CN109912811A - A kind of preparation method of amphiphilic sericin polymer and the application of polymer - Google Patents
A kind of preparation method of amphiphilic sericin polymer and the application of polymer Download PDFInfo
- Publication number
- CN109912811A CN109912811A CN201910250498.XA CN201910250498A CN109912811A CN 109912811 A CN109912811 A CN 109912811A CN 201910250498 A CN201910250498 A CN 201910250498A CN 109912811 A CN109912811 A CN 109912811A
- Authority
- CN
- China
- Prior art keywords
- sericin
- amphiphilic
- polymer
- preparation
- compound
- 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
- 108010013296 Sericins Proteins 0.000 title claims abstract description 69
- 229920000642 polymer Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002537 cosmetic Substances 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 11
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- -1 ion salts Chemical class 0.000 claims description 8
- 229940126062 Compound A Drugs 0.000 claims description 7
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 5
- 108090000623 proteins and genes Proteins 0.000 claims description 5
- 102000004169 proteins and genes Human genes 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 230000008961 swelling Effects 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 241000219000 Populus Species 0.000 claims 1
- 229910017435 S2 In Inorganic materials 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 12
- 239000004753 textile Substances 0.000 abstract description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 5
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 abstract description 4
- 239000012675 alcoholic extract Substances 0.000 abstract description 4
- 230000032050 esterification Effects 0.000 abstract description 4
- 238000005886 esterification reaction Methods 0.000 abstract description 4
- 150000002466 imines Chemical class 0.000 abstract description 4
- UTCFOFWMEPQCSR-UHFFFAOYSA-N 5-formylsalicylic acid Chemical compound OC(=O)C1=CC(C=O)=CC=C1O UTCFOFWMEPQCSR-UHFFFAOYSA-N 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 150000004705 aldimines Chemical class 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 125000000879 imine group Chemical group 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000037394 skin elasticity Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000004744 fabric Substances 0.000 description 6
- 230000003712 anti-aging effect Effects 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 239000006071 cream Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 230000002335 preservative effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000003020 moisturizing effect Effects 0.000 description 2
- 230000009759 skin aging Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- 206010012442 Dermatitis contact Diseases 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 0.000 description 1
- 208000001126 Keratosis Diseases 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 208000002029 allergic contact dermatitis Diseases 0.000 description 1
- 230000000172 allergic effect Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 230000036074 healthy skin Effects 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
- 229960003160 hyaluronic acid Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Cosmetics (AREA)
- Peptides Or Proteins (AREA)
Abstract
The invention discloses the applications of a kind of preparation method of amphiphilic sericin polymer and polymer, histidine is esterified under concentrated sulfuric acid catalyst with octadecyl alcolol first, histidine stearyl is obtained, then it is condensed with 5- formylsalicylic acid, compound B is obtained, the imines that aldimine condensation is formed, since imine group is connect with phenyl ring, so that the imines formed is stable structure, to which compound B is also more stable, contain a large amount of alcoholic extract hydroxyl group on sericin, it is esterified under the catalysis of the concentrated sulfuric acid with compound B, and the phenolic hydroxyl group on compound B and the more difficult direct esterification of carboxylic acid, reduce the generation of by-product, so the alcoholic extract hydroxyl group on sericin and the carboxyl esterification on compound B, form the single amphiphilic sericin polymer of formula C-structure；Hydrophobic grouping is introduced on sericin, amphiphilic sericin polymer obtained can be applied in cosmetics and textile, have a good application prospect.
Description
Technical field
The invention belongs to cosmetic technical fields, and in particular to a kind of preparation method of amphiphilic sericin polymer with
The application of polymer.
