CN107956118B - Fibroin modification method of pure cotton fabric - Google Patents
Fibroin modification method of pure cotton fabric Download PDFInfo
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- CN107956118B CN107956118B CN201711223677.1A CN201711223677A CN107956118B CN 107956118 B CN107956118 B CN 107956118B CN 201711223677 A CN201711223677 A CN 201711223677A CN 107956118 B CN107956118 B CN 107956118B
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- silk fibroin
- fabric
- pure cotton
- molecular weight
- fibroin
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- 108010022355 Fibroins Proteins 0.000 title claims abstract description 217
- 239000004744 fabric Substances 0.000 title claims abstract description 146
- 229920000742 Cotton Polymers 0.000 title claims abstract description 93
- 238000002715 modification method Methods 0.000 title claims abstract description 14
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims abstract description 54
- 230000003647 oxidation Effects 0.000 claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 39
- 238000011282 treatment Methods 0.000 claims abstract description 38
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims abstract description 27
- 229960002218 sodium chlorite Drugs 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 20
- 238000009990 desizing Methods 0.000 claims abstract description 18
- 238000002791 soaking Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 65
- 239000007864 aqueous solution Substances 0.000 claims description 63
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 37
- 241000255789 Bombyx mori Species 0.000 claims description 28
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 20
- 229920001503 Glucan Polymers 0.000 claims description 19
- 238000004108 freeze drying Methods 0.000 claims description 18
- 229920005654 Sephadex Polymers 0.000 claims description 16
- 239000012507 Sephadex™ Substances 0.000 claims description 16
- 238000012216 screening Methods 0.000 claims description 14
- 150000001718 carbodiimides Chemical class 0.000 claims description 13
- 238000001962 electrophoresis Methods 0.000 claims description 12
- 238000002415 sodium dodecyl sulfate polyacrylamide gel electrophoresis Methods 0.000 claims description 12
- 229920002307 Dextran Polymers 0.000 claims description 11
- 238000004949 mass spectrometry Methods 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 238000010828 elution Methods 0.000 claims description 7
- GDESEHSRICGNDP-UHFFFAOYSA-L [Cl-].[Cl-].[Ca+2].CCO Chemical compound [Cl-].[Cl-].[Ca+2].CCO GDESEHSRICGNDP-UHFFFAOYSA-L 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000008223 sterile water Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 abstract description 14
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 239000008367 deionised water Substances 0.000 description 33
- 229910021641 deionized water Inorganic materials 0.000 description 33
- 239000000463 material Substances 0.000 description 29
- 238000001035 drying Methods 0.000 description 28
- 239000011259 mixed solution Substances 0.000 description 26
- 230000002572 peristaltic effect Effects 0.000 description 20
- 238000005303 weighing Methods 0.000 description 20
- 239000003480 eluent Substances 0.000 description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 16
- 239000011521 glass Substances 0.000 description 15
- 239000008399 tap water Substances 0.000 description 13
- 235000020679 tap water Nutrition 0.000 description 13
- 238000009835 boiling Methods 0.000 description 12
- 230000004048 modification Effects 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 10
- 108010064995 silkworm fibroin Proteins 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 238000011049 filling Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 230000004584 weight gain Effects 0.000 description 8
- 235000019786 weight gain Nutrition 0.000 description 8
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000011859 microparticle Substances 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000502 dialysis Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000218652 Larix Species 0.000 description 1
- 235000005590 Larix decidua Nutrition 0.000 description 1
- 150000004753 Schiff bases Chemical group 0.000 description 1
- 108010013296 Sericins Proteins 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- -1 for example Polymers 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000000007 visual effect Effects 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/15—Proteins or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
- D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
- D06L1/14—De-sizing
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/30—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with oxides of halogens, oxyacids of halogens or their salts, e.g. with perchlorates
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
-
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Cosmetics (AREA)
Abstract
The invention provides a fibroin modification method of pure cotton fabric, which comprises the following steps: desizing the pure cotton fabric to obtain a desized fabric; performing oxidation treatment on the desized fabric by using sodium periodate, washing and performing oxidation treatment on sodium chlorite to obtain an oxidized fabric; providing silk fibroin with the molecular weight of 1000-5000 Da; and soaking the oxidized fabric in a cross-linking agent solution, and mixing and reacting with the silk fibroin. The modification method comprises the steps of oxidizing the desized fabric with sodium periodate, then oxidizing with sodium chlorite, and releasing reaction sites at specific positions on a cotton fiber molecular chain by the two-time oxidation treatment; the silk fibroin modified and oxidized fabric with the molecular weight of 1000-5000 Da enables silk fibroin with a specific small molecular weight to be firmly introduced to the fiber surface of a pure cotton fabric by utilizing the principle of covalent bonding, so that the softness, smoothness, mechanical property and silk fibroin stability of the pure cotton fabric are improved.
Description
Technical Field
The invention relates to the technical field of textiles, in particular to a fibroin modification method of a pure cotton fabric.
Background
The cotton fiber is a natural raw material which is most applied in the field of textile and clothing, has a large amount of hydroxyl groups, has good hygroscopicity and small heat conductivity coefficient, and enables the fabric to have good heat preservation performance. However, the cotton fiber has high rigidity, which affects the skin touch feeling of the product, and only hydroxyl groups exist on the molecular chain, which limits the functional modification of the fiber. The silk is a natural protein fiber, has excellent moisture absorption, air permeability and moisture permeability, is soft and smooth and skin-friendly, and has a much lower friction stimulation coefficient to skin than other various fibers; also has excellent oxidation resistance and ultraviolet resistance, and can safely care the skin of every inch in a body-fitting manner. The silk protein molecules can introduce various functional factors by adopting the principle of electrostatic attraction or covalent bonding, and the innovation and the upgrade of the application value of the textile are promoted. Thus, fibroin can be used to surface modify cotton.
