Synthesis and characterization of thermo-sensitive semi-IPN hydrogels based on poly(ethylene glycol)-co-poly(ε-caprolactone) macromer, N-isopropylacrylamide, and sodium alginate

Thermo-sensitive semi-IPN hydrogels were prepared via in situ copolymerization of N-isopropylacrylamide (NIPAAm) with poly(ethylene glycol)-co-poly(ε-caprolactone) (PEG-co-PCL) macromer in the presence of sodium alginate by UV irradiation technology. The effects of the sodium alginate content, temperature, and salt on the swelling behavior of the as-obtained hydrogels were studied. The results showed that the swelling ratio of the hydrogels increased with the increasing sodium alginate content at the same temperature, and decreased with the increase in temperature. The salt sensitivity of the semi-IPN hydrogels was dependent on the content of sodium alginate introduced in the hydrogels. The mechanical rheology of the hydrogels and in vitro release behavior of bovine serum albumin (BSA) in situ encapsulated within the hydrogels were also investigated. It was found that the introduction of sodium alginate with semi-IPN structure improved mechanical strength of the hydrogels and the cumulative release percentage of BSA from the hydrogels. Such double-sensitive semi-IPN hydrogel materials could be exploited as potential candidates for drug delivery carriers.     

Electrospun water-soluble carboxyethyl chitosan/poly(vinyl alcohol) nanofibrous membrane as potential wound dressing for skin regeneration

Biocompatible carboxyethyl chitosan/poly(vinyl alcohol) (CECS/PVA) nanofibers were successfully prepared by electrospinning of aqueous CECS/PVA solution. The composite nanofibrous membranes were subjected to detailed analysis by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and X-ray diffraction (XRD). SEM images showed that the morphology and diameter of the nanofibers were mainly affected by the weight ratio of CECS/PVA. XRD and DSC demonstrated that there was strong intermolecular hydrogen bonding between the molecules of CECS and PVA. The crystalline microstructure of the electrospun fibers was not well developed. The potential use of the CECS/PVA electrospun fiber mats as scaffolding materials for skin regeneration was evaluated in vitro using mouse fibroblasts (L929) as reference cell lines. Indirect cytotoxicity assessment of the fiber mats indicated that the CECS/PVA electrospun mat was nontoxic to the L929 cell. Cell culture results showed that fibrous mats were good in promoting the cell attachment and proliferation. This novel electrospun matrix would be used as potential wound dressing for skin regeneration.     

Synthesis and characterization of chitosan-based hydrogels

Biocompatible hydrogels based on water-soluble chitosan–ethylene glycol acrylate methacrylate (CS–EGAMA) and polyethylene glycol diamethacrylate (PEGDMA) were synthesized by photopolymerization. Characterization of morphology, weight loss, water state of hydrogel, pH-sensitivity and cytotoxicity were investigated by scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), X-ray diffraction (XRD), differential scanning calorimetry (DSC), Fourier transform infrared (FTIR), swelling test and methylthiazolydiphenyl-tetrazolium bromide (MTT) assay. The results indicated that the hydrogels were sensitive to pH of the medium, no cytotoxicity for L929 and SW1353, satisfactory for the composite to be used in bioapplications.     

Synthesis of interpenetrating network hydrogel from poly(acrylic acid-co-hydroxyethyl methacrylate) and sodium alginate: Modeling and kinetics study for removal of synthetic dyes from water

Several interpenetrating network (IPN) hydrogels were made by free radical in situ crosslink copolymerization of acrylic acid (AA) and hydroxy ethyl methacrylate in aqueous solution of sodium alginate. N,N′-methylenebisacrylamide (MBA) was used as comonomer crosslinker for making these crosslink hydrogels. All of these hydrogels were characterized by carboxylic content, FTIR, SEM, XRD, DTA–TGA and mechanical properties. Swelling, diffusion and network parameters of the hydrogels were studied. These hydrogels were used for adsorption of two important synthetic dyes, i.e. Congo red and methyl violet from water. Isotherms, kinetics and thermodynamics of dye adsorption by these hydrogels were also studied.     

