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1.
Gelatin/chitosan hydrogels have attracted considerable attention over the last 2 decades in various fields of applications. In this paper, chemically crosslinked composite hydrogels with different gelatin-to-chitosan weight ratios were fabricated and crosslinked with different amounts of genipin via the solvent casting technique combined with freeze-drying. Fourier-transform infrared, scanning electron microscopy (SEM), liquid displacement method, and gravimetric analysis were used to examine the chemical, microstructural, and physical properties of the hydrogels. IR spectra confirmed the formation of covalent bonds between the amino groups of the parent's macromolecules and genipin. SEM micrographs indicated that the hydrogels possessed a highly porous structure with well-defined pore geometries. The swelling capacity and degradation rate of the specimens reduced with increasing the amounts of chitosan and/or genipin. In-depth swelling measurements revealed that the first-order kinetic model was only applicable in the early stage of the swelling study; however, the water absorption behavior of the hydrogels was best described by the pseudo-second-order kinetic model (Schott's model) throughout the swelling experiment. The genipin-crosslinked hydrogels were found to support MC3T3-E1 cell proliferation. The results of this paper thus suggest the 1.5% genipin-crosslinked gelatin/chitosan hydrogels as promising candidates for on-demand drug delivery applications or more precisely osteoarthritis drug delivery systems.  相似文献   

2.
It was suggested in our previous studies that carbodiimide‐ and genipin‐crosslinked gelatin hydrogels could be used as bioadhesives to overcome the cytotoxicity problem associated with formaldehyde‐crosslinked gelatin hydrogels. In this study, we investigated the crosslinking structures of carbodiimide‐ and genipin‐crosslinked gelatin hydrogels. We found that crosslinking gelatin hydrogels with carbodiimide or genipin could produce distinct crosslinking structures because of the differences in their crosslinking types. Carbodiimide could form intramolecular crosslinks within a gelatin molecule or short‐range intermolecular crosslinks between two adjacent gelatin molecules. On the basis of gel permeation chromatography, we found that the polymerization of genipin molecules could occur under the conditions used in crosslinking gelatin hydrogels via a possible aldol condensation. Therefore, besides intramolecular and short‐range intermolecular crosslinks, additional long‐range intermolecular crosslinks could be introduced into genipin‐crosslinked gelatin hydrogels. Crosslinking a gelatin hydrogel with carbodiimide was more rapid than crosslinking with genipin. Therefore, the gelation time for the carbodiimide‐crosslinked gelatin hydrogels was significantly shorter than that of the genipin‐crosslinked gelatin hydrogels. However, the cohesive (interconnected) structure of the carbodiimide‐crosslinked gelatin hydrogels was readily broken because, unlike the genipin‐crosslinked gelatin hydrogels, there were simply intramolecular and short‐range intermolecular crosslinks present in the carbodiimide‐crosslinked hydrogel. In the cytotoxicity study, the carbodiimide‐crosslinked gelatin hydrogels were dissolved into small fragments in the cultural medium within 10 min. In contrast, the genipin‐crosslinked gelatin hydrogels remained intact in the medium throughout the entire course of the study. Again, this may be attributed to the differences in their crosslinking structures. The genipin‐crosslinked gelatin hydrogels were less cytotoxic than the carbodiimide‐crosslinked gelatin hydrogels. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4017–4026, 2004  相似文献   

