CN107956118A - A kind of fibroin method of modifying of pure-cotton fabric - Google Patents
A kind of fibroin method of modifying of pure-cotton fabric Download PDFInfo
- Publication number
- CN107956118A CN107956118A CN201711223677.1A CN201711223677A CN107956118A CN 107956118 A CN107956118 A CN 107956118A CN 201711223677 A CN201711223677 A CN 201711223677A CN 107956118 A CN107956118 A CN 107956118A
- Authority
- CN
- China
- Prior art keywords
- fibroin
- fibroin albumen
- fabric
- destarch
- pure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 108010022355 Fibroins Proteins 0.000 title claims abstract description 215
- 239000004744 fabric Substances 0.000 title claims abstract description 121
- 229920000742 Cotton Polymers 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 48
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims abstract description 54
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 49
- 230000003647 oxidation Effects 0.000 claims abstract description 48
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims abstract description 25
- 229960002218 sodium chlorite Drugs 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 23
- 238000012545 processing Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 93
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 43
- 241000255789 Bombyx mori Species 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 33
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 27
- 229920001503 Glucan Polymers 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 24
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 20
- 238000010828 elution Methods 0.000 claims description 15
- 229920005654 Sephadex Polymers 0.000 claims description 14
- 239000012507 Sephadex™ Substances 0.000 claims description 14
- 238000012216 screening Methods 0.000 claims description 14
- 238000001962 electrophoresis Methods 0.000 claims description 12
- 238000002415 sodium dodecyl sulfate polyacrylamide gel electrophoresis Methods 0.000 claims description 12
- 239000006166 lysate Substances 0.000 claims description 11
- 150000001718 carbodiimides Chemical class 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 8
- 230000001954 sterilising effect Effects 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 7
- 238000001819 mass spectrum Methods 0.000 claims description 6
- 238000010612 desalination reaction Methods 0.000 claims description 4
- 238000011067 equilibration Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- JOAISNMPBNLOCX-UHFFFAOYSA-N [Ca].CCO Chemical compound [Ca].CCO JOAISNMPBNLOCX-UHFFFAOYSA-N 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 150000003384 small molecules Chemical class 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 16
- 239000008367 deionised water Substances 0.000 description 33
- 229910021641 deionized water Inorganic materials 0.000 description 33
- 239000011259 mixed solution Substances 0.000 description 26
- 230000002572 peristaltic effect Effects 0.000 description 20
- 238000009835 boiling Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- 235000013601 eggs Nutrition 0.000 description 15
- 239000011521 glass Substances 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 239000003480 eluent Substances 0.000 description 13
- 230000004048 modification Effects 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 238000007598 dipping method Methods 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 229940059936 lithium bromide Drugs 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 230000037396 body weight Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000005374 membrane filtration Methods 0.000 description 7
- 239000012460 protein solution Substances 0.000 description 7
- 239000011800 void material Substances 0.000 description 7
- 235000019786 weight gain Nutrition 0.000 description 7
- 101710198774 Envelope protein US9 Proteins 0.000 description 6
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 6
- 239000011859 microparticle Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010129 solution processing Methods 0.000 description 5
- GDESEHSRICGNDP-UHFFFAOYSA-L [Cl-].[Cl-].[Ca+2].CCO Chemical compound [Cl-].[Cl-].[Ca+2].CCO GDESEHSRICGNDP-UHFFFAOYSA-L 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 2
- 102000002322 Egg Proteins Human genes 0.000 description 2
- 108010000912 Egg Proteins Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000014103 egg white Nutrition 0.000 description 2
- 210000000969 egg white Anatomy 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 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
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 150000004753 Schiff bases Chemical group 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- OEMUKJZHMHTYSL-UHFFFAOYSA-N [Na].OCl=O Chemical compound [Na].OCl=O OEMUKJZHMHTYSL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229960002317 succinimide Drugs 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 present invention provides a kind of fibroin method of modifying of pure-cotton fabric, including：Pure-cotton fabric destarch is handled, obtains the fabric of destarch；The fabric of destarch is handled using sodium periodate oxidation, washing, sodium chlorite oxidation processes, the fabric after being aoxidized；The fibroin albumen of 1000~5000Da molecular weight is provided；Fabric after oxidation is impregnated in cross-linking agent solution, with the fibroin albumen hybrid reaction.For the fabric that the method for modifying of the present invention handles destarch using sodium chlorite oxidation processes are used again after sodium periodate oxidation processing, the setting of oxidation processes twice make it that specific location discharges reaction site on cotton fiber strand；Fabric after the fibroin albumen of the present invention 1000~5000Da molecular weight is modified oxidized, the fibroin albumen for causing specific small-molecular-weight using covalently bound principle firmly introduces the fiber surface of pure-cotton fabric, and the flexibility, slipping, mechanical property for improving pure-cotton fabric are good, silk-fibroin stability is good.
Description
Technical field
The present invention relates to textile technology field, more particularly, to a kind of fibroin method of modifying of pure-cotton fabric.
Background technology
Cotton fiber is a kind of most natural material of textile garment field application, has substantial amounts of hydroxyl and has preferable suction
Moist, thermal conductivity factor is small and fabric is had preferable thermal property.But cotton fiber is rigidly big, the skin contact of product have impact on
Sense, and there was only hydroxyl on strand, limit the functional modification of fiber.Silk is a kind of natural protein fibre, has pole
Hygroscopicity well, breathable moisture permeability, soft smooth skin-friendly, the friction to skin stimulate the more other kinds fiber of coefficient low
It is more；Also there is excellent anti-oxidant, anti-ultraviolet property, show consideration for and safely take good care of per one-inch skin.Silk-fibroin point
Son can use electrostatic attraction or covalently bound principle to introduce the various functions factor, promote the innovation liter of textile application value
Level.Therefore surface modification can be carried out to cotton with fibroin.