There are some reports about the modification of cotton, for example, cotton can be treated by sodium hydroxide to improve the luster (mercerized cotton) and the dyeing property, and becomes smooth, but the strength is reduced; and the biological enzyme is grafted on the cotton fiber by means of covalent bonding, adsorption, crosslinking and the like to improve the visual and hand feeling effects (retrogradation finishing of the jean). Regarding the modification of silk protein of cotton, the research disclosed in the prior art selects sodium periodate to oxidize cotton fiber, and then reacts with amino on sericin or silk fibroin, but the Schiff base structure formed by aldehyde group generated by oxidation and amino is unstable. In the literature, after a film is formed by soaking silk fibroin on a cotton fabric, methanol is subjected to insolubilization treatment, and silk fibroin is coated on the surface of the cotton fabric, so that the modification in the mode can influence the surface structure of the fabric, and the fabric is brittle and hard and is easy to fall off. The silk protein modified by the silk protein of the cotton fabric reported in the prior art has large molecular weight dispersity, and is abundant in tens of thousands to hundreds of thousands of macromolecules, and the macromolecular silk protein not only affects the grafting efficiency, but also is easy to form a film, is hard, affects the surface structure and is easy to fall off. In conclusion, the surface modification of cotton fibers or fabrics by comfortable and skin-friendly fibroin has been rarely studied and has not been applied in the market.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for modifying fibroin of a pure cotton fabric, and the pure cotton fabric modified by the modification method provided by the present invention has good mechanical properties and good stability.
The invention provides a fibroin modification method of pure cotton fabric, which comprises the following steps:
A) desizing the pure cotton fabric to obtain a desized fabric;
B) performing oxidation treatment on the desized fabric by using sodium periodate, washing and performing oxidation treatment on sodium chlorite to obtain an oxidized fabric;
C) providing silk fibroin with a defined molecular weight of 1000-5000 Da;
D) and soaking the oxidized fabric in a cross-linking agent solution, and mixing and reacting with the silk fibroin.
Preferably, the cross-linking agent comprises carbodiimide.
Preferably, the carbodiimide accounts for 20-40% of the silk fibroin by mass percent.
Preferably, the desizing in the step A) is specifically desizing treatment by adopting sodium carbonate; the concentration of the sodium carbonate solution is 6 g/L; the desizing treatment temperature is 90-100 ℃; the desizing treatment time is 1 h.
Preferably, the concentration of the sodium periodate in the step B) is 10 g/L; the oxidation temperature of the sodium periodate is 30-40 ℃; the oxidation time of the sodium periodate is 1-3 h; the concentration of the sodium chlorite is 0.025-0.1M; the oxidation temperature of the sodium chlorite is 30-40 ℃; the oxidation time of the sodium chlorite is 1-2 h.
Preferably, the reaction temperature in the step D) is 25-35 ℃; the reaction time is 1-3 h.
Preferably, the silk fibroin with the molecular weight of 1000-5000 Da is prepared by the following method:
a) degumming silkworm silk by using sodium carbonate, and then adding a neutral salt solution to dissolve to prepare a silk fibroin dissolving solution;
the dextran Sephadex G50 and G25 columns are balanced for standby;
b) adding the silk fibroin dissolving solution into a glucan Sephadex G50 column, eluting the silk fibroin with sterile water, and collecting desalted silk fibroin aqueous solution in a branch pipe;
c) and (b) screening the silk fibroin with the molecular weight of less than 10kD in the collection tube in the step b) by SDS-PAGE electrophoresis or mass spectrometry, adding the silk fibroin into a dextran Sephadex G25 column again, eluting the silk fibroin by using sterilized water, collecting the silk fibroin in different tubes, and screening to obtain the silk fibroin with the small molecular weight of 1000-5000 Da.
Preferably, the neutral salt solution of step a) is selected from lithium bromide or calcium chloride-ethanol; the dissolving time is 5-7 hours; the concentration of the silk fibroin dissolving solution is 10-50 mg/mL.
Preferably, the silk fibroin in the collection tube in the step b) of screening in the step c) is further lyophilized, and then prepared into 30-80 mg/mL aqueous solution.
Preferably, the elution flow rate in the step b) is 200-400 mL/h; and c) the elution flow rate is 30-70 mL/h.
Compared with the prior art, the invention provides a fibroin modification method of pure cotton fabric, which comprises the following steps: A) desizing the pure cotton fabric to obtain a desized fabric; B) performing oxidation treatment on the desized fabric by using sodium periodate, washing and performing oxidation treatment on sodium chlorite to obtain an oxidized fabric; C) providing silk fibroin with a defined molecular weight of 1000-5000 Da; D) and soaking the oxidized fabric in a cross-linking agent solution, and mixing and reacting the oxidized fabric with the small molecular weight silk fibroin. According to the modification method provided by the invention, the desized fabric is subjected to sodium periodate oxidation treatment and then is subjected to sodium chlorite oxidation treatment again, and the two oxidation treatments are arranged to release reaction sites at specific positions on a cotton fiber molecular chain; meanwhile, the silk fibroin graft modification and oxidation fabric with a small relative molecular weight of 1000-5000 Da and concentrated distribution is adopted, and the silk fibroin with a specific small molecular weight is firmly introduced to the fiber surface of the pure cotton fabric by utilizing the principle of covalent bonding, so that the softness and the smoothness of the pure cotton fabric are improved, and meanwhile, the silk fibroin graft modification and oxidation fabric has good mechanical properties and good silk fibroin stability.
Detailed Description
The invention provides a fibroin modification method of pure cotton fabric, which comprises the following steps:
A) desizing the pure cotton fabric to obtain a desized fabric;
B) performing oxidation treatment on the desized fabric by using sodium periodate, washing and performing oxidation treatment on sodium chlorite to obtain an oxidized fabric;
C) providing silk fibroin with the molecular weight of 1000-5000 Da;
D) and soaking the oxidized fabric in a cross-linking agent solution, and mixing and reacting with the silk fibroin.
The pure cotton fabric is not limited, can be a cotton fiber fabric, can be a machine-made pure cotton fabric, has no limitation on the content of cotton fibers, and can be defined as the pure cotton fabric well known to those skilled in the art. The source of the present invention is not limited, and may be commercially available.
The invention firstly desizes the pure cotton fabric to obtain the desized fabric.
In the present invention, the desizing treatment is preferably a sodium carbonate desizing treatment; preferably, the pure cotton fabric is heated in an aqueous solution of sodium carbonate. The heating is preferably boiling heating.
The concentration of the sodium carbonate solution is preferably 6 g/L; the preferable desizing treatment temperature is 90-100 ℃; the desizing treatment time is preferably 1 h.
After heating, washing, dehydration, and drying are preferable.
The washing in the invention is preferably tap water, and the washing mode in the invention is not limited, and the washing mode is well known to those skilled in the art; the dehydration mode is not limited in the invention, and the dehydration mode is well known to those skilled in the art; the drying mode is not limited, and the drying method is well known to those skilled in the art; can be air-dried or oven-dried.
