CN113817183A - Preparation method of calcium carbonate/fibroin composite ultrafine powder - Google Patents
Preparation method of calcium carbonate/fibroin composite ultrafine powder Download PDFInfo
- Publication number
- CN113817183A CN113817183A CN202111066125.0A CN202111066125A CN113817183A CN 113817183 A CN113817183 A CN 113817183A CN 202111066125 A CN202111066125 A CN 202111066125A CN 113817183 A CN113817183 A CN 113817183A
- Authority
- CN
- China
- Prior art keywords
- fibroin
- calcium
- carbonate
- silk
- calcium carbonate
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/10—General cosmetic use
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Inorganic Chemistry (AREA)
- Cosmetics (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides calcium carbonate/fibroin composite ultrafine powder and a preparation method thereof, and the preparation method comprises the following steps: degumming silk to remove sericin, dissolving the degumming silk by using a calcium salt solution, adding a carbonate solution, reacting to obtain a fibroin protein/calcium carbonate suspension, centrifuging, washing, drying and crushing the suspension to obtain calcium carbonate/fibroin composite ultrafine powder. The method can regulate and control the crystal form and the particle size and morphology of calcium carbonate by changing the concentration of the silk fibroin, has simple preparation method, short flow, convenient operation and easy control, and is suitable for industrialized quantitative production. The calcium carbonate/fibroin composite ultrafine powder prepared by the invention has adjustable particle size and inorganic/organic ratio, good skin-friendly performance, oil absorption and sweat absorption, and is very suitable for the field of cosmetics.
Description
Technical Field
The invention relates to the field of regenerated silk fibroin, and in particular relates to a preparation method of calcium carbonate/fibroin composite ultrafine powder.
Background
The silk fibroin is natural high molecular protein existing in silk, mainly contains 18 amino acids, and has excellent physical and chemical properties and biocompatibility. Fibroin powder has been used as a base material for cosmetics or as an additive for medical ointment, because of its properties such as moderate hygroscopicity, water-retaining property, good affinity and smoothness for human skin, good balance between hydrophilicity and lipophilicity, and ultraviolet absorbability. However, it is very difficult to pulverize silk into fine powder in a pulverizer. Therefore, various methods of treating silk and powdering the silk have been studied. One is to add human chemical reagent or enzyme into natural silk, and hydrolyze to moderately break or completely hydrolyze long-chain protein to produce products with different molecular weights, such as silk peptide and amino acid. The method cannot ensure the pure naturalness of the product due to the introduction of an additional chemical reagent; meanwhile, only part of nutrient components in the raw materials are reserved in the product, so that the utilization rate of the raw materials is low; in addition, the process is complex and difficult to control, and the effect is not ideal. Or the silk fiber is prepared into white or light yellow fibroin powder by partial hydrolysis, purification, crushing and drying, and the product has a relatively thick granularity, so that the absorption of the product by human skin is limited, and the due health care and skin care effects of the silk cannot be fully exerted. Another method is to deep-freeze and pulverize silk, which is very expensive and produces the same coarse (generally over 200 mesh) product, which is not easy to be absorbed by human body. These processes, whether they are drug-treated dissolution dialysis or dissociation, relaxation, etc. of the macromolecular linkage of proteins, are very complicated, and as a result, the yield and price of silk protein powder are prohibitive for widespread use.
Disclosure of Invention
The technical problem to be solved is as follows: the invention overcomes the problems of complex traditional process and unsatisfactory obtained protein powder particles, adopts a brand-new preparation method of the protein powder, combines calcium carbonate and the protein powder, can realize large-scale production, and has high efficiency and controllable particle size.
The technical scheme is as follows: a preparation method of calcium carbonate/fibroin composite ultrafine powder comprises the following steps:
s1, degumming silk to obtain silk fibroin fibers, and dissolving the silk fibroin fibers in a calcium salt solution to obtain a silk protein-calcium salt solution;
s2, diluting the fibroin-calcium salt solution obtained in the step S1, adjusting the pH value, adding a carbonate solution, fully stirring and mixing, and reacting to obtain a calcium carbonate-fibroin suspension;
s3, centrifuging the calcium carbonate-fibroin suspension obtained in the step S2 at a high speed, pouring out supernatant, adding deionized water for full cleaning, centrifuging, pouring out supernatant, cleaning, drying, and finally grinding into calcium carbonate-fibroin composite ultrafine powder.
Preferably, the silk in step S1 is one or a combination of two or more of mulberry silk, tussah silk and castor-oil plant silk.
