Photo-responsive polymer materials for biological applications

In this review, we briefly summarized the remarkable progress of photo-responsive polymer materials from zero-dimensional micelles, twodimensional surfaces to three-dimensional hydrogels with irreversible or reversible moieties. Based on the photo-responsiveness, polymer have been designed, synthesized and applied for various biological fields including drug delivery and cell manipulation.     

Metal-organic framework-based nanomaterials for biomedical applications

In the past decade,nanoscale metal-organic frameworks(nMOFs) have drawn a great attention due to their high porosity,wide range of pore shapes,tunable frameworks and relatively low toxic.With the development of nanotechnology,many researchers studied the synthesis,characterization,functionalization and biotoxicity of nMOFs,and a more thorough understanding was developed about numerous nMOFs as promising platforms for biomedical applications.This review highlights the up-to-date progress of nMOFs...     

Stabilization of an asymmetric bolaamphiphilic sugar-based crown ether hydrogel by hydrogen bonding interaction and its sol-gel transcription

Asymmetric bolaamphiphilic sugar-based hydrogelators (1-3) were synthesized and their gelation ability with and without alkylammonium ions was investigated by CD, TEM, FTIR and NMR. These compounds acted as versatile gelators for organic solvents and water. The xerogels 1-3 obtained from water showed well-developed structures of fibrils with diameters of 10-38 nm and length of several hundred micrometers. Particularly, the gelation ability of crown-appended gelator 1 was drastically enhanced by addition of alkylammonium ions 4 and 5, suggesting that the bridging effect of alkyldiammonium ions could be the primary driving-force for the stabilization due to the intermolecular hydrogen bonding and electrostatic interactions. The present result is a rare case of a hydrogel being stabilized by a host-guest interaction. In addition, the hydrogel 1 with AgNO₃ and KClO₄ induced the formation of nanotubular and vesicular structures of silica by sol-gel polymerization of TEOS, respectively. These results indicate that hydrogel 1 acted as a template to produce inorganic nanomaterials.     

非共价键交联海藻酸钠水凝胶的制备与性能

天然多糖海藻酸钠制备的水凝胶具有优越的生物相容性和生物组织相似性,作为生物医用材料在药物控制释放、组织工程支架、抗菌材料及创伤敷料等领域发挥着越来越大的作用。本文在介绍海藻酸钠物化性质的基础上,重点综述了非共价键交联(静电作用、氢键、范德华力、亲疏水作用等)海藻酸钠水凝胶的制备方法以及性能表征方法,最后讨论了制备方法及性能表征研究中的一些需要解决的问题。     

How the structural and physicochemical properties of polyacrylamide/alginate hydrogel influence its oxygen permeability

Interpenetrating hydrogels based on sodium-alginate and crosslinked poly(acrylamide) were studied in term of their oxygen permeability. Such properties as the equilibrium water content, the free water content and the porosity are known to be preponderant for the oxygen transport through hydrated polymeric materials but are also strongly affected by the crosslinking density of the network. In the present work, these relations were studied and described. The amount of non-bound adsorbed water was determined thanks to DSC analysis. The thermoporosity method allowed the evaluation of the apparent hydrogel porosity and the electrochemical polarographic method was applied for determining the oxygen permeability level. Relations between oxygen transport properties, “free water” content and structural parameters of polymer networks were discussed.     

Drug carrying hydrogel base wound dressing

A special drug carrying hydrogel base wound dressing by radiation preparation is developed for hospital uses. The dressing possesses high water absorption property. Radiation preparation is carried out using a Van de Graaff Accelerator as an electron radiation source. The effect of absorbed dose and cmount of crosslinking agent on the gel fraction and swelling ratio of the hydrogel were determined respectively. As a bio-medical material, standard tests were made. Results showed properties conforming with requirements for clinical applications. Results obtained from clinical tests were good.     