And drying to obtain a desized fabric, and oxidizing the desized fabric by using sodium periodate.
In the present invention, the concentration of the sodium periodate is preferably 10 g/L; the oxidizing temperature of the sodium periodate is preferably 30-40 ℃; the time for oxidizing the sodium periodate is preferably 1-3 h;
the source of the sodium periodate is not limited in the present invention, and may be commercially available.
After the sodium periodate treatment, washing and drying are preferable.
The washing in the invention is preferably tap water, and the washing mode in the invention is not limited, and the washing mode is well known to those skilled in the art; the drying mode is not limited, and the drying method is well known to those skilled in the art; can be air-dried or oven-dried.
And after the fabric is washed and dried, performing oxidation treatment by adopting sodium chlorite to obtain the oxidized fabric.
In the invention, the concentration of the sodium chlorite is 0.025-0.1M; the oxidation temperature of the sodium chlorite is 30-40 ℃; the oxidation time of the sodium chlorite is 1-2 h.
The invention preferably adopts the mixed oxidation treatment of sodium chlorite and hydrogen peroxide to obtain the oxidized fabric.
In the invention, the concentration of the mixed liquid of sodium chlorite and hydrogen peroxide is 0.025-0.1M; the temperature of the oxidation is 30-40 ℃; the oxidation time is 1-2 h.
In the present invention, the mixing ratio of sodium chlorite and hydrogen peroxide is not limited, and preferably may be 1: 1.
and after the oxidation is finished, soaking the oxidized fabric in a cross-linking agent solution, and mixing and reacting the fabric with silk fibroin with the molecular weight of 1000-5000 Da to obtain the silk fibroin modified pure cotton fabric.
According to the invention, the cross-linking agent comprises a carbodiimide; the crosslinker may also include N-acyl succinimide; wherein the carbodiimide accounts for preferably 20-40% of the silk fibroin by mass percent; more preferably 25%. The N-acyl succinimide accounts for 10% of the silk fibroin by mass preferably.
According to the invention, after dipping, adding the prepared silk fibroin with the molecular weight of 1000-5000 Da for grafting reaction, wherein the concentration of the silk fibroin solution is preferably 1-5%;
the reaction temperature is preferably 25-35 ℃; the reaction time is preferably 1-3 h.
After the grafting reaction, it is preferable to dry, wash, and dry again.
The drying is preferably air drying; the washing is preferably a water rinse; the re-drying is preferably air drying. The present invention is not limited to the specific operations of drying and rinsing, and those skilled in the art will be familiar with the present invention.
In the present invention, the silk fibroin is silk fibroin that has a relatively small molecular weight and is distributed intensively.
The silk fibroin graft modification oxidation fabric adopting the small molecular weight limited by the invention creatively utilizes the principle of covalent bonding to lead the silk fibroin with the specific small molecular weight to be firmly introduced to the fiber surface of the pure cotton fabric, improves the softness, smoothness, coolness and glossiness of the pure cotton fabric, improves the skin affinity, and has good mechanical property and silk fibroin stability.
The silk fibroin source with the molecular weight of 1000-5000 Da is not limited, can be commercially available, and is preferably prepared by the following method:
a) degumming silkworm silk by using sodium carbonate, and then adding a neutral salt solution to dissolve to prepare a silk fibroin dissolving solution;
the dextran Sephadex G50 and G25 columns are balanced for standby;
b) adding the silk fibroin dissolving solution into a glucan Sephadex G50 column, eluting the silk fibroin with sterile water, and collecting desalted silk fibroin aqueous solution in a branch pipe;
c) and (b) screening the silk fibroin with the molecular weight of less than 10kD in the collection tube in the step b) by SDS-PAGE electrophoresis or mass spectrometry, adding the silk fibroin into a dextran Sephadex G25 column again, eluting the silk fibroin by using sterilized water, collecting the silk fibroin in different tubes, and screening to obtain the silk fibroin with the small molecular weight of 1000-5000 Da.
Firstly, degumming silkworm silk by using sodium carbonate; preferably, the silkworm silk is put into a sodium carbonate aqueous solution according to a specific bath ratio, treated, cleaned and dried to obtain the degummed silk.
The silkworm silk is not limited in the present invention, and may be a raw silkworm silk known to those skilled in the art, and may be commercially available.
The bath ratio of the present invention is preferably 1:50 (g/mL); the mass concentration of the sodium carbonate aqueous solution is preferably 0.2%; the treatment temperature is preferably 98-100 ℃; the treatment frequency is preferably 1-5 times; more preferably 2-3 times; the treatment time is preferably 30min per treatment.
And cleaning after the treatment is finished, and drying to obtain the degummed silk.
The cleaning is preferably deionized water washing, and the cleaning mode is not limited in the invention and is well known to those skilled in the art; after washing, preferably larch, which is well known to those skilled in the art; the drying method is not limited in the invention, and the drying method is well known to those skilled in the art; drying in an oven may be used. The drying temperature is preferably 65 ℃.
And (3) adding the degummed silk into a neutral salt solution to dissolve, and preparing the silk fibroin dissolving solution.
In the present invention, the neutral salt solution is preferably selected from lithium bromide or calcium chloride-ethanol; the bath ratio of the silk to the neutral salt solution is preferably 1: 15-1: 20 (g/mL);
the concentration of the lithium bromide solution is preferably 9-10M; in the calcium chloride-ethanol, the mol ratio of calcium chloride to ethanol is preferably 1: 2;
the dissolving time is 5-7 hours; the preferred dissolving temperature is 60-70 ℃; more preferably 65 ℃ to 70 ℃; the concentration of the obtained silk fibroin dissolving solution is preferably 10-50 mg/mL.
The dextran Sephadex G50 and G25 columns were equilibrated for use. The sources of the dextran Sephadex G50 and G25 columns are not limited, and the columns can be commercially available or self-made.
The preferable concrete is as follows: boiling dextran Sephadex G50 and G25 with sterilized deionized water until the dextran Sephadex G50 and G25 is fully expanded, continuously filling the dextran Sephadex G50 and G25 into a hollow column made of glass, standing and settling the column, and balancing the column material with the sterilized deionized water; more preferably specifically: respectively putting glucan G-50 and G-25 into deionized water, carrying out boiling water bath for 1.5-2 h, carrying out cooling at normal temperature, then carrying out drainage by using a glass rod, filling into a hollow column made of glass, naturally settling for 2-3 h, then pressurizing by using a peristaltic pump, and balancing the column by using deionized water with 5 times of column volume for three times.