Preferably, the calcium salt in step S1 is one or a combination of two or more of calcium chloride, calcium bromide, calcium iodide, calcium nitrate, and calcium phosphate.
Preferably, in the step S1, the concentration of the silk fibroin fibers in the fibroin-calcium salt solution is 1-50 w/v%, the concentration of the calcium salt is 0.1-90 w/v%, the dissolving temperature is 25-100 ℃, and the dissolving time is 0.5-24 hours.
Preferably, the carbonate in step S2 is one or a combination of two or more of ammonium carbonate, sodium carbonate and sodium bicarbonate.
Preferably, the molar ratio of calcium ions in the fibroin-calcium salt solution to carbonate ions in the carbonate solution in the step S2 is Ca2+：CO3 2-1:1, gradually dripping the carbonate solution into the fibroin protein-calcium salt solution until the carbonate is completely dripped, and after the dripping is completed, reacting the carbonate with the calcium salt for 0.1-24 h at the reaction temperature of 10-100 ℃.
Preferably, in the step S3, the particle size of the calcium carbonate-fibroin composite ultrafine powder is 1 to 10 μm, the content of fibroin in the ultrafine powder is 1 to 50 wt%, and the crystalline form of calcium carbonate is one or a combination of two or more of calcite, aragonite and spherulite.
The calcium carbonate/fibroin composite ultrafine powder prepared by the preparation method is applied to the field of cosmetics.
Has the advantages that:
1. the invention relates to a method for preparing regenerated silk protein material by dissolving silk by calcium salt, which comprises the steps of dissolving silk by calcium salt, and preparing calcium carbonate/silk protein composite superfine powder by carbonate coprecipitation, wherein the method avoids environmental pollution caused by calcium chloride dialysis and directly recovers calcium and generates composite superfine powder;
2. calcium ions directly participate in swelling and dissociation of silk protein molecules in the silk dissolving process, the dissolved calcium ions still have a close connection effect with the silk protein molecules, and then carbonate and the calcium ions are introduced for mineralization to naturally generate calcium carbonate/silk protein composite ultrafine powder of firm composite silk protein;
3. the preparation method is simple, mild in condition, convenient to operate, easy to control, free of any chemical solvent and suitable for quantitative production;
4. the silk protein powder prepared by the invention is white or light yellow in appearance, has the particle size of 1-10 mu m and uniform size, and the combination of silk protein and calcium carbonate ensures that the composite ultrafine powder has fine hand feeling, smooth skin and soft luster, thereby being very suitable for cosmetic raw materials.
Drawings
FIG. 1 is a scanning electron microscope image of calcium carbonate/fibroin composite ultrafine powder;
FIG. 2 is a scanning electron microscope image of calcium carbonate/fibroin composite ultrafine powder;
FIG. 3 is an infrared spectrum of calcium carbonate/fibroin composite ultrafine powder;
figure 4 is an XRD pattern of calcium carbonate/fibroin composite ultrafine powder.
Detailed Description
The invention provides a preparation method of calcium carbonate/fibroin composite ultrafine powder, and in order to make the purpose, technical scheme and effect of the invention clearer and clearer, the invention is further described in detail with the cooperation of the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A preparation method of calcium carbonate/fibroin composite ultrafine powder comprises the following steps:
s1, degumming silk to obtain silk fibroin fibers, dissolving the silk fibroin fibers in a 5 w/v% calcium bromide solution at 25 ℃ for 0.5h to obtain a 5 w/v% fibroin-calcium salt solution;
s2, diluting the fibroin-calcium salt solution obtained in the step S1, adjusting the pH value, adding a sodium carbonate solution, wherein the molar ratio of calcium ions in the fibroin-calcium salt solution to carbonate ions in the carbonate solution is Ca2+：CO3 2-Gradually dropwise adding the carbonate solution into the fibroin-calcium salt solution until the carbonate is completely dropwise added, reacting the carbonate with the calcium salt for 0.1h at the reaction temperature of 60 ℃ after the dropwise addition is completed, and obtaining calcium carbonate-fibroin suspension after the reaction;
s3, centrifuging the calcium carbonate-fibroin suspension obtained in the step S2 at a high speed, pouring out supernatant, adding deionized water for full cleaning, centrifuging and pouring out supernatant, cleaning and drying, and finally grinding into calcium carbonate-fibroin composite ultrafine powder with the particle size of 1 mu m, wherein the content of fibroin in the ultrafine powder is 20 wt%, and the crystalline form of calcium carbonate is a composition of calcite, aragonite and spherulite.