Modification on cotton has some reports, as cotton can improve gloss (mercerized cotton), dye after naoh treatment
Color performance, becomes smooth, but intensity declines；Biology enzyme is and for example grafted to by cotton fibre by modes such as covalent bonding, absorption, crosslinkings
Improve the effect (the returning old arrangement of denim) of vision and feel in dimension.Silk-fibroin on cotton is modified, and the prior art discloses
Research select sodium periodate oxidation cotton fiber, then reacted with the amino on silk gum or fibroin albumen, but aoxidize what is produced
The schiff base structure that aldehyde radical is formed with amino is unstable.Have document using cotton fabric dipping fibroin albumen film forming after methanol not
Processing is dissolved, fibroin albumen is coated in surface of cotton fabric, this mode is modified the surface texture, brittle and easily de- that can influence fabric
Fall.The Silk Protein Molecules amount dispersiveness that the cotton fabric silk-fibroin of existing report is modified is very big, and with tens of thousands of dividing greatly to hundreds of thousands
Son is in the majority, and the fibroin albumen of macromolecular not only influences grafting efficiency, but also easily forms a film, is hard, influencing surface texture and easily come off.
In short, the research that the fibroin of comfortable pro-skin carries out cotton fiber or fabric surface modification is few, yet applied without market.
The content of the invention
In view of this, the technical problem to be solved in the present invention is the fibroin modification side for providing a kind of pure-cotton fabric
Method, pure-cotton fabric mechanical property that method of modifying provided by the invention is modified is good, stability is good.
The present invention provides a kind of fibroin method of modifying of pure-cotton fabric, including：
A) pure-cotton fabric destarch is handled, obtains the fabric of destarch；
B) fabric of destarch is handled using sodium periodate oxidation, washing, sodium chlorite oxidation processes, after being aoxidized
Fabric；
C) fibroin albumen of the 1000~5000Da molecular weight limited is provided；
D) fabric after oxidation is impregnated in cross-linking agent solution, with the fibroin albumen hybrid reaction.
Preferably, the crosslinking agent includes carbodiimides.
Preferably, the mass percent that the carbodiimides accounts for fibroin albumen is 20%~40%.
Preferably, step A) destarch is specially to be handled using sodium carbonate destarch；The concentration of the sodium carbonate liquor is
6g/L；The destarch treatment temperature is 90~100 DEG C；The destarch processing time is 1h.
Preferably, step B) concentration of the sodium metaperiodate is 10g/L；The temperature of the oxidation of the sodium metaperiodate for 30~
40℃；The time of the oxidation of the sodium metaperiodate is 1~3h；The concentration of the sodium chlorite is 0.025~0.1M；The Asia chlorine
The temperature of the oxidation of sour sodium is 30~40 DEG C；The time of the oxidation of the sodium chlorite is 1~2h.
Preferably, step D) reaction temperature is 25~35 DEG C；The reaction time is 1~3h.
Preferably, the fibroin albumen of 1000~5000Da molecular weight is prepared as follows：
A) silkworm silk is subjected to degumming using sodium carbonate and then adds neutral salt solution dissolving, it is molten to prepare fibroin albumen
Solve liquid；
Glucan Sephadex G50 and G25 column equilibrations is stand-by；
B) fibroin albumen lysate is added in glucan Sephadex G50 columns, with sterilizing water elution fibroin albumen, divided
Pipe collects the silk fibroin water solution of desalination；
C) using the fibroin albumen of below 10kD in SDS-PAGE electrophoresis or mass spectrum screening step b) collecting pipes, add again
In glucan Sephadex G25 columns, with sterilizing water elution fibroin albumen, it is in charge of collection, screening obtains the small of 1000~5000Da
Molecular weight fibroin albumen.
Preferably, the step a) neutral salt solutions are selected from lithium bromide or calcium chloride-ethanol；The dissolution time is 5~7
Hour；The fibroin albumen lysate concentration is 10~50mg/mL.
Preferably, further included in the step c) screening step b) collecting pipes after the fibroin albumen of below 10kD it is lyophilized and
After be configured to 30~80mg/mL aqueous solutions.
Preferably, the step b) elution flow rates are 200~400mL/h；Step c) the elution flow rates are 30~70mL/
h。
Compared with prior art, the present invention provides a kind of fibroin method of modifying of pure-cotton fabric, including：A) will be pure
Cotton face fabric destarch is handled, and obtains the fabric of destarch；B) fabric of destarch is handled using sodium periodate oxidation, washing, chlorous acid
Sodium oxidation processes, the fabric after being aoxidized；C) fibroin albumen of the 1000~5000Da molecular weight limited is provided；D) will oxidation
Fabric afterwards is impregnated in cross-linking agent solution, with the small-molecular-weight fibroin albumen hybrid reaction.Modification side provided by the invention
The fabric that method handles destarch uses sodium chlorite oxidation processes again after being handled using sodium periodate oxidation, above-mentioned to aoxidize twice
The setting of processing make it that specific location discharges reaction site on cotton fiber strand；Meanwhile the present invention is using 1000 limited
~5000Da relative molecular weights are smaller and the fibroin albumen graft modification of integrated distribution oxidation after fabric, utilize covalent bond
Principle make it that the fibroin albumen of above-mentioned specific small-molecular-weight firmly introduces the fiber surface of pure-cotton fabric, improve pure-cotton fabric
Flexibility, slipping while mechanical property be good, silk-fibroin stability is good.
Embodiment
The present invention provides a kind of fibroin method of modifying of pure-cotton fabric, including：
A) pure-cotton fabric destarch is handled, obtains the fabric of destarch；
B) fabric of destarch is handled using sodium periodate oxidation, washing, sodium chlorite oxidation processes, after being aoxidized
Fabric；
C) fibroin albumen of 1000~5000Da molecular weight is provided；
D) fabric after oxidation is impregnated in cross-linking agent solution, with the fibroin albumen hybrid reaction.
The present invention for the pure-cotton fabric without limit, can be cotton fiber fabric, can be mechanism pure-cotton fabric,
Its cotton fiber content is well known to those skilled in the art to be defined as pure-cotton fabric without limiting.The present invention is right
Can be commercially available in its source without limiting.
The present invention first will be handled pure-cotton fabric destarch, obtain the fabric of destarch.
In the present invention, the destarch processing is preferably handled using sodium carbonate destarch；It is preferred that it is specially that pure-cotton fabric exists
The heated in water solution of sodium carbonate.The mode of the heating is preferably to boil heating.
The concentration of the sodium carbonate liquor is preferably 6g/L；The destarch treatment temperature is preferably 90~100 DEG C；It is described de-
It is preferably 1h to starch processing time.
After heating, preferably wash, be dehydrated, drying.
Washing of the present invention is preferably originally water washing, the present invention for the mode of washing without limiting, ability
Known to field technique personnel；The present invention for the dewatering type without limit, it is well known to those skilled in the art i.e.
