共轭聚合物材料及电致发光器件

共轭聚合物是一种极有应用前景的有机半导体材料,本文综述其研究进展,包括典型共轭聚合物材料PPV、PT、PF等及PPP的工作原理,发展前景和存在的问题。     

Biomolecules-carbon nanotubes doped conducting polymer nanocomposites and their sensor application

A simple method for preparing bio-functionalized soluble single-walled carbon nanotubes (SWNTs) is described. Different proteins such as bovine serum albumin (BSA), cytochrome c and horseradish peroxidase (HRP) were used to solubilize low functionality SWNTs in water aided by sonication. The unbound proteins were removed by column chromatography and the SWNT-protein conjugate was used as the sole anionic dopant in electropolymerization of polypyrrole from polymerization solution at pH above the isoelectric point of the protein to provide a negative charge. The morphology of the polypyrrole with SWNT-protein dopant was found to be three-dimensional and fibrous with wide open interlocking pores in contrast to smooth and cauliflower-like for chloride doped polypyrrole. Enhanced sensor performance was demonstrated for hydrogen peroxide detection on polypyrrole/SWCNT-HRP nanocomposites modified electrode. Such nanocomposites can be potentially applied for other biosensor and bio-fuel cell applications.     

Acrylamide–itaconic acid superabsorbent polymers and superabsorbent polymer/mica nanocomposites

Superabsorbent polymer acrylamide (AM)/itaconic acid (IA) and its nanocomposite were synthesized by redox polymerization in an aqueous solution of both monomers with mica used as an inorganic additive. The influences of IA concentration, mica content, and crosslinker concentration on the water absorption and physical properties of the superabsorbent polymer and its nanocomposite were examined. Water absorbency in artificial urine by the synthesized copolymers, and the gel strength of the superabsorbent copolymers and their nanocomposites, were tested with loads of 0.28 or 0.70 psi. Transmission electron micrographs and X‐ray diffraction confirmed that the polymer chains were successfully intercalated into the silicate layers in the mica. The water absorbency and the artificial urine absorbency of the composite with an AM‐to‐IA mole ratio of 95:5, 0.2% mol N‐MBA, and 5% w/w mica were 748 ± 5 and 76 ± 2 g g^?1, respectively, whilst the neat copolymer achieved only 640 ± 7 and 72 ± 2 g g^?1 in water and artificial urine, respectively. The viscoelastic behavior suggested that the swollen gel of the nanocomposites exhibited mechanical stability and elasticity. Copyright © 2009 John Wiley & Sons, Ltd.     

易衍生化温敏高分子刷的制备及其温敏行为研究

温敏材料由于优异的性能和潜在的应用价值而具有良好的发展前景.利用超分子自组装单层(SAM)与表面引发聚合(SIP)技术将2-(2-甲氧乙氧基)甲基丙烯酸乙酯(MEO2MA)与聚乙二醇甲基丙烯酸酯(OEGMA526)的共聚物poly(MEO2MAco-OEGMA526)接枝于金表面,探索了不同引发剂溶液浓度(χIsol)、单体OEGMA526摩尔浓度(C526)与干态膜厚度(d)对该高分子刷性质的影响.应用石英晶体微天平(QCM)对其温敏行为进行研究,结果表明:在χIsol=1%与C526=5%条件下制备的高分子刷,最低临界溶解温度(LCST)为34℃;其LCST由OEGMA526的单体摩尔浓度决定,不受膜厚的影响.该高分子刷在接枝生物素后其与链霉亲和素的结合实验证明,高分子刷末端的羟基为其官能团化提供了契机.该易衍生化温敏高分子刷为发展新型温敏材料提供了研究基础.     

