CN107459662B - Preparation method of nano composite hydrogel - Google Patents
Preparation method of nano composite hydrogel Download PDFInfo
- Publication number
- CN107459662B CN107459662B CN201710796464.1A CN201710796464A CN107459662B CN 107459662 B CN107459662 B CN 107459662B CN 201710796464 A CN201710796464 A CN 201710796464A CN 107459662 B CN107459662 B CN 107459662B
- Authority
- CN
- China
- Prior art keywords
- chitin
- nano
- composite hydrogel
- preparation
- gelatin
- 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.)
- Active
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
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L89/00—Compositions of proteins; Compositions of derivatives thereof
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Medicinal Preparation (AREA)
- Colloid Chemistry (AREA)
- Cosmetics (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to a preparation method of nano composite hydrogel, belonging to the technical field of hydrogel preparation. The preparation method of the nano composite hydrogel provided by the invention comprises the following steps: 1) performing acidolysis on chitin with acetylation degree of 0.94 to obtain chitin nano whisker enhancer dispersion liquid; 2) and mixing the chitin nano whisker reinforcer dispersion liquid with a gelatin solution, and cooling to obtain the nano composite hydrogel. The nano composite hydrogel prepared by the preparation method has good mechanical property, high gelation temperature and excellent stability in strong acid and high salt ion concentration environment, and can be widely applied to the fields of food, cosmetics and medicines.
Description
Technical Field
The invention relates to the technical field of hydrogel preparation, in particular to a preparation method of nano composite hydrogel.
Background
Hydrogels are three-dimensional polymeric networks that absorb and retain large amounts of water and are widely used in the food, cosmetic, biomedical, and bone tissue and drug loading fields. Hydrogels require high strength and flexibility in application, as well as reversible deformation characteristics. However, conventional chemically crosslinked polymer hydrogels are brittle and brittle under certain pressures. Crosslinked hydrogels, double-network hydrogels and nanocomposite hydrogels are all common hydrogels. The prior art has investigated the enhancement of the mechanical properties of the above-mentioned hydrogels. Among them, studies have shown that double-network hydrogels can enhance the mechanical properties of the gel, but most of these polymer hydrogels require the addition of high concentrations of reinforcing agents, which is not suitable for the food industry. At present, various crosslinking agents (glutaraldehyde, transglutaminase, genipin, etc.) are applied to gelatin hydrogel by a crosslinking method in order to enhance the mechanical properties of the gelatin hydrogel, but these crosslinking agents have problems of potential toxicity and high consumption.
Disclosure of Invention
The invention aims to provide a preparation method of a nano composite hydrogel. The nano composite hydrogel prepared by the preparation method has good mechanical property, high gelation temperature and excellent stability in strong acid and high salt ion concentration environment, and can be widely applied to the fields of food, cosmetics and medicines.
The invention provides a preparation method of nano composite hydrogel, which comprises the following steps:
1) performing acidolysis on chitin with acetylation degree of 0.94 to obtain chitin nano whisker enhancer dispersion liquid;
2) mixing the chitin nano-whisker reinforcer dispersion liquid with a gelatin solution, and cooling to obtain the nano-composite hydrogel.
Preferably, the acidolysis in the step 1) adopts hydrochloric acid solution or sulfuric acid solution
Preferably, the acidolysis temperature in the step 1) is 80-120 ℃.
Preferably, the acidolysis time in the step 1) is 2-16 h.
Preferably, the mass concentration of the gelatin in the gelatin solution in the step 2) is 10-14%.
Preferably, the chitin nanowhisker enhancer of step 2) is added into the gelatin solution in an amount of 0.25-1% w/v.
Preferably, the mixing temperature in the step 2) is 40-60 ℃.
Preferably, the cooling temperature in the step 2) is 4-14 ℃.
Preferably, the cooling time in the step 2) is 12-24 h.
Preferably, the source of chitin comprises shrimp shells, crab shells and insect shells.
The invention provides a preparation method of nano composite hydrogel. The nano chitin whisker is prepared to prepare the nano composite hydrogel, and the nano chitin whisker has the advantages of simple preparation method, rich raw material sources, low price and better biocompatibility; smaller nano chitin whiskers can be prepared, and can be filled into a gelatin matrix to interact with gelatin to prepare the nano composite hydrogel; the obtained hydrogel has high mechanical property and gelation temperature, and has good acid and alkali resistance and salt resistance. Has good application in the fields of food, medicine and cosmetics.