Can；The present invention for the drying mode without limit, it is well known to those skilled in the art；Can be to dry or dry
It is dry.
The fabric of destarch is obtained after drying, the fabric of destarch is handled using sodium periodate oxidation.
In the present invention, the concentration of the sodium metaperiodate is preferably 10g/L；The temperature of the oxidation of the sodium metaperiodate is preferred
For 30~40 DEG C；The time of the oxidation of the sodium metaperiodate is preferably 1~3h；
Source of the invention for the sodium metaperiodate is commercially available without limiting.
After sodium metaperiodate processing, preferably wash, dry.
Washing of the present invention is preferably originally water washing, the present invention for the mode of washing without limiting, ability
Known to field technique personnel；The present invention for the drying mode without limit, it is well known to those skilled in the art i.e.
Can；Can be to dry or dry.
After fabric washing, drying, using sodium chlorite oxidation processes, the fabric after being aoxidized.
In the present invention, the concentration of the sodium chlorite is 0.025~0.1M；The temperature of the oxidation of the sodium chlorite is
30~40 DEG C；The time of the oxidation of the sodium chlorite is 1~2h.
The present invention preferably can also be to be handled using sodium chlorite and hydrogen peroxide mixed oxidization, the fabric after being aoxidized.
In the present invention, it is described in the present invention, the concentration of sodium chlorite and the dioxygen water mixed liquid for 0.025~
0.1M；The temperature of the oxidation is 30~40 DEG C；The time of the oxidation is 1~2h.
The present invention, without limiting, preferably can be 1 for the sodium chlorite and hydrogen peroxide mixed proportion：1.
After the completion of oxidation, the fabric after oxidation is impregnated in cross-linking agent solution, the silk with 1000~5000Da molecular weight
Fibroin hybrid reaction, obtains the modified pure-cotton fabric of silk-fibroin.
According to the present invention, the crosslinking agent includes carbodiimides；The crosslinking agent can also include N- acyl group succinyls
Imines；Wherein, the mass percent that the carbodiimides accounts for fibroin albumen is preferably 20%~40%；More preferably 25%.
The mass percent that the N- acylsuccinimides account for fibroin albumen is preferably 10%.
According to the present invention, after dipping, the fibroin albumen for adding the 1000~5000Da molecular weight being prepared is grafted
Reaction, final silk fibroin protein solution concentration is preferably 1-5%；
The reaction temperature is preferably 25~35 DEG C；The reaction time is preferably 1~3h.
After graft reaction, preferably dry, washing, dry again.
Drying of the present invention is preferably to dry；The washing is preferably water rinsing；The drying again is preferably to dry.
The present invention for the concrete operations dried and rinse without restriction, it is well known to those skilled in the art.
In the present invention, the fibroin albumen is relative molecular weight is smaller and the fibroin albumen of integrated distribution.
Fabric after the fibroin albumen graft modification oxidation of the small-molecular-weight using above-mentioned restriction of the invention, profit
Cause the fibroin albumen of above-mentioned specific small-molecular-weight firmly to introduce the fiber surface of pure-cotton fabric with covalently bound principle, carry
Flexibility, slipping, the refrigerant and glossiness of high pure-cotton fabric, improve the compatibility of skin, while mechanical property is good, silk egg
White stability is good.
The present invention for 1000~5000Da molecular weight fibroin albumen source without limit, can be it is commercially available,
It is preferred that prepare with the following method：
A) silkworm silk is subjected to degumming using sodium carbonate and then adds neutral salt solution dissolving, it is molten to prepare fibroin albumen
Solve liquid；
Glucan Sephadex G50 and G25 column equilibrations is stand-by；
B) fibroin albumen lysate is added in glucan Sephadex G50 columns, with sterilizing water elution fibroin albumen, divided
Pipe collects the silk fibroin water solution of desalination；
C) using the fibroin albumen of below 10kD in SDS-PAGE electrophoresis or mass spectrum screening step b) collecting pipes, add again
In glucan Sephadex G25 columns, with sterilizing water elution fibroin albumen, it is in charge of collection, screening obtains the small of 1000~5000Da
Molecular weight fibroin albumen.
Silkworm silk is carried out degumming by the present invention using sodium carbonate first；It is preferred that it is specially according to specific bath by silkworm silk
Than being put into aqueous sodium carbonate, handle, cleaning, is dried to obtain silk after degumming.
For the present invention for the silkworm silk without limiting, silkworm raw silk well known to those skilled in the art can
Think commercially available.
Bath raio of the present invention is preferably 1:50(g/mL)；The mass concentration of the aqueous sodium carbonate is preferably 0.2%；
The treatment temperature is preferably 98~100 DEG C；The number of processes is preferably 1~5 time；More preferably 2~3 times；It is described each
Processing time is preferably 30min.
Cleaned after being disposed, be dried to obtain silk after degumming.
It is of the present invention cleaning be preferably deionized water washing, the present invention for the cleaning way without limit, this
Known to field technology personnel；It is preferably well known to those skilled in the art pull loose after cleaning；The present invention is for described dry
Dry mode is well known to those skilled in the art without limiting；Can be dry in baking oven.The drying temperature is preferably
65℃。
By the silk after degumming and then neutral salt solution dissolving is added, prepares fibroin albumen lysate.
In the present invention, the neutral salt solution is preferably selected from lithium bromide or calcium chloride-ethanol；The silk and neutral salt
The bath raio of solution dissolving is preferably 1:15~1:20(g/mL)；
The concentration of the lithium-bromide solution is preferably 9~10M；In the calcium chloride-ethanol, mole of calcium chloride and ethanol
Than being preferably 1:2；
When the dissolution time is 5~7 small；The solution temperature is preferably 60 DEG C~70 DEG C；More preferably 65 DEG C~70
℃；The obtained fibroin albumen lysate concentration is preferably 10~50mg/mL.
Glucan Sephadex G50 and G25 column equilibrations is stand-by.The present invention is for the glucan Sephadex G50
Source with G25 columns can be commercially available without limiting, or self-control.