Background technique
Sericin is a kind of water-soluble globular preteins, containing multiple polypeptides, is made of 18 kinds of amino acid, containing compared with
More serine, asparatate and glycine, polar side chains account for 74.61%.Contain in sericin molecular structure
The hydrophilic radicals such as a large amount of hydroxyl, carboxyl, amino, thus there is excellent moisture pick-up properties, sericin is used in cosmetics,
These hydrophilic radicals can make internal water be transferred to keratoderma and combine, so that skin be made to keep certain moisture, skin
It is soft and smooth, it is natural moisturizing factor；Sericin is added as individual raw material in existing cosmetics, parents' sex pilus
Glue protein in cosmetics for rarely having, and the preservative added in cosmetics is unfavorable to human body, and single sericin is added to
Moisture-keeping function is only played in cosmetics, it is unobvious in the anti-oxidant anti-aging but effect of skin.
Summary of the invention
The purpose of the present invention is to provide the application of a kind of preparation method of amphiphilic sericin polymer and polymer,
By hydrophobic grouping (- (CH2)CH3、Phenyl) it has been introduced on sericin, amphiphilic sericin polymer obtained
It can be applied in cosmetics and textile, have a good application prospect.
A kind of preparation method of amphiphilic sericin polymer, specifically includes the following steps:
Step 1: the preparation of sericin powder
It takes silk cocoon to be put into cold water rinsing and removes dust and impurities, be subsequently placed into that temperature is 40-45 DEG C, mass fraction is
40min is impregnated in 5% sodium hydroxide solution, makes the abundant swelling of the silk gum on silk cocoon, then 40min is boiled in heating, and degumming will
Silk cocoon clothing after degumming is washed repeatedly with 60-70 DEG C of hot water, and cleaning solution and degumming liquid are merged, and is packed into molecular cut off and is
The bag filter of 9000-13000Da, 2 days removing ion salts of dialysing in pure water, spray-dried obtained sericin powder；
The preparation of second step, hydrophobic compound
S1,11-12mmol octadecyl alcolol is dissolved in 50ml solvent, the 5ml concentrated sulfuric acid is added dropwise, stirred after being added dropwise mixed
10-15min is closed, is subsequently added into 10mmol histidine, heating reflux reaction, after reaction, rotary evaporation remove solvent, through water
It washes, obtain compound A after alcohol is washed；Reaction equation is as follows:
S2, the compound A that step S1 is obtained is dissolved in 100ml solvent, 2g anhydrous sodium sulfate and 10mml 5- first is added
Acyl salicylic acid is heated to reflux and is stirred to react 2-3h, and rotary evaporation removes solvent and obtained hydrophobic compound through column chromatography for separation
B；Reaction equation is as follows:
The preparation of third step, amphiphilic sericin polymer
Compound B prepared by step S2 is dissolved in the anhydrous DMSO of 200ml, the 5ml concentrated sulfuric acid is added dropwise, is added dropwise
After be stirred 10-15min, 10g anhydrous sodium sulfate, the 10-15g sericin powder that then first step is prepared is added
It being added in mixed solution, is warming up to 60-65 DEG C, insulated and stirred reacts 6-8h, after reaction, purified formula C-structure to obtain the final product
Amphiphilic sericin polymer.
Further, solvent described in step S1 is anhydrous tetrahydro furan.
Further, in step S1, heating reflux reaction is specially to be heated to 95-105 DEG C of back flow reaction 4-5h.
Further, solvent described in step S2 is dry toluene.
Further, in step S2, column chromatography eluant, eluent used is petroleum ether: methylene chloride: ethyl acetate=6:2:5.
Further, purifying described in third step specifically: after reaction, be cooled to 5-8 DEG C, 300ml deionization is added
Precipitating is precipitated in water, and filtering is washed through 100ml*3 5-10 DEG C of cold water, and 50ml*3 times 5-10 DEG C of dehydrated alcohol alcohol is washed, filtering,
Finally it is freeze-dried the amphiphilic sericin polymer up to formula C-structure.
A kind of application of amphiphilic sericin polymer, the amphiphilic sericin polymer are applied in cosmetics.
