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.     

Antimicrobial-modified sulfite pulps prepared by in situ copolymerization

Grafting guanidine polymer (PHGH) onto cellulose fibers was conducted via in situ free-radical polymerization using ceric ammonium nitrate (CAN) as an initiator. The optimum reaction conditions were obtained, under which the grafting percentage and the grafting efficiency reached over 20% and 50%, respectively. Atomic force microscopy (AFM) images revealed that the grafted polymer tended to form grains with diameters ranging from 60 to 200 nm. AFM also enabled us to identify the location of the grafts on the surfaces of cellulose fibers by the measurements of the adhesion and attraction forces between a colloid probe and the samples. The cellulose fibers were rendered antimicrobial in the presence of 1.0% (wt) grafted polymer, and an excellent antimicrobial activity (over 99% inhibition) toward Escherichia coli was achieved. The AFM results also demonstrated that the antimicrobial mechanism of PHGH is to destroy the membrane of the cells.     

Sugar-linked biodegradable polymers: Regio-specific ester bonds of glucose hydroxyls in their reaction with maleic anhydride functionalized polystyrene and elucidation of the polymer structures formed

In the development of sugar-linked synthetic polymers as biodegradable polymers, it is imperative to know the variety of polymer structures formed by the reaction of a multi-functional sugar molecule with the functionalized synthetic polymer on which the sugar is to be anchored. Enzymes produced by the microorganisms causing the polymer to biodegrade can be sensitive to the particular type of sugar hydroxyl utilized (such as anomeric, primary, or secondary hydroxyl group) for getting anchored to the polymer. In this paper, we present synthesis of regio-specific ester derivatives of glucose with anhydride, functionalized polymers, i.e., ester formation specifically with the anomeric, primary or secondary hydroxyls of glucose. Characterization of these different esters groups was done using FTIR spectroscopy; each ester peak was further deconvoluted to yield its different components. For this purpose, we studied the reactions of d-glucose, 6-O-trityl glucose, methyl glucoside, 1,2-5,6-diisopropylidene-d-glucose, and 1,2,3,4-tetraacetyl-d-glucose with maleic anhydride functionalized polystyrene (PSMAH). In this study, the primary hydroxyl of glucose was found to be even more reactive than the anomeric hydroxyl. The peaks at 1716, 1725, and 1729–1737 cm⁻¹ were assigned to the ester carbonyl of the anomeric, primary, and secondary hydroxyls of glucose (C2, C3, and C4), respectively. An attempt was made to quantify the extent to which the different polymer structures are formed in a particular reaction by taking ratios of non-variable reference peaks (polystyrene peak at 1493 cm⁻¹) and variable peaks caused by the reaction (the residual anhydride carbonyl at 1780 cm⁻¹).     

Insights into the fine architecture of the active site of chicory fructan 1-exohydrolase: 1-kestose as substrate vs sucrose as inhibitor

* Invertases and fructan exohydrolases (FEHs) fulfil important physiological functions in plants. Sucrose is the typical substrate for invertases and bacterial levansucrases but not for plant FEHs, which are usually inhibited by sucrose. * Here we report on complexes between chicory (Cichorium intybus) 1-FEH IIa with the substrate 1-kestose and the inhibitors sucrose, fructose and 2,5 dideoxy-2,5-imino-D-mannitol. Comparisons with other family GH32 and 68 enzyme-substrate complexes revealed that sucrose can bind as a substrate (invertase/levansucrase) or as an inhibitor (1-FEH IIa). * Sucrose acts as inhibitor because the O2 of the glucose moiety forms an H-linkage with the acid-base catalyst E201, inhibiting catalysis. By contrast, the homologous O3 of the internal fructose in the substrate 1-kestose forms an intramolecular H-linkage and does not interfere with the catalytic process. Mutagenesis showed that W82 and S101 are important for binding sucrose as inhibitor. * The physiological implications of the essential differences in the active sites of FEHs and invertases/levansucrases are discussed. Sucrose-inhibited FEHs show a K(i) (inhibition constant) well below physiological sucrose concentrations and could be rapidly activated under carbon deprivation.     