Mobility-sensitive fluorescence probes for quantitative monitoring of water sorption and diffusion in polymer coatings

The fluorescent molecular rotor probes 4-tricyanovinyl-[N-(2-hydroxyethyl)-N-ethyl]-aniline, tricyano-4-(dimethylamino) benzylidene, and tricyanovinyljulolidene have been used as extrinsic fluorescence probes for quantitative monitoring of water uptake in polymeric coatings. The presence of water causes plasticization of the polymer, which results in increased local mobility within the film. The nonradiative decay pathways of the rotor probes are increased as local mobility increases, and the resulting decrease in fluorescence intensity of the probes is directly proportional to the amount of water sorbed. Beyond allowing for the characterization of sorbent content, this fluorescence technique can be used to determine the diffusion coefficient of water in a polymer film. The relative change in fluorescence fits well to a Fickian diffusion model, yielding a diffusion coefficient for water of 3 × 10^-8 cm²/s in poly(vinyl acetate), and a value of 6 × 10^-9 cm²/s in a room-temperature cured epoxypolyamide, in excellent agreement with diffusion coefficient values determined from gravimetric analysis. Preliminary studies also demonstrate the utility of molecular rotor probes to monitor water uptake in individual layers of multilayered polymer systems. © 1995 John Wiley & Sons, Inc.     

Synthesis of new lamellar materials by self-assembly and coordination chemistry in the solids

We report the preparation of a new class of lamellar hybrid organic–inorganic materials obtained by self-assembly of bridged organosilica precursors containing long alkylene chains during the sol–gel process. The self-assembly is induced by lipophilic van der Waals interactions. The introduction of –SS– bonds in the core of the alkylene chains permitted the functionalisation of lamellar materials, which were subsequently transformed into SH and –SO₃H groups. This methodology was extended to the formation of lamellar hybrid materials containing amino groups thanks to CO₂ as bridging groups as well as the formation of lamellar hybrid materials containing carboxylic groups. In this last case, the hydrolysis and polycondensation of cyanoalkyltrialkoxysilanes permitted the one pot synthesis of lamellar hybrid materials thanks to in situ hydrogen bonds formation between carboxylic acids groups. All these functional lamellar materials exhibit a very high chelating capability towards transition metal and lanthanide ions.     

SiO2/COPs的合成及其在光催化反应中的协同效应

共价有机聚合物(COPs)是一类由轻质元素(C,H,O,N和B等)通过共价键的方式连接而成的有机多孔材料.COPs的共轭结构赋予其优异的可见光吸收特性,已经在光催化水分解制氢、二氧化碳还原、有机合成和污染物降解等领域显示出巨大的应用潜力.虽然COPs具有能带结构易调控和高孔隙率等优点,但其光催化活性仍有待提升.使用助催化剂是提升COPs的光催化活性,促进表面反应普遍采用的策略.此外,底物活化官能团的引入和光催化剂表面性质的调控也是提高光催化剂反应活性的有效方法.虽然可以通过改变COPs单体种类、化学键的类型和拓扑结构来调控COPs的组成,但要同时兼顾COPs的结构和亲疏水性的调控以及底物活化官能团的引入仍十分困难.与纯COPs相比,与其他材料进行杂化为扩大COPs的化学组成和功能性提供了更多可能.迄今为止,在COPs纳米孔中封装分子、纳米颗粒或将COPs涂覆在其他固体材料上是制备基于COPs复合材料的常用策略.但是,考虑到COPs和无机材料合成条件的不相容性,在纳米尺度精确控制复合材料的组分、结构和形貌仍然是一项艰巨的任务.本文制备了稳定在十六烷基三甲基溴化铵(CTAB)疏水核中的COPs胶体,其粒度分布在16 nm左右.通过溶胶-凝胶法在CTAB周围水解聚合四乙氧基硅烷,得到SiO2/COPs复合材料.表征结果表明,COPs均匀分布在氧化硅的骨架中.该复合材料具有分别来自于SiO2和COPs的介孔和微孔结构.与纯COPs相比,复合材料的表面疏水性降低.SiO2/COPs具有可见光响应特性,其吸收带边随COPs含量的增加而红移,表明在复合材料中COPs在高含量时发生团聚.SiO2/COPs作为光催化剂,可高效催化α-溴代苯乙酮的还原脱卤反应(汉斯酯为还原剂),其催化活性和SiO2/COPs比例相关,在COPs含量为22.6 wt％时达到最优.SiO2/COPs的催化活性较COPs有大幅度提高.在优化的SiO2/COPs比例下,SiO2/COPs的TOF是COPs的近12倍.控制实验表明,SiO2中的羟基对汉斯酯为还原剂有活化作用.此外,本文研究发现,复合材料的活性与SiO2/COPs的比值呈火山型曲线,表明在光催化反应中SiO2和COPs之间存在协同效应.由此可见,将光催化剂和反应物活化材料耦合是提高光催化反应活性的有效策略.     