It is preferred that it is specially：The boiling of glucan Sephadex G50 and G25 sterile deionized water is boiled to abundant and is expanded, continuously
Pour into the hollow column of glass material, standing sedimentation simultaneously balances column material with sterile deionized water；More preferably it is specially：Portugal is gathered
Sugared G-50 and G-25 are respectively put into deionized water, 1.5~2h of boiling water bath, are drained after room temperature cooling with glass bar and are loaded glass
In the void column of material, when natural subsidence 2~3 is small after pressurizeed with peristaltic pump, the deionized water balance pillar of 5 times of column volumes three times.
The bed volume of the present invention for preparing is preferably 2cm × 60cm.
After balance, fibroin albumen lysate is added in glucan Sephadex G50 columns, with sterilizing water elution fibroin egg
In vain, it is in charge of the silk fibroin water solution for collecting desalination.
It is preferred that it is specially：Last time adds dissolving into glucan G-50 when equilibrium water drops to column material surface
Concentration be 10~50mg/mL fibroin albumen 5~15mL of mixed solution, when fibroin albumen mixed solution is completely into column material
When expecting surface, continue to be eluted with sterile deionized water, peristaltic pump control eluent flow rate, is in charge of collection efflux, until flowing to end
Fibroin albumen.
The elution flow rate is preferably 200~400mL/h；More preferably 250~350mL/h.
Using the fibroin albumen of below 10kD in SDS-PAGE electrophoresis or mass spectrum screening step b) collecting pipes.
Fibroin albumen of the present invention for below 10kD in the SDS-PAGE electrophoresis or mass spectrum screening step b) collecting pipes
Concrete mode without limit, it is well known to those skilled in the art.
In the present invention, further included in the screening step b) collecting pipes after the fibroin albumen of below 10kD lyophilized, then
It is configured to 30~80mg/mL aqueous solutions.Then filter, filtering of the present invention is preferably the membrane filtration using 0.45 μm.
The present invention for the lyophilized concrete mode without limit, it is well known to those skilled in the art.
Using it is lyophilized then dissolve by the way of carry out below 10kD fibroin albumen molecular weight further separation.
After filtering, solution after filtering is added in glucan Sephadex G25 columns, with sterilizing water elution fibroin albumen, is divided
Pipe is collected, and screening obtains the small-molecular-weight fibroin albumen of 1000~5000Da.
The flow velocity of elution of the present invention is preferably 30~70mL/h；More preferably 35~50mL/h.
After elution, using the small-molecular-weight fibroin egg of 1000~5000Da in SDS-PAGE electrophoresis or mass spectrum screening collecting pipe
In vain, then freeze and preserve.
The present invention can the easier small-molecular-weight fibroin egg for more accurately obtaining 1000~5000Da using aforesaid way
In vain.
The present invention for the screening and lyophilized concrete mode without limiting, it is well known to those skilled in the art i.e.
Can.
The present invention provides a kind of fibroin method of modifying of pure-cotton fabric, including：A) pure-cotton fabric destarch is handled,
Obtain the fabric of destarch；B) fabric of destarch is handled using sodium periodate oxidation, washing and drying, sodium chlorite oxidation processes,
Fabric after being aoxidized；C) fibroin albumen of the molecular weight of the 1000~5000Da limited is provided；D) by the fabric after oxidation
It is impregnated in cross-linking agent solution, with the fibroin albumen hybrid reaction.The face that method of modifying provided by the invention handles destarch
For material using sodium chlorite oxidation processes are used again after sodium periodate oxidation processing, the setting of above-mentioned oxidation processes twice causes cotton
Specific location discharges reaction site on fiber molecule chain；Meanwhile the present invention is using restriction 1000~5000Da relative molecular weights
Fabric after smaller and integrated distribution fibroin albumen graft modification oxidation, is caused above-mentioned specific using covalently bound principle
The fibroin albumen of molecular weight firmly introduces the fiber surface of pure-cotton fabric, improves the flexibility of pure-cotton fabric, slipping, at the same time
Mechanical property is good, silk-fibroin stability is good.
It is the modified obtained cotton face fabric soft surface of the present invention, smooth, refrigerant, there is soyeux skin compatibility, production
Product are mainly used in high-grade underwear, the summer hangs out and the exploitation of bedding.
The mechanical property of fabric is measured present invention preferably employs following manner：
The pure-cotton fabric that fibroin albumen is modified is cut into the sample of 15cm × 30cm, using material mechanical performance testing machine
Measure.
In order to further illustrate the present invention, the fibroin of pure-cotton fabric provided by the invention is changed with reference to embodiments
Property method is described in detail.
Embodiment 1
(1) silkworm raw silk is pressed 1:The bath raio of 50 (g/mL) is put into the aqueous sodium carbonate that concentration is 0.2%, in 98~
Silk three times, 30 minutes per treatment, is then fully cleaned up, pulled loose by 100 DEG C of processing with deionized water, is placed in baking oven and is done
It is dry, obtain the bombyx mori silk fibroin fiber after degumming.
(2) bombyx mori silk fibroin after degumming is weighed by 1:The bath raio of 15 (g/mL) is dissolved in 9.3M lithium bromide water solutions, and 65
DEG C dissolving 5~7 it is small when obtain bombyx mori silk fibroin dissolving mixed solution.
(3) glucan G-50 and G-25 are weighed to be respectively put into the deionized water of abundance, when boiling water bath 1.5 is small, treats room temperature
After cooling with glass bar drain load glass material void column in, prepare bed volume 2cm × 60cm, when natural subsidence 2 is small after
Pressurizeed with peristaltic pump, the deionized water balance pillar of 5 times of column volumes three times.
(4) for the last time when equilibrium water drops to column material surface, the fibroin egg of dissolving is added into glucan G-50
White 5~15ml of mixed solution (10~50mg/ml), when fibroin albumen mixed solution is completely into column material surface, continues
Eluted with sterile deionized water, peristaltic pump control eluent flow rate 300mL/h；It is in charge of collection efflux, until flowing to end fibroin egg
In vain.
(5) using the molecular weight distribution of SDS-PAGE electrophoresis or each pipe of Mass Spectrometric Identification, by fibroin of the molecular weight less than 10kDa
Protein solution is freeze-dried mixed, is then configured to the aqueous solution of 30~80mg/ml, and microparticle is removed with 0.45 μm of membrane filtration.
(6) similar step (4), the silk fibroin water solution of appropriate step (5), peristaltic pump control are added to the column material of G-25
Eluent flow rate 50mL/h processed, is in charge of collection efflux, until flowing to end fibroin albumen, obtains the silk of 1000~5000Da molecular weight
Fibroin aqueous solution, finally freezes and preserves.