Beneficial effects of the present invention:
The present invention provides a kind of preparation methods of amphiphilic sericin polymer, and histidine and octadecyl alcolol first is dense
It is esterified under sulfuric acid catalysis, has obtained histidine stearyl, be then condensed, changed with 5- formylsalicylic acid
Conjunction object B, the imines that aldimine condensation is formed, since imine group is connect with phenyl ring, so that the imines formed is stable structure, from
And compound B is also more stable, and a large amount of alcoholic extract hydroxyl group is contained on sericin, and ester is carried out under the catalysis of the concentrated sulfuric acid with compound B
Change, and the phenolic hydroxyl group on compound B and the more difficult direct esterification of carboxylic acid, the generation of by-product is reduced, so on sericin
Carboxyl esterification on alcoholic extract hydroxyl group and compound B, by hydrophobic grouping (- (CH2)CH3、Phenyl) it has been introduced into sericin
On, form the single amphiphilic sericin polymer of formula C-structure；
Amphiphilic sericin polymer obtained can be applied in cosmetics and textile；It is double when applied to cosmetics
Close sex pilus glue protein polymer there is hydrophily to have lipophilic again, convenient for being matched with other formula constituents in cosmetics
5, it is easier to be emulsified into homogeneous phase, contains antibacterial complexing group on amphiphilic sericin polymerAnd phenolic hydroxyl group,
The antibacterial and mouldproof of cosmetics can be kept, preservative is added without additional, in additionAnd-C=N-CH-COO- can absorb network
The heavy metal color make-up residue on skin is closed, phenolic hydroxyl group can remove the free radical in skin, in conjunction with the inoxidizability of sericin,
Further improve anti-oxidant anti-aging effect of cosmetics；
Applied in textile, the hygroscopicity and antistatic performance of most of synthetic fibers are poor, amphiphilic sericin
The anti-microbial property of fabric can be improved in fiber surface in polymer-coated, and sericin can be improved the hygroscopicity of fabric and put
The anti-pollution characteristic of textile fabric can be improved in static behaviour, hydrophobic grouping.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, will be described below to embodiment required
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for ability
For the those of ordinary skill of domain, without creative efforts, it can also be obtained according to these attached drawings other attached
Figure.
Fig. 1 is the reaction equation of the compounds of this invention A；
Fig. 2 is the reaction equation of hydrophobic compound B；
Fig. 3 is the response diagram of amphiphilic sericin polymer.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts all other
Embodiment shall fall within the protection scope of the present invention.
It please refers to shown in Fig. 1-3, a kind of preparation method of amphiphilic sericin polymer and the application of polymer, specifically
The following steps are included:
Step 1: the preparation of sericin powder
It takes silk cocoon to be put into cold water rinsing and removes dust and impurities, be subsequently placed into that temperature is 45 DEG C, mass fraction is 5%
40min is impregnated in sodium hydroxide solution, makes the abundant swelling of the silk gum on silk cocoon, and then 40min, degumming, by degumming are boiled in heating
Silk cocoon clothing afterwards is washed repeatedly with 65 DEG C of hot water, and cleaning solution and degumming liquid are merged, and loading molecular cut off is 9000-
The bag filter of 13000Da, 2 days removing ion salts of dialysing in pure water, spray-dried obtained sericin powder；
The preparation of second step, hydrophobic compound
S1,12mmol octadecyl alcolol is dissolved in 50ml anhydrous tetrahydro furan, the 5ml concentrated sulfuric acid is added dropwise, after being added dropwise
It is stirred 10min, is subsequently added into 10mmol histidine, is heated to 100 DEG C of back flow reaction 5h, after reaction, rotary evaporation
Solvent is removed, obtains compound A after washing, alcohol are washed；Yield is 95.7%；Reaction equation is shown in Fig. 1；
The mass spectral results of gained compound A are as follows: HRMS m/z (ESI+)calcd for C24H45N3O2([M]+),
407.58,found 407.3545；
S2, the compound A that step S1 is obtained is dissolved in the dry toluene of 100ml, 2g anhydrous sodium sulfate and 10mml is added