Synthesis and application of a molecularly imprinted polymer in the solid-phase extraction of ketoprofen from wastewater

Ketoprofen is a nonsteroidal anti-inflammatory drug widely consumed by humans as it possesses analgesic activities. A selective molecularly imprinted polymer (MIP) for ketoprofen was synthesized and applied as a solid-phase extraction sorbent. MIP was synthesized using 2-vinylpyridine, ethylene glycol dimethacrylate, 1,1′-azobis(cyclohexanecarbonitrile), toluene/acetonitrile (9:1, v/v), and ketoprofen as a functional monomer, cross-linker, initiator, porogenic mixture, and template, respectively. The polymerization was performed at 60 °C for 16 h, and thereafter the temperature was increased to 80 °C for 24 h to achieve a solid monolith polymer. Nonimprinted polymer was synthesized in a similar manner with the omission of ketoprofen. Characterization with thermogravimetric analysis and X-ray diffraction showed that the synthesized polymers were thermally stable and amorphous. Solid-phase extraction cartridges packed with MIP were used with high-performance liquid chromatography for quantitative analysis of ketoprofen in wastewater. The analytical method gave detection limits of 0.23, 0.17, and 0.09 μg/L in wastewater influent, effluent, and deionized water, respectively. The recovery for the wastewater influent and effluent spiked with 5 μg/L of ketoprofen was 68%, whereas 114% was obtained for deionized water. The concentrations of ketoprofen in the influent and effluent samples were in the ranges of 22.5–34.0 and 1.14–5.33 μg/L, respectively. Overall, the analytical method for the analysis of ketoprofen in wastewater was rapid, affordable, accurate, precise, sensitive, and selective.     

A pre-concentration procedure employing a new imprinted polymer for the determination of copper in water

This work describes the development by response surface methodology (RSM) of a procedure for copper determination by inductively coupled plasma optical emission spectrometry (ICP OES) in water samples after extraction by copper imprinted polymer. Results of the two-level full factorial design (2⁴) based on an analysis of variance demonstrated that only the solution pH; amount of polymer and adsorption time were statistically significant. Optimal conditions for the extraction of copper samples were obtained by using Box-Behnken design. Solution pH; amount of polymer and adsorption time were regarded as factors in the optimisation study. The working conditions were 4.6, 0.03?g and 3.5?h, for solution pH, amount of polymer; and adsorption time, respectively. Under the optimised experimental conditions, the detection limit of the proposed method followed by ICP OES was found to be 0.8?µg?L^?1. The relative standard deviation (RSD) was found to less than 0.81%. The pre-concentration factor was 22.5. The accuracy of the optimised procedure was evaluated by analysis of certified reference material. The method was applied to the determination of copper in water samples.     