Effect of organic and inorganic acids on chitosan/glycerophosphate thermosensitive hydrogel

The influence of organic and inorganic acids on chitosan/glycerophosphate (CS/GP) hydrogel has been investigated by dissolving chitosan in different acids. The results of gelation showed that all of the chitosan dissolved in monovalent acid solutions (i.e., formic, acetic, propionic, butyric, isobutyric, lactic, nitric, hydrochloric, and chloroacetic acid), when neutralized by GP solution, could transform into hydrogel after 2–5 min at 37 °C, while those dissolved in multivalent acids failed in gel formation. The inner structures of CS/GP hydrogels prepared with monovalent acids depended on the ionic strength and chain length of acids. Morphological examination by scanning electron microphotography demonstrated that large pores occurred during the gel-forming process, and the aperture size was also related to different acids. The cytotoxicity studies indicated that CS/GP systems prepared by dissolving chitosan in tested acids except chloroacetic acid were nontoxic to mouse embryonic fibroblasts and Hela cells.     

Direct incorporation of carbon dioxide in poly(glycidyl methacrylate) and its application to the synthesis of hydrogel

This study is related to an integrated process for the application of CO₂ to poly(hydroxy urethane) and hydrogel viapoly(1,3-dioxolane-2-oxo-4-yl)methyl methacrylate [poly (DOMA)]. Quaternary ammonium salts showed good catalytic activity in the synthesis of poly(DOMA) by the direct incorporation of CO₂ into poly(glycidyl methacrylate) [poly(GMA)]. Poly[3-(N-butylcarbamoyloxy)-2-hydroxypropyl methacrylate] [poly(CHPMA)] was successfully synthesized from poly(DOMA) and n-butylamine. Hydrogels were also prepared from the poly(CHPMA), using several diisocyanates as crosslinkers, and their swelling degrees were studied by measuring water content in the hydrogels.     

Gelator-polysaccharide hybrid hydrogel for selective and controllable dye release

In this paper, 1,4-bi(phenylalanine-diglycol)-benzene (PDB) based Low-Molecular-Weight-Gelator (LMWG) hydrogels are modified using hydrophilic polysaccharide (sodium alginate). A set of techniques including Fourier transform infrared (FT-IR) spectroscopy, ¹H Nuclear Magnetic Resonance (¹H NMR), X-ray powder diffraction (XRD), Ultraviolet-Visible (UV-Vis), and circular dichroism (CD) had confirmed a β-turn arrangement of PDB gelators and a semi-interpenetrating network (semi-IPN), which was formed through hydrogen bonds between LMWG fibers and polysaccharide chains. The evaluation of physicochemical properties of hydrogels indicates that gelator-polysaccharide hybrid hydrogels possess better mechanical and water retention properties than LMWG hydrogels. The release study of dyes (model drug) from both LMWG and hybrid hydrogels was carried out. Compared with PDB based hydrogels, hybrid hydrogels show a selective and controllable release property for certain dyes. The results suggest LMWG-polysaccharide hybrid gels may find potential applications as promising drug delivery vehicles for drug molecules.     

Preparation and controlled degradation of oxidized sodium alginate hydrogel

Degradation is often a critical property of materials utilized in tissue engineering. Although alginate, a naturally derived polysaccharide, is an attractive material due to its biocompatibility and ability to form hydrogels, its slow and uncontrollable degradation can be an undesirable feature. In this study, the degradation behavior of hydrogel based on oxidized sodium alginate (OSA) crosslinked with Ca²⁺ was studied in phosphate buffer solution (PBS, pH = 7.4) and Tris-(hydroxymethyl) aminomethane–HCl (Tris–HCl, pH = 7.4) at 37 °C. The degradation behavior of OSA hydrogels with different degrees of oxidation was evaluated as a function of degradation time by monitoring the changes of molecular weight and weight loss. It was found that the degradation behavior relied heavily on the degree of oxidation and the surrounding medium. This result indicates that the degradation rates of OSA hydrogels can be controlled by changing the degree of oxidation.     

A polysaccharide/tetraphenylethylene-mediated blue-light emissive and injectable supramolecular hydrogel

A luminescent and injectable supramolecular hydrogel was successfully constructed through the non-covalent cross-linking of polymers mediated by tetraphenylethylene-bridged cyclodextrin oligomers, presenting the strong blue fluorescence, the reversible gelation behavior responsive to various external stimuli and the good mechanical property of shear thinning.     