3.
4.
A variety of polymers of synthetic origins (e.g., poly(ethylene glycol) or PEG) and macromolecules derived from natural resources (e.g., silk fibroin or SF) have been explored as the backbone materials for hydrogel crosslinking. Purely synthetic PEG‐based hydrogels are often chemically crosslinked to possess limited degradability, unless labile motifs are designed and integrated into the otherwise non‐degradable macromers. On the other hand, SF produced by Bombyx mori silkworm can be easily formulated into physical hydrogels. These physical gels, however, are less stable than the chemically crosslinked gels. Here, we present a simple strategy to prepare hybrid PEG‐SF hydrogels with chemically crosslinked PEG network and physically entrapped SF. Visible light irradiation initiated rapid thiol‐acrylate gelation to produce a network composed of non‐degradable poly(acrylate‐co‐NVP) chains, hydrolytically labile thioether ester bonds, and interpenetrating SF fibrils. We evaluated the effect of SF entrapment on the crosslinking efficiency and hydrolytic degradation of thiol‐acrylate PEG hydrogels. We further examined the effect of adding soluble SF or sonicated SF (S‐SF) on physical gelation of the hybrid materials. The impacts of SF or S‐SF inclusion on the properties of chemically crosslinked hybrid hydrogels were also studied, including gel points, gel fraction, equilibrium swelling ratio, and mesh size. We also quantified the fraction of SF retention in PEG hydrogels, as well as the influence of remaining SF on moduli and degradation of chemically crosslinked thiol‐acrylate PEG hydrogels. This simple hybrid hydrogel fabrication strategy should be highly useful in future drug delivery and tissue engineering applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43075.  相似文献   

5.
The purpose of this study was to improve the biocompatibility of glutaraldehyde (GA) cross‐linked chitosan coated collagen scaffold for cartilage tissue regeneration. In order to prevent the potential toxicity of GA, we treated the designed scaffold with either glutamic acid or glycine. Amino acid treated scaffolds were characterized by scanning electron microscopy (SEM) techniques. Afterward, chondrocyte interaction with the composite scaffold was investigated assessing cell adhesion and proliferation using Hoechst staining and MTT cell proliferation assay, respectively. The SEM analyses of the scaffolds’ surface and cross‐section confirmed the adhesion of amino acids on the surface of the scaffolds. We also observed that scaffolds’ porosity was reduced due to the coverage of the pores by chitosan and amino acids, leading to low porosity. The use of amino acid improved the chondrocyte adhesion and proliferation inside the scaffolds’ pores when cells were cultured onto the chitosan‐coated collagen scaffolds. Overall, our in vitro results suggest the use of amino acid to improve the biocompatibility of natural polymer composite scaffold being crosslinked with glutaraldehyde. Such scaffold has improved mechanical properties; biocompatibility thus may be useful for tissue regeneration such as cartilage.
  相似文献   

6.
BACKGROUND: Stimuli‐sensitive or intelligent hydrogels have been investigated for many biomedical and pharmaceutical applications. Those hydrogels with dual sensitivity will have more extensive potential applications. The aim of the work presented was to prepare a series of thermo‐ and pH‐sensitive hydrogels based on poly(vinylmethyl ether) (PVME) and carboxymethylchitosan (CMCS). The hydrogels were crosslinked using electron beam irradiation (EB) or using glutaraldehyde (GA) as a crosslinker at room temperature. RESULTS: The structures of the PVME/CMCS hydrogels obtained using the two crosslinking methods are proposed. The effects of component polymer ratio, GA content, irradiation dose, temperature and pH on the swelling behavior of the PVME/CMCS hydrogels were studied. There is a sharp decrease in the swelling ratios when the temperature increases from 25 to 37 °C. At low pH and also at high pH, the hydrogels have a higher swelling ratio; however, deswelling occurs evidently at a pH of around 3. CONCLUSION: The study shows that both EB and GA crosslinked hydrogels are thermo‐ and pH‐ sensitive, simultaneously. Thus, they may be potential candidates for both thermo‐ and pH‐sensitive applications. Copyright © 2009 Society of Chemical Industry  相似文献   

