Deposition Strategies for Osmium/Enzyme Films on Gold Electrode Based Sensing Arrays

Multi‐analyte real‐time interrogation of cellular activity allows for the potential discovery of novel insights into disease. In this report, the addition of electrochemical biosensors to a previously developed platform utilizing Au microfabricated electrodes was explored. Glucose oxidase was immobilized at the electrode surface with an osmium redox polymer, using hand‐casting and electrodeposition techniques, allowing for the first comparison of deposition techniques at a Au microfabricated array. This preliminary work is the first step toward the goal of creating a multi‐analyte array for cellular analysis.     

Chemometric Strategies to Develop a Nanocomposite Electrode for Simultaneous Determination of Ascorbic Acid,Dopamine, and Uric Acid

A simple and sensitive method for simultaneously measuring dopamine (DA), ascorbic acid (AA), and uric acid (UA) using a poly(1‐aminoanthracene) and carbon nanotubes nanocomposite electrode is presented. The experimental parameters for composite film synthesis as well as the variables related to simultaneous determination of DA, AA, and UA were optimized at the same time using fractional factorial and Doehlert designs. The use of carbon nanotubes and poly(1‐aminoanthracene) in association with a cathodic pretreatment led to three well‐defined oxidation peaks at potentials around ?0.039, 0.180 and 0.351 V (vs. Ag/AgCl) for AA, DA, and UA, respectively. Using differential pulse voltammetry, calibration curves for AA, DA, and UA were obtained over the range of 0.16–3.12×10^?3 mol L^?1, 3.54–136×10^?6 mol L^?1, and 0.76–2.92×10^?3 mol L^?1, with detection limits of 3.95×10^?5 mol L^?1, 2.90×10^?7 mol L^?1, and 4.22×10^?5 mol L^?1, respectively. The proposed method was successfully applied to determine DA, AA, and UA in biological samples with good results.     

Synthesis of Methyl N‐Aryl Oxamate Using Soluble Polymer Support

A variety of methyl N‐aryl oxamates were synthesized using poly(ethylene glycol) (PEG) as a soluble polymer support and a monoproctection group with excellent yields.     

Synthesis and properties of sulfur‐contained poly(silylene arylacetylene)s

Poly(silylene arylacetylene) (PSA) is a kind of poly(arylacetylene) silicon‐containing resins with excellent heat resistance and good mechanical performances. In this article, the sulfur atom is introduced into the main chain of the PSA molecule to obtain a sulfur‐containing poly(silylene arylacetylene), named S‐PSA. By Williamson and Sonogashira reactions, bis(4‐ethynylphenyl)sulfide and bis(4‐ethynylphenyl)sulfone were synthesized. Thereafter, through Grignard reagent way, the poly(silylene ethynylene phenylene sulfide phenylene ethynylene) (PSESE) and poly(silylene ethynylene phenylene sulfone phenylene ethynylene) (PSESO₂E) were synthesized from bis(4‐ethynylphenyl)sulfide, bis(4‐ethynylphenyl)sulfone, and methylphenyl dichlorosilane. Poly(silylene ethynylene phenylene sulfoxide phenylene ethynylene) (PSESOE) was synthesized by the oxidation of PSESE. The structures and properties of these resins were characterized and the mechanical properties of the T300 reinforced composites were tested. The results show that the novel S‐PSA resins have excellent heat resistance and good mechanical properties, and could be used as resin matrices for high‐performance composites in high‐tech fields. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2324–2332     

Organizing thermodynamic data obtained from multicomponent polymer electrolytes: Salt‐containing polymer blends and block copolymers

The objective of this review is to organize literature data on the thermodynamic properties of salt‐containing polystyrene/poly(ethylene oxide) (PS/PEO) blends and polystyrene‐b‐poly(ethylene oxide) (SEO) diblock copolymers. These systems are of interest due to their potential to serve as electrolytes in all‐solid rechargeable lithium batteries. Mean‐field theories, developed for pure polymer blends and block copolymers, are used to describe phenomenon seen in salt‐containing systems. An effective Flory–Huggins interaction parameter, χ_eff , that increases linearly with salt concentration is used to describe the effect of salt addition for both blends and block copolymers. Segregation strength, χ_effN , where N is the chain length of the homopolymers or block copolymers, is used to map phase behavior of salty systems as a function of composition. Domain spacing of salt‐containing block copolymers is normalized to account for the effect of copolymer composition using an expression obtained in the weak segregation limit. The phase behavior of salty blends, salty block copolymers, and domain spacings of the latter systems, are presented as a function of chain length, composition and salt concentration on universal plots. While the proposed framework has limitations, the universal plots should serve as a starting point for organizing data from other salt‐containing polymer mixtures. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1177–1187     

