for free cells, pouring out all fermentation liquor for immobilized cells, only leaving immobilized cells, supplementing fresh sterile fermentation liquor with corresponding volume, then carrying out the fermentation of the second batch, and after the glucose consumption is finished, carrying out the replacement of fermentation liquor and the fermentation of the third batch by referring to the fermentation step of the second batch until 6 batches are continuously fermented. Wherein, the immobilized cells are prepared by respectively carrying out immobilized multi-batch continuous fermentation on cotton fibers, functionalized cotton fibers and modified SI-ATRP. The corresponding multi-batch continuous fermentation results are shown in FIG. 3.
In the multi-batch fermentation, the fermentation period of the improved SI-ATRP immobilized saccharomyces cerevisiae can be shortened from 14h to 3h, the glucose consumption rate is increased from 4.29g/L/h to 20g/L/h, and the ethanol yield can reach 26.34g/L and 8.78g/L/h in the sixth batch.
For continuous fermentation of cotton fiber immobilized cells, the fermentation period was shortened from 12h to 6h, the glucose consumption rate was increased from 5g/L/h to 10g/L/h, and the ethanol yield and ethanol yield remained only at 22.17g/L and 3.64g/L in the sixth batch.
For continuous fermentation of the functionalized cotton fiber immobilized cells, the fermentation period is shortened from 12h to 6h, the glucose consumption rate is increased from 5g/L/h to 10g/L/h, and the ethanol yield only remain 20.08g/L and 3.35g/L/h in the sixth batch.
Compared with the immobilized cell continuous fermentation, the period of the free cell continuous fermentation is shortened from 12h to 9h, the glucose consumption rate is improved from 5g/L/h to 6.67g/L/h, but the ethanol yield and the ethanol yield only remain 16.95g/L and 1.88g/L/h in the sixth batch.
Comparative example 1:
the same as in example 1, a functionalized cotton fiber is obtained by polymerizing a mixed solution of 4- (2-ethylamino) benzene-1, 2-diphenol and polyethyleneimine on the surface of the cotton fiber; the surface initiation-atom transfer radical polymerization reaction was carried out on the surface of the functionalized cotton fiber by the same method as in example 2, except that ascorbic acid was not added to the system, to obtain PNIPAM grafted cotton fiber, which was designated as conventional SI-ATRP.
Immobilized cell fermentation was performed by the method described in example 3, and the corresponding fermentation results for the commercially available cotton fibers of examples 1-2 and the prepared functionalized cotton fibers, modified SI-ATRP and conventional SI-ATRP of comparative example 1 are shown in FIG. 4.
In the fermentation process of the cotton fiber immobilized cells, the fermentation liquid OD is fermented to 6 hours 600 2.082 hours, a fermentation period of 12 hours, a glucose consumption rate of 5g/L/h, an ethanol yield of 21.08g/L, and an ethanol yield of 1.76g/L/h.
In the fermentation process of the functionalized cotton fiber immobilized cells, the fermentation liquid OD is fermented to 6 hours 600 2.548 the fermentation period was 12 hours, the glucose consumption rate was 5g/L/h, the ethanol yield was 20.96g/L, and the ethanol yield was 1.75g/L/h.
In contrast, during the fermentation of conventional SI-ATRP immobilized cells, at fermentation time of 6h, the fermentation broth OD 600 The glucose concentration remained at 43.10g/L and the ethanol yield was 5.58g/L at 0.961.
In summary, the invention combines the characteristics of SI-ATRP, utilizes a green nontoxic reducer, and carries out SI-ATRP by weakening the oxidation rate of a catalyst, so that the polymerization degree of the polymer on the surface of the obtained carrier is effectively improved, and the potential toxicity of residual organic chemical reagent to cells in the process of immobilizing the cells is further weakened.
The invention provides an intelligent fiber material for rapidly adhering cells, a preparation method and an application thought and a method thereof, and particularly the method and the method for realizing the technical scheme are numerous, the above is only a preferred embodiment of the invention, and it should be pointed out that a plurality of improvements and modifications can be made to a person skilled in the art without departing from the principle of the invention, and the improvements and modifications are also regarded as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (8)
1. A preparation method of an intelligent fiber material for rapidly adhering cells is characterized in that functional fibers with hydroxyl groups and amino groups on the surfaces are placed in a polymerization solution containing a monomer capable of free radical polymerization, an initiator, a complexing agent, a catalyst, a reducing agent and a solvent to react, and the intelligent fiber material is obtained; the reaction is carried out under anhydrous and anaerobic conditions;
wherein the functional fiber with hydroxyl and amino on the surface is prepared by preprocessing any one or a combination of a plurality of natural cotton fiber, polyester fiber, polyvinyl alcohol fiber, polyamide fiber, boron fiber, collagen fiber, ceramic fiber and acetate fiber;
wherein the free radical polymerizable monomer is any one or a combination of a plurality of methyl methacrylate, acrylonitrile, glycidyl methacrylate, N-isopropyl acrylamide, isobutene, styrene, sodium styrene sulfonate and N-methylol acrylamide;
wherein the catalyst is CuX or FeX 2 Any one or a combination of a plurality of the above, wherein X=Cl or Br;
wherein the reducing agent is any one or a combination of more of citric acid, sodium citrate, ascorbic acid, sodium sulfite, sodium bisulphite and glucose.
2. The method for preparing an intelligent fiber material according to claim 1, wherein the amount of the free radical polymerizable monomer is 0.5-2 g/g of the functionalized fiber.
3. The method for preparing an intelligent fiber material according to claim 1, wherein the mole ratio of the monomer, the initiator, the complexing agent, the catalyst and the reducing agent in the free radical polymerization is (100-1000): 1: (0.5-2): (0.5-2): (0.1 to 10).
4. The method for preparing an intelligent fiber material according to claim 2, wherein the reaction is performed at 50-110 ℃ for more than 6h.
5. The intelligent fiber material of claim 1 or the intelligent fiber material prepared by the method of any one of claims 2-4, and the application of the intelligent fiber material in immobilized cell fermentation.
6. The use according to claim 5, characterized in that the amount of smart fiber material is 30-80 g/L fermentation medium.
7. The use according to claim 5, wherein the immobilized cells adhere to the surface of the smart fiber material within 2-6 hours.
8. The use according to claim 5, wherein the fermentation broth OD is within 2-6 hours 600 The content of the active components is reduced to 1-10% of the original system.
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