5- formylsalicylic acid is heated to reflux and is stirred to react 3h, and rotary evaporation removes solvent, and through column chromatography for separation, having obtained purity is
99.65% hydrophobic compound B, yield 92.3%；Column chromatography eluant, eluent used is petroleum ether: methylene chloride: acetic acid second
Ester=6:2:5；Reaction equation is shown in Fig. 2；
The mass spectral results of gained compound B are as follows: HRMS m/z (ESI+)calcd for C32H49N3O5([M]+),
555.65,found 555.3714；
The preparation of third step, amphiphilic sericin polymer
Compound B prepared by step S2 is dissolved in the anhydrous DMSO of 200ml, the 5ml concentrated sulfuric acid is added dropwise, is added dropwise
After be stirred 15min, 10g anhydrous sodium sulfate is added, the 13g sericin powder that then first step is prepared is added mixed
It closes in solution, is warming up to 65 DEG C, insulated and stirred reacts 8h, after reaction, is cooled to 5 DEG C, and 300ml deionized water, analysis is added
It precipitates, filters out, washed through 100ml*3 5-10 DEG C of cold water, 50ml*3 times 5-10 DEG C of dehydrated alcohol alcohol is washed, filtering, finally
The amphiphilic sericin polymer up to formula C structure is freeze-dried at -20 DEG C；Reaction equation is shown in Fig. 3；
The IR Characterization of amphiphilic sericin polymer D is as follows: IR (KBr):(- OH, Qiang Kuanfeng,
For unreacted-OH on sericin, there are also phenolic hydroxyl groups), 3143 (- NH- on imidazoles), 3064,3025 (imidazoles, phenyl ring), 1735 (-
), CO- 1675 (- C=N- on-C=N-, imidazoles) cm-1。
Using the amphiphilic sericin polymer of determined by ultraviolet spectrophotometry to DPPH free radical, hydroxy radical, super oxygen
The clearance rate of ion radical；Clearance rate to DPPH free radical is 99.1%, and the clearance rate to hydroxy radical is 98.2%, right
The clearance rate of Superoxide anion free radical is 98.7%.
Tested through antibiotic property, find amphiphilic sericin polymer to staphylococcus aureus, Escherichia coli it is antibacterial
Rate is respectively 98.8%, 99.4%.
The amphiphilic sericin polymer can be applied in cosmetics and textile；It is double when applied to cosmetics
Close sex pilus glue protein polymer there is hydrophily to have lipophilic again, convenient for being matched with other formula constituents in cosmetics
5, it is easier to be emulsified into homogeneous phase, contains antibacterial complexing group on amphiphilic sericin polymerAnd phenolic hydroxyl group,
Cosmetics antibacterial and mouldproof can be kept, preservative is added without additional, in additionAnd the absorbable complexing of-C=N-CH-COO-
Heavy metal color make-up residue on skin, phenolic hydroxyl group can remove the free radical in skin, in conjunction with the inoxidizability of sericin, into
Anti-oxidant anti-aging effect for improving cosmetics of one step；
Applied in textile, the hygroscopicity and antistatic performance of most of synthetic fibers are poor, amphiphilic sericin
The anti-microbial property of fabric can be improved in fiber surface in polymer-coated, and sericin can be improved the hygroscopicity of fabric and put
The anti-pollution characteristic of textile fabric can be improved in static behaviour, hydrophobic grouping.
Skin elasticity test
Skin elasticity is reduced with skin aging, therefore skin elasticity is the one of the important signs that for judging skin aging, is
The effect of anti-aging cosmetics, detects essential project.
The formula (parts by weight) of face cream are as follows:
Formula one: 25 parts of glycerol, 12 parts of dormant oil, 15 parts of hyaluronic acid, 8 parts of Trivent OCG, amphiphilic sericin 3
Part, 4 parts of dimethyl silicone polymer, 0.2 part of EDETATE SODIUM, 32.8 parts of deionized water；
Comparative formula: being changed to sericin for amphiphilic sericin, remaining is the same as formula one；
Blank formula: not adding amphiphilic sericin, remaining is the same as formula one；
Experimental method: select healthy skin it is normal, without the tested women of cosmetic allergic contact dermatitis history 30, the age 20-45 years old, with
Machine respectively distributes 10 people to every group, and with week for 1 course for the treatment of, 4 courses for the treatment of, clean by facial cleansing before smearing every time in total, and every time
The time of face cleaning is all identical, and corresponding product is smeared after skin dries, and each group smears corresponding product 2 times daily, each 1g.