7.
In this study, freezing was used to separate a solute (polymer) and solvent (deionized water). The polymer in the ice crystals was then crosslinked with solvents, and this diminished the linear pores to form a porous structure. Gelatin and chitosan were blended and frozen, after which crosslinking agents were added, and the whole was frozen again and then freeze‐dried to form chitosan/gelatin porous bone scaffolds. Stereomicroscopy, scanning electron microscopy, compressive strength testing, porosity testing, in vitro biocompatibility, and cytotoxicity were used to evaluate the properties of the bone scaffolds. The test results show that both crosslinking agents, glutaraldehyde (GA) and 1‐ethyl‐3‐(3‐dimethylaminopropyl) carbodiimide, were able to form a porous structure. In addition, the compressive strength increased as a result of the increased crosslinking time. However, the porosity and cell viability were not correlated with the crosslinking times. The optimal porous and interconnected pore structure occurred when the bone scaffolds were crosslinked with GA for 20 min. It was proven that crosslinking the frozen polymers successfully resulted in a division of the linear pores, and this resulted in interconnected multiple pores and a compressively strong structure. The 48‐h cytotoxicity did not affect the cell viability. This study successfully produced chitosan/gelatin porous materials for biomaterials application. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41851.  相似文献   

8.
In the last few years, several strategies have been proposed to fabricate scaffolds for tissue engineering (TE) applications; however, they are based on harsh and time‐consuming techniques. The choice for natural polymers such as cashew gum (CG) allows to circumvent the demands of biocompatibility and degradability of TE systems. In this work, CG, a polysaccharide derived from Anacardium occidentale trees, is functionalized with aldehyde groups through periodate oxidation. The resultant oxidized cashew gum (CGO) is mixed with gelatin (GE) to yield a covalently crosslinked hydrogel. CGO/GE sponges are obtained by employing a freeze‐drying methodology to the previously obtained hydrogels. The mechanical properties, swelling ability, and porosity of the GE/CGO sponges are tuned by using CGO with different degrees of oxidation. The resultant sponges can maintain high levels of water absorption and recover their initial mechanical properties after cyclic compression. Moreover, these porous and mechanically robust devices can support the adhesion and proliferation of cells, which can envision their application for the regeneration of soft tissues.  相似文献   

9.
The design of scaffolding materials that mimic the properties of the target tissue to be regenerated is a mandatory requirement to engineer a successful scaffold; however, the heterogeneous properties of adipose tissue (AT), strictly dependent on the AT depot, are often underestimated when engineering AT scaffolds. Moreover, a scaffolding material with versatile properties, suitable for the regeneration of different AT depots, is currently missing. Chemically crosslinked gelatin hydrogels are here prepared, and their properties tuned by varying gelatin concentration and reaction stoichiometry to obtain hydrogels suitable for AT regeneration. All hydrogel formulations are stable in water at 37 °C, showing swelling behavior dependent on synthesis parameters. The mechanical compressive response mimics the viscoelastic response typical of native AT, with elastic modulus values covering the range of breast and heel pad AT. The rheological properties vary among the hydrogel formulations, showing a typical shear thinning response, comparable to other AT scaffolds described in literature. In vitro cytotoxicity tests using 3T3-L1 preadipocytes show no cytotoxic effects up to 7 days. 3T3-L1 cells seeded on the hydrogels show good adhesion, proliferation, and adipogenic differentiation, confirmed by an increase in peroxisome proliferator-activated receptor gamma gene expression and lipid droplets accumulation observed by Oil Red O staining. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47104.  相似文献   

10.
This work presents the synthesis of polyacrylamide-gelatin (PAM-G) semi-interpenetrating hydrogels, as well as the study of the swelling capacity of this material at different pH’s, and we report its Young modulus. The hydrogels were crosslinked with N,N′-methylenebisacrylamide and synthesized at different acrylamide/gelatin weight relationship. It was observed that the swelling capacity of the hydrogels increases when the gelatin concentration is increased; while the Young modulus (at the swelling equilibrium) decreases lightly. Therefore, the gelatin has a small effect in the Young modulus, unlike its influence in the swelling ability. The swelling experiments reveal that the PAM-G hydrogels increase its swelling capacity in alkaline mediums because the presence of the hydrophobic functional groups (mainly COO) in the gelatin structure.  相似文献   