木质素复合水凝胶性能及应用的研究进展北大核心CSCD

木质素是自然界中储量仅次于纤维素的木质纤维素资源,也是唯一的天然芳香族聚合物,其衍生的高值化产品可以应用于多个领域。木质素的高效高值高质生产是木质纤维素生物炼制的关键所在,但木质素大分子结构复杂多变、反应的活性差、官能团冗杂,制备出性能稳定的高分子材料有一定的难度。随着木质素改性的研究越来越深入,木质素复合水凝胶的应用也受到了极大的关注。本文从木质素的基本结构组成与反应特性出发,简要概括了木质素复合水凝胶的制备方法;具体介绍了木质素复合水凝胶的应用现状,包括生物传感器、控制释放材料、环境响应材料、吸附材料、电极材料以及其他材料的应用;综述了木质素复合水凝胶的最新研究与应用进展,并对木质素制备复合水凝胶的发展前景进行了评述。     

自由基聚合反应修饰的金纳米粒子用于高灵敏度免疫传感器研究

目的:将原子转移自由基聚合物(ATRP)修饰金纳米粒子(GNps)引入传统的免疫传感器,提出一种新的免疫传感器策略。方法:用ATRP反应修饰GNps,增加活性位点,提高传感器的检查灵敏度。结果:该免疫传感器能够对0.5fg/mL促肾上腺皮质激素释放激素(CRH)产生应答,线性标定范围为0.5~250fg/mL。结论:新研制的免疫传感器具有良好的选择性、重复性和稳定性。     

Significantly Enhanced Electrostatic Energy Storage Performance of Flexible Polymer Composites by Introducing Highly Insulating‐Ferroelectric Microhybrids as Fillers

A hybrid nanoparticle, consisting of BaTiO₃ nanoparticles tightly embedded in bronnitride (BN) nanosheets, has been fabricated based on a daring supposition that BN may act as a host to incorporate ferroelectric nanoparticles to improve insulation and polarization under a high electric field. Using the hybrids as fillers in poly(vinylidene fluoride) (PVDF) composites, a high electric breakdown strength (E_b ≈580 kV/mm), which is 1.76 times of the PVDF film, is obtained when the filler content is 5 wt%. A large displacement (9.3 µC/cm² under 580 kV/mm) is observed so as to obtain a high discharged energy density (U_d ≈17.6 J/cm³) of the BT@BN/PVDF composites, which is 2.8 times of the PVDF film. The enhancement ratio of E_b achieved in this study demonstrates the highest among the reported results. This hybrid structure of fillers provides an effective way to adjust and improve the energy storage properties of the polymer‐based dielectrics.     

Boosting Organic–Metal Oxide Heterojunction via Conjugated Small Molecules for Efficient and Stable Nonfullerene Polymer Solar Cells

Charge events across organic–metal oxide heterointerfaces routinely occur in organic electronics, yet strongly influence their overall performance and stability. They become even more complicated and challenging for the heterojunction conditions in polymer solar cells (PSCs), especially when nonfullerene acceptors with varied energetics are employed. In this work, an effective interfacial strategy that utilizes novel small molecule self‐assembled monolayers (SAMs) is developed to improve the electronic and electric, as well as chemical properties of organic–zinc oxide (ZnO) interfaces for nonfullerene PSCs. It is revealed that the tailored SAMs with well‐controlled energy levels and molecular dipoles can effectively optimize the energetic barrier and work function (WF) of heterointerface for optimal electron extraction. In addition, the introduction of SAMs atop of ZnO facilitates not only acceptor segregation near the n‐contact interface, but also passivation of the photocatalytic activities for ZnO, to improve overall performance and photo stability of the derived nonfullerene PSCs. Overall, the methodology and structure–property relationship revealed herein would be beneficial for a wide range of hybrid electronics.     

Wide Potential Window Supercapacitors Using Open‐Shell Donor–Acceptor Conjugated Polymers with Stable N‐Doped States

Supercapacitors have emerged as an important energy storage technology offering rapid power delivery, fast charging, and long cycle lifetimes. While extending the operational voltage is improving the overall energy and power densities, progress remains hindered by a lack of stable n‐type redox‐active materials. Here, a new Faradaic electrode material comprised of a narrow bandgap donor?acceptor conjugated polymer is demonstrated, which exhibits an open‐shell ground state, intrinsic electrical conductivity, and enhanced charge delocalization in the reduced state. These attributes afford very stable anodes with a coulombic efficiency of 99.6% and that retain 90% capacitance after 2000 charge–discharge cycles, exceeding other n‐dopable organic materials. Redox cycling processes are monitored in situ by optoelectronic measurements to separate chemical versus physical degradation mechanisms. Asymmetric supercapacitors fabricated using this polymer with p‐type PEDOT:PSS operate within a 3 V potential window, with a best‐in‐class energy density of 30.4 Wh kg^?1 at a 1 A g^?1 discharge rate, a power density of 14.4 kW kg^?1 at a 10 A g^?1 discharge rate, and a long cycle life critical to energy storage and management. This work demonstrates the application of a new class of stable and tunable redox‐active material for sustainable energy technologies.