Measurement: selecting Face and cheek as test zone, and 10min is tested after product to be used.It is surveyed using skin elasticity
It tries instrument and measures skin elasticity curve, it, can moisturizing to skin care item and anti-aging function according to the amount of tension of skin and resilience data
Effect is evaluated, and result is as shown in Table 1；
Table one, skin elasticity test result
As shown in Table 1, it is gradually risen using elasticity number at cheek behind one face cream of formula, uses the elasticity of skin after 2 weeks
Value starts to significantly improve.It is formulated the elasticity that skin can be remarkably reinforced in a face cream, works rapidly, illustrates parents' sex pilus of the present invention
Glue protein has enhancing skin elasticity, improves the function of skin state, and 10 people use the face cream process of formula one,
Without allergic phenomena.
The above content is just an example and description of the concept of the present invention, affiliated those skilled in the art
It makes various modifications or additions to the described embodiments or is substituted in a similar manner, without departing from invention
Design or beyond the scope defined by this claim, be within the scope of protection of the invention.
Claims (7)
1. a kind of preparation method of amphiphilic sericin polymer, it is characterised in that: specifically includes the following steps:
Step 1: the preparation of sericin powder
It takes silk cocoon to be put into cold water rinsing and removes dust and impurities, be subsequently placed into that temperature is 40-45 DEG C, mass fraction is 5%
40min is impregnated in sodium hydroxide solution, makes the abundant swelling of the silk gum on silk cocoon, and then 40min, degumming, by degumming are boiled in heating
Silk cocoon clothing afterwards is washed repeatedly with 60-70 DEG C of hot water, and cleaning solution and degumming liquid are merged, and loading molecular cut off is 9000-
The bag filter of 13000Da, 2 days removing ion salts of dialysing in pure water, spray-dried obtained sericin powder；
The preparation of second step, hydrophobic compound
S1,11-12mmol octadecyl alcolol is dissolved in 50ml solvent, the 5ml concentrated sulfuric acid is added dropwise, be stirred after being added dropwise
10-15min is subsequently added into 10mmol histidine, and heating reflux reaction, after reaction, rotary evaporation remove solvent, through water
It washes, obtain compound A after alcohol is washed；Reaction equation is as follows:
S2, the compound A that step S1 is obtained is dissolved in 100ml solvent, 2g anhydrous sodium sulfate and 10mml 5- formyl water is added
Poplar acid, is heated to reflux and is stirred to react 2-3h, and rotary evaporation removes solvent and obtained hydrophobic compound B through column chromatography for separation；Instead
Answer formula as follows:
The preparation of third step, amphiphilic sericin polymer
Compound B prepared by step S2 is dissolved in the anhydrous DMSO of 200ml, the 5ml concentrated sulfuric acid is added dropwise, is stirred after being added dropwise
10-15min is mixed, 10g anhydrous sodium sulfate is added, mixing is added in the 10-15g sericin powder that then first step is prepared
In solution, it is warming up to 60-65 DEG C, insulated and stirred reacts 6-8h, after reaction, purified parents' sex pilus up to formula C-structure
Glue protein polymer.
2. a kind of preparation method of amphiphilic sericin polymer according to claim 1, it is characterised in that: step S1
The solvent is anhydrous tetrahydro furan.
3. a kind of preparation method of amphiphilic sericin polymer according to claim 1, it is characterised in that: step S1
In, heating reflux reaction is specially to be heated to 95-105 DEG C of back flow reaction 4-5h.
4. a kind of preparation method of amphiphilic sericin polymer according to claim 1, it is characterised in that: step S2
The solvent is dry toluene.
5. a kind of preparation method of amphiphilic sericin polymer according to claim 1, it is characterised in that: step S2
In, column chromatography eluant, eluent used is petroleum ether: methylene chloride: ethyl acetate=6:2:5.