Example 2
A preparation method of calcium carbonate/fibroin composite ultrafine powder comprises the following steps:
s1, degumming silk to obtain silk fibroin fibers, dissolving the silk fibroin fibers in a calcium chloride solution with the concentration of 2.5 w/v%, wherein the dissolving temperature is 60 ℃, and the dissolving time is 24 hours to obtain a fibroin-calcium salt solution with the concentration of 10 w/v%;
s2, diluting the fibroin-calcium salt solution obtained in the step S1, adjusting the pH value, adding a sodium bicarbonate solution, wherein the molar ratio of calcium ions in the fibroin-calcium salt solution to carbonate ions in the carbonate solution is Ca2+：CO3 2-1:1, gradually dripping the carbonate solution into the fibroin protein-calcium salt solution until the carbonate is completely dripped, and reacting the carbonate with the calcium salt after the dripping is completedThe time is 24 hours, the reaction temperature is 10 ℃, and calcium carbonate-fibroin suspension is obtained after reaction;
s3, centrifuging the calcium carbonate-fibroin suspension obtained in the step S2 at a high speed, pouring out supernatant, adding deionized water for full cleaning, centrifuging and pouring out supernatant, cleaning and drying, and finally grinding into calcium carbonate-fibroin composite ultrafine powder with the particle size of 10 mu m, wherein the fibroin content in the ultrafine powder is 30 wt%, and the calcium carbonate crystal form is a composition of calcite, aragonite and spherulite.
Example 3
A preparation method of calcium carbonate/fibroin composite ultrafine powder comprises the following steps:
s1, degumming silk to obtain silk fibroin fibers, dissolving the silk fibroin fibers in 0.5 w/v% calcium chloride solution at 25 ℃ for 5 hours to obtain 10 w/v% fibroin-calcium salt solution;
s2, diluting the fibroin-calcium salt solution obtained in the step S1, adjusting the pH value, adding a sodium carbonate solution, wherein the molar ratio of calcium ions in the fibroin-calcium salt solution to carbonate ions in the carbonate solution is Ca2+：CO3 2-1:1, gradually dropwise adding a carbonate solution into the fibroin-calcium salt solution until the carbonate is completely dropwise added, reacting the carbonate with the calcium salt for 2 hours at the reaction temperature of 10 ℃ after the dropwise addition is completed, and reacting to obtain a calcium carbonate-fibroin suspension;
s3, centrifuging the calcium carbonate-fibroin suspension obtained in the step S2 at a high speed, pouring out supernatant, adding deionized water for full cleaning, centrifuging and pouring out supernatant, cleaning and drying, and finally grinding into calcium carbonate-fibroin composite ultrafine powder with the particle size of 5 mu m, wherein the fibroin content in the ultrafine powder is 22.3 wt%, and the calcium carbonate crystal form is a composition of calcite, aragonite and spherulite.
Example 4
A preparation method of calcium carbonate/fibroin composite ultrafine powder comprises the following steps:
s1, degumming silk to obtain silk fibroin fibers, dissolving the silk fibroin fibers in 20 w/v% calcium phosphate solution at 30 ℃ for 10 hours to obtain 12 w/v% fibroin-calcium salt solution;
s2, diluting the fibroin-calcium salt solution obtained in the step S1, adjusting the pH value, adding an ammonium carbonate solution, wherein the molar ratio of calcium ions in the fibroin-calcium salt solution to carbonate ions in the carbonate solution is Ca2+：CO3 2-1:1, gradually dropwise adding a carbonate solution into the fibroin-calcium salt solution until the carbonate is completely dropwise added, reacting the carbonate with the calcium salt for 5 hours at the reaction temperature of 20 ℃ after the dropwise addition is completed, and reacting to obtain a calcium carbonate-fibroin suspension;
s3, centrifuging the calcium carbonate-fibroin suspension obtained in the step S2 at a high speed, pouring out a supernatant, adding deionized water for full cleaning, centrifuging and pouring out the supernatant, cleaning and drying, and finally grinding into calcium carbonate-fibroin composite ultrafine powder with the particle size of 1-10 mu m, wherein the content of fibroin in the ultrafine powder is 23.6 wt%, and the crystalline form of the calcium carbonate is a calcite, aragonite and spherulite composition.
Example 5
A preparation method of calcium carbonate/fibroin composite ultrafine powder comprises the following steps:
s1, degumming silk to obtain silk fibroin fibers, dissolving the silk fibroin fibers in a 2.8 w/v% calcium chloride solution at 50 ℃ for 1h to obtain a 15 w/v% fibroin-calcium salt solution;
s2, diluting the fibroin-calcium salt solution obtained in the step S1, adjusting the pH value, adding a sodium carbonate solution, wherein the molar ratio of calcium ions in the fibroin-calcium salt solution to carbonate ions in the carbonate solution is Ca2+：CO3 2-1:1, gradually dropwise adding a carbonate solution into the fibroin-calcium salt solution until the carbonate is completely dropwise added, reacting the carbonate with the calcium salt for 5 hours at the reaction temperature of 20 ℃ after the dropwise addition is completed, and reacting to obtain a calcium carbonate-fibroin suspension;
s3, centrifuging the calcium carbonate-fibroin suspension obtained in the step S2 at a high speed, pouring out supernatant, adding deionized water for full cleaning, centrifuging and pouring out supernatant, cleaning and drying, and finally grinding into calcium carbonate-fibroin composite ultrafine powder with the particle size of 6 mu m, wherein the content of fibroin in the ultrafine powder is 45.2 wt%, and the crystalline form of calcium carbonate is a composition of calcite, aragonite and spherulite. The calcium carbonate/silk fibroin composite ultrafine powder prepared in the embodiment is shot by a scanning electron microscope, infrared and XRD detection is carried out, and the electron microscope picture shows that the particle size of the calcium carbonate-silk fibroin powder is 2-10 mu m, the calcium carbonate-silk fibroin powder is uniformly dispersed without agglomeration, the powder is cubic or rhombic, and the surface of the calcium carbonate is wrapped by silk fibroin, which shows that the calcium carbonate particles and the silk fibroin are successfully compounded; from the infrared spectrum, 1626cm-1 belongs to the characteristic peak of the silk fibroin amide I, and the characteristic peaks of calcium carbonate are 874cm-1 and 713cm-1, which shows that the calcium carbonate is mainly calcite and aragonite. The infrared spectrum proves that the powder prepared by the invention is a calcium carbonate and silk fibroin complex; the XRD pattern proves that the calcium carbonate crystal structure in the calcium carbonate-silk fibroin composite powder mainly takes calcite as a main component and is mixed with a small amount of aragonite and aragonite.
Claims (8)
1. A preparation method of calcium carbonate/fibroin composite ultrafine powder is characterized by comprising the following steps:
s1, degumming silk to obtain silk fibroin fibers, and dissolving the silk fibroin fibers in a calcium salt solution to obtain a silk protein-calcium salt solution;
s2, diluting the fibroin-calcium salt solution obtained in the step S1, adjusting the pH value, adding a carbonate solution, fully stirring and mixing, and reacting to obtain a calcium carbonate-fibroin suspension;
s3, centrifuging the calcium carbonate-fibroin suspension obtained in the step S2 at a high speed, pouring out supernatant, adding deionized water for full cleaning, centrifuging, pouring out supernatant, cleaning, drying, and finally grinding into calcium carbonate-fibroin composite ultrafine powder.
2. The method of claim 1, wherein: the silk in the step S1 is one or a combination of two or more of mulberry silk, tussah silk and castor-oil plant silk.
3. The method of claim 1, wherein: in the step S1, the calcium salt is one or a combination of two or more of calcium chloride, calcium bromide, calcium iodide, calcium nitrate and calcium phosphate.
4. The method of claim 1, wherein: in the step S1, the concentration of silk fibroin fibers in the fibroin-calcium salt solution is 1-50 w/v%, the concentration of calcium salt is 0.1-90 w/v%, the dissolving temperature is 25-100 ℃, and the dissolving time is 0.5-24 h.
5. The method of claim 1, wherein: the carbonate in the step S2 is one or a combination of two or more of ammonium carbonate, sodium carbonate and sodium bicarbonate.
6. The method of claim 1, wherein: the molar ratio of calcium ions in the fibroin-calcium salt solution in the step S2 to carbonate ions in the carbonate solution is Ca2+：CO3 2-1:1, gradually dripping the carbonate solution into the fibroin protein-calcium salt solution until the carbonate is completely dripped, and after the dripping is completed, reacting the carbonate with the calcium salt for 0.1-24 h at the reaction temperature of 10-100 ℃.
7. The method of claim 1, wherein: in the step S3, the particle size of the calcium carbonate-fibroin composite ultrafine powder is 1-10 μm, the content of fibroin in the ultrafine powder is 1-50 wt%, and the crystalline form of calcium carbonate is one or a combination of two or more of calcite, aragonite and spherulite.