Polymer chain diffusion in polymer blends: A theoretical interpretation based on a memory function formalism

The diffusion of polymer chains in miscible polymer blends with large dynamic asymmetry—those where the two blend components display very different segmental mobility—is not well understood yet. In the extreme case of the blend system of poly(ethylene oxide) (PEO) and poly(methyl methacrylate)(PMMA), the diffusion coefficient of PEO chains in the blend can change by more than five orders of magnitude while the segmental time scale hardly changes with respect to that of pure PEO. This behavior is not observed in blend systems with small or moderate dynamic asymmetry as, for instance, polyisoprene/poly(vinyl ethylene) blends. These two very different behaviors can be understood and quantitatively explained in a unified way in the framework of a memory function formalism, which takes into account the effect of the collective dynamics on the chain dynamics of a tagged chain. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1239–1245     

The direct architecture of carbon fiber‐carbon nanofiber hierarchical reinforcements for superior interfacial properties of CF/epoxy composites

A simple and efficient chemical method was developed to graft directly carbon nanofibers (CNFs) onto carbon fiber (CF) surface to construct a CF‐CNF hierarchical reinforcing structure. The grafted CF reinforcements via covalent ester linkage at low temperature without any usage of dendrimer or catalyst was investigated by FTIR, X‐ray photoelectron spectroscopy, Raman, scanning electron microscopy, atomic force microscopy, dynamic contact angle analysis, and single fiber tensile testing. The results indicated that the CNFs with high density could effectively increase the polarity, wettability, and roughness of the CF surface. Simultaneous enhancements of the interfacial shear strength, flexural strength, and dynamic mechanical properties as well as the tensile strength of CFs were achieved, for an increase of 75.8%, 21.9%, 21.7%, and 0.5%, respectively. We believe the facile and effective method may provide a novel and promising interface design strategy for next‐generation advanced composite structures.     

通过调节共轭聚合物侧链实现可绿色溶剂加工的非富勒烯太阳能电池

有机太阳能电池(OSC)经过长期的发展,其能量转换效率(PCE)已快速推进至14%–16%,基本接近可商业化应用的范围,但在目前所见报道的高效率OSC器件的制备过程中,活性层薄膜的加工大多采用氯苯、二氯苯、氯仿等毒性较高的含卤/芳香性试剂,此类试剂对环境及人类健康的危害非常高。在本工作中,我们基于已报道的高效率给体共轭聚合物PBDB-T,通过扩大共轭侧链结构与增长柔性烷基侧链的方式,合成了新型给体聚合物PBDB-DT。PBDB-DT中较长的柔性烷基侧链保证了其在低毒性溶剂四氢呋喃(THF)溶液中良好的溶解度,同时,扩大的共轭侧链也有效增强了其在THF中的溶液聚集作用,这一特性对于在非富勒烯型OSC器件中获得较好的光伏性能尤其重要。当采用非富勒烯小分子IT-M作为电子受体材料时,以THF为主溶剂加工的基于PBDB-DT:IT-M的OSC器件可以获得10.2%的能量转换效率。     

A personal journey on using polymerization in aqueous dispersed media to synthesize polymers with branched structures

This short review is dedicated to celebrate Prof.Shoukuan Fu's 80 th birthday by discussing several of my accomplished projects over the past twenty years,which all applied radical polymerization in aqueous dispersed media for producing polymers with branched structures.These projects include the use of microemulsion polymerization for syntheses of fluorescent nanoparticles,hairy nanoparticles and hyperbranched polymers;the use of miniemulsion polymerization for synthesis of star polymers and light-emitting nanoparticles;the use of seeded emulsion polymerization for synthesis of hairy nanoparticles and hyperstar polymers;and the use of precipitation polymerization for synthesis of hollow polymer nanocapsules.Discussion of these projects demonstrates intriguing features of polymerization in biphasic dispersed media via either conventional radical polymerization or controlled radical polymerization to effectively regulate the branched structure of functional polymers.     