Synthesis of well-defined polymers with protected silanol groups by atom transfer radical polymerization and their use for the fabrication of polymeric nanoparticles

Copper-mediated atom transfer radical polymerization (ATRP) of a protected silanol group-holding methacrylate, methacryloxypropyltrimethoxysilane (MOPS), was investigated. In a dry condition using carefully distilled solvent and monomer, the polymerization proceeded in a living fashion providing a low-polydispersity polymer with a predicted molecular weight. The ATRP in conjunction with the sequential monomer addition of methyl methacrylate (MMA) and MOPS afforded a block copolymer of the type PMMA-b-poly(MMA-r-MOPS). The heat treatment of a solution of the block copolymer in the presence of a catalytic amount of ammonia gave a polymeric core-shell nanoparticle with a shell of PMMA moieties and a core of the poly(MMA-r-MOPS) blocks cross-linked via the condensation of the trimethoxysilane groups of the MOPS moieties.     

Gene-expression profiling in gill and liver of zebrafish exposed to produced water

The effects of produced water (a by-product of oil and gas extraction) on gene expression were studied in gills and liver tissues of zebrafish. Adult, non-breeding zebrafish were exposed to control (freshwater mixed with 5% seawater) or produced water (freshwater mixed with 5% of produced water from the Oceberg C Oil Platform in the North Sea). A zebrafish library was used to make a microarray that consisted of 15,806 unique genes. The results indicate that 27 genes in the gills and 55 genes in the liver show significantly altered expression (greater than two-fold change). More than 70% of these gene sequences have not been annotated in the Gene Ontology (GO) database, making it difficult to characterize the affected genes. CYP1A displayed the greatest upregulation in the gills (eightfold, verified with quantitative real-time PCR). This study illustrates the utility of microarray approaches in investigations of environmental effects of toxicants.     

孤岛油田含聚污水中酸性组分的分离与组成结构研究

采用石油醚和三氯甲烷分级萃取孤岛油田含聚污水中的油分,得到两个不同极性的组分F1和F2;用碱抽提法从酸值较高的F2组分中分离酸性物质并将其甲酯化,通过柱层析法将甲酯化物分成Ⅰ、Ⅱ和Ⅲ三个甲酯组分。用元素分析、红外光谱分析等对上述各组分的组成及结构进行鉴定,对甲酯组分Ⅰ进行GC MS 结构鉴定。结果表明,含聚污水中酸性乳化活性物质主要富集在F2组分中,降解HPAM是酸性物质的主要的组成部分;甲酯组分Ⅰ主要为石油酸甲酯,甲酯组分Ⅱ主要为含酰胺基的脂肪酸甲酯,甲酯组分Ⅲ除含有较多酰胺基脂肪酸甲酯外,还含有一定量的强极性含硫化合物;孤岛油田含聚污水中的轻质石油酸以单环环烷酸、四环环烷酸和脂肪酸为主,其中环烷酸的含量明显大于脂肪酸的含量。脂肪酸以C16和C18为主,单环环烷酸以C14~18为主,四环环烷酸以C18~21为主。     

Occurrence patterns of pharmaceuticals in water and wastewater environments

The occurrence of pharmaceuticals and their metabolites and transformation products in the environment is becoming a matter of concern, because these compounds, which may have adverse effects on living organisms, are extensively and increasingly used in human and veterinary medicine and are released continuously into the environment. A variety of pharmaceuticals have been detected in many environmental samples worldwide. Their occurrence has been reported in sewage-treatment-plant effluents, surface water, seawater, groundwater, soil, sediment and fish. This paper provides an overview of recent scientific research on the sources, occurrence, and fate of pharmaceuticals in water and wastewater.     

Effect of water adsorption onto the polymer layer produced from the monomer carrying amide group in liquid crystal cells

The voltage holding ratio (VHR) of an active-matrix liquid crystal display (AMLCD) is a significant parameter because the image quality of the AMLCD decreases in case of low VHR. In some cases, the VHR of the LC cell, which is a prototype of the AMLCD, is decreased under an environment of high humidity and temperature. In order to restrict the significant decrease in the VHR, we proposed an LC cell with the polymer layer produced from the monomer 1-acryloyl-oxy-5-acryloyl-amino-naphthalene (1-AO-5-AANp). The LC cell exhibited comparably high VHR after being placed in an environment of high humidity and temperature. We presume that water molecules would be effectively adsorbed onto the polymer layer carrying the amide group, leading to a restriction of the significant decrease in VHR.     