The volume of the preparative bed according to the invention is preferably 2cm × 60 cm.
After balancing, adding the silk fibroin dissolving solution into a glucan Sephadex G50 column, eluting the silk fibroin by using sterilized water, and collecting the desalted silk fibroin aqueous solution by virtue of a branch pipe.
The preferable concrete is as follows: and when the balance water is lowered to the surface of the column material for the last time, adding 5-15 mL of the dissolved silk fibroin mixed solution with the concentration of 10-50 mg/mL into the glucan G-50, continuously eluting with the sterilized deionized water when the silk fibroin mixed solution completely enters the surface of the column material, controlling the flow rate of the eluent by using a peristaltic pump, and collecting the effluent liquid in different tubes until the silk fibroin is completely drained.
The elution flow rate is preferably 200-400 mL/h; more preferably 250 to 350 mL/h.
Screening the silk fibroin with the concentration of less than 10kD in the collection tube in the step b) by SDS-PAGE electrophoresis or mass spectrometry.
The present invention does not limit the specific mode of the SDS-PAGE electrophoresis or mass spectrometry screening step b) to collect the silk fibroin with the kD below in the tube, and the silk fibroin is well known to those skilled in the art.
In the invention, after the silk fibroin with the concentration of less than 10kD in the collection tube in the screening step b), freeze-drying is further carried out, and then 30-80 mg/mL aqueous solution is prepared. Then filtering, wherein the filtration is preferably performed by using a membrane with the diameter of 0.45 mu m.
The present invention is not limited to the specific manner of lyophilization, as will be apparent to those skilled in the art.
Further separation of the molecular weight of silk fibroin below 10kD was performed by means of lyophilization followed by dissolution.
And (3) after filtering, adding the filtered solution into a glucan Sephadex G25 column, eluting silk fibroin by using sterilized water, collecting by tubes, and screening to obtain the silk fibroin with the small molecular weight of 1000-5000 Da.
The flow rate of elution is preferably 30-70 mL/h; more preferably 35 to 50 mL/h.
After elution, screening and collecting 1000-5000 Da low-molecular-weight silk fibroin in the tube by SDS-PAGE electrophoresis or mass spectrum, and freeze-drying and storing.
By adopting the method, the silk fibroin with the small molecular weight of 1000-5000 Da can be obtained more simply, conveniently and accurately.
The present invention is not limited to the specific manner of screening and lyophilization, as will be apparent to those skilled in the art.
The invention provides a fibroin modification method of pure cotton fabric, which comprises the following steps: A) desizing the pure cotton fabric to obtain a desized fabric; B) performing oxidation treatment on the desized fabric by using sodium periodate, washing, drying and performing oxidation treatment on sodium chlorite to obtain an oxidized fabric; C) providing silk fibroin with a defined molecular weight of 1000-5000 Da; D) and soaking the oxidized fabric in a cross-linking agent solution, and mixing and reacting with the silk fibroin. According to the modification method provided by the invention, the desized fabric is subjected to sodium periodate oxidation treatment and then is subjected to sodium chlorite oxidation treatment again, and the two oxidation treatments are arranged to release reaction sites at specific positions on a cotton fiber molecular chain; meanwhile, the silk fibroin graft modification oxidized fabric with the relatively small molecular weight of 1000-5000 Da and concentrated distribution is adopted, the silk fibroin with the specific molecular weight is firmly introduced to the fiber surface of the pure cotton fabric by utilizing the principle of covalent bonding, and the softness and the smoothness of the pure cotton fabric are improved, and meanwhile, the mechanical property is good, and the silk fibroin stability is good.
The modified cotton fabric has soft, smooth and cool surface and general skin affinity, and is mainly applied to the development of high-grade underwear, summer clothes and bedding.
The invention preferably adopts the following method to measure the mechanical property of the fabric:
the silk fibroin modified pure cotton fabric is cut into a sample of 15cm multiplied by 30cm, and the sample is measured by a material mechanical property tester.
In order to further illustrate the present invention, the following describes the fibroin modification method of pure cotton fabric in detail with reference to the examples.
Example 1
(1) The method comprises the steps of putting silkworm raw silk into a sodium carbonate aqueous solution with the concentration of 0.2% according to the bath ratio of 1:50(g/mL), treating for three times at the temperature of 98-100 ℃ for 30 minutes each time, then fully cleaning the silk with deionized water, loosening, and drying in an oven to obtain the degummed silkworm fibroin fiber.
(2) Weighing degummed bombyx mori silk fibroin, dissolving in 9.3M lithium bromide aqueous solution according to a bath ratio of 1:15(g/mL), and dissolving at 65 ℃ for 5-7 hours to obtain a bombyx mori silk fibroin dissolving mixed solution.
(3) Weighing glucan G-50 and G-25, respectively putting into sufficient deionized water, boiling water bath for 1.5 hours, cooling at normal temperature, then draining with a glass rod, filling into a hollow column made of glass, preparing a column bed with a volume of 2cm multiplied by 60cm, naturally settling for 2 hours, pressurizing with a peristaltic pump, and balancing the column with 5 times of column volume of deionized water for three times.
(4) When the balance water is lowered to the surface of the column material for the last time, adding 5-15 mL (10-50 mg/mL) of dissolved silk fibroin mixed solution into the glucan G-50, when the silk fibroin mixed solution completely enters the surface of the column material, continuously eluting with sterilized deionized water, and controlling the flow rate of eluent by using a peristaltic pump to be 300 mL/h; collecting effluent liquid in different tubes until silk fibroin is completely drained.
(5) And (3) identifying the molecular weight distribution of each tube by SDS-PAGE electrophoresis or mass spectrometry, mixing and freeze-drying the silk fibroin solution with the molecular weight of less than 10kDa, preparing into 30-80 mg/ml aqueous solution, and filtering by using a 0.45 mu m membrane to remove microparticles.
(6) Similar to the step (4), adding a proper amount of the silk fibroin aqueous solution obtained in the step (5) into the column material of G-25, controlling the flow rate of the eluent by a peristaltic pump to be 50mL/h, collecting the eluent in different tubes until the silk fibroin is completely drained to obtain the silk fibroin aqueous solution with the molecular weight of 1000-5000 Da, and finally freeze-drying and storing.