Preparation of pH- and ionic-strength responsive biodegradable fumaric acid crosslinked carboxymethyl cellulose

A novel biodegradable sodium carboxymethyl cellulose (NaCMC)-based hydrogel was synthesized by using fumaric acid (FA) as a crosslinking agent at various ratios. Hydrogels (CMCF) were characterized using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM). Swelling behaviors of hydrogels were investigated in distilled water, various salt, and pH solutions. The FTIR results indicated the crosslinking between carboxyl groups of FA with hydroxyl group of NaCMC through ester formation. AFM analyses showed that roughness of hydrogel surface decreased with increasing crosslinker concentration. The swelling capacity decreased with an increase in charge of the metal cation (Al(3+)相似文献   

Smart hydrogels based on semi-interpenetrating polymeric networks of collagen-polyurethane-alginate for soft/hard tissue healing,drug delivery devices,and anticancer therapies

In this work, hydrogels based on semi-interpenetrating polymeric networks (semi-IPN) based on collagen-polyurethane-alginate were studied physicochemically and from different approaches for biomedical application. It was determined that the matrices in the hydrogel state are crosslinked by the formation of urea and amide bonds between the biopolymer chains and the polyurethane crosslinker. The increment in alginate content (0–40 wt%) significantly increases the swelling capacity, generating semi-crystalline granular structures with improved storage modulus and resistance to thermal, hydrolytic, and proteolytic degradation. The in vitro bioactivity results indicated that the composition of these novel hydrogels stimulates the metabolic activity of monocytes and fibroblasts, benefiting their proliferation; while in cancer cell lines, it was determined that the composition of these biomaterials decreases the metabolic activity of breast cancer cells after 48 h of stimulation, and for colon cancer cells their metabolic activity decreases after 72 h of contact for the hydrogel with 40 wt% alginate. The matrices show a behavior of multidose release of ketorolac, and a higher concentration of analgesic is released in the semi-IPN matrix. The inhibition capacity of Escherichia coli is higher if the polysaccharide concentration is low (10 wt%). The in vitro wound closure test (scratch test) results indicate that the hydrogel with 20 wt% alginate shows an improvement in wound closure at 15 days of contact. Finally, the bioactivity of mineralization was evaluated to demonstrate that these hydrogels can induce the formation of carbonated apatite on their surface. The engineered hydrogels show biomedical multifunctionality and they could be applied in soft and hard tissue healing strategies, anticancer therapies, and drug release devices.     

Novel complex hydrogels based on N-carboxyethyl chitosan and quaternized chitosan and their controlled in vitro protein release property

A novel pH-responsive hydrogel (CHC) composed of N-carboxyethyl chitosan (CEC) and N-[(2-hydroxy-3-trimethylammonium) propyl] chitosan chloride (HTCC) was synthesized by the redox polymerization technique. Turbidimetric titrations were used to determine the stoichiometric ratio of these two chitosan derivatives. The hydrogel was characterized by FT-IR, thermal gravimetric analysis (TGA), X-ray diffractometry (XRD), and scanning electron microscopy (SEM). The dynamic transport of water showed that the hydrogel reached equilibrium within 48 h. The swelling ratio of CHC hydrogel depended significantly on the pH of the buffer solution. The performance of the CHC as a matrix for the controlled release of BSA was investigated. It was found that the release behavior was determined by pH value of the medium as well as the intermolecular interaction between BSA and the hydrogels.     

Preparation, characterization and properties of aminoethyl chitin hydrogels

Aminoethyl chitins (AEC) with different amino contents were synthesized from chitin and 2-chlorethylamine hydrochloride, and the AEC hydrogels were prepared by crosslinking with glutaraldehyde. The microstructures, swelling behaviors and antibacterial activities of the hydrogels were investigated. The results of Fourier transform infrared spectroscopy (FTIR), (1)H nuclear magnetic resonance ((1)H NMR) spectrum and scanning electron microscopy (SEM) showed that the hydrogels were prepared by forming the Schiff base from AEC and glutaraldehyde. The aminoethyl chitin hydrogels were sensitive to acidic environment. The swelling ratio changed with the amino content of AEC, declined with the increase of the crosslinking agent concentration and increased with the increase of the AEC concentration. In addition, the antibacterial results of the hydrogels against Staphylococcus aureus (S. aureus) indicated that the hydrogels had good antibacterial activities, and the antibacterial properties were affected by the amino content of AEC and the crosslinking agent concentration.     