(7) by woven pure-cotton fabric with the boiling of the aqueous sodium carbonate of 6g/1L boil 1 it is small when or so, take out with originally water washing,
It is dehydrated, dry or dries.Then use 30 DEG C of 10g/L sodium periodate solutions at handle pure-cotton fabric 2~3 it is small when, tap water rinse
When using 0.025M hydrogen peroxide/sodium chlorite mixed solution processing 2 small after clean, the carbonization of certain mass concentration is impregnated in after rinsing
The mixed aqueous solution of diimine and n-hydroxysuccinimide (quality, which respectively may be about, adds 25%, the 10% of fibroin albumen quality)
In, when dipping 1 is small or so, add fibroin albumen dry powder (fibroin albumen final mass concentration is 1%) dissolving that step 6 obtains
Afterwards, 3h is reacted, taking-up is dried, rinsed, drying again.
(8) pure-cotton fabric that fibroin albumen is modified is cut into the sample of 15cm × 30cm, is tried using material mechanical performance
The machine of testing measures 88% or so that fracture strength is original fabric, and elongation at break is 96% or so of original fabric.
(9) the fibroin albumen rate of body weight gain 3.08% on pure-cotton fabric, the face that fibroin albumen is modified are measured using weight method
After material is impregnated in when vibration 24 is small in 37 DEG C of warm water, the dissolve-loss ratio for measuring fibroin albumen is less than 2%.
Embodiment 2
(1) silkworm raw silk is pressed 1:The bath raio of 50 (g/mL) is put into the aqueous sodium carbonate that concentration is 0.2%, in 98~
Silk three times, 30 minutes per treatment, is then fully cleaned up, pulled loose by 100 DEG C of processing with deionized water, is placed in baking oven and is done
It is dry, obtain the bombyx mori silk fibroin fiber after degumming.
(2) bombyx mori silk fibroin after degumming is weighed by 1:The bath raio of 15 (g/mL) is dissolved in 9.3M lithium bromide water solutions, and 65
DEG C dissolving 5~7 it is small when obtain bombyx mori silk fibroin dissolving mixed solution.
(3) glucan G-50 and G-25 are weighed to be respectively put into the deionized water of abundance, when boiling water bath 1.5 is small, treats room temperature
After cooling with glass bar drain load glass material void column in, prepare bed volume 2cm × 60cm, when natural subsidence 2 is small after
Pressurizeed with peristaltic pump, the deionized water balance pillar of 5 times of column volumes three times.
(4) for the last time when equilibrium water drops to column material surface, the fibroin egg of dissolving is added into glucan G-50
White 5~15ml of mixed solution (10~50mg/ml), when fibroin albumen mixed solution is completely into column material surface, continues
Eluted with sterile deionized water, peristaltic pump control eluent flow rate 300mL/h；It is in charge of collection efflux, until flowing to end fibroin egg
In vain.
(5) using the molecular weight distribution of SDS-PAGE electrophoresis or each pipe of Mass Spectrometric Identification, by fibroin of the molecular weight less than 10kDa
Protein solution is freeze-dried mixed, is then configured to the aqueous solution of 30~80mg/ml, and microparticle is removed with 0.45 μm of membrane filtration.
(6) similar step (4), the silk fibroin water solution of appropriate step (5), peristaltic pump control are added to the column material of G-25
Eluent flow rate 50mL/h processed, is in charge of collection efflux, until flowing to end fibroin albumen, obtains the silk of 1000~5000Da molecular weight
Fibroin aqueous solution, finally freezes and preserves.
(7) by woven pure-cotton fabric with the boiling of the aqueous sodium carbonate of 6g/1L boil 1 it is small when or so, take out with originally water washing,
It is dehydrated, dry or dries.Then use 30 DEG C of 10g/L sodium periodate solutions at handle pure-cotton fabric 2~3 it is small when, tap water rinse
When using 0.025M hydrogen peroxide/sodium chlorite mixed solution processing 2 small after clean, the carbonization of certain mass concentration is impregnated in after rinsing
The mixed aqueous solution of diimine and n-hydroxysuccinimide (quality, which respectively may be about, adds 25%, the 10% of fibroin albumen quality)
In, when dipping 1 is small or so, add fibroin albumen dry powder (fibroin albumen final mass concentration is 5%) dissolving that step 6 obtains
Afterwards, 3h is reacted, taking-up is dried, rinsed, drying again.
(8) pure-cotton fabric that fibroin albumen is modified is cut into the sample of 15cm × 30cm, is tried using material mechanical performance
The machine of testing measures 87% or so that fracture strength is original fabric, and elongation at break is 97% or so of original fabric.
(9) the fibroin albumen rate of body weight gain 4.9% on pure-cotton fabric, the fabric that fibroin albumen is modified are measured using weight method
After being impregnated in when vibration 24 is small in 37 DEG C of warm water, the dissolve-loss ratio for measuring fibroin albumen is less than 2%.
Embodiment 3
(1) silkworm raw silk is pressed 1:The bath raio of 50 (g/mL) is put into the aqueous sodium carbonate that concentration is 0.2%, in 98~
Silk three times, 30 minutes per treatment, is then fully cleaned up, pulled loose by 100 DEG C of processing with deionized water, is placed in baking oven and is done
It is dry, obtain the bombyx mori silk fibroin fiber after degumming.
(2) bombyx mori silk fibroin after degumming is weighed by 1:The bath raio of 15 (g/mL) is dissolved in 9.3M lithium bromide water solutions, and 65
DEG C dissolving 5~7 it is small when obtain bombyx mori silk fibroin dissolving mixed solution.
(3) glucan G-50 and G-25 are weighed to be respectively put into the deionized water of abundance, when boiling water bath 1.5 is small, treats room temperature
After cooling with glass bar drain load glass material void column in, prepare bed volume 2cm × 60cm, when natural subsidence 2 is small after
Pressurizeed with peristaltic pump, the deionized water balance pillar of 5 times of column volumes three times.
(4) for the last time when equilibrium water drops to column material surface, the fibroin egg of dissolving is added into glucan G-50
White 5~15ml of mixed solution (10~50mg/ml), when fibroin albumen mixed solution is completely into column material surface, continues
Eluted with sterile deionized water, peristaltic pump control eluent flow rate 300mL/h；It is in charge of collection efflux, until flowing to end fibroin egg
In vain.