Materials and biological applications of 1,2,3-selenadiazoles: a review

In recent years, chemistry of metal-nitrogen–bonded compounds have attracted tremendous attention mainly because of unusual properties resulting from such a bond involving carbon and other heteroatoms. M?N–bonded compounds, when containing group VI elements, especially selenium, has attracted great attention in materials chemistry. In addition, the increased interest in synthesis of N-containing bioactive compounds with other heteroatoms such as selenium, sulfur, etc is mainly because of their tremendous potential as antioxidants, additives, dyes for polymers, and as insecticides, in solvent extraction, and in nanotechnology. Thus, the synthesis and applications of 1,2,3-selenadiazoles have attracted recent interest of materials scientists, including nanotechnologists, pharmaceutical chemists, and organic chemists. The chemistry of 1,2,3-selenadiazoles is highly rich and has been practiced ever since its first report in 1972. Such N-containing Se-heterocycles form several types of selenadiazoles that are a rich source of selenium for semiconductor nanoparticles of metal selenides. The materials chemistry of such molecules has been documented for over three decades, and their great scope in semiconductors has emerged. This review article is an attempt to bring a variety of materials and biological application of 1,2,3-selenadiazoles for better understanding of the researchers.     

Ultrasonic quantification using smart hydrogel sensors

Analyte quantification in samples with extensive matrix effects can be challenging using conventional analytical techniques. Ultrasound has been shown to easily penetrate samples that can be difficult to measure optically or electrochemically, though it provides little chemical information. Recent ultrasound contrast agents provide highly localized contrast within a sample based on concentration. We have developed a general approach for creating smart biosensors based on molecularly imprinted hydrogel polymers that recognize and bind a target analyte, changing ultrasonic properties with analyte concentration. Multilinear analyte calibration in hydrogel solutions provided quantification of the chosen analyte, theophylline, from 8.4 μM to 6.1 mM with a high degree of linearity (correlation coefficient exceeding 0.99). Simultaneous quantification of both theophylline and of an interfering species, caffeine, was also carried out, providing an avenue for simultaneous analyte analysis with one smart biosensor that can be dispersed and remotely detected.     

P（DMAA-co—AM）水凝胶制备及其固定a-淀粉酶研究

采用氧化还原引发体系,水溶液聚合法制备P（DMAA-co-AM）水凝胶,并以其作为载体固定a-淀粉酶。采用单一变量法研究交联剂（N,N＇-亚甲基双丙烯酰胺）用量、引发剂（过硫酸铵）用量、单体浓度和单体配比对凝胶性能的影响。以水凝胶的最大平衡溶胀度为指标,得出制备P（DMAA-co-AM）水凝胶的优化条件：交联剂用量为0．3％,引发剂用量为0．6％,单体浓度为20％,N,N’-二甲基丙烯酰胺与丙烯酰胺的摩尔比为2：1。在优化条件下,采用原位聚合法固定a-淀粉酶,测定不同单体配比的P（DMAA-co-AM）水凝胶固定化a-淀粉酶的活性。     

Gas permeation through water-swollen hydrogel membranes

This work deals with water-swollen hydrogel membranes for potential CO₂ separation applications, with an emphasis on elucidating the role of water in the membrane for gas permeation. A series of hydrogel membranes with a wide range of water contents (0.9–10 g water/g polymer) were prepared from poly(vinyl alcohol), chitosan, carboxyl methyl cellulose, alginic acid and poly(vinylamine), and the permeation of CO₂, H₂, He and N₂ through the membranes at different pressures (200–800 kPa) was studied. The gas permeabilities through the dry dense membranes were measured as well to evaluate the resistance of the polymer matrix in the hydrogel membranes. It was shown that the gas permeability in water-swollen membrane is lower than the gas permeability in water, and the selectivity of the water-swollen membranes to a pair of gases is close to the ratios of their permeabilities in water. The permeability of the water-swollen membranes increases with an increase in the swelling degree of the membrane, and the membrane permeability tends to level off when the water content is sufficiently high. A resistance model was proposed to describe gas permeation through the hydrogel membranes, where the immobilized water retained in the polymer matrix was considered to form transport passageways for gas permeation through the membrane. It was shown that the permeability of hydrogel membranes was primarily determined by the water content in the membrane. The model predictions were consistent with the experimental data for various hydrogel membranes with a wide range of water contents (0.4–10 g water/g polymer).     