11.
Semi-IPN hydrogels based gelatin (GEL) and/or poly (ethylene glycol) (PEG) were prepared with acrylamide (AAm) and 4-styrenesulfonic acid sodium salt, (SSS) as a water adsorbent for cationic dye (methyl violet, MV) sorption. For this, chemically crosslinked copolymer of AAm/SSS copolymer with GEL and/or PEG were prepared by polymerization of aqueous solution of AAm and SSS using ammonium persulfate (APS)/N,N,N′,N′-tetramethylethylenediamine (TEMED) as redox initiating pair in presence of poly(ethylene glycol)diacrylate (PEGDA) as crosslinker. FT-IR analysis was used to identify the presence of different repeating units in the semi-IPNs. Surface morphology was characterized by scanning electron microscopy (SEM). Some swelling and diffusion characteristics were calculated for different semi-IPNs and hydrogels prepared under various formulations. Water uptake, and dye sorption properties of the crosslinked polymeric systems such as AAm/SSS, AAm/GEL/SSS, AAm/PEG/SSS and AAm/GEL/PEG/SSS hydrogel systems were investigated as a function of chemical composition of the hydrogels. MV have used in sorption studies.  相似文献   

12.
In this study, synergistic effects of crosslinking and chitosan molecular weight on the microstructure, molecular mobility, thermal, and sorption properties of porous chitosan/gelatin/hyaluronic acid hybrid foams are reported. Fourier transform infrared spectroscopy has been utilized to confirm the covalent attachment of hyaluronic acid to gelatin and chitosan, and covalent chemical crosslinking between gelatin and chitosan. Detailed image analysis of scanning electron microscopy images of the porous scaffold hydrids reveal that the pore size of the materials formulated using either low‐ or high‐molecular‐weight chitosan increases significantly upon crosslinking using ethyl(dimethylaminopropyl) carbodiimide/N‐Hydroxysuccinimide. These microstructural changes are even more pronounced for the crosslinked hybrid scaffolds formulated using low‐molecular‐weight chitosan, highlighting a synergistic effect between crosslinking and the use of low‐molecular‐weight chitosan. Results obtained using differential scanning calorimetry demonstrate a significant reduction in molecular mobility reduction in molecular mobility for crosslinked scaffolds formed using high‐molecular‐weight chitosan compared to non‐crosslinked hybrids and crosslinked hybrids formulated using low‐molecular‐weight chitosan. Correspondingly, dynamic vapor sorption evidenced significantly lower water vapor sorption for crosslinked scaffolds formulated using high‐molecular‐weight chitosan. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44772.  相似文献   

13.
ABSTRACT

Gelatin hydrogel has been widely applied in bio-applications due to their good biocompatibility and high water content. However, poor mechanical properties of gelatin hydrogel greatly limit their application. Here we present a facile one-step soaking method to fabricate a recoverable gelatin hydrogel with high mechanical property, which is based on hydrogen bonds and metal ionic interaction. The mechanical properties of gelatin hydrogels can be tuned with different metal ions, temperatures and soaking times. Especially, gelatin-Fe3+ hydrogel can reach to 65 MPa compression stress with the compressive strain over 99% and possess good fatigue resistance under cyclic loadings. Besides, hydrogels crosslinked with metal ions show better antibacterial ability against Escherichia coli and Staphylococcus aureus. This work suggested an alternative for the design of tough gelatin-based hydrogels with desirable properties, which may hold promising for potential bio-applications under physiological conditions.  相似文献   