6. a kind of preparation method of amphiphilic sericin polymer according to claim 1, it is characterised in that: third step
The purifying specifically: after reaction, it is cooled to 5-8 DEG C, 300ml deionized water is added, precipitating is precipitated, filtered, warp
The washing of 100ml*3 5-10 DEG C of cold water, 50ml*3 time 5-10 DEG C of dehydrated alcohol alcohol is washed, and is filtered, is finally freeze-dried formula C to obtain the final product
The amphiphilic sericin polymer of structure.
7. a kind of application of amphiphilic sericin polymer, it is characterised in that: the amphiphilic sericin polymer is applied to
In cosmetics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910250498.XA CN109912811B (en) | 2019-03-29 | 2019-03-29 | Preparation method of amphiphilic sericin polymer and application of polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910250498.XA CN109912811B (en) | 2019-03-29 | 2019-03-29 | Preparation method of amphiphilic sericin polymer and application of polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109912811A true CN109912811A (en) | 2019-06-21 |
| CN109912811B CN109912811B (en) | 2021-04-06 |
Family
ID=66967702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910250498.XA Active CN109912811B (en) | 2019-03-29 | 2019-03-29 | Preparation method of amphiphilic sericin polymer and application of polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109912811B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2023550522A (en) * | 2021-05-26 | 2023-12-01 | ザ プロクター アンド ギャンブル カンパニー | Pro-beneficial agent compounds with carbon/nitrogen bonds |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19960924A1 (en) * | 1999-12-17 | 2001-07-05 | Oliver Keil | Amphiphilic polyamines, their applications and processes for their synthesis |
| US20110111031A1 (en) * | 2009-04-20 | 2011-05-12 | Guang-Liang Jiang | Drug Delivery Platforms Comprising Silk Fibroin Hydrogels and Uses Thereof |
| CN106729742A (en) * | 2017-04-01 | 2017-05-31 | 中山大学 | A kind of cancer target sericin micella and its preparation method and application |
| CN106963732A (en) * | 2017-02-15 | 2017-07-21 | 胡彦锋 | The preparation and its application in neoplasm tracing and treatment of a kind of sericin mating type paclitaxel nano medicine |
| CN107022088A (en) * | 2017-02-15 | 2017-08-08 | 胡彦锋 | A kind of amphipathic sericin polymer and preparation method and application |
| CN108478527A (en) * | 2018-04-19 | 2018-09-04 | 中原工学院 | A kind of Preparation method and use of sericin and gamma-polyglutamic acid self-assembly nano-micelle |
| CN108815534A (en) * | 2018-09-13 | 2018-11-16 | 中山大学 | A kind of isotope of redox-sensitive sericin derivative with anti-tumor activity and its preparation and application |
| CN108840896A (en) * | 2018-04-23 | 2018-11-20 | 上海大学 | Stimuli responsive type parents' macromolecular and preparation method thereof |
-
2019
- 2019-03-29 CN CN201910250498.XA patent/CN109912811B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19960924A1 (en) * | 1999-12-17 | 2001-07-05 | Oliver Keil | Amphiphilic polyamines, their applications and processes for their synthesis |
| US20110111031A1 (en) * | 2009-04-20 | 2011-05-12 | Guang-Liang Jiang | Drug Delivery Platforms Comprising Silk Fibroin Hydrogels and Uses Thereof |
| CN106963732A (en) * | 2017-02-15 | 2017-07-21 | 胡彦锋 | The preparation and its application in neoplasm tracing and treatment of a kind of sericin mating type paclitaxel nano medicine |
| CN107022088A (en) * | 2017-02-15 | 2017-08-08 | 胡彦锋 | A kind of amphipathic sericin polymer and preparation method and application |
| CN106729742A (en) * | 2017-04-01 | 2017-05-31 | 中山大学 | A kind of cancer target sericin micella and its preparation method and application |
| CN108478527A (en) * | 2018-04-19 | 2018-09-04 | 中原工学院 | A kind of Preparation method and use of sericin and gamma-polyglutamic acid self-assembly nano-micelle |
| CN108840896A (en) * | 2018-04-23 | 2018-11-20 | 上海大学 | Stimuli responsive type parents' macromolecular and preparation method thereof |