Three new ZnII coordination polymers constructed from a semi‐rigid tricarboxylic acid: structural changes caused by flexibility and luminescence sensing for hexavalent chromate anions

Coordination polymers (CPs) with specific structures and functional luminescence have been widely designed as sensors for detecting small molecules and ions. In this study, with or without the help of an N‐donor auxiliary linker, three new Zn^II CPs, namely, three‐dimensional (3D) poly[[pentaaquabis[μ₃‐5‐(4‐carboxybenzyloxy)isophthalato]bis[μ₆‐5‐(4‐carboxylatobenzyloxy)isophthalato]di‐μ₃‐hydroxido‐hexazinc(II)] trihydrate], {[Zn₆(C₁₆H₁₀O₇)₂(C₁₆H₉O₇)₂(OH)₂(H₂O)₅]·3H₂O}_n or {[Zn₆(μ₃‐HL)₂(μ₆‐L)₂(μ₃‐OH)₂(H₂O)₅]·3H₂O}_n, ( I ), one‐dimensional (1D) catena‐poly[[[aqua(1,10‐phenanthroline)zinc(II)]‐μ₂‐5‐(4‐carboxybenzyloxy)isophthalato] dihydrate], {[Zn(C₁₆H₁₀O₇)(C₁₂H₈N₂)(H₂O)]·2H₂O}_n or {[Zn(μ₂‐HL)(phen)(H₂O)]·2H₂O}_n (phen is 1,10‐phenanthroline), ( II ), and 3D poly[diaquatetrakis(4,4′‐bipyridine)bis[μ₆‐5‐(4‐carboxylatobenzyloxy)isophthalato]di‐μ₃‐formato‐di‐μ₃‐hydroxido‐pentazinc(II)], [Zn₅(C₁₆H₉O₇)₂(HCOO)₂(OH)₂(C₁₀H₈N₂)₄(H₂O)₂]_n or [Zn₅(μ₄‐L)₂(bpy)₄(μ₂‐OH)₂(μ₃‐HCOO)₂(H₂O)₂]_n (bpy is 4,4′‐bipyridine), ( III ), have been constructed from the semi‐rigid tricarboxylic acid 5‐(4‐carboxybenzyloxy)isophthalic acid (H₃L) under hydrothermal conditions. CP ( I ) exhibits a twofold interpenetrated 3D+3D→3D skeleton with a 3 , 5 ‐conn topology constructed from triangular trinuclear [Zn₃(COO)₄(μ₃‐OH)] clusters, in which the H₃L ligand adopts three different coordination modes. CP ( II ) exhibits a 1D infinite chain and stacking that gives a 3D structure mediated by hydrogen bonds and weak interactions. CP ( III ) is an interesting 3D 3 , 4 , 8 ‐conn network including linear tetranuclear [Zn₄(μ₂‐OH)₂(HCOO)₂(COO)₂] clusters with a new {4·6²}₂{4·6⁴·8}{4⁶·6¹⁹·8³} topological symbol. The influences of the flexible –CH₂–O– linker of the H₃L ligand and subtle environmental factors, such as solvent, pH value and auxiliary ligands, on the formation of the final structures are also discussed. The solid‐state fluorescence spectra of CPs ( I )–( III ) were recorded at room temperature and all show better fluorescence performances than H₃L. In particular, ( II ) can act as a potential multifunctional fluorescent material for sensing hexavalent chromium ions in aqueous solution with high stability, selectivity and sensitivity. Under ultraviolet light of 365 nm from a UV lamp, a signal response of fluorescence from turning on to off can be observed with the naked eye. It was found that the detection for hexavalent chromium (i.e. Cr₂O₇^2?) by ( II ) has a high selectivity [K_SV = 1.61 × 10⁴M^?1 and limit of detection (LOD) = 0.434 µM] in aqueous solution. Quenching mechanisms were also studied in detail.