Poly(methyl acrylate)/poly(hydroxyethyl acrylate) sequential interpenetrating polymer networks. Miscibility and water sorption behavior

Sequential poly(methyl acrylate)/poly(hydroxyethyl acrylate) interpenetrating polymer networks with different poly(hydroxyethyl acrylate) contents were prepared by free radical polymerization of hydroxyethyl acrylate inside the previously polymerized poly(methyl acrylate) network. Differential scanning calorimetry on dry samples shows that the interpenetrating polymer networks exhibit phase separation, and no differences are found between the glass transition temperatures of the two phases present in the interpenetrating polymer network and those of the pure components. Thermally stimulated depolarization current experiments were used to study the influence of water sorption on the mobility of the different molecular groups in the poly(hydroxyethyl acrylate) phase of the interpenetrating polymer network. Isothermal water sorption of the interpenetrating polymer networks and pure poly(methyl acrylate) and poly(hydroxyethyl acrylate) networks is analyzed with different theories to compare the behavior of the poly(hydroxyethyl acrylate) phase in the interpenetrating polymer networks with that of the pure poly(hydroxyethyl acrylate) network. Diffusion coefficients of water in the interpenetrating polymer networks are obtained by means of dynamic sorption experiments. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1587–1599, 1999     

Controlled synthesis of hydrophilic concentrated polymer brushes and their friction/lubrication properties in aqueous solutions

Polymer brushes of water‐soluble polymers, poly(2‐hydroxyethyl acrylate) (PHEA) and poly(poly(oxyethyleneglycol)methylether acrylate) (PPEGA), were synthesized on a silicon wafer and a silica particle by applying photo‐induced organotellurium‐mediated radical polymerization to surface‐initiated graft polymerization. High graft densities were obtained, corresponding to reduced graft densities of about 0.32 and 0.42 for the PHEA and PPEGA brushes, respectively. These values were high enough to be categorized in the regime of “concentrated” polymer brushes (CPBs). Atomic force microscopic (AFM) study revealed that the CPB of PPEGA was allowed to be highly swollen in water but the CPB of PHEA did not. This means that water is reasonably good for PPEGA but not for PHEA. The AFM microtribological study between swollen brushes revealed two lubrication regimes, namely, boundary‐ and hydrodynamic‐lubrication regimes, with different shear‐velocity dependencies. Reflecting insufficient quality of water as a solvent, the CPB of PHEA showed adhesive interaction and thereby a higher frictional coefficient μ in the boundary lubrication. More interestingly, super lubrication was achieved for the CPB of PPEGA with a μ value in the order of 10^?4 in water and in 0.1 M aqueous NaCl solution (without the help of electrostatic repulsion). Super lubrication was concluded to be a characteristic feature of the CPB, even in an aqueous system. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Properties of conductive polymer hydrogels and their application in sensors

Conductive polymer hydrogels (CPHs), which combine the unique advantages of hydrogels and organic conductors, have received wide attention due to their adjustable mechanical properties, biocompatibility, self‐healing, hydrophilicity, and ease of preparation. With doping engineering and incorporation with other functional nanomaterials, CPHs have exhibited excellent physical/chemical properties. CPHs have been widely used in various electronic devices, especially in the field of sensors due to its sensitivity to external stimuli. This review summarizes recent progress in CPHs from the aspect of the CPHs' properties and their application in advanced sensor technology. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1606–1621     