Drawings
Fig. 1 is a projection electron microscope image of nano chitin, gelatin hydrogel and nano composite hydrogel provided in embodiment 4 of the present invention; wherein: a. b is nano chitin; c is gelatin hydrogel; d is nano composite hydrogel;
FIG. 2 is a zeta potential diagram of gelatin solution and chitin suspension provided in inventive example 4; wherein: a is gelatin solution; b is nano chitin;
FIG. 3 is an infrared spectrum of a nano chitin, gelatin, nano composite hydrogel provided in embodiment 4 of the present invention;
fig. 4 is a scanning electron microscope image of the nano composite hydrogel of nano chitin with different concentrations provided in embodiment 4 of the invention;
fig. 5 is a temperature scan graph and a gelation temperature curve graph of the nano composite hydrogel of nano chitin with different concentrations provided in embodiment 4 of the invention;
fig. 6 is a frequency scan of the nano composite hydrogel of nano chitin with different concentrations provided in embodiment 4 of the present invention;
fig. 7 is a graph of compressive stress-strain curves of nanocomposite hydrogels of different concentrations of nanocalcium provided in embodiment 4 of the present invention;
fig. 8 is a graph of the compressive stress strain curves of the nanocomposite hydrogel with different concentrations of nano chitin provided in embodiment 4 of the present invention with different maximum compression ratios;
fig. 9 is a swelling curve diagram of the nanocomposite hydrogel of the nano chitin with different concentrations provided in embodiment 4 of the present invention;
fig. 10 is a frequency scan of the nano composite hydrogel of nano chitin with different pH provided in embodiment 4 of the invention;
fig. 11 is a frequency scan of the nano composite hydrogel of nano chitin with different salt ion concentrations provided in embodiment 4 of the present invention.
Detailed Description
The invention provides a preparation method of nano composite hydrogel, which comprises the following steps:
1) performing acidolysis on chitin with acetylation degree of 0.94 to obtain chitin nano whisker enhancer dispersion liquid;
2) mixing the chitin nano-whisker reinforcer dispersion liquid with a gelatin solution, and cooling to obtain the nano-composite hydrogel.
The invention carries out acidolysis on chitin with acetylation degree of 0.94 to obtain the chitin nanowhisker reinforcing agent. In the invention, hydrochloric acid solution or sulfuric acid solution is adopted in the step 1) acidolysis. When a hydrochloric acid solution is selected for acidolysis, the mass ratio of the chitin to the hydrochloric acid solution is 1 g: 30mL, wherein the molar concentration of the hydrochloric acid solution is preferably 3 mol/L; when the sulfuric acid solution is adopted for acidolysis, the mass ratio of the chitin to the sulfuric acid solution is 1 g: 30mL, and the molar concentration of the sulfuric acid solution is preferably 3 mol/L. In the invention, the acidolysis temperature is 80-120 ℃, and more preferably 95 ℃. In the invention, the acidolysis time is 2-16 h, more preferably 8-12 h, and most preferably 10 h. In the present invention, the acidolysis process preferably includes steps of dialysis, centrifugal water washing, and drying. The conditions of the dialysis are not particularly limited in the present invention, and a dialysis method known to those skilled in the art may be used, and it is preferable to perform centrifugal washing after the dialysis, and the dialysis and centrifugal washing of the present invention serve to remove the acid in the dispersion to make the pH of the dispersion neutral. The method of the centrifugal washing is not particularly limited in the present invention, and the operation conditions of the centrifugal washing known to those skilled in the art may be adopted. The drying method according to the present invention is preferably a lyophilization method, and the conditions for the lyophilization are not particularly limited in the present invention, and may be those well known to those skilled in the art.
After the chitin nano-whisker reinforcing agent is obtained, the invention mixes the chitin nano-whisker reinforcing agent dispersion liquid with gelatin solution and cools to obtain the nano-composite hydrogel. In the invention, the mass concentration of the gelatin in the gelatin solution is 10-14%, and more preferably 12%. In the invention, the addition amount of the chitin nanowhisker enhancer in the gelatin solution is 0.25-1% w/v, and more preferably 0.5-0.7% w/v. In the invention, the mixing temperature is 40-60 ℃, and more preferably 55 ℃. In the invention, the cooling temperature is 4-14 ℃, and more preferably 10-12 ℃. In the invention, the cooling time is 12-24 h, more preferably 15-20 h, the cooling effect is to enable gelatin to form gel, and in the cooling process, the gelatin and the nano chitin are subjected to hydrogen bond interaction and electrostatic interaction to form gel.