An amino acid-based gelator for injectable and multi-responsive hydrogel

A novel multi-responsive amino acid-based gelator is developed.     

聚丙烯酸/氧化石墨烯复合水凝胶摩擦学性能研究

通过自由基聚合制备了聚丙烯酸(PAA)水凝胶。在水凝胶体系中掺入氧化石墨烯(GO),改善其机械强度。用往复摩擦试验机,在面-面接触的条件下考察了在不同载荷、速度、接触面积下,摩擦力和摩擦系数变化。实验结果表明,PAA水凝胶摩擦行为不遵从传统的固体摩擦定律(Amonton’s law)。通过与铜(Ⅱ)离子络合和去络合作用可实现摩擦系数从极低到较高的可逆调节。     

Development of honey hydrogel dressing for enhanced wound healing

Radiation at 25 and 50 kGy showed no effect on the acidic pH of the local honey, Gelam, and its antimicrobial property against Staphylococcus aureus but significantly reduced the viscosity. Honey stored up to 2 years at room temperature retained all the properties studied. Radiation sterilized Gelam honey significantly stimulated the rate of burn wound healing in Sprague-Dawley rats as demonstrated by the increased rate of wound contraction and gross appearance. Gelam honey attenuates wound inflammation; and re-epithelialization was well advanced compared to the treatment using silver sulphadiazine (SSD) cream. To enhance further the use of honey in wound treatment and for easy handling, Gelam honey was incorporated into our hydrogel dressing formulation, which was then cross-linked and sterilized using electron beam at 25 kGy. Hydrogel with 6% of honey was selected based on the physical appearance.     

Physically crosslinked poly(vinyl alcohol)-hydroxyethyl starch blend hydrogel membranes: Synthesis and characterization for biomedical applications

Poly(vinyl alcohol), PVA is a polymer of great importance because of its many appealing characteristics specifically for various pharmaceutical and biomedical applications. Physically crosslinked hydrogel membranes composed of different amounts of hydroxyethyl starch (HES) in (PVA) and ampicillin were prepared by applying freeze–thawing method. This freezing–thawing cycle was repeated for three consecutive cycles. Physicochemical properties of PVA–HES membrane gel such as gel fraction, swelling, morphology, elongation, tensile strength, and protein adsorption were investigated. Introducing HES into freeze–thawed PVA structure affected crystal size distribution of PVA; and hence physicochemical properties and morphological structure have been affected. Increased HES concentration decreased the gel fraction %, maximum strength and break elongation. Indeed it resulted into a significant incrementing of the swelling ability, amount of protein adsorption, broader pore size, and pore distribution of membrane morphological structure. Furthermore, an increase in HES concentration resulted in better and still lower thermal stability compared to virgin PVA and freeze–thawed PVA. The maximum weight loss of PVA–HES hydrogel membranes ranged between 18% and 60% according to HES content, after two days of degradation in phosphate buffer saline (PBS), which indicates they are biodegradable. Thus, PVA–HES hydrogel membranes containing ampicillin could be a novel approach for biomedical application e.g. wound dressing purposes.     

A novel amphiphilic pH-sensitive hydrogel based on pullulan

Novel polyelectrolyte and amphiphilic hydrogels based on pullulan have been prepared using 1-ethyl-3-[3-(dimethylamino)-propyl]carbodiimide hydrochloride and N-hydroxysuccinimide. The cross-linking reaction is fast and lead to zero length ester cross-links by the reaction of a carboxylate group with an alcohol function of the polysaccharide. The charge density and the hydrophobic rate of the precursor carboxymethylpullulan (CMP) are controlled during the carboxymethylation of pullulan and the grafting reaction of octyl chains on CMP, respectively. The grafting degree influences the conformation of the hydrophobically modified CMP (HMCMP) in solution and leads to the formation of hydrophobic clusters firstly in the HMCMP solutions and further in the HMCMP hydrogels. The swelling measurements of HMCMP hydrogels at different salt concentrations (0–0.2 M NaCl) and different pH (3–11) shows the ionic strength and pH sensitivity of the gels. The loading of a hydrophobic probe molecule can be controlled by the grafting degree of HMCMP hydrogels.