(7) The woven pure cotton fabric is boiled for about 1 hour by using 6g/1L sodium carbonate aqueous solution, taken out and washed by tap water, dehydrated, aired or dried. And then treating the pure cotton fabric for 2-3 hours at 30 ℃ by using 10g/L sodium periodate solution, rinsing the pure cotton fabric by using tap water, treating the pure cotton fabric for 2 hours by using 0.025M hydrogen peroxide/sodium chlorite mixed solution, soaking the pure cotton fabric in a mixed aqueous solution of carbodiimide and N-hydroxysuccinimide (the mass of the mixed aqueous solution is about 25% and 10% of that of the silk fibroin respectively) with a certain mass concentration for about 1 hour after rinsing, adding the silk fibroin dry powder (the final mass concentration of the silk fibroin is 1%) obtained in the step 6 to dissolve the silk fibroin, reacting for 3 hours, taking out, airing, rinsing and then airing.
(8) The silk fibroin modified pure cotton fabric is cut into a sample of 15cm multiplied by 30cm, the breaking strength is about 88% of the original fabric, and the breaking elongation is about 96% of the original fabric, which are measured by a material mechanical property tester.
(9) The weight gain of the silk fibroin on the pure cotton fabric is measured by adopting a weighing method to be 3.08%, and the dissolution rate of the silk fibroin is measured to be less than 2% after the silk fibroin modified fabric is soaked in warm water at 37 ℃ and oscillated for 24 hours.
Example 2
(1) The method comprises the steps of putting silkworm raw silk into a sodium carbonate aqueous solution with the concentration of 0.2% according to the bath ratio of 1:50(g/mL), treating for three times at the temperature of 98-100 ℃ for 30 minutes each time, then fully cleaning the silk with deionized water, loosening, and drying in an oven to obtain the degummed silkworm fibroin fiber.
(2) Weighing degummed bombyx mori silk fibroin, dissolving in 9.3M lithium bromide aqueous solution according to a bath ratio of 1:15(g/mL), and dissolving at 65 ℃ for 5-7 hours to obtain a bombyx mori silk fibroin dissolving mixed solution.
(3) Weighing glucan G-50 and G-25, respectively putting into sufficient deionized water, boiling water bath for 1.5 hours, cooling at normal temperature, then draining with a glass rod, filling into a hollow column made of glass, preparing a column bed with a volume of 2cm multiplied by 60cm, naturally settling for 2 hours, pressurizing with a peristaltic pump, and balancing the column with 5 times of column volume of deionized water for three times.
(4) When the balance water is lowered to the surface of the column material for the last time, adding 5-15 mL (10-50 mg/mL) of dissolved silk fibroin mixed solution into the glucan G-50, when the silk fibroin mixed solution completely enters the surface of the column material, continuously eluting with sterilized deionized water, and controlling the flow rate of eluent by using a peristaltic pump to be 300 mL/h; collecting effluent liquid in different tubes until silk fibroin is completely drained.
(5) And (3) identifying the molecular weight distribution of each tube by SDS-PAGE electrophoresis or mass spectrometry, mixing and freeze-drying the silk fibroin solution with the molecular weight of less than 10kDa, preparing into 30-80 mg/ml aqueous solution, and filtering by using a 0.45 mu m membrane to remove microparticles.
(6) Similar to the step (4), adding a proper amount of the silk fibroin aqueous solution obtained in the step (5) into the column material of G-25, controlling the flow rate of the eluent by a peristaltic pump to be 50mL/h, collecting the eluent in different tubes until the silk fibroin is completely drained to obtain the silk fibroin aqueous solution with the molecular weight of 1000-5000 Da, and finally freeze-drying and storing.
(7) The woven pure cotton fabric is boiled for about 1 hour by using 6g/1L sodium carbonate aqueous solution, taken out and washed by tap water, dehydrated, aired or dried. And then treating the pure cotton fabric for 2-3 hours at 30 ℃ by using 10g/L sodium periodate solution, rinsing the pure cotton fabric by using tap water, treating the pure cotton fabric for 2 hours by using 0.025M hydrogen peroxide/sodium chlorite mixed solution, soaking the pure cotton fabric in a mixed aqueous solution of carbodiimide and N-hydroxysuccinimide (the mass of the mixed aqueous solution is about 25% and 10% of that of the silk fibroin respectively) with a certain mass concentration for about 1 hour after rinsing, adding the silk fibroin dry powder (the final mass concentration of the silk fibroin is 5%) obtained in the step 6 to dissolve the silk fibroin, reacting for 3 hours, taking out, airing, rinsing and then airing.
(8) The silk fibroin modified pure cotton fabric is cut into a sample of 15cm multiplied by 30cm, the breaking strength is about 87% of the original fabric, and the breaking elongation is about 97% of the original fabric, which are measured by a material mechanical property tester.
(9) The weight gain of silk fibroin on the pure cotton fabric is measured by adopting a weighing method to be 4.9 percent, and the dissolution rate of the silk fibroin is measured to be less than 2 percent after the silk fibroin modified fabric is soaked in warm water at 37 ℃ and oscillated for 24 hours.
Example 3
(1) The method comprises the steps of putting silkworm raw silk into a sodium carbonate aqueous solution with the concentration of 0.2% according to the bath ratio of 1:50(g/mL), treating for three times at the temperature of 98-100 ℃ for 30 minutes each time, then fully cleaning the silk with deionized water, loosening, and drying in an oven to obtain the degummed silkworm fibroin fiber.
(2) Weighing degummed bombyx mori silk fibroin, dissolving in 9.3M lithium bromide aqueous solution according to a bath ratio of 1:15(g/mL), and dissolving at 65 ℃ for 5-7 hours to obtain a bombyx mori silk fibroin dissolving mixed solution.
(3) Weighing glucan G-50 and G-25, respectively putting into sufficient deionized water, boiling water bath for 1.5 hours, cooling at normal temperature, then draining with a glass rod, filling into a hollow column made of glass, preparing a column bed with a volume of 2cm multiplied by 60cm, naturally settling for 2 hours, pressurizing with a peristaltic pump, and balancing the column with 5 times of column volume of deionized water for three times.