IPNs based on chitosan with NVP and NVP/HEMA synthesised through photoinitiator-free photopolymerisation technique for biomedical applications

Biocompatible interpenetration polymeric network (IPN) hydrogels based on chitosan with N-vinylpyrrolidinone (NVP) as well as its copolymer with 2-hydroxymethyl methacrylate (HEMA) were synthesised using the photopolymerisation technique without the inclusion of any photoinitiator or crosslinking agent. These hydrogels were characterised using the Fourier-transform infrared spectroscopy (FTIR) technique. Equilibrium swelling of these hydrogels was performed in Milli-Q water and drug release studies were carried out using theophylline as the model drug. These tests showed that the IPN comprised of chitosan and NVP with a very small amount of N-hydroxymethyl maleimide (HMMI) included exhibited higher swelling abilities and fast drug release rates than the IPN which contained chitosan, NVP and HEMA. Kinetic studies of water diffusion into these hydrogels and drug release revealed that with the exception of the IPN with HEMA incorporated, the other hydrogels did not adhere to the Fickian diffusion model. These hydrogels were tested for their biocompatibility with human epidermal keratinocyte cells (HaCaT). A positive cell growth as evidenced by the 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl tetrazolium bromide (MTT) cell proliferation assay indicated that these hydrogels are non-toxic to human keratinocytes and can be potentially used as biomaterials for biomedical applications.     

Synthesis and characterization of thermosensitive graft copolymer of N-isopropylacrylamide with biodegradable carboxymethylchitosan

A novel thermosensitive and hydrogel was designed and synthesized by graft copolymerization of N-isopropylacrylamide (NIPAAm) with biodegradable carboxymethylchitosan (CMCS). The influence of the content of CMCS grafted on the properties of the resulted hydrogels was examined. The morphology of the hydrogels was observed by scanning electron microscopy (SEM), their thermal property was characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and deswelling/swelling kinetics upon external temperature changes. In comparison with the conventional PNIPAAm hydrogels, the resulted hydrogels have improved thermosensitive properties, including enlarged water content at room temperature and faster deswelling/swelling rate upon heating. The strategy described here presents a potential alternative to the traditional synthesis techniques for thermosensitive hydrogels.     

Structure and characterization of amphoteric semi-IPN hydrogel based on cationic starch

A series of semi-interpenetrating polymer network (semi-IPN) materials were prepared by blending polymerization of acrylic acid (AA) in cationic starch (CS) and poly(methacryloyloxyethyl trimethylammonium chloride) (PDMC) solution. The crosslinker concentration, the feed ratio of the CS-g-AA to PDMC was discussed in term of the swelling capacity, and hydrogel properties were evaluated by network parameters M_c, morphological and compressive load tests. The semi-IPN hydrogels were also characterized by FT-IR spectroscopy to confirm the interactions between CS-g-AA and PDMC. Electron microscopy involved to staining of the anionic phases using CsF showed a transition from two-phase to compatible structure with the increasing content of PDMC, and further confirmed that the semi-IPN structure in hydrogels along with DSC. The resultant semi-IPN hydrogels were found to possess appreciable compatibility, good swellability and mechanical strength.     

Preparation and characterization of films based on zirconium sulfophenyl phosphonate and chitosan

Zirconium sulfophenyl phosphonate (ZrSP), Zr(O₃P-C₆H₄SO₃H)₂, was synthesized and characterized to prepare nanocomposites based on chitosan (CS). The effects of ZrSP on the structure, morphology, and thermal properties, as well as the mechanical properties of the films were investigated by Fourier-transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM), and tensile tests. FTIR spectroscopy revealed that electrostatic interactions had been formed in the nanocomposites, which improved the compatibility between CS and ZrSP. XRD and SEM results indicated the ZrSP nanoparticles were uniformly distributed in the chitosan matrix at low loading, and obvious aggregations existed at high loading. In addition, compared with neat CS, the values of tensile strength (σ_b), elongation at break (ε_b), and water resistance of CS/ZrSP-3 containing 0.6 wt % ZrSP had been improved by 60.0%, 69.7%, and 41.8%, respectively.     