| CN108815534A (en) * | 2018-09-13 | 2018-11-16 | 中山大学 | A kind of isotope of redox-sensitive sericin derivative with anti-tumor activity and its preparation and application |
Non-Patent Citations (5)
| Title |
|---|
| SONG YANG 等: "Removal of trivalent chromium from aqueous solutions by amphiphilic core-shell poly(methyl acrylate)/silk sericin nanospheres", 《POLIMERY》 * |
| WEIHONG GUO 等: "Sericin nanomicelles with enhanced cellular uptake and pH-triggered release of doxorubicin reverse cancer drug resistance", 《DRUG DELIVERY》 * |
| 吴赞敏: "《纺织品清洁染整加工技术》", 31 January 2007, 中国纺织出版社 * |
| 宋世洪: "丝胶蛋白的改性与固定研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
| 李梅 等: "蚕丝丝胶蛋白在化妆品领域的开发与应用", 《轻纺工业与技术》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2023550522A (en) * | 2021-05-26 | 2023-12-01 | ザ プロクター アンド ギャンブル カンパニー | Pro-beneficial agent compounds with carbon/nitrogen bonds |
| JP7695359B2 (en) | 2021-05-26 | 2025-06-18 | ザ プロクター アンド ギャンブル カンパニー | Pro-Benefit Agent Compounds Having Carbon/Nitrogen Bonds |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109912811B (en) | 2021-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6500470B1 (en) | Use of at least one protein extract of the moringa genus plant seeds and corresponding cosmetic and/or pharmacological composition | |
| CN104940038B (en) | Application of the lycium ruthenicum anthocyanidin in preparing cosmetics and the cosmetics containing lycium ruthenicum anthocyanidin | |
| Norman et al. | Anthocyanin dye conjugated with Hippospongia communis marine demosponge skeleton and its antiradical activity | |
| CN101760963B (en) | Antibiotic-mould proof textile fabric and method for preparing same | |
| CN105297426A (en) | Fabric softener | |
| CN109864930A (en) | A kind of composition of plant extracts with inflammation-resisting itch-stopping and preparation method thereof, application | |
| CN109322164A (en) | A kind of multifunctional finishing agent based on hyperbranched polyester derivatives and its preparation and application | |
| CN109912811A (en) | A kind of preparation method of amphiphilic sericin polymer and the application of polymer | |
| CN103893028A (en) | Seaweed facial mask | |
| CN105310893A (en) | Condensate water mask and production method thereof | |
| US20140076195A1 (en) | Silk Protein Composite Coating Solution and its Preparation Method and Application | |
| CN108409848A (en) | The preparation method and applications of sericin polypeptide | |
| CN105168017B (en) | A kind of effectively plant polyose composition of moisturizing, anti-acne and anti-aging and its preparation method and application | |
| CN116536910B (en) | A baby headrest based on skin-friendly fabric | |
| CN1986952A (en) | Process for preparing poly modified chitosan anti-bacteria wet keeping finishing agent | |
| CN115414302A (en) | Skin-moistening and nourishing type moisturizing emulsion and preparation method thereof | |
| CN105155065A (en) | Bacteriostasis stinking-proof yarn | |
| CN109485856B (en) | Betaine modified polyether epoxy silicone oil and preparation method and application thereof | |
| CN116270264A (en) | Aromatic microcapsule, aromatic chemical fiber false eyelash and preparation method thereof | |
| CN103387598A (en) | Polypeptide material, method for its preparation, and method for finishing textiles using it | |
| CN108619020B (en) | A facial mask containing herba Ixeritis Sonchifoliae extract and its preparation method | |
| JP2009161519A (en) | Cosmetic base material and hair cosmetic | |
| KR20170086951A (en) | Method for preparation of functional fabric containing paper mulberry extract and functional fabric prepared by the method | |
| CN108892794B (en) | Multifunctional beauty membrane material and preparation method and application thereof | |
| EP3381441B1 (en) | External use skin composition for antiaging containing germinated glycine gracilis extract as active ingredient |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |