Analysis of Preparation of Dextran Hydrogel Membranes as a Wound Dressing

Several variables which could affect the polymerization and physico-chemical properties of dextran hydrogel were investigated. The dextran hydrogels were prepared at multiple level of each variable. Water uptake capacity and handling characteristics were employed to evaluate the hydrogels. The effect of each variable on the polymerization of dextran is discussed and an optimum formulation of dextran hydrogel is presented.     

Using hydrophilic polysaccharide to modify supramolecular hydrogel from a low-molecular-mass gelator

Small molecular hydrogels hold important potential applications in bioengineering and biomedicine. However, they suffer usually from weak mechanical and water-retention properties. In this work, hydrophilic dextran polysaccharide was used for the first time to modify the properties of the supramolecular hydrogel derived from a low-molecular-mass gelator, 2, 6-di[N-(carboxyethyl carbonyl)amino]pyridine (DAP). When the DAP hydrogel was formed in aqueous dextran solution with a rather low viscosity, we found that it could be significantly reinforced with respect to its viscoelastic moduli, complex viscosity and hydrogel strength. Moreover, the modified DAP hydrogel has a higher bound water content. These property changes could be attributed to the formation of intermolecular hydrogen bonds between DAP and dextran. By relating the dynamic rheological data with a scaling model, it was found that native and modified DAP hydrogels had both a fractal aggregate structure and the incorporation of dextran resulted in an increase of the fractal dimension. Scanning electron microscopy revealed that a more complex network structure was formed in the DAP hydrogel with dextran.     

Wetting-Enabled Three-Dimensional Interfacial Polymerization (WET-DIP) for Bioinspired Anti-Dehydration Hydrogels

Anti-dehydration hydrogels have attracted considerable attention due to their promising applications in stretchable sensors, flexible electronics, and soft robots. However, anti-dehydration hydrogels prepared by conventional strategies inevitably depend on additional chemicals or suffer from cumbersome preparation processes. Here, inspired by the succulent Fenestraria aurantiaca a one-step wetting-enabled three-dimensional interfacial polymerization (WET-DIP) strategy for constructing organogel-sealed anti-dehydration hydrogels is developed. By virtue of the preferential wetting on the hydrophobic-oleophilic substrate surfaces, the organogel precursor solution can spread on the three-dimensional (3D) surface and encapsulate the hydrogel precursor solution, forming anti-dehydration hydrogel with 3D shape after in situ interfacial polymerization. The WET-DIP strategy is simple and ingenious, and accessible to discretionary 3D-shaped anti-dehydration hydrogels with a controllable thickness of the organogel outer layer. Strain sensors based on this anti-dehydration hydrogel also exhibit long-term stability in signal monitoring. This WET-DIP strategy shows great potentialities for constructing hydrogel-based devices with long-term stability.     

Poly(vinyl alcohol)/poly(acrylic acid)/TiO2/graphene oxide nanocomposite hydrogels for pH-sensitive photocatalytic degradation of organic pollutants

Poly(vinyl alcohol)/poly(acrylic acid)/TiO₂/graphene oxide nanocomposite hydrogels were prepared using radical polymerization and condensation reaction for the photocatalytic treatment of waste water. Graphene oxide was used as an additive to improve the photocatalytic activity of poly(vinyl alcohol)/poly(acrylic acid)/TiO₂ nanocomposite hydrogels. Both TiO₂ and graphene oxide were immobilized in poly(vinyl alcohol)/poly(acrylic acid) hydrogel matrix for an easier recovery after the waste water treatment. The photocatalytic activity of poly(vinyl alcohol)/poly(acrylic acid)/TiO₂/graphene oxide nanocomposite hydrogels was evaluated on the base of the degradation of pollutants by using UV spectrometer. The improved removal of pollutants was due to the two-step mechanism based on the adsorption of pollutants by nanocomposite hydrogel and the effective decomposition of pollutants by TiO₂ and graphene oxide. The highest swelling of nanocomposite hydrogel was observed at pH 10 indicating that poly(vinyl alcohol)/poly(acrylic acid)/TiO₂/graphene oxide nanocomposite hydrogels were suitable as a promising system for the treatment of basic waste water.     

Design and optimization of thermosensitive nanoemulsion hydrogel for sustained-release of praziquantel

Objective: This work aimed to develop an alternative sustained-release thermosensitive praziquantel-loaded nanoemulsion (PZQ-NE) hydrogel for better schistosomiasis treatment.

Significance: PZQ-NE-dispersed chitosan/glycerol 2-phosphate disodium/HPMC (NE/CS/β-GP/HMPC) hydrogel was successfully prepared to improve bioavailability of PZQ.

Methods: Solubility tests and pseudo-ternary phase diagrams were applied to screen optimal oils, surfactants and co-surfactants of NE. The hydrogels were characterized for gelling time, surface exudates, rheological properties and in vitro drug release. Formulation optimization of NE/CS/β-GP/HMPC hydrogel was conducted by Box–Behnken experimental design combined with response surface methodology. In vitro cytotoxicity of hydrogel was studied by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide method. The sustained-release property of PZQ in NE and optimized hydrogel was evaluated by pharmacokinetic study in rabbits.

Results: The formulation of PZQ-NE consisted of mass ratio of 12.5% capryol 90 containing PZQ (160?mg/g), 40% cremophor RH 40/tween 20 and transcutol HP (S/CoS?=?2:1), 47.5% deionized water. PZQ releasing from NE/CS/β-GP/HMPC hydrogels was best fitted to Higuchi model and governed by diffusion. Rheological investigation evidenced the themosensitive gelation of different hydrogel systems and their gel-like character at 37?°C. The optimized hydrogel formulation consisted of HPMC solution (103.69?mg/g), 3.03% (w/v) chitosan and 14.1% (w/v) β-GP showed no cytotoxicity when the addition of NE was no more than 100?mg/g. Pharmacokinetic parameters indicated that NE/CS/β-GP/HMPC hydrogel can significantly slow down drug elimination, prolong mean residence time and improve bioavailability of PZQ.

Conclusions: NE/CS/β-GP/HMPC hydrogel possessed sustained-release property and could be an alternative antischistosomal drug delivery system with improved therapeutic effect.     

Highly Conductive,Stretchable, and Cell‐Adhesive Hydrogel by Nanoclay Doping

Electrically conductive materials that mimic physical and biological properties of tissues are urgently required for seamless brain–machine interfaces. Here, a multinetwork hydrogel combining electrical conductivity of 26 S m^?1, stretchability of 800%, and tissue‐like elastic modulus of 15 kPa with mimicry of the extracellular matrix is reported. Engineering this unique set of properties is enabled by a novel in‐scaffold polymerization approach. Colloidal hydrogels of the nanoclay Laponite are employed as supports for the assembly of secondary polymer networks. Laponite dramatically increases the conductivity of in‐scaffold polymerized poly(ethylene‐3,4‐diethoxy thiophene) in the absence of other dopants, while preserving excellent stretchability. The scaffold is coated with a layer containing adhesive peptide and polysaccharide dextran sulfate supporting the attachment, proliferation, and neuronal differentiation of human induced pluripotent stem cells directly on the surface of conductive hydrogels. Due to its compatibility with simple extrusion printing, this material promises to enable tissue‐mimetic neurostimulating electrodes.     

A comparative study of chitosan and poloxamer based thermosensitive hydrogel for the delivery of PEGylated melphalan conjugates

Abstract

Objective: Although the melphalan (ML) used extensively for the management of breast cancer, its clinical application is limited due to significant hemolytic activity. In the present work, a comparative analysis of two distinct in situ-based thermogelling polymers of PEGylated ML was performed.

Methods: Briefly, the PEGylated conjugate of the melphalan (MLPEG 5000) for local and sustained drug release action is loaded into two different thermogelling polymeric systems, namely chitosan- and poloxamer-based systems. The synthesized conjugate was loaded to a chitosan (MLP 5000) and poloxamer-based (MPX-CG) thermogelling injectable hydrogels. These thermogelling hydrogels were evaluated for in vitro hydrolysis, in vitro hemolytic activity. and in vitro anticancer activity.

Results: The lower percent cumulative hydrolysis was witness for both the hydrogels. MPX-CG and MLP 5000 hydrogels as predicted had shown lower percent cumulative hydrolysis of 3.31?±?0.1 and 1.67?±?0.1 after 6?h. The percentage hemolysis of MPX-CG and MLP 5000 even at a concentration of 32?µg/ml was found to be 39.23?±?1.24% and 34.23?±?2.24%, observed at 1?h, respectively. Both the hydrogels showed similar anticancer pattern, the MPX-CG hydrogel showed low cell viability of 8.4?±?1.1% at a concentration of 150?µM and the MLP-5000 hydrogel showed slight higher cell viability (13.12?±?5.4%) as compared with MPX-CG hydrogel.

Conclusion: Hence, from the present study it can be well understood that both the chitosan- and the poloxamer-based thermogelling hydrogel proves to be an effective drug delivery systems for the delivery of the PEGylated conjugates.     

In situ controlled synthesis of thermosensitive poly(N-isopropylacrylamide)/Au nanocomposite hydrogels by gamma radiation for catalytic application

Thermosensitive poly(N‐isopropylacrylamide) (PNIPAM)/Au nanoparticle (NP) nanocomposite hydrogels are synthesized by in situ γ‐radiation‐assisted polymerization of N‐isopropylacrylamide monomer aqueous solution in the presence of HAuCl₄·4H₂O. In this reaction, the PNIPAM hydrogels and the Au NPs are formed simultaneously, thus demonstrating an easy and straightforward synthetic strategy for the preparation of a uniform nanocomposite. The results suggest that increasing the monomer content during the preparation of nanocomposite materials can increase the sizes of Au NPs. The effects of irradiation dose and concentration of HAuCl₄·4H₂O on the optical and thermal properties of the hydrogel are also investigated. The PNIPAM/Au nanocomposite hydrogels act as an excellent catalyst for the conversion of o‐nitroaniline to 1,2‐benzenediamine, and the catalytic activity of the composite hydrogel can be tuned by the volume transition of PNIPAM. The in situ polymerization of monomer and reduction of metal ions initiated by a “clean” and “green” γ‐radiation technique can be extended to the efficient synthesis of other nanocomposite materials.     

Synthesis of polyacrylate/polyethylene glycol interpenetrating network hydrogel and its sorption for Fe<Superscript>3+</Superscript> ion

A simple two-step aqueous polymerization method was introduced to synthesize polyacrylate/polyethylene glycol (PAC/PEG) interpenetrating network (IPN) hydrogel. The sorption behaviors and mechanism were studied by the sorption of PAC/PEG IPN hydrogel to Fe³⁺ ion from aqueous solution. The experimental results revealed that the adsoption amount of Fe³⁺ ion using swollen hydrogels was much higher than that using the dried composite, they were 75.69 mg/g and 14.25 mg/g, respectively. The parameters, such as neutralization degree, acrylic acid (AA) dosages and temperature, on the sorption amount of PAC/PEG IPN hydrogel were detailedly investigated.     

Effect of Multiwalled Carbon Nanotubes on the Conductivity and Swelling Properties of Porous Polyacrylamide Hydrogels

Multiwalled carbon nanotubes (MWCNTs) were added to polyacrylamide (PAM) hydrogels in different proportions to tune their electrical and mechanical properties. The choice of MWCNTs as a reinforcement is justified by the fact that these are highly conducting, fairly stable and flexible particles. A series of MWCNT/PAM hydrogels were prepared by freezing method. The characteristic absorption peaks at 1480 and 1213 cm^?1 in the FTIR spectra reveal that MWCNTs are embedded in the PAM hydrogels. Powder x-ray diffractograms and thermogravimetric analysis (TGA) images show that the MWCNT/PAM hydrogels are crystalline, more thermally stable and have a higher electrical conductivity than a traditional PAM hydrogel. Scanning electron micrographs reveal about reduced pore size, homogeneous and denser texture. The swelling properties of all these hybrid hydrogels were found to be better than those of the parent PAM hydrogel. The Li–Tanaka equation was employed to produce the swelling parameters. The diffusion coefficients (D _c ) of PAM hydrogel is 10 times higher than the literature value. 0.8% MWCNTs reinforced PAM hydrogel has excellent τ_c and electrical conductivity (0.76 mS/cm) with improvements in all properties. Lower D _c of 0.8% MWCNTs/PAM hydrogel reveal that extent of crosslinking is much important than density of the system for a better collective diffusion of the respective solvent.     

快速响应的聚(N-异丙基丙烯酰胺)水凝胶的合成及性能

以羧甲基纤维素的水溶液为反应介质制备了快速响应的温度敏感性聚(N-异丙基丙烯酰胺)水凝胶。利用DSC对其相转变温度进行了表征,并测定了不同温度下达到平衡时水凝胶的溶胀比,研究了水凝胶的去溶胀动力学。结果表明,在聚合/交联过程中羧甲基纤维素的存在对PN IPA水凝胶的相转变温度几乎没有影响;与传统水凝胶相比,该水凝胶的溶胀性能有所提高,并且具有较快的响应速率。     

Effect of silver nanoparticles content on the various properties of nanocomposite hydrogels by in situ polymerization

A series of nanocomposite hydrogels (APEAg series gels) were prepared from acrylic acid, poly(ethylene glycol) methyl ether acrylate, and silver nanoparticles through in situ polymerization by UV irradiation. The effect of the content of silver nanoparticle on the properties of the nanocomposite hydrogels was investigated. Results showed that, with increasing of the content of the silver nanoparticle in the hydrogels, the crosslinking density and shear modulus of the hydrogel were not obviously changed, the electrical conductivities of the nanocomposite hydrogels increased, and their initial rate of Escherichia coli inactivation significantly increased, but their adhesive force only slightly decreased. These materials can be assessed as promising bioadhesive patch or wound-dressing material or electrical massage patch.     

Novel PAAm/Laponite clay nanocomposite hydrogels with improved cationic dye adsorption behavior

A nanocomposite (NC) hydrogel was prepared by incorporating the nanoclay (Laponite (Lap) XLS) into a poly(acrylamide) (PAAm) hydrogel by the in situ polymerization method without any organic cross-linker. The parameters pertaining to the swelling (Q) and diffusion (D) of water for the PAAm/Lap NC hydrogels were estimated. The crystal violet (CV) dye adsorption properties of the PAAm/Lap NC hydrogels were investigated. The adsorption of CV dye by the hydrogel increases as the concentration of the dye increases. The cationic dye adsorption ability of the NC hydrogel increased with increasing clay content in the NC hydrogel. The NC hydrogels containing CV dye were characterized by FT-IR. A sigmoidal type of adsorption isotherm was observed for the CV-NC hydrogels. The effects of heat treatment on the dye adsorption behavior of the NC hydrogels were studied.     

Evaluation of hydrogels for soft tissue adhesives <Emphasis Type="Italic">in vitro</Emphasis> and <Emphasis Type="Italic">in vivo</Emphasis> analyses

In this study, natural materials (sodium alginate, dextran, gelatin and carboxymethyl chitosan) were modified to get aldehyde components and amino components. Upon mixing the two-component solutions together, four kinds of Schiff base hydrogels formed successfully within 5-300 s and could seal the wound tissue. The cytotoxicity tests of hydrogel extraction solution confirmed that the hydrogels are nontoxic materials. The adhesive ability was evaluated in vivo by measuring the adhesive strength after sealing the skin incisions on the back of rats. All the hydrogels showed higher adhesive strength than that of commercial fibrin glue and the blank control. The histological staining observation by hematoxylin and eosin staining (HE) and Masson’s trichrome staining (MTC) methods suggested that the hydrogels had good biocompatibility and biodegradation in vivo. They have only normal initial inflammation to skin tissue and could improve the formation of new collagen in the incision section. So, the prepared hydrogels were both safe and effective tissue adhesive, which had the great potentials to be used as skin tissue adhesive.     

聚N-异丙基丙烯酰胺水凝胶的制备及热致聚集行为

以异丙基丙烯酰胺(NIPAM)为单体、N,N’-亚甲基双丙烯酰胺(MBA)为交联剂、过硫酸钾(KPS)为引发剂,采用无皂乳液聚合法制备聚N-异丙基丙烯酰胺(PNIPAM),考察了聚合时间、温度、浓度、pH值、共存NaCl和MgCl2浓度对PNIPAM热致聚集行为的影响,并通过扫描电镜(SEM)、红外光谱(FTIR)等手段对PNIPAM的形貌和分子结构进行了表征。结果表明:线型PNIPAM更易在水中稳定存在,采用无皂乳液聚合技术制备PNIPAM过程简单、易操作,产物温敏效应明显。PNIPAM的热致聚集行为随聚合时间的延长、PNIPAM悬浊液浓度的增加、pH值的减小、共存盐浓度的增大而更为显著。     

Thermoresponsive hydrogel with rapid response dynamics

Intelligent hydrogels, particularly poly(N-isopropylacrylamide) (PNIPAAm)-based hydrogels, have attracted extensive interest because the soft wet hydrogels can change their shapes in response to the small changes of environmental factors like temperature. In order to fully make use of this unique property of PNIPAAm-based hydrogels, the response rates of the PNIPAAm hydrogels have to be improved since the dynamics property is critical to certain applications of this material. In this paper, the thermo-sensitive PNIPAAm hydrogels were successfully synthesized by carrying out the polymerization of N-isopropylacrylamide monomer in vacuum (–100 kPa) at room temperature (22 °C). The resultant hydrogel has tremendously improved shrinking rate as well as the large volume changes upon temperature stimulation when comparing with the normal PNIPAAm hydrogel. The SEM micrographs revealed that the improved properties were attributed to the macroporous network structure generated during the synthesis under vacuum.     

Thermosensitive in situ-forming dextran–pluronic hydrogels through Michael addition

A thiolated dextran (Dex-SH) with a degree of substitution of 10 was synthesized and used for in situ hydrogel formation via Michael-type addition using vinyl sulfone functionalized Pluronic 127 (PL-VS) or acrylated Pluronic 127 (PL-Ar). Dextran/Pluronic hydrogels were rapidly formed in situ under physiological conditions upon mixing the solutions of Dex-SH and PL-VS or PL-Ar at a PL concentration of 10 or 20 w/v%. Rheological studies showed that these hydrogels with a broad range of storage moduli of 0.3 to 80 kPa could be obtained by varying PL concentration from 5% to 20 w/v%. Moreover, the hydrogels at a PL concentration of 10% or 20 w/v% revealed thermosensitive property with a temperature increase from 10 to 37 °C. Dex-SH/PL-Ar hydrogels were degradable under physiological conditions and had lower cytotoxicity than Dex-SH/PL-VS hydrogels. These thermosensitive injectable hydrogels show promise for biomedical applications.     

Cationic poly(VCL–AETA) hydrogels and ovalbumin (OVA) release in vitro

The objective of this research is to explore the synthesis of a new family of water soluble polycationic copolymeric precursors that could be photo-crosslinked into hydrogels. The in vitro control release of ovalbumin protein (OVA) from this family of hydrogels was also studied to assess the biomedical potential of this new family polycationic hydrogels. A series of novel poly(VCL–AETA) copolymer hydrogels was fabricated in an aqueous medium via photo-induced polymerization and crosslinking of hydrophobic N-vinylcaprolactam (VCL) and hydrophilic [2-(acryloxy)ethyl]trimethylammonium chloride (AETA) monomers over a wide range of VCL to AETA feed molar ratios of 2:1, 1:1, 1:2, 1:5. N,N′-methylene bisacrylamide (MBA) was used as a crosslinker. Ovalbumin (OVA), a model antigen, was preloaded into poly(VCL–AETA) hydrogel precursors and its release profiles in pH 7.4 PBS at 37°C were investigated as a function of VCL to AETA monomer feed ratios over a period of 4 weeks. The in vitro results showed that OVA initial burst and subsequent sustained releases could be controlled by 3 material parameters: the hydrophobic VCL to hydrophilic AETA monomer feed ratios, crosslinking density and hydrogel degradation rate. Thus, the hydrophobic-hydrophilic VCL–AETA hydrogel network for controlled OVA release could offer advantages over organic solvent-based single component polymer system. However, these in vitro OVA release profiles may change in an in vivo environment.     

聚丙烯酸/活性炭复合凝胶的制备及溶胀行为

采用自由基溶液聚合的方法,以过硫酸铵(APS)为引发剂,N,N′-亚甲基双丙烯酰胺(NNMBA)为交联剂,制备了聚丙烯酸(PAA)复合活性炭凝胶(PAA/AC)。考察了凝胶在生理盐水和不同pH值缓冲溶液中的平衡溶胀比及溶胀动力学,结果表明,活性炭能有效提高PAA凝胶的平衡溶胀比。蒸馏水中PAA/AC凝胶的平衡溶胀比可达到303(g/g),约为PAA凝胶平衡溶胀比的2.3倍;生理盐水(0.9%g/mL NaCl水溶液)中PAA/AC凝胶的平衡溶胀比可达到60(g/g),约为PAA凝胶平衡溶胀比的2.4倍;在实验设计的pH范围内PAA/AC凝胶的平衡溶胀比比PAA凝胶更高,具有更好的pH值敏感特性。     

Biodegradation of hydrophilic–hydrophobic hydrogels and its effect on albumin release

The objective of this study was to examine the effects of composition ratio of a new class of bicomponent biodegradable hydrogels and the molecular weights of the constituents on the hydrolytic degradability of the hydrogels and their release of bovine serum albumin (BSA). Biodegradable hydrogels were prepared from dextran derivative of allyl isocyanate (dex-AI) and poly (D,L) lactide diacrylate macromer (PDLLAM) over a wide range of dex-AI to PDLLAM composition ratio. The results obtained indicated that the hydrolytic degradation of these biodegradable hydrogels could be controlled by adjusting the composition ratio of dex-AI to PDLLAM or by changing their molecular weights. Along with the hydrogel degradation, water content of the hydrogels changed, and 3D porous network structure was observed. Generally, as the PDLLAM composition in the hydrogels increased, the rate of weight loss increased due to the hydrolytic degradation of the PDLLAM. The increase in molecular weights of either dex-AI or PDLLAM would decrease the degradation rate of the dex-AI/PDLLAM hydrogels. BSA release data correlated well with the hydrogel degradation profiles, suggesting that the extent and rate of BSA release would be mainly controled by hydrogel degradation. As the PDLLAM composition in the hydrogel increased, the extent and rate of BSA release also increased. An increase in the molecular weights of the hydrogel constituents, however, led to a decrease in BSA release.