The source of the chitin is not particularly limited in the present invention, and in the present invention, the source of the chitin preferably includes shrimp shell, crab shell and insect shell.
The preparation method of a nanocomposite hydrogel according to the present invention is further described in detail with reference to the following specific examples, and the technical solutions of the present invention include, but are not limited to, the following examples.
Example 1
1. Chitin nano whisker enhancer dispersion liquid: chitin with acetylation degree of 0.94 and hydrochloric acid are mixed according to the proportion of 1 g: 30mL of the chitin nano crystal whisker enhancer dispersion liquid is obtained by acidolysis at the acidolysis temperature of 95 ℃ for 10 hours. After the acidolysis process, dialysis, centrifugal water washing and drying are carried out.
2. Nano composite hydrogel: preparing the chitin nano whisker enhancer dispersion liquid into different concentrations, adding the chitin nano whisker enhancer dispersion liquid into a 14% gelatin solution (45 ℃), uniformly mixing the chitin nano whisker enhancer dispersion liquid and the gelatin solution to obtain the final nano chitin solution with the content of 0.25%, 0.5% and 1.0% of the whole solution, and cooling the mixed solution at 4 ℃ for 12 hours to obtain the nano composite hydrogel. In addition, in order to investigate the influence of the pH value and the ion concentration on the composite hydrogel, 1M NaOH or HCl was used to adjust the pH value to 3.0, 4.0, 5.0, 7.0, 8.0 or 9.0, and NaCl was used to adjust the ion concentration to 10, 30, 50, 70, 90 mM.
Example 2
Measurement of gelation temperature and viscoelasticity: the dynamic rheological measurement of the nano composite hydrogel is measured by using a strain controllable rheometer, and the parameters are set as follows: the temperature was 25 ℃, the rotor diameter and the parallel plate gap were 50mm and 1mm, respectively, the frequency sweep was in the angular frequency range 0.1-100rad/s, the constant strain was 1% (in the linear viscoelastic region), and the storage modulus (G') and loss modulus (G ") were recorded. To observe the maturation of the gel samples, time scans were determined, scanning at 10 ℃ for 2.5 h. The temperature was ramped from 40 ℃ to 10 ℃ and then ramped up to 40 ℃ at a rate of 1 ℃ per minute.
Example 3
1. Measurement of mechanical properties: pouring the nano composite hydrogel into a mold with the diameter of 20mm and the height of 10mm, and placing for 12 hours at the temperature of 4 ℃. TPA testing was performed with a physical analyzer and the parameters hardness (g), elasticity, cohesion, tack (g), chewing (g) and recovery were recorded.
The hydrogel was subjected to compression measurement using a physical property analyzer. A block of hydrogel (length: 20mm, width: 10mm, height: 20mm) was placed on the lower plate, covering the entire surface of the gel sample with a P36R probe, and compressed at a strain rate of 1 mm/s. Stress and stress data were recorded during the experiment. Cycling experiments were also performed by repeated compressions.
2. Measurement of swelling characteristics: the swelling characteristics of the nanocomposite hydrogel were studied and calculated according to the following formula:
degree of swelling (W-Wd)/Wd × 100 (1)
These samples were soaked in phosphoric acid buffer solution for 24h, and the wet weight (W) was measured. Then, after freeze-drying, the dry weight (Wd) was measured.
Example 4
1. Microstructure and infrared spectrum analysis of nano chitin and composite hydrogel
FIG. 1 is a projection electron microscope image of nano chitin, gelatin hydrogel and nano composite hydrogel in the invention. Note: FIG. a, FIG. b: nano chitin; and (c) figure: gelatin hydrogel; figure d nanocomposite hydrogels
FIG. 2 is a zeta potential diagram of gelatin solution and chitin suspension. Note: a: gelatin solution; b: nanometer chitin.
FIG. 3 is the infrared spectrum of nano chitin, gelatin and nano composite hydrogel of the present invention.
FIG. 4 is the scanning electron microscope images of the nano composite hydrogel of nano chitin with different concentrations in the invention.
As shown in figures 1-3, the acid-hydrolyzed nano chitin has the average length of 300nm and the diameter of 20nm, and has good dispersibility and no aggregation in aqueous solution and gelatin solution. The infrared spectrum shows that the nano chitin and the gelatin have hydrogen bond interaction in the composite hydrogel matrix. Fig. 4 illustrates a scanning electron micrograph that the pore diameter of the gel is gradually reduced and the number of pores is gradually increased along with the increase of the concentration of the added nano chitin, so that a compact network structure is formed. The infrared spectroscopy experiment proves that the gelatin and the nano chitin have hydrogen bond interaction.
2. Influence of different concentrations of nano chitin on gelation temperature and viscoelasticity of gelatin
FIG. 5 is a temperature scanning graph and a gelation temperature curve graph of the nano-composite hydrogel of nano chitin with different concentrations.
FIG. 6 is a frequency scanning diagram of the nano composite hydrogel of nano chitin with different concentrations in the invention.
FIGS. 5 to 6 show that the gelation temperature increases with increasing concentration of the nano chitin, and when the addition amount is 0.5%, the gelation temperature and the melting temperature are maximum, and the viscoelasticity gradually increases. The frequency scanning result shows that when the concentration of the added nano chitin is 0.5%, the elastic modulus of the composite hydrogel is increased by 42.4%. The nano chitin is shown to increase the viscoelasticity of the gel.
3. Influence of nano chitin with different concentrations on mechanical property and swelling property of gelatin
FIG. 7 is a graph of compressive stress-strain curves of nanocomposite hydrogels of different concentrations of nano chitin according to the present invention.
Fig. 8 is a graph of the compressive stress strain curves of the nanocomposite hydrogel with different concentrations of the nano chitin according to the present invention under different maximum compression ratios.
FIG. 9 is a swelling curve diagram of the nano composite hydrogel of nano chitin with different concentrations in the invention.
Table 1 shows the influence of the nano chitin with different concentrations on the texture properties of the nano composite hydrogel, and fig. 7 to 9 and table 1 show that the addition of the nano chitin increases the gel strength, and TPA analysis shows that the hardness, chewiness and viscosity of the composite hydrogel gradually increase with the increase of the nano chitin concentration, and when the addition amount is 1.0%, the hardness is 1.5% of the hardness of pure gelatin. Compression experiments show that the stress required to break gelatin increases after adding nano chitin, and the force required is the greatest when the addition amount is 0.5%. Swelling experiments show that the swelling property of the gelatin is reduced by adding the nano chitin, and the high mechanical property and the low swelling property of the nano composite hydrogel are shown.
TABLE 1 influence of different concentrations of nano chitin on the texture characteristics of nanocomposite hydrogels
4. Effect of sensitive Environment (salt ion, pH, etc.) on composite hydrogel
FIG. 10 is a frequency scan of the nano-composite hydrogel of nano-chitin with different pH values in the invention.
FIG. 11 is a frequency scanning diagram of nano-composite hydrogel of nano chitin with different salt ion concentrations in the invention
Fig. 10 to 11 show that the nanocomposite hydrogel shows high storage modulus under different PH values and salt ion concentrations, and the composite hydrogel prepared under strong acid, strong base and high salt ion concentrations has a larger elastic modulus than gelatin prepared under the same conditions, indicating that the composite hydrogel has better salt resistance and strong acid resistance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A preparation method of a nano-composite hydrogel comprises the following steps:
1) performing acidolysis, dialysis, centrifugal water washing and drying on chitin with acetylation degree of 0.94 to obtain chitin nanowhisker reinforcing agent;
2) mixing the chitin nano whisker reinforcing agent with a gelatin solution, and cooling to obtain nano composite hydrogel; the mass concentration of gelatin in the gelatin solution is 10-14%; the addition amount of the chitin nano whisker reinforcing agent in the gelatin solution is 0.25-1% w/v; the mixing temperature is 40-60 ℃; the cooling temperature is 4-14 ℃; the cooling time is 12-24 h.
2. The method as claimed in claim 1, wherein the step 1) acid hydrolysis is carried out using a hydrochloric acid solution or a sulfuric acid solution.
3. The preparation method of claim 1, wherein the temperature for acid hydrolysis in step 1) is 80-120 ℃.
4. The preparation method of claim 1, wherein the acidolysis time in the step 1) is 2-16 h.
5. The method according to any one of claims 1 to 4, wherein the source of chitin comprises shrimp shell, crab shell and insect shell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710796464.1A CN107459662B (en) | 2017-09-06 | 2017-09-06 | Preparation method of nano composite hydrogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710796464.1A CN107459662B (en) | 2017-09-06 | 2017-09-06 | Preparation method of nano composite hydrogel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107459662A CN107459662A (en) | 2017-12-12 |
| CN107459662B true CN107459662B (en) | 2020-09-08 |
Family
ID=60551061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710796464.1A Active CN107459662B (en) | 2017-09-06 | 2017-09-06 | Preparation method of nano composite hydrogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107459662B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109897194B (en) * | 2019-01-29 | 2021-09-21 | 南京林业大学 | Preparation method of high-strength hydrogel imitating insect epidermis structure |
| CN114672173B (en) * | 2022-04-24 | 2023-06-20 | 罗赛洛(温州)明胶有限公司 | Water-absorbing gelatin sponge and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102044709B (en) * | 2010-11-05 | 2014-04-02 | 华南师范大学 | Storage battery colloidal electrolyte and preparation method thereof |
| US8911780B2 (en) * | 2011-02-11 | 2014-12-16 | Zx Pharma, Llc | Multiparticulate L-menthol formulations and related methods |
| CN104001208B (en) * | 2014-04-22 | 2015-07-22 | 中国科学院宁波材料技术与工程研究所 | Preparation method for biomacromolecule/chitin nanocrystalline composite scaffold material |
| NZ729417A (en) * | 2014-08-05 | 2024-02-23 | The Univ Of Memphis | Compositions and methods for enhancing healing and regeneration of bone and soft tissue |
| CN106868631A (en) * | 2017-03-02 | 2017-06-20 | 北京理工大学 | A kind of chitin nano whisker, chitin nano fiber and preparation method thereof |
-
2017
- 2017-09-06 CN CN201710796464.1A patent/CN107459662B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107459662A (en) | 2017-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ge et al. | Enhanced mechanical properties and gelling ability of gelatin hydrogels reinforced with chitin whiskers | |
| Chang et al. | Novel hydrogels prepared via direct dissolution of chitin at low temperature: structure and biocompatibility | |
| Afshar et al. | Preparation of aminated chitosan/alginate scaffold containing halloysite nanotubes with improved cell attachment | |
| Ding et al. | A dynamic and self-crosslinked polysaccharide hydrogel with autonomous self-healing ability | |
| Hsieh et al. | Preparation of γ-PGA/chitosan composite tissue engineering matrices | |
| Lin et al. | Effect of polysaccharide nanocrystals on structure, properties, and drug release kinetics of alginate-based microspheres | |
| Marrella et al. | Enhanced mechanical performances and bioactivity of cell laden-graphene oxide/alginate hydrogels open new scenario for articular tissue engineering applications | |
| Schuster et al. | Microstructural, mechanical and mass transport properties of isotropic and capillary alginate gels | |
| Chen et al. | Strong fish gelatin hydrogels enhanced by carrageenan and potassium sulfate | |
| Chang et al. | Nano-biomaterials application: Morphology and physical properties of bacterial cellulose/gelatin composites via crosslinking | |
| Tan et al. | Direct Synthesis of Biodegradable Polysaccharide Derivative Hydrogels through Aqueous Diels‐Alder Chemistry | |
| Jin et al. | In-situ formation of the hydroxyapatite/chitosan-alginate composite scaffolds | |
| Liu et al. | Chitin-natural clay nanotubes hybrid hydrogel | |
| Cheng et al. | Addition of κ-carrageenan increases the strength and chewiness of gelatin-based composite gel | |
| Amaral et al. | Responsive laminarin-boronic acid self-healing hydrogels for biomedical applications | |
| Soares et al. | Development and characterization of hydrogels based on natural polysaccharides: Policaju and chitosan | |
| Onyianta et al. | The effects of morpholine pre-treated and carboxymethylated cellulose nanofibrils on the properties of alginate-based hydrogels | |
| CN107459662B (en) | Preparation method of nano composite hydrogel | |
| Liu et al. | Effects of sodium carbonate and potassium carbonate on colloidal properties and molecular characteristics of konjac glucomannan hydrogels | |
| CN108727610A (en) | A kind of double-network hydrogel and preparation method thereof with high tough, shape memory and self-healing properties | |
| Zhu et al. | A pH-sensitive semi-interpenetrating polymer network hydrogels constructed by konjac glucomannan and poly (γ-glutamic acid): Synthesis, characterization and swelling behavior | |
| Huang et al. | A novel dual crosslinked polysaccharide hydrogel with self-healing and stretchable properties | |
| KR102067187B1 (en) | A preparing method of tissue repair treatment composition using the two step cross-linking and the composition therefrom | |
| Lin et al. | The Hofmeister effect on protein hydrogels with stranded and particulate microstructures | |
| CN110698719A (en) | Preparation of polyvinyl alcohol-based hydrogel |
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 |