(4) When the balance water is lowered to the surface of the column material for the last time, adding 5-15 mL (10-50 mg/mL) of dissolved silk fibroin mixed solution into the glucan G-50, when the silk fibroin mixed solution completely enters the surface of the column material, continuously eluting with sterilized deionized water, and controlling the flow rate of eluent by using a peristaltic pump to be 300 mL/h; collecting effluent liquid in different tubes until silk fibroin is completely drained.
(5) And (3) identifying the molecular weight distribution of each tube by SDS-PAGE electrophoresis or mass spectrometry, mixing and freeze-drying the silk fibroin solution with the molecular weight of less than 10kDa, preparing into 30-80 mg/ml aqueous solution, and filtering by using a 0.45 mu m membrane to remove microparticles.
(6) Similar to the step (4), adding a proper amount of the silk fibroin aqueous solution obtained in the step (5) into the column material of G-25, controlling the flow rate of the eluent by a peristaltic pump to be 50mL/h, collecting the eluent in different tubes until the silk fibroin is completely drained to obtain the silk fibroin aqueous solution with the molecular weight of 1000-5000 Da, and finally freeze-drying and storing.
(7) The woven pure cotton fabric is boiled for about 1 hour by using 6g/1L sodium carbonate aqueous solution, taken out and washed by tap water, dehydrated, aired or dried. And then treating the pure cotton fabric for 2-3 hours at 30 ℃ by using 10g/L sodium periodate solution, rinsing the pure cotton fabric by using tap water, treating the pure cotton fabric for 2 hours by using 0.1M hydrogen peroxide/sodium chlorite mixed solution, soaking the pure cotton fabric in a mixed aqueous solution of carbodiimide and N-hydroxysuccinimide (the mass of the mixed aqueous solution is about 25% and 10% of that of the silk fibroin respectively) with a certain mass concentration after rinsing the pure cotton fabric, soaking the pure cotton fabric for about 1 hour, adding the silk fibroin dry powder (the final mass concentration of the silk fibroin is 5%) obtained in the step 6 to dissolve the silk fibroin, reacting for 3 hours, taking out, airing, rinsing and then airing.
(8) The silk fibroin modified pure cotton fabric is cut into a sample of 15cm multiplied by 30cm, the breaking strength is about 82% of the original fabric, and the breaking elongation is about 95% of the original fabric, which are measured by a material mechanical property tester.
(9) The weight gain of silk fibroin on the pure cotton fabric is measured by adopting a weighing method to be 6.5% (compared with comparative example 3, the weight gain is obviously higher than the grafting effect of silk fibroin containing a large amount of large molecular weight obtained by a conventional preparation method), and the dissolution rate of the silk fibroin is measured to be less than 2% after the silk fibroin modified fabric is soaked in warm water at 37 ℃ and oscillated for 24 hours.
Comparative example 1
(1) The method comprises the steps of putting silkworm raw silk into a sodium carbonate aqueous solution with the concentration of 0.2% according to the bath ratio of 1:50(g/mL), treating for three times at the temperature of 98-100 ℃ for 30 minutes each time, then fully cleaning the silk with deionized water, loosening, and drying in an oven to obtain the degummed silkworm fibroin fiber.
(2) Weighing degummed bombyx mori silk fibroin, dissolving in a calcium chloride-ethanol aqueous solution with a molar ratio of 1:2 according to a bath ratio of 1:20(g/mL), and dissolving at 70 ℃ for 5-7 hours to obtain a bombyx mori silk fibroin dissolved mixed solution.
(3) Weighing glucan G-50 and G-25, respectively putting into sufficient deionized water, boiling water bath for 1.5 hours, cooling at normal temperature, then draining with a glass rod, filling into a hollow column made of glass, preparing a column bed with a volume of 2cm multiplied by 60cm, naturally settling for 2 hours, pressurizing with a peristaltic pump, and balancing the column with 5 times of column volume of deionized water for three times.
(4) When the balance water is lowered to the surface of the column material for the last time, adding 5-15 mL (10-50 mg/mL) of dissolved silk fibroin mixed solution into the glucan G-50, when the silk fibroin mixed solution completely enters the surface of the column material, continuously eluting with sterilized deionized water, and controlling the flow rate of eluent by using a peristaltic pump to be 300 mL/h; collecting effluent liquid in different tubes until silk fibroin is completely drained.
(5) And (3) identifying the molecular weight distribution of each tube by SDS-PAGE electrophoresis or mass spectrometry, mixing and freeze-drying the silk fibroin solution with the molecular weight of less than 10kDa, preparing into 30-80 mg/ml aqueous solution, and filtering by using a 0.45 mu m membrane to remove microparticles.
(6) Similar to the step (4), adding a proper amount of the silk fibroin aqueous solution obtained in the step (5) into the column material of G-25, controlling the flow rate of the eluent by a peristaltic pump to be 50mL/h, collecting the eluent in different tubes until the silk fibroin is completely drained to obtain the silk fibroin aqueous solution with the molecular weight of 1000-5000 Da, and finally freeze-drying and storing.
(7) Boiling the woven pure cotton fabric for about 1 hour by using 6g/1L sodium carbonate aqueous solution, taking out, washing, dehydrating, airing or drying by using tap water, then soaking in a mixed aqueous solution of carbodiimide and N-hydroxysuccinimide (the mass of which is respectively about 25% and 10% of the mass of the silk fibroin) with certain mass concentration for about 1 hour, adding the silk fibroin dry powder (the final mass concentration of the silk fibroin is 1%) obtained in the step 6 to dissolve, reacting for 3 hours, taking out, airing, rinsing and airing again.
(8) The silk fibroin modified pure cotton fabric is cut into a sample of 15cm multiplied by 30cm, the breaking strength is about 100% of the original fabric, and the breaking elongation is about 100% of the original fabric, which is measured by a material mechanical property tester.
(9) The weight gain of the silk fibroin on the pure cotton fabric is measured by adopting a weighing method to be 0.56 percent, and the dissolution rate of the silk fibroin is measured to be more than 50 percent after the silk fibroin modified fabric is soaked in warm water at 37 ℃ and oscillated for 24 hours.
Comparative example 2
(1) The method comprises the steps of putting silkworm raw silk into a sodium carbonate aqueous solution with the concentration of 0.2% according to the bath ratio of 1:50(g/mL), treating for three times at the temperature of 98-100 ℃ for 30 minutes each time, then fully cleaning the silk with deionized water, loosening, and drying in an oven to obtain the degummed silkworm fibroin fiber.