14.
Thiol–norbornene (thiol–ene) photoclick hydrogels have emerged as a diverse material system for tissue engineering applications. These hydrogels are crosslinked through light‐mediated orthogonal reactions between multifunctional norbornene‐modified macromers [e.g., poly(ethylene glycol) (PEG), hyaluronic acid, gelatin] and sulfhydryl‐containing linkers (e.g., dithiothreitol, PEG–dithiol, biscysteine peptides) with a low concentration of photoinitiator. The gelation of thiol–norbornene hydrogels can be initiated by long‐wave UV light or visible light without an additional coinitiator or comonomer. The crosslinking and degradation behaviors of thiol–norbornene hydrogels are controlled through material selections, whereas the biophysical and biochemical properties of the gels are easily and independently tuned because of the orthogonal reactivity between norbornene and the thiol moieties. Uniquely, the crosslinking of step‐growth thiol–norbornene hydrogels is not oxygen‐inhibited; therefore, gelation is much faster and highly cytocompatible compared with chain‐growth polymerized hydrogels with similar gelation conditions. These hydrogels have been prepared as tunable substrates for two‐dimensional cell cultures as microgels and bulk gels for affinity‐based or protease‐sensitive drug delivery, and as scaffolds for three‐dimensional cell encapsulation. Reports from different laboratories have demonstrated the broad utility of thiol–norbornene hydrogels in tissue engineering and regenerative medicine applications, including valvular and vascular tissue engineering, liver and pancreas‐related tissue engineering, neural regeneration, musculoskeletal (bone and cartilage) tissue regeneration, stem cell culture and differentiation, and cancer cell biology. This article provides an up‐to‐date overview on thiol–norbornene hydrogel crosslinking and degradation mechanisms, tunable material properties, and the use of thiol–norbornene hydrogels in drug‐delivery and tissue engineering applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41563.  相似文献   

15.
In this work, chemical crosslinking with 1,4-butanediol diglycidyl ether (BDDGE) is used as strategy to enhance mechanical performance of fish gelatin (FG) gels in order to meet the properties' range of mammalian gelatin physical gels. Joint analysis of free amino groups, swelling ratio, and total soluble material indicates that crosslinking degree increases with increasing FG concentration and it is favored by a 0.2 BDDGE/FG ratio. Increasing crosslinking degree enhances gel indentation strength and shear modulus (μ) while decreases fracture toughness (GIC). Measured μ and GIC values lies within the range exhibited by mammalian gelatin physical gels, but the relationship between these parameters is opposite. This is due to the different fracture mechanisms occurring in chemically crosslinked and physical gels.  相似文献   

16.
Summary Synthesis of superabsorbent hydrogels from pectin was investigated using three kinds of crosslinkers, CaCl2, ethylene glycol diglycidyl ether (EGE), and glutaraldehyde (GA). Among them, GA was the most suitable to attain high absorbency, reaching ca. 500 g/g in pure water. On the contrary, hydrogels crosslinked by CaCl2 and EGE absorbed much less water, their maximum absorbency was around 200 g/g and 40 g/g, respectively. Absorbency in 0.9% NaCl solution of hydrogel crosslinked by GA was as low as 15 g/g, which indicates absorbency of hydrogels in the present study is sensitive to salt concentration. Biodegradability of pectin-based hydrogels in activated sludge at 25 °C for 18 days was 60–65%.  相似文献   

17.
A three dimensional porous hydrogel with suitable biological and mechanical properties are required for bone tissue engineering. Hydrogels of poly(lactic-ethylene oxide fumarate) (PLEOF), crosslinked with poly(ethylene glycol)-diacrylate (PEG-da) have desirable mechanical properties, however, their application for bone regeneration is limited due to the lack of cell motif sites within their structure. The aim of this study was to incorporate a naturally derived polymer such as gelatin into PLEOF hydrogels to promote their biological properties. Interpenetrating polymer network (IPN) was used as an efficient technique to acquire uniform mixture of these two polymers. Additionally gas foaming agents were used to create pores with average diameter of 250 μm in these IPN hydrogels. The concentrations of PEG-da and gelatin were optimized to tune the mechanical strength and degradation properties of these hydrogels. A compression modulus of 500 kPa was achieved for hydrogel fabricated with 400 mg/ml PLEOF, 200 mg/ml PEG-da and 150 mg/ml gelatin. The addition of gelatin to PLEOF elevated the compression modulus by two-fold and decreased the energy loss by 40%. The result of protein analysis demonstrated that IPN substantially enhanced the retention of physically crosslinked gelatin in the 3D structure of hydrogel. More than 50% of gelatin was retained in IPN hydrogel after two weeks of incubation in simulated physiological environment. Preserving gelatin in the hydrogel structure provides cell motif sites for a longer period of time, which is desirable for uniform cell proliferation. In vitro studies showed that primary human osteoblast cells adhered and proliferated in PLEOF-gelatin hydrogel. These results demonstrated the potential of using this IPN hydrogel for bone tissue engineering.  相似文献   