(5) using the molecular weight distribution of SDS-PAGE electrophoresis or each pipe of Mass Spectrometric Identification, by fibroin of the molecular weight less than 10kDa
Protein solution is freeze-dried mixed, is then configured to the aqueous solution of 30~80mg/ml, and microparticle is removed with 0.45 μm of membrane filtration.
(6) similar step (4), the silk fibroin water solution of appropriate step (5), peristaltic pump control are added to the column material of G-25
Eluent flow rate 50mL/h processed, is in charge of collection efflux, until flowing to end fibroin albumen, obtains the silk of 1000~5000Da molecular weight
Fibroin aqueous solution, finally freezes and preserves.
(7) by woven pure-cotton fabric with the boiling of the aqueous sodium carbonate of 6g/1L boil 1 it is small when or so, take out with originally water washing,
It is dehydrated, dry or dries.Then use 30 DEG C of 10g/L sodium periodate solutions at handle pure-cotton fabric 2~3 it is small when, tap water rinse
When using 0.1M hydrogen peroxide/sodium chlorite mixed solution processing 2 small after clean, the carbonization two of certain mass concentration is impregnated in after rinsing
The mixed aqueous solution of imines and n-hydroxysuccinimide (quality, which respectively may be about, adds 25%, the 10% of fibroin albumen quality)
In, when dipping 1 is small or so, add fibroin albumen dry powder (fibroin albumen final mass concentration is 5%) dissolving that step 6 obtains
Afterwards, 3h is reacted, taking-up is dried, rinsed, drying again.
(8) pure-cotton fabric that fibroin albumen is modified is cut into the sample of 15cm × 30cm, is tried using material mechanical performance
The machine of testing measures 82% or so that fracture strength is original fabric, and elongation at break is 95% or so of original fabric.
(9) the fibroin albumen rate of body weight gain 6.5% measured using weight method on pure-cotton fabric is (significantly high compared with comparative example 3
In the graft effect for the fibroin albumen containing a large amount of macromolecules that customary preparation methods obtain), the face that fibroin albumen is modified
After material is impregnated in when vibration 24 is small in 37 DEG C of warm water, the dissolve-loss ratio for measuring fibroin albumen is less than 2%.
Comparative example 1
(1) silkworm raw silk is pressed 1:The bath raio of 50 (g/mL) is put into the aqueous sodium carbonate that concentration is 0.2%, in 98~
Silk three times, 30 minutes per treatment, is then fully cleaned up, pulled loose by 100 DEG C of processing with deionized water, is placed in baking oven and is done
It is dry, obtain the bombyx mori silk fibroin fiber after degumming.
(2) bombyx mori silk fibroin after degumming is weighed by 1:The bath raio of 20 (g/mL) is dissolved in molar ratio 1:2 calcium chloride-ethanol
Aqueous solution in, 70 DEG C dissolving 5~7 it is small when obtain bombyx mori silk fibroin dissolving mixed solution.
(3) glucan G-50 and G-25 are weighed to be respectively put into the deionized water of abundance, when boiling water bath 1.5 is small, treats room temperature
After cooling with glass bar drain load glass material void column in, prepare bed volume 2cm × 60cm, when natural subsidence 2 is small after
Pressurizeed with peristaltic pump, the deionized water balance pillar of 5 times of column volumes three times.
(4) for the last time when equilibrium water drops to column material surface, the fibroin egg of dissolving is added into glucan G-50
White 5~15ml of mixed solution (10~50mg/ml), when fibroin albumen mixed solution is completely into column material surface, continues
Eluted with sterile deionized water, peristaltic pump control eluent flow rate 300mL/h；It is in charge of collection efflux, until flowing to end fibroin egg
In vain.
(5) using the molecular weight distribution of SDS-PAGE electrophoresis or each pipe of Mass Spectrometric Identification, by fibroin of the molecular weight less than 10kDa
Protein solution is freeze-dried mixed, is then configured to the aqueous solution of 30~80mg/ml, and microparticle is removed with 0.45 μm of membrane filtration.
(6) similar step (4), the silk fibroin water solution of appropriate step (5), peristaltic pump control are added to the column material of G-25
Eluent flow rate 50mL/h processed, is in charge of collection efflux, until flowing to end fibroin albumen, obtains the silk of 1000~5000Da molecular weight
Fibroin aqueous solution, finally freezes and preserves.
(7) by woven pure-cotton fabric with the boiling of the aqueous sodium carbonate of 6g/1L boil 1 it is small when or so, take out with originally water washing,
It is dehydrated, dries or dries, is then impregnated in the carbodiimides and n-hydroxysuccinimide (quality difference of certain mass concentration
About add the 25% of fibroin albumen quality, in mixed aqueous solution 10%), when dipping 1 is small or so, add what step 6 obtained
After fibroin albumen dry powder (fibroin albumen final mass concentration is 1%) dissolving, 3h is reacted, taking-up is dried, rinsed, drying again.
(8) pure-cotton fabric that fibroin albumen is modified is cut into the sample of 15cm × 30cm, is tried using material mechanical performance
The machine of testing measures 100% or so that fracture strength is original fabric, and elongation at break is 100% or so of original fabric.
(9) the fibroin albumen rate of body weight gain 0.56% on pure-cotton fabric, the face that fibroin albumen is modified are measured using weight method
After material is impregnated in when vibration 24 is small in 37 DEG C of warm water, the dissolve-loss ratio for measuring fibroin albumen is more than 50%.
Comparative example 2
(1) silkworm raw silk is pressed 1:The bath raio of 50 (g/mL) is put into the aqueous sodium carbonate that concentration is 0.2%, in 98~
Silk three times, 30 minutes per treatment, is then fully cleaned up, pulled loose by 100 DEG C of processing with deionized water, is placed in baking oven and is done
It is dry, obtain the bombyx mori silk fibroin fiber after degumming.
(2) bombyx mori silk fibroin after degumming is weighed by 1:The bath raio of 15 (g/mL) is dissolved in 9.3M lithium bromide water solutions, and 65
DEG C dissolving 5~7 it is small when obtain bombyx mori silk fibroin dissolving mixed solution.
(3) glucan G-50 and G-25 are weighed to be respectively put into the deionized water of abundance, when boiling water bath 1.5 is small, treats room temperature
After cooling with glass bar drain load glass material void column in, prepare bed volume 2cm × 60cm, when natural subsidence 2 is small after
Pressurizeed with peristaltic pump, the deionized water balance pillar of 5 times of column volumes three times.
(4) for the last time when equilibrium water drops to column material surface, the fibroin egg of dissolving is added into glucan G-50
White 5~15ml of mixed solution (10~50mg/ml), when fibroin albumen mixed solution is completely into column material surface, continues
Eluted with sterile deionized water, peristaltic pump control eluent flow rate 300mL/h；It is in charge of collection efflux, until flowing to end fibroin egg
In vain.
(5) using the molecular weight distribution of SDS-PAGE electrophoresis or each pipe of Mass Spectrometric Identification, by fibroin of the molecular weight less than 10kDa
Protein solution is freeze-dried mixed, is then configured to the aqueous solution of 30~80mg/ml, and microparticle is removed with 0.45 μm of membrane filtration.
(6) similar step (4), the silk fibroin water solution of appropriate step (5), peristaltic pump control are added to the column material of G-25
Eluent flow rate 50mL/h processed, is in charge of collection efflux, until flowing to end fibroin albumen, obtains the silk of 1000~5000Da molecular weight
Fibroin aqueous solution, finally freezes and preserves.
(7) by woven pure-cotton fabric with the boiling of the aqueous sodium carbonate of 6g/1L boil 1 it is small when or so, take out with originally water washing,
It is dehydrated, dry or dries.Then use 30 DEG C of 10g/L sodium periodate solutions at handle pure-cotton fabric 2~3 it is small when, tap water rinse
Be impregnated in after clean certain mass concentration carbodiimides and n-hydroxysuccinimide (quality, which respectively may be about, adds fibroin egg
White matter amount 25%, in mixed aqueous solution 10%), when dipping 1 is small or so, add the fibroin albumen dry powder (silk that step 6 obtains
5%) fibroin final mass concentration is dissolves after, 3h is reacted, taking-up is dried, rinsed, drying again.
(8) pure-cotton fabric that fibroin albumen is modified is cut into the sample of 15cm × 30cm, is tried using material mechanical performance
The machine of testing measures 95% or so that fracture strength is original fabric, and elongation at break is 96% or so of original fabric.
(9) the fibroin albumen rate of body weight gain 2.33% on pure-cotton fabric, the face that fibroin albumen is modified are measured using weight method
After material is impregnated in when vibration 24 is small in 37 DEG C of warm water, the dissolve-loss ratio for measuring fibroin albumen is more than 50%.
Comparative example 3
(1) silkworm raw silk is pressed 1:The bath raio of 50 (g/mL) is put into the aqueous sodium carbonate that concentration is 0.2%, in 98~
Silk three times, 30 minutes per treatment, is then fully cleaned up, pulled loose by 100 DEG C of processing with deionized water, is placed in baking oven and is done
It is dry, obtain the bombyx mori silk fibroin fiber after degumming.
(2) bombyx mori silk fibroin after degumming is weighed by 1:The bath raio of 15 (g/mL) is dissolved in 9.3M lithium bromide water solutions, and 65
DEG C dissolving 5~7 it is small when obtain bombyx mori silk fibroin dissolving mixed solution.
(3) bombyx mori silk fibroin lysate is poured into bag filter, bag filter wall is pellicle, molecular cut off for 12.0~
16.0kDa scopes, the bag filter for being filled with bombyx mori silk fibroin lysate is placed in the container for filling deionized water, when 2 is small
The water in container is replaced with new deionized water or pure water, persistently dialyses 3 days, obtains silk fibroin protein aqueous solution after purification
(preparation of conventional silk fibroin water solution), then freezes and preserves.
(4) by woven pure-cotton fabric with the boiling of the aqueous sodium carbonate of 6g/1L boil 1 it is small when or so, take out with originally water washing,
Be dehydrated, dry or dry, then with handled at 30 DEG C of 10g/L sodium periodate solutions pure-cotton fabric 2~3 it is small when, then use 0.1M
When hydrogen peroxide/sodium chlorite mixed solution processing 2 is small, the carbodiimides and N- hydroxyls of certain mass concentration are impregnated in after rinsing
It is left when dipping 1 is small in the mixed aqueous solution of succinimide (quality, which respectively may be about, adds 25%, the 10% of fibroin albumen quality)
The right side, after adding lyophilized fibroin albumen (fibroin albumen final mass concentration is 5%) dissolving that step 3 obtains, reacts 3h, takes out
Dry, rinse, dry again.
(8) pure-cotton fabric that fibroin albumen is modified is cut into the sample of 15cm × 30cm, is tried using material mechanical performance
The machine of testing measures 83% or so that fracture strength is original fabric, and elongation at break is 94% or so of original fabric.
(9) the fibroin albumen rate of body weight gain 2.3% on pure-cotton fabric, the fabric that fibroin albumen is modified are measured using weight method
After being impregnated in when vibration 24 is small in 37 DEG C of warm water, the dissolve-loss ratio for measuring fibroin albumen is less than 10%.
Comparative example 4
(1) silkworm raw silk is pressed 1:The bath raio of 50 (g/mL) is put into the aqueous sodium carbonate that concentration is 0.2%, in 98~
Silk three times, 30 minutes per treatment, is then fully cleaned up, pulled loose by 100 DEG C of processing with deionized water, is placed in baking oven and is done
It is dry, obtain the bombyx mori silk fibroin fiber after degumming.
(2) bombyx mori silk fibroin after degumming is weighed by 1:The bath raio of 15 (g/mL) is dissolved in 9.3M lithium bromide water solutions, and 65
DEG C dissolving 5~7 it is small when obtain bombyx mori silk fibroin dissolving mixed solution.
(3) glucan G-50 and G-25 are weighed to be respectively put into the deionized water of abundance, when boiling water bath 1.5 is small, treats room temperature
After cooling with glass bar drain load glass material void column in, prepare bed volume 2cm × 60cm, when natural subsidence 2 is small after
Pressurizeed with peristaltic pump, the deionized water balance pillar of 5 times of column volumes three times.
(4) for the last time when equilibrium water drops to column material surface, the fibroin egg of dissolving is added into glucan G-50
White 5~15ml of mixed solution (10~50mg/ml), when fibroin albumen mixed solution is completely into column material surface, continues
Eluted with sterile deionized water, peristaltic pump control eluent flow rate 300mL/h；It is in charge of collection efflux, until flowing to end fibroin egg
In vain.
(5) using the molecular weight distribution of SDS-PAGE electrophoresis or each pipe of Mass Spectrometric Identification, by fibroin of the molecular weight less than 10kDa
Protein solution is freeze-dried mixed, is then configured to the aqueous solution of 30~80mg/ml, and microparticle is removed with 0.45 μm of membrane filtration.
(6) similar step (4), the silk fibroin water solution of appropriate step (5), peristaltic pump control are added to the column material of G-25
Eluent flow rate 50mL/h processed, is in charge of collection efflux, until flowing to end fibroin albumen, obtains the silk of 1000~5000Da molecular weight
Fibroin aqueous solution, finally freezes and preserves.
(7) by woven pure-cotton fabric with the boiling of the aqueous sodium carbonate of 6g/1L boil 1 it is small when or so, take out with originally water washing,
It is dehydrated, dry or dries；When then using 0.1M hydrogen peroxide/sodium chlorite mixed solution processing 2 small, certain matter is impregnated in after rinsing
Measure the carbodiimides and n-hydroxysuccinimide of concentration (quality, which respectively may be about, adds 25%, the 10% of fibroin albumen quality)
Mixed aqueous solution in, dipping 1 it is small when or so, add step 6 obtain fibroin albumen dry powder (fibroin albumen final mass concentration
After 5%) dissolving, 3h is reacted, taking-up is dried, rinsed, drying again.
(8) pure-cotton fabric that fibroin albumen is modified is cut into the sample of 15cm × 30cm, is tried using material mechanical performance
The machine of testing measures 85% or so that fracture strength is original fabric, and elongation at break is 97% or so of original fabric.
(9) the fibroin albumen rate of body weight gain 3.2% on pure-cotton fabric, the fabric that fibroin albumen is modified are measured using weight method
After being impregnated in when vibration 24 is small in 37 DEG C of warm water, the dissolve-loss ratio for measuring fibroin albumen is less than 2%.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
- A kind of 1. fibroin method of modifying of pure-cotton fabric, it is characterised in that including：A) pure-cotton fabric destarch is handled, obtains the fabric of destarch；B) fabric of destarch is handled using sodium periodate oxidation, washing, sodium chlorite oxidation processes, the face after being aoxidized Material；C) fibroin albumen of 1000~5000Da molecular weight is provided；D) fabric after oxidation is impregnated in cross-linking agent solution, with the fibroin albumen hybrid reaction.
- 2. according to the method described in claim 1, it is characterized in that, the crosslinking agent includes carbodiimides.
- 3. according to the method described in claim 2, it is characterized in that, the carbodiimides accounts for the mass percent of fibroin albumen For 20%~40%.
- 4. according to the method described in claim 1, it is characterized in that, step A) destarch is specially using at sodium carbonate destarch Reason；The concentration of the sodium carbonate liquor is 6g/L；The destarch treatment temperature is 90~100 DEG C；The destarch processing time is 1h。
- 5. according to the method described in claim 1, it is characterized in that, step B) concentration of the sodium metaperiodate is 10g/L；It is described The temperature of the oxidation of sodium metaperiodate is 30~40 DEG C；The time of the oxidation of the sodium metaperiodate is 1~3h；The sodium chlorite Concentration is 0.025~0.1M；The temperature of the oxidation of the sodium chlorite is 30~40 DEG C；The time of the oxidation of the sodium chlorite For 1~2h.
- 6. according to the method described in claim 1, it is characterized in that, step D) reaction temperature is 25~35 DEG C；It is described anti- It is 1~3h between seasonable.
- 7. according to the method described in claim 1, it is characterized in that, the fibroin albumen of 1000~5000Da molecular weight according to It is prepared by following method：A) silkworm silk is subjected to degumming using sodium carbonate and then adds neutral salt solution dissolving, prepare fibroin albumen lysate；Glucan Sephadex G50 and G25 column equilibrations is stand-by；B) fibroin albumen lysate is added in glucan Sephadex G50 columns, with sterilizing water elution fibroin albumen, is in charge of receipts Collect the silk fibroin water solution of desalination；C) using the fibroin albumen of below 10kD in SDS-PAGE electrophoresis or mass spectrum screening step b) collecting pipes, Portugal is added again and is gathered In sugared Sephadex G25 columns, with sterilizing water elution fibroin albumen, it is in charge of collection, screening obtains the small molecule of 1000~5000Da Measure fibroin albumen.
- 8. the method according to the description of claim 7 is characterized in that the step a) neutral salt solutions are selected from lithium bromide or chlorination Calcium-ethanol；When the dissolution time is 5~7 small；The fibroin albumen lysate concentration is 10~50mg/mL.
- 9. the method according to the description of claim 7 is characterized in that below 10kD in the step c) screening step b) collecting pipes Fibroin albumen after further include it is lyophilized, be then configured to 30~80mg/mL aqueous solutions.
- 10. the method according to the description of claim 7 is characterized in that the step b) elution flow rates are 200~400mL/h；Step Rapid c) described elution flow rate is 30~70mL/h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115852691A (en) * | 2022-12-29 | 2023-03-28 | 山东鹿优数字科技有限公司 | Thermal knitted fabric based on biological protein aerogel and preparation method thereof |
| CN116289295A (en) * | 2023-03-28 | 2023-06-23 | 江阴云智医疗无纺布制品有限公司 | Cotton-milk moisturizing soft towel and production process thereof |
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| CN115852691A (en) * | 2022-12-29 | 2023-03-28 | 山东鹿优数字科技有限公司 | Thermal knitted fabric based on biological protein aerogel and preparation method thereof |
| CN116289295A (en) * | 2023-03-28 | 2023-06-23 | 江阴云智医疗无纺布制品有限公司 | Cotton-milk moisturizing soft towel and production process thereof |
| CN116289295B (en) * | 2023-03-28 | 2024-03-29 | 江阴云智医疗无纺布制品有限公司 | Cotton-milk moisturizing soft towel and production process thereof |
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| CN107956118B (en) | 2020-10-16 |
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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 |