Physicochemical characteristics of microbial content in a modified anaerobic inclining-baffled reactor (MAI-BR) treating recycled paper mill effluent (RPME)

Abstract

Microbial content formed in bioreactors plays a significant role in the anaerobic process. Therefore, the physicochemical characteristics of microbial content in a modified anaerobic inclining-baffled reactor (MAI-BR) treating recycled paper mill effluent (RPME) were investigated using Fourier transform infrared (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric (TG), and derivative thermogravimetric (DTG) analyses, scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), Brunauer-Emmett-Teller (BET), and surface area analyzer. FTIR spectra revealed that the microbial content had stronger characteristic peaks corresponding to alcohols, water, lipids carbohydrates, proteins, and mineral compounds. Calcite, muscovite, and lepidolite were the prevalent mineral phases found by XRD analysis. The elemental of these minerals like C, Ca, N, O, and Si was confirmed by XPS results. The microbial content samples from each compartment showed similar thermal behavior. SEM images showed that straight rod-shaped and Methanosaeta-like microorganisms were predominant, whereas C, O, and Ca were noticed by EDS on the surface of granules. The BET surface areas and pores of granules are found to decline throughout the reactor’s compartment, where Compartment 1 had the largest values. Thus, the findings of this study establish further understanding of the physicochemical properties of microbial content formed in MAI-BR during the RPME treatment.     

Preparation,characterization, bioactive and cell attachment studies of α-chitin/gelatin composite membranes

The chitin/gelatin composite membranes were prepared by mixing of chitin hydrogel with gelatin. The prepared composite membranes were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), mechanical, swelling, enzymatic degradation and thermal studies. The XRD pattern of the chitin/gelatin composite membranes showed almost the same pattern as α-chitin. The bioactivity studies of these chitin/gelatin membranes were carried out with the simulated body fluid solution (SBF) for 7, 14 and 21 days followed by the characterization with the scanning electron microscopy (SEM) and Energy Dispersive Spectrum (EDS) studies. The SEM and EDS studies confirmed the formation of calcium phosphate layer on the surface of chitin/gelatin membranes. Biocompatibility of the chitin/gelatin membrane was assessed using human MG-63 osteoblast-like cells. After 48 h of incubation, it was found that the cells had attached and completely covered the membrane surface. Thus, the prepared chitin/gelatin membranes are bioactive and are suitable for cell adhesion suggesting that these membranes can be used for tissue-engineering applications.     

Preparation and properties of a pH/temperature-responsive carboxymethyl chitosan/poly(N-isopropylacrylamide)semi-IPN hydrogel for oral delivery of drugs

Thermo- and pH-responsive semi-IPN polyampholyte hydrogels were prepared by using carboxymethylchitosan and poly(N-isopropylacrylamide) with N,N'-methylenebisacrylamide (BIS) as the crosslinking agent. The swelling characteristics of these hydrogels at distinct compositions as a function of pH and temperature were investigated. It was found that the semi-IPN hydrogels demonstrated the pH- and temperature-responsive nature of the materials, and it also showed good reversibility. The study on the release of coenzyme A (CoA) showed that within 24h the cumulative release ratio of CoA was 22.6% in pH 2.1 solution and 89.1% in pH 7.4 solution at 37 degrees C, respectively. The release rate of CoA was higher at 37 degrees C than 25 degrees C in a pH 7.4 buffer solution. An increased release rate of CoA was observed with the content of carboxymethylchitosan increasing in the hydrogel at 25 degrees C in pH 7.4 solution. These results show that semi-IPN hydrogel seems to be of great promise in pH-temperature oral drug delivery systems.     

Photopolymerization of methacrylated chitosan/PNIPAAm hybrid dual-sensitive hydrogels as carrier for drug delivery

A series of hybrid hydrogels based on glycidyl methacrylated chitosan (CS-GMA) and N-isopropylacrylamide (NIPAAm) were designed and prepared via photopolymerization technology. The hydrogels were characterized by Fourier transform infrared (FT-IR), differential scanning calorimetry (DSC) and optical transmittance. The interior morphology of hydrogels was investigated by scanning electron microscopy (SEM). The swelling experiment results revealed that hybrid hydrogel exhibited combined pH and temperature sensitivities. Acid orange 8 (AO8) and 5-flurouracil (5-Fu) were selected as model drugs for examining their release from hydrogels. The results suggested that hydrogel composition and pH value of buffer solution had great influences on release profiles.     