(2) Weighing degummed bombyx mori silk fibroin, dissolving in 9.3M lithium bromide aqueous solution according to a bath ratio of 1:15(g/mL), and dissolving at 65 ℃ for 5-7 hours to obtain a bombyx mori silk fibroin dissolving mixed solution.
(3) Weighing glucan G-50 and G-25, respectively putting into sufficient deionized water, boiling water bath for 1.5 hours, cooling at normal temperature, then draining with a glass rod, filling into a hollow column made of glass, preparing a column bed with a volume of 2cm multiplied by 60cm, naturally settling for 2 hours, pressurizing with a peristaltic pump, and balancing the column with 5 times of column volume of deionized water for three times.
(4) When the balance water is lowered to the surface of the column material for the last time, adding 5-15 mL (10-50 mg/mL) of dissolved silk fibroin mixed solution into the glucan G-50, when the silk fibroin mixed solution completely enters the surface of the column material, continuously eluting with sterilized deionized water, and controlling the flow rate of eluent by using a peristaltic pump to be 300 mL/h; collecting effluent liquid in different tubes until silk fibroin is completely drained.
(5) And (3) identifying the molecular weight distribution of each tube by SDS-PAGE electrophoresis or mass spectrometry, mixing and freeze-drying the silk fibroin solution with the molecular weight of less than 10kDa, preparing into 30-80 mg/ml aqueous solution, and filtering by using a 0.45 mu m membrane to remove microparticles.
(6) Similar to the step (4), adding a proper amount of the silk fibroin aqueous solution obtained in the step (5) into the column material of G-25, controlling the flow rate of the eluent by a peristaltic pump to be 50mL/h, collecting the eluent in different tubes until the silk fibroin is completely drained to obtain the silk fibroin aqueous solution with the molecular weight of 1000-5000 Da, and finally freeze-drying and storing.
(7) The woven pure cotton fabric is boiled for about 1 hour by using 6g/1L sodium carbonate aqueous solution, taken out and washed by tap water, dehydrated, aired or dried. And then treating the pure cotton fabric with 10g/L sodium periodate solution at 30 ℃ for 2-3 hours, rinsing the pure cotton fabric with tap water, soaking the pure cotton fabric in mixed aqueous solution of carbodiimide and N-hydroxysuccinimide (the mass of the mixed aqueous solution is about 25% and 10% of that of the silk fibroin respectively) at certain mass concentration for about 1 hour, adding the silk fibroin dry powder (the final mass concentration of the silk fibroin is 5%) obtained in the step 6 to dissolve the silk fibroin, reacting for 3 hours, taking out, airing, rinsing and airing again.
(8) The silk fibroin modified pure cotton fabric is cut into a sample of 15cm multiplied by 30cm, the breaking strength is about 95% of the original fabric, and the breaking elongation is about 96% of the original fabric, which are measured by a material mechanical property tester.
(9) The weight gain of the silk fibroin on the pure cotton fabric is measured by adopting a weighing method to be 2.33 percent, and the dissolution rate of the silk fibroin is measured to be more than 50 percent after the silk fibroin modified fabric is soaked in warm water at 37 ℃ and oscillated for 24 hours.
Comparative example 3
(1) The method comprises the steps of putting silkworm raw silk into a sodium carbonate aqueous solution with the concentration of 0.2% according to the bath ratio of 1:50(g/mL), treating for three times at the temperature of 98-100 ℃ for 30 minutes each time, then fully cleaning the silk with deionized water, loosening, and drying in an oven to obtain the degummed silkworm fibroin fiber.
(2) Weighing degummed bombyx mori silk fibroin, dissolving in 9.3M lithium bromide aqueous solution according to a bath ratio of 1:15(g/mL), and dissolving at 65 ℃ for 5-7 hours to obtain a bombyx mori silk fibroin dissolving mixed solution.
(3) The silkworm fibroin dissolving solution is filled into a dialysis bag, the wall of the dialysis bag is a semipermeable membrane, the molecular weight cutoff is within the range of 12.0-16.0 kDa, the dialysis bag filled with the silkworm fibroin dissolving solution is placed into a container filled with deionized water, the water in the container is replaced by new deionized water or pure water every 2 hours, dialysis is continued for 3 days, and a purified silkworm fibroin aqueous solution (the preparation of a conventional fibroin aqueous solution) is obtained and then freeze-dried for storage.
(4) Boiling a woven pure cotton fabric for about 1 hour by using 6g/1L of sodium carbonate aqueous solution, taking out, washing, dehydrating, airing or drying by using tap water, treating the pure cotton fabric for 2-3 hours at 30 ℃ by using 10g/L of sodium periodate solution, treating the pure cotton fabric for 2 hours by using 0.1M of hydrogen peroxide/sodium chlorite mixed solution, soaking the pure cotton fabric for about 1 hour in a mixed aqueous solution of carbodiimide and N-hydroxysuccinimide (the mass of each of the solutions is about 25% and 10% of the mass of the silk fibroin), adding the freeze-dried silk fibroin (the final mass concentration of the silk fibroin is 5%) obtained in the step 3, dissolving the mixture, reacting for 3 hours, taking out, airing, rinsing and airing.
(8) The silk fibroin modified pure cotton fabric is cut into a sample of 15cm multiplied by 30cm, the breaking strength is about 83% of the original fabric, and the breaking elongation is about 94% of the original fabric, which is measured by a material mechanical property tester.
(9) The weight gain of the silk fibroin on the pure cotton fabric is measured by adopting a weighing method to be 2.3 percent, and the dissolution rate of the silk fibroin is measured to be less than 10 percent after the silk fibroin modified fabric is soaked in warm water at 37 ℃ and oscillated for 24 hours.
Comparative example 4
(1) The method comprises the steps of putting silkworm raw silk into a sodium carbonate aqueous solution with the concentration of 0.2% according to the bath ratio of 1:50(g/mL), treating for three times at the temperature of 98-100 ℃ for 30 minutes each time, then fully cleaning the silk with deionized water, loosening, and drying in an oven to obtain the degummed silkworm fibroin fiber.
(2) Weighing degummed bombyx mori silk fibroin, dissolving in 9.3M lithium bromide aqueous solution according to a bath ratio of 1:15(g/mL), and dissolving at 65 ℃ for 5-7 hours to obtain a bombyx mori silk fibroin dissolving mixed solution.