18.
A novel method, the hydrogel foaming, is used in this work for the production of porous, polymer-based materials by processing with supercritical carbon dioxide (CO2). This method is applied to crystalline hydrophilic polymers that, practically, exhibit no phase transition (melting or glass transition) below thermal decomposition temperature and, due to their crystallinity, do not absorb CO2. Such polymers are mainly natural (semi)-crystalline polymers (e.g. chitosan, cellulose, etc.) for which the classical polymer foaming method with supercritical carbon dioxide is not applicable. The hydrogel foaming process (similar to classical polymer foaming) is applied to gelatin, chitosan, and gelatin/chitosan blend hydrogels that are physically crosslinked and may also be chemically crosslinked with glutaraldehyde vapour. After the foaming process, water is removed from the gels by mild freeze-drying leading to porous materials. Pore size control can be achieved by controlling different process parameters. Gelatin exhibits solubility in water up to high concentrations and forms thermoreversible hydrogels, rendering it a suitable choice for the investigation of the process mechanism. The mechanism of hydrogel foaming is explored on the basis of X-ray diffraction, calorimetry, rheology, sorption, Raman spectroscopy measurements and theoretical calculations with the NRHB (Non Random Hydrogen Bonding) equation-of-state model. The sorption and Raman spectroscopy measurements suggest that, besides dissolution in water (of the hydrogel), extensive CO2 sorption by the polymer also occurs. Based on these results, a critical discussion is made and a mechanism for the hydrogel foaming is proposed.  相似文献   

19.
A double-network (DN) polyethylene glycol/polyacrylic acid (PEG/PAA) hydrogel with high compressive strength was synthesized by one-pot solution polymerization. The PEG network crosslinked by glutaraldehyde (GA) was fabricated via condensation reaction while the PAA network crosslinked by N,N’-dimethylenebiacrylamide (MBAM) via free-radical polymerization. The components of hydrogel were analyzed with Fourier transform infrared spectroscopy (FTIR). Mechanical strength of PEG/PAA hydrogels was examined, and the results showed that the addition of GA and PEG endowed the DN hydrogel with a high compressive strength of 10.9 MPa in a water content of 90 wt% due to lightly crosslinking and special entangled bundles morphology. Morphological studies showed that the hydrogels exhibited various pore structures when they were synthesized using different molar ratio of GA to PEG. This work provided a simple way to prepare ultrastrong DN hydrogels.  相似文献   

20.
Photoactive antimicrobial hydrogels were produced by incorporating benzophenone (BP) into glutaraldehyde (GA) crosslinked polyvinyl alcohol (PVA). Structural and functional properties of the BP incorporated PVA/GA (BP:PVA/GA) hydrogels were investigated by FTIR, XRD, SEM, and antimicrobial tests. The durability of the functions was also examined by UV‐Vis spectroscopy, HPLC, MS, and antimicrobial tests. The concentrations of BP and GA in the BP:PVA/GA hydrogels affected the formation of the hydrogels as well as their structures. All BP:PVA/GA hydrogels showed antimicrobial abilities under UVA (365 nm) irradiation, and the effectiveness increased as the amounts of BP in the hydrogels increased. In particular, as‐prepared BP:PVA/GA hydrogels exhibited prominent durability in the photo‐induced antimicrobial ability. POLYM. ENG. SCI., 50:1780–1787, 2010. © 2010 Society of Plastics Engineers  相似文献   

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