8. The use of calcium carbonate/fibroin composite micropowder prepared by the preparation method according to claims 1-8 in the cosmetic field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111066125.0A CN113817183A (en) | 2021-09-13 | 2021-09-13 | Preparation method of calcium carbonate/fibroin composite ultrafine powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111066125.0A CN113817183A (en) | 2021-09-13 | 2021-09-13 | Preparation method of calcium carbonate/fibroin composite ultrafine powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113817183A true CN113817183A (en) | 2021-12-21 |
Family
ID=78914382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111066125.0A Pending CN113817183A (en) | 2021-09-13 | 2021-09-13 | Preparation method of calcium carbonate/fibroin composite ultrafine powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113817183A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116474177A (en) * | 2023-05-30 | 2023-07-25 | 山东大学 | Unilateral in-situ mineralized barrier membrane and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0025993A1 (en) * | 1979-09-20 | 1981-04-01 | Kanebo, Ltd. | Fibroin-coated pigment and processes for producing same |
| CN101081932A (en) * | 2007-06-06 | 2007-12-05 | 浙江理工大学 | Silk fibroin /calcium carbonate nano composite material and preparation method thereof |
| CN106587126A (en) * | 2016-12-09 | 2017-04-26 | 宁波芸生纺织品科技有限公司 | Calcium carbonate nanowire and preparation method thereof |
-
2021
- 2021-09-13 CN CN202111066125.0A patent/CN113817183A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0025993A1 (en) * | 1979-09-20 | 1981-04-01 | Kanebo, Ltd. | Fibroin-coated pigment and processes for producing same |
| CN101081932A (en) * | 2007-06-06 | 2007-12-05 | 浙江理工大学 | Silk fibroin /calcium carbonate nano composite material and preparation method thereof |
| CN106587126A (en) * | 2016-12-09 | 2017-04-26 | 宁波芸生纺织品科技有限公司 | Calcium carbonate nanowire and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116474177A (en) * | 2023-05-30 | 2023-07-25 | 山东大学 | Unilateral in-situ mineralized barrier membrane and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105935455A (en) | Cellulose/hydroxyapatite nano composite material and preparation method thereof | |
| CN108821322B (en) | Preparation method of microsphere precipitated calcium carbonate with layered structure | |
| Wang et al. | Processing and characterization of powdered silk micro-and nanofibers by ultrasonication | |
| CN113817183A (en) | Preparation method of calcium carbonate/fibroin composite ultrafine powder | |
| CN106587126B (en) | A kind of calcium carbonate nano wire and preparation method thereof | |
| Wei et al. | Novel synthesis strategy for composite hydrogel of collagen/hydroxyapatite-microsphere originating from conversion of CaCO3 templates | |
| JPH04337331A (en) | Modified silk fine powder and production thereof | |
| CN110357978A (en) | A kind of preparation method of selenide of carragheen | |
| Chen et al. | Biomimetic synthesis of coexistence of vaterite-calcite phases controlled by histidine-grafted-chitosan | |
| CN110713738A (en) | Novel formaldehyde-removing inorganic shell powder coating and preparation method thereof | |
| KR101676796B1 (en) | A method for manufacturing of sponge powder having acicular structure and a sponge powder having acicular structure manufactured therefrom | |
| CN104692439A (en) | Vaterite calcium carbonate microspheres and preparation method thereof | |
| CN110357056B (en) | Preparation method of hydroxyapatite | |
| CN111517352B (en) | Preparation method of high-purity vaterite type calcium carbonate microspheres | |
| Yu et al. | Recent advances in polymer directed crystal growth and mediated self-assembly of nanoparticles | |
| JP4728430B2 (en) | Powder cosmetic and method for producing flat calcium sulfate dihydrate used therefor | |
| JP4441252B2 (en) | Calcium carbonate having an uneven surface and method for producing the same | |
| WO2006011661A1 (en) | Cosmetic composition | |
| CN102328922A (en) | Preparation method of nano hydroxyapatite | |
| Liu et al. | Morphologies-controlled synthesis of CaWO4 crystals by a novel supramolecular template method | |
| CN111003714A (en) | Modification method of attapulgite clay for cosmetics | |
| JPS6110503A (en) | Cosmetic | |
| CN102558292A (en) | Preparation method of fibroins of different forms | |
| Shi et al. | Regulation of the micromorphology and performance of cellulose hydrogels by silk nanofibers | |
| CN113350381A (en) | Method for improving protein ratio of pearl hydrolysate and treatment solution |
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 |