二苯磷酰基取代四苯基硅的合成及在构筑宽禁带聚合物中的应用

设计并合成了二苯磷酰基取代的四苯基硅基团,并将其作为宽禁带聚合物母体材料构筑基元,通过Suzuki反应偶连3,6位取代的咔唑合成了聚合物SiCzP.对聚合物的结构进行了系统的表征.与模型聚合物SiCz相比,二苯磷酰基的强吸电子能力,降低聚合物母体材料的LUMO能级,更有利于电子的注入.SiCzP与SiCz的玻璃化转变温度分别为219与227℃,失重5%时的分解温度分别为441与426℃.二者均具有良好的成膜性,掺杂器件初步结果表明,二苯磷酰基的引入使器件的亮度和效率都得到提高,其最大流明效率和功率效率比SiCz分别提高了98%和75%.     

Synthesis of a molecularly imprinted polymer and its application for microextraction by packed sorbent for the determination of fluoroquinolone related compounds in water

Molecularly imprinted polymer (MIP) has been synthesized by precipitation polymerization using ciprofloxacin (CIP) as template for the analysis of fluoroquinolone antibiotics (FQs). This MIP material was packed as sorbent in a device for microextraction by packed sorbent (MEPS) combined with liquid chromatography–tandem mass spectrometry (LC–MS/MS) for the analysis of selected FQs drugs including CIP, norfloxacin (NOR) and ofloxacin (OFLO) in municipal wastewater samples. In comparison to the new MIP-MEPS procedure, the target compounds were also determined by solid-phase extraction (MISPE) using the new molecular imprinted polymer material to validate the new MIP-MEPS method. The ability of the MIP for molecular recognition of CIP, NOR and OFLO was proved in presence of structurally different environmental relevant substances such as quinolones (Qs), flumequine (FLU), di(methyl)phthalate (DMP), technical 4-nonylphenol (NP), caffeine, Galaxolide^®, Tonalid^®, di(butyl)phthalate (DBP), Triclosan, bisphenol-A (BPA), carbamazepine, di(ethylhexyl)phthalate (DEHP), estradiol and octocrylene. The analysis of wastewater samples revealed the high selectivity of the synthesized polymer which was able to recognize and retain the target analytes by both extraction methods, the offline SPE with MIP material and the semi-automated MEPS packed with MIP material.     

Gold nanoparticles decorated covalent organic polymer as a bimodal catalyst for total water splitting and nitro compound reduction

The design and construction of a bimodal catalyst with magnificent performance and high stability is a debatable one for total water splitting and nitro compound reduction. Herein, we report the synthesis of a covalent organic polymer network based on 1,4-phenylenediamine based covalent organic polymer (PD-COP) and its decoration with Au nanoparticles (Au NPs) as well as their confirmation using various analytical and surface techniques. The electrocatalytic activity toward total water-splitting reaction (OER and HER) in KOH solution (1.0 M) was investigated. In addition, the reduction of aromatic nitro compounds (4-nitrophenol (4-NP) and 2-nitroaniline (2-NA)) was carried out in the presence of NaBH₄. Among the different electrocatalysts (PD-COP, Au@PD-COP-I, Au@PD-COP-II, Au@PD-COP-III and Au@PD-COP-IV) studied in this work, the Au@PD-COP-II demands a low overpotential of 288 mV and 184 mV to attain a 50-mA/cm² geometrical current density with a lowest Tafel slope value of 56 and 85 mV/dec for OER and HER respectively. From the OER and HER phenomenal activity, a two-electrode system was constructed, and it needs a cell voltage of 1.615 V to conquer a current density of 10 mA/cm² with outstanding stability for 34 h. The high electroactivity of Au@PD-COP-II may be allied with the presence of innumerable redox-active sites and high electrochemical active surface area (ECSA) towards effective water electrolysis. Further, the catalytic activity performed towards the reduction of 4-NP to 4-aminophenol (4-AP) and 2-NA to o-PDA (o-phenylenediamine), Au@PD-COP-II showed good catalytic activity with a reduction time of 20 and 14 min respectively.