NMR imaging of the diffusion of water at 310 K into semi-IPNs of PEM and poly(HEMA-co-THFMA) with and without chlorhexidine diacetate

Magnetic resonance imaging has been used to monitor the diffusion of water at 310 K into a series of semi-IPNs of poly(ethyl methacrylate), PEM, and copolymers of 2-hydroxyethyl methacrylate, HEMA, and tetrahydrofurfuryl methacrylate, THFMA. The diffusion was found to be well described by a Fickian kinetic model in the early stages of the water sorption process, and the diffusion coefficients were found to be slightly smaller than those for the copolymers of HEMA and THFMA, P(HEMA-co-THFMA), containing the same mole fraction of HEMA in the matrix. A second stage sorption process was identified in the later stage of water sorption by the PEM/PTHFMA semi-IPN and for the systems containing a P(HEMA-co-THFMA) component with a mole fraction HEMA of 0.6 or less. This was characterized by the presence of water near the surface of the cylinders with a longer NMR T(2) relaxation time, which would be characteristic of mobile water, such as water present in large pores or surface fissures. The presence of the drug chlorhexidine in the polymer matrixes at a concentration of 5.625 wt % was found not to modify the properties significantly, but the diffusion coefficients for the water sorption were systematically smaller when the drug was present.     

One-step synthesis of interpenetrating network hydrogels: Environment sensitivities and drug delivery properties

A novel interpenetrating network hydrogel for drug controlled release, composed of modified poly(aspartic acid) (KPAsp) and carboxymethyl chitosan (CMCTS), was prepared in aqueous system. The surface morphology and composition of hydrogels were characterized by SEM and FTIR. The swelling properties of KPAsp, KPAsp/CMCTS semi-IPN and KPAsp/CMCTS IPN hydrogels were investigated and the swelling dynamics of the hydrogels was analyzed based on the Fickian equation. The pH, temperature and salt sensitivities of hydrogels were further studied, and the prepared hydrogels showed extremely sensitive properties to pH, temperature, the ionic salts kinds and concentration. The results of controlled drug release behaviors of the hydrogels revealed that the introduction of IPN observably improved the drug release properties of hydrogels, the release rate of drug from hydrogels can be controlled by the structure of the hydrogels and pH value of the external environment, a relative large amount of drug released was preferred under simulated intestinal fluid. These results illustrated high potential of the KPAsp/CMCTS IPN hydrogels for application as drug carriers.     

Synthesis and properties of thermo- and pH-sensitive poly(N-isopropylacrylamide)/polyaspartic acid IPN hydrogels

Various interpenetrating polymer network (IPN) hydrogels with sensitivity to temperature and pH were prepared by introducing the pH-sensitive polymer polyaspartic acid (PASP) hydrogel, into the poly(N-isopropylacrylamide) (PNIPAAm) hydrogel system for the purpose of improving its response rate to temperature. The morphologies and thermal behavior of the prepared IPN hydrogels were studied by both scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). The IPN hydrogels showed a large and uneven porous network structure, without showing the common PNIPAAm hydrogel structure. The paper moreover studied their swelling properties, such as temperature dependence of equilibrium swelling ratio, shrinking kinetics, re-swelling kinetics and oscillatory swelling behavior in water. The swelling experiment results revealed that IPN hydrogels exhibited much faster shrinking and re-swelling in function of the composition ratio of the two network components. These fast responsive hydrogels foster potential applications in biomedical and biotechnology fields.     

Rapid deswelling response of poly(N-isopropylacrylamide)/poly(2-alkyl-2-oxazoline)/poly(2-hydroxyethyl methacrylate) hydrogels

Ternary poly( N-isopropylacrylamide)/poly(2-alkyl-2-oxazoline)/poly(2-hydroxyethyl methacrylate) (PNIPAAm/PROZO/PHEMA) hydrogels were prepared by the free-radical copolymerization of N-isopropylacrylamide (NIPAAm), 2-hydroxyethyl methacrylate (HEMA), and poly(2-alkyl-2-oxazoline) (PROZO) multifunctional macromonomers. The resulting polymeric materials were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM), as well as by equilibrium swelling experiments. All synthesized hydrogels display temperature sensitivity in the 28-38 degrees C range. A high rate of response was registered as compared to that of materials based only on PNIPAAm. The swelling-deswelling peculiar behavior was related to the chemical composition (hydrophile/hydrophobe balance), the length of the inserted PROZO sequence, and inner morphology, an aspect which points on its possible control by synthesis. It was evidenced that the architecture of the resulting porous materials has a high order degree, emerging from the self-assembling of the microgel particles, which provided numerous, nearly uniform, large water release channels.