Molecularly imprinted macroporous polymer monolithic layers for L-phenylalanine recognition in complex biological fluids

In present work, the development of macroporous monolithic layers bearing the artificial recognition sites toward L-phenylalanine has been carried out. The set of macroporous poly(2-aminoethyl methacrylate-co-2-hydroxyethyl methacrylate-co-ethylene glycol dimethacrylate) materials with average pore size ranged in 340–1200 nm was synthesized. The applicability of Hildebrand's and Hansen's theories for the prediction of polymer compatibility with porogenic solvents was evaluated. The dependences of average pore size on theoretically calculated parameters were plotted. The linear trend detected for Hansen's theory has indicated the high suitability of this approach to select appropriate porogens. The synthesized monolithic MIP layers were tested toward the ability to rebind phenylalanine-derivative in microarray format. The influence of such factors as average pore size of the material, the concentration of template molecule in polymerization mixture, interaction time of analyte with its imprinted sites on binding efficiency were studied. The developed materials demonstrated good analyte rebinding from buffer solution with recognition factors 2.5–3.4 depending on the MIP sample. The comparable rebinding efficiency was also detected when the analysis was carried using complex biological media. The selectivity of phenylalanine binding from the equimolar mixture of structural analogues was 81.9% for free amino acid and 91.2% for labeled one.     

Influence of fluorine-containing side chain on the properties of waterborne polyurethane-urea

In order to prepare waterborne polyurethane with excellent water resistance and thermodynamic properties, a series of side chain fluorinated waterborne polyurethane-urea (FWPU-UA) was synthesized with polytetramethylene ether glycol, N-(2-methyl-1,3-propanediol-2′-)-perfluoro-1-butanesulfonyl amine (NPBA), isophorone diisocyanate, and isophoronediamine. With the increase of NPBA content, the weight loss temperature, glass transition temperature, and tensile strength of FWPU-UA were all improved. Gaussian fitting analysis of infrared data and density functional theory simulation proved that the introduction of fluorine side chains increased the interaction of hydrogen bonding in the FWPU-UA. X-ray photoelectron spectroscopy analysis indicated that the aggregation of fluorine atoms on the surface of film were caused by the migration and enrichment of fluorine side chains. Furthermore, the water resistance of polyurethane-urea film could be significantly improved by adding a small amount of NPBA, and the seven-day water absorption rate of polyurethane-urea film was reduced from 30.13% to 12.55%.     

Superconducting Quantum Metamaterials from High Pressure Melt Infiltration of Metals into Block Copolymer Double Gyroid Derived Ceramic Templates

Mesoscale order can lead to emergent properties including phononic bandgaps or topologically protected states. Block copolymers offer a route to mesoscale periodic architectures, but their use as structure directing agents for metallic materials has not been fully realized. A versatile approach to mesostructured metals via bulk block copolymer self-assembly derived ceramic templates, is demonstrated. Molten indium is infiltrated into mesoporous, double gyroidal silicon nitride templates under high pressure to yield bulk, 3D periodic nanocomposites as free-standing monoliths which exhibit emergent quantum-scale phenomena. Vortices are artificially introduced when double gyroidal indium metal behaves as a type II superconductor, with evidence of strong pinning centers arrayed on the order of the double gyroid lattice size. Sample behavior is reproducible over months, showing high stability. High pressure infiltration of bulk block copolymer self-assembly based ceramic templates is an enabling tool for studying high-quality metals with previously inaccessible architectures, and paves the way for the emerging field of block-copolymer derived quantum metamaterials.     

高性能有机氟材料制备科学及应用进展

有机氟材料具有优异的热氧稳定性、耐化学腐蚀性、耐老化性、不黏性、电绝缘性以及极小的摩擦系数等特性，因此作为一种不可替代的材料广泛应用于高新技术产业。近年来高新技术产业发展对高性能有机氟材料的需求引发了学术界和工业界对氟材料的研究兴趣。依据本文作者的研究经历及有机氟材料的发展方向，本文介绍了氟树脂（新型含氟聚合物、电活性含氟聚合物、新型全氟磺酸聚合物、聚四氟乙烯3D打印）及氟橡胶（过氧化物硫化氟橡胶、耐低温氟醚橡胶、耐高温全氟醚橡胶、全氟聚醚基类玻璃橡胶）的制备科学及应用进展，特别阐述为了满足航空航天、能源、信息等高新技术产业需求发展的新一代高性能有机氟材料。本文也介绍了近期出现的聚四氟乙烯新成型技术及类玻璃氟橡胶。文章指出发展绿色环保和高效的高性能有机氟材料制备及成型加工方法是今后的发展方向。     

Physical and thermal properties of l‐lactide/ϵ‐caprolactone copolymers: the role of microstructural design

Understanding the underlying role of microstructural design in polymers allows for the manipulation and control of properties for a wide range of specific applications. As such, this work focuses on the study of microstructure–property relationships in l‐ lactide/?‐caprolactone (LL/CL) copolymers. One‐step and two‐step bulk ring‐opening polymerization (ROP) procedures were employed to synthesize LL/CL copolymers of various compositions and chain microstructures. In the one‐step procedure, LL and CL were simultaneously copolymerized to yield P(LL‐stat‐CL) statistical copolymers. In the two‐step procedure, poly(l‐ lactide) (PLL) and poly(?‐caprolactone) (PCL) prepolymers were synthesized in the first step before CL and LL respectively were added in the second step to yield P[LL‐b‐(CL‐stat‐LL)‐b‐LL] and P[CL‐b‐(LL‐stat‐CL)‐b‐CL] block copolymers as the final products. The findings reveal that, in addition to the copolymerization procedure employed, the length and type of the prepolymer play important roles in determining the chain microstructure and thereby the overall properties of the final copolymer. Moreover, control over the degree of crystallinity and the type of crystalline domains, which is controlled during the polymer chemistry process, heavily influences the physical and mechanical properties of the final polymer. In summary, this work describes an interesting approach to the microstructural design of biodegradable copolymers of LL and CL for potential use in biomedical applications. © 2019 Society of Chemical Industry     

Novel hydrophilic N-halamine polymer with enhanced antibacterial activity synthesized by inverse emulsion polymerization

N-halamine-based antibacterial agents have high efficiency and rechargeable antibacterial properties. However, their applications are limited due to their complex synthetic process and fuzzy antibacterial mechanism. In this study, a novel N-halamine antibacterial polymer was synthesized by inverse emulsion polymerization and characterized by Fourier transform infrared, nuclear magnetic resonance, scanning electron microscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy. Due to the difficulty of purification, most of the subjects studied previously were hydrophobic polymers, while little research on hydrophilic polymers. In this experiment, this difficulty was overcome by controlling the dosage of sodium hypochlorite and methods of dialysis. Because of the complex cell structure of Gram-negative bacteria, it is difficult for N-halamines to release the oxidizing chlorine into the cell. However, the hydrophilic N-halamines can solve this problem, which showed a stronger antibacterial effect on Gram-negative Escherichia coli synthesized in this study. In addition, the particle size and hydrophilic property of the polymer were changed by changing the amount of initiator, and the differences in their antibacterial properties were studied. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47419.     

DOPO‐Based Phosphorus‐Containing Methacrylic (Co)Polymers: Glass Transition Temperature Investigation

A two‐step synthetic procedure is designed for preparing new flame‐retardant methacrylic monomers containing 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) as a substituent side group. DOPO and methacrylate moieties are linked by linear aliphatic hydrocarbon spacers (3 to 11 carbon atoms). Copolymerization with methyl methacrylate is carried out leading to copolymers containing between 2 and 10 wt% phosphorus. All homo‐ and copolymers exhibit a unique glass transition temperature (T_g ). A new group contribution for DOPO‐based substituent is extracted that leads to reasonable estimations of T_g s of other published polymers. The Fox equation provides a good estimation of T_g s for most copolymers and for physical blends of poly(methyl methacrylate) (PMMA) and DOPO. When using monomers having three and four carbon atoms in the hydrocarbon spacer, the T_g of copolymers remains close to that of PMMA over a wide range of composition.     

New water-soluble copolymers of 2-methacryloyloxyethyl phosphorylcholine for surface modification

New copolymers of 2-methacryloyloxyethyl phosphorylcholine with 2-Deoxy-2-methacrylamido-D-glucose, N-vinylpyrrolidone, and N-vinyl-N-methylacetamide were synthesized and characterized; the obtained copolymers contained 10–50 mol% of phosphorylcholine moieties, and their molecular masses ranged from 1.05 × 10⁵ to 4.40 × 10⁵. Reactivity ratios of the monomers were estimated. Conformational states of the copolymers in aqueous solutions were studied. The synthesized copolymer was grafted onto the surface of carbon fiber biosorbent using γ-radiation.     

Physicochemical Characterization of Polymer-Stabilized Coacervate Protocells

The bottom-up construction of cell mimics has produced a range of membrane-bound protocells that have been endowed with functionality and biochemical processes reminiscent of living systems. The contents of these compartments, however, experience semidilute conditions, whereas macromolecules in the cytosol exist in protein-rich, crowded environments that affect their physicochemical properties, such as diffusion and catalytic activity. Recently, complex coacervates have emerged as attractive protocellular models because their condensed interiors would be expected to mimic this crowding better. Here we explore some relevant physicochemical properties of a recently developed polymer-stabilized coacervate system, such as the diffusion of macromolecules in the condensed coacervate phase, relative to in dilute solutions, the buffering capacity of the core, the molecular organization of the polymer membrane, the permeability characteristics of this membrane towards a wide range of compounds, and the behavior of a simple enzymatic reaction. In addition, either the coacervate charge or the cargo charge is engineered to allow the selective loading of protein cargo into the coacervate protocells. Our in-depth characterization has revealed that these polymer-stabilized coacervate protocells have many desirable properties, thus making them attractive candidates for the investigation of biochemical processes in stable, controlled, tunable, and increasingly cell-like environments.