(3) Weighing glucan G-50 and G-25, respectively putting into sufficient deionized water, boiling water bath for 1.5 hours, cooling at normal temperature, then draining with a glass rod, filling into a hollow column made of glass, preparing a column bed with a volume of 2cm multiplied by 60cm, naturally settling for 2 hours, pressurizing with a peristaltic pump, and balancing the column with 5 times of column volume of deionized water for three times.
(4) When the balance water is lowered to the surface of the column material for the last time, adding 5-15 mL (10-50 mg/mL) of dissolved silk fibroin mixed solution into the glucan G-50, when the silk fibroin mixed solution completely enters the surface of the column material, continuously eluting with sterilized deionized water, and controlling the flow rate of eluent by using a peristaltic pump to be 300 mL/h; collecting effluent liquid in different tubes until silk fibroin is completely drained.
(5) And (3) identifying the molecular weight distribution of each tube by SDS-PAGE electrophoresis or mass spectrometry, mixing and freeze-drying the silk fibroin solution with the molecular weight of less than 10kDa, preparing into 30-80 mg/ml aqueous solution, and filtering by using a 0.45 mu m membrane to remove microparticles.
(6) Similar to the step (4), adding a proper amount of the silk fibroin aqueous solution obtained in the step (5) into the column material of G-25, controlling the flow rate of the eluent by a peristaltic pump to be 50mL/h, collecting the eluent in different tubes until the silk fibroin is completely drained to obtain the silk fibroin aqueous solution with the molecular weight of 1000-5000 Da, and finally freeze-drying and storing.
(7) Boiling the woven pure cotton fabric for about 1 hour by using 6g/1L of sodium carbonate aqueous solution, taking out, washing with tap water, dehydrating, airing or drying; and then treating the silk fibroin powder with 0.1M hydrogen peroxide/sodium chlorite mixed solution for 2 hours, rinsing, soaking the silk fibroin powder in a mixed aqueous solution of carbodiimide and N-hydroxysuccinimide (the mass of the mixed aqueous solution is about 25 percent and 10 percent of the mass of the added silk fibroin respectively) with certain mass concentration for about 1 hour, adding the silk fibroin powder obtained in the step 6 (the final mass concentration of the silk fibroin is 5 percent) to dissolve the silk fibroin powder, reacting for 3 hours, taking out, drying in the air, rinsing and drying in the air again.
(8) The silk fibroin modified pure cotton fabric is cut into a sample of 15cm multiplied by 30cm, the breaking strength is about 85% of the original fabric, and the breaking elongation is about 97% of the original fabric, which are measured by a material mechanical property tester.
(9) The weight gain of silk fibroin on the pure cotton fabric is measured by adopting a weighing method to be 3.2 percent, and the dissolution rate of the silk fibroin is measured to be less than 2 percent after the silk fibroin modified fabric is soaked in warm water at 37 ℃ and oscillated for 24 hours.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A fibroin modification method for pure cotton fabric is characterized by comprising the following steps:
A) desizing the pure cotton fabric to obtain a desized fabric;
B) performing oxidation treatment on the desized fabric by using sodium periodate, washing and performing oxidation treatment on sodium chlorite to obtain an oxidized fabric;
C) providing silk fibroin with the molecular weight of 1000-5000 Da;
the silk fibroin with the molecular weight of 1000-5000 Da is prepared by the following method:
a) degumming silkworm silk by using sodium carbonate, and then adding a neutral salt solution to dissolve to prepare a silk fibroin dissolving solution; the neutral salt solution is selected from lithium bromide or calcium chloride-ethanol; the dissolving time is 5-7 hours; the concentration of the silk fibroin dissolving solution is 10-50 mg/mL;
the dextran Sephadex G50 and G25 columns are balanced for standby;
b) adding the silk fibroin dissolving solution into a glucan Sephadex G50 column, eluting the silk fibroin with sterile water, and collecting desalted silk fibroin aqueous solution in a branch pipe; the elution flow rate is 200-400 mL/h;
c) screening the silk fibroin with the molecular weight of less than 10kD in the collection tube in the step b) by SDS-PAGE electrophoresis or mass spectrometry, adding the silk fibroin into a dextran Sephadex G25 column again, eluting the silk fibroin by using sterilized water, collecting the silk fibroin in different tubes, and screening to obtain the silk fibroin with the small molecular weight of 1000-5000 Da; the elution flow rate is 30-70 mL/h;
D) soaking the oxidized fabric in a cross-linking agent solution, and mixing and reacting with the silk fibroin; the crosslinking agent includes carbodiimide.
2. The method as claimed in claim 1, wherein the carbodiimide accounts for 20-40% by mass of the silk fibroin.
3. The method according to claim 1, characterized in that the desizing in step a) is in particular a desizing treatment with sodium carbonate; the concentration of the sodium carbonate solution is 6 g/L; the desizing treatment temperature is 90-100 ℃; the desizing treatment time is 1 h.
4. The method according to claim 1, wherein the concentration of the sodium periodate in step B) is 10 g/L; the oxidation temperature of the sodium periodate is 30-40 ℃; the oxidation time of the sodium periodate is 1-3 h; the concentration of the sodium chlorite is 0.025-0.1M; the oxidation temperature of the sodium chlorite is 30-40 ℃; the oxidation time of the sodium chlorite is 1-2 h.
5. The method according to claim 1, wherein the reaction temperature in step D) is 25-35 ℃; the reaction time is 1-3 h.
6. The method of claim 1, wherein the step c) of screening the silk fibroin with a molecular weight of less than 10kD in the collection tube of step b) further comprises freeze-drying, and then preparing into an aqueous solution of 30-80 mg/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711223677.1A CN107956118B (en) | 2017-11-29 | 2017-11-29 | Fibroin modification method of pure cotton fabric |
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| CN105133287A (en) * | 2015-08-19 | 2015-12-09 | 张家港市金陵纺织有限公司 | Manufacture method for all-cotton super-soft silk-protein silk-like yarn-dyed fabric |
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Denomination of invention: A Silk Protein Modification Method for Pure Cotton Fabric Granted publication date: 20201016 Pledgee: Agricultural Bank of China Limited Nantong TongZhou sub branch Pledgor: JIANGSU BERMO HOME TEXTILE TECHNOLOGY CO.,LTD. Registration number: Y2024980010714 |
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