基于苯乙烯和苯并噻二唑共聚场效应发光高分子材料的设计合成及性能研究

共轭高分子材料由于其优异的光电性能和可溶液加工等特性在有机光电器件中具有重要应用.本工作采用Stille偶联和Suzuki聚合反应,合成了两个由经典发光基元苯乙烯片段和共轭吸电子结构基元苯并噻二唑共聚的高分子材料聚（1,2-双（2,5-双（异辛氧基）亚苯基亚乙烯基-2,1,3-苯并噻二唑））（PVBT）和聚（1,2-双（2,5-双（正辛氧基）亚苯基亚乙烯基-2,1,3-苯并噻二唑））（nPVBT）.通过凝胶渗透色谱（GPC）、元素分析及差式扫描量热法（DSC）对PVBT和nPVBT两种高分子材料的结构及热稳定性进行表征,结果表明它们均具有良好的热稳定性,分解温度约380℃.由于烷氧基链的存在,两个材料具有良好的溶解性及成膜加工性.PVBT和nPVBT均表现出优异的发光特性,最大发射波长在590~605 nm范围,溶液下荧光量子产率为23%~35%,固态薄膜下量子产率为12%~20%.以这两个高分子材料薄膜作为活性层,所制备的顶栅-底接触型有机场效应晶体管器件显示出典型的p型电荷传输性能,空穴迁移率可达1.1×10^-4 cm²·V^-1·s^-1,开关比为10³~10⁴.本研究为发展高性能光电集成高分子材料提供了新思路,有望推动有机光电集成器件的研究.     

Two-dimensional Molecular Phase Transition of Alkylated-TDPB on Au(111) and Cu(111) Surfaces

The derivatives of aromatic cores bearing alkyl chains with different lengths are of potential interest in on-surface chemistry, and thus have been widely investigated both at liquid-solid interfaces and in vacuum. Here, we report on the structural evaluation of self-assembled 1,3,5-tri(4-dodecylphenyl)benzene(TDPB) molecules with increased molecular coverages on both Au(111) and Cu(111) surfaces. As observed on Au(111), rhombic and herringbone structures emerge successively depending on surface coverage. In the case of Cu(111), the same process of phase conversion is also observed, but with two distinct structures. In comparison, the self-assembled structures on Au(111) surface are packed more densely than that on Cu(111) surface under the same preparation conditions. This may fundamentally result from the higher adsorption energy of TDPB molecules on Cu(111), restricting their adjustment to optimize a thermodynamically favorable molecular packing.     

The Effect of Enantiomer Elution Order on the Determination of Minor Enantiomeric Impurity in Ketoprofen and Enantiomeric Purity Evaluation of Commercially Available Dexketoprofen Formulations

In a recent study, opposite enantiomer elution order was observed for ketoprofen enantiomers on two amylose-phenylcarbamate-based chiral columns with the same chemical composition of the chiral selector but in one case with coated while in the other with an immobilized chiral selector. In the present study, the influence of this uncommon effect on method validation parameters for the determination of minor enantiomeric impurity in dexketoprofen was studied. The validated methods with two alternative elution orders for enantiomers were applied for the evaluation of enantiomeric impurity in six marketed dexketoprofen formulations from various vendors. In most of these formulations except one the content of enantiomeric impurity exceeded 0.1% (w/w).     

The effect of 3D printing on the morphological and mechanical properties of polycaprolactone filament and scaffold

Three‐dimensional (3D) printing becomes an attractive technique to fabricate tissue engineering scaffolds through its high control on fabrication and repeatability using the printing parameters. This technique can be combined by the finite element method (FEM), and tissue‐specific scaffolds with desirable morphological and mechanical properties can be designed and manufactured. In this study, the influential 3D printing parameters on the morphological and mechanical properties of polycaprolactone (PCL) filament and scaffold were studied experimentally and numerically. First, the effects of printing parameters and process on the properties of extruded PCL filament were investigated. Then, using FEM, the effects of filament specifications on the overall characteristics of the scaffold were evaluated. Results showed that both the printing process in terms of resting time and remaining time and the printing parameters like pressure, printing speed, and printing path length have influenced the filament properties. In addition, both the filament diameter and elastic modulus had significant effects on the properties of scaffold especially, a 20% increase in the filament diameter caused the scaffold compressive elastic modulus to rise by around 72%. It is concluded that the printing parameters and process must be tuned very well in fabricating scaffolds with the desired morphology and mechanical property.     

Natural Melanin Nanoparticle‐decorated Screen‐printed Carbon Electrode: Performance Test for Amperometric Determination of Hexavalent Chromium as Model Trace

A biosensor was prepared with natural melanin nanoparticles (MNP) decorated on a screen‐printed carbon electrode (SPCE). Hexavalent chromium was selected as a well‐known heavy metal ion to be detected for testing the performance of novel biosensor. Natural MNP was extracted from cuttlefish (Sepia officinalis) ink. Surface decoration of SPCEs with MNP was performed by two different methods. The first one was layer‐by‐layer assembly (LBL‐A) for different cycle times(n). In the second one, plasma treatment of SPCE incorporated with evaporation‐induced self‐assembly (EI‐SA) techniques including different incubation times in MNP solutions. The performance of both modified SPCEs were tested for amperometric detection of Cr(VI) in various water samples, and peak reduction of Cr(VI) was determined at 0.33 V. Amperometric results showed wide linear ranges of 0.1–2 μM and 0.1–5 μM of Cr(VI) for SPCEs modified with 14n‐LBL‐A and 12h‐EI‐SA, respectively. The sensitivities of SPCEs modified with 14n‐LBL‐A and 12h‐EI‐SA techniques were 0.27 μA μM^?1 and 0.52 μA μM^?1, respectively. In addition, both modified SPCEs selectively detected Cr(VI) in a model aqueous system composed of certain other heavy metals and minerals, and tap and lake water samples. The LOD and LOQ values for 12h‐EI‐SA were 0.03 μM and 0.1 μM, respectively. This showed that MNP‐modified‐SPCEs generated via EI‐SA techniques have the potential to be an alternative to conventional detection methods such as ICP‐MS.     

不同烟草生物质热解释放致香物质的研究

采用烟叶和烟梗为原料,使用热裂解气相色谱法对烟草的燃烧时间、燃烧温度进行控制,精确模拟实际烟草致香物质释放环境,精确捕获、并半定量物质,从而在实验室模拟、分析、研究烟草燃烧物中致香物质的组成和特点。研究分别考察了两种生物质在500℃、550℃下释放的致香物质组成。结果表明,烟梗、烟叶中元素组成中硫、氮两种元素含量低,而C/H比值两种烟草生物质均较高。两个热解温度下烟叶的热解产物中致香物质的含量均明显高于烟梗。升高热解温度均有利于获得更高相对含量的热解成分。烟叶热解产物中烯烃类物质相对含量比烟梗中多,而烟梗热解产物中酚类物质含量比烟叶中多。提高热解温度有利于酮类致香物质含量产生。     

Understanding energetic disorder in electron-deficient-core-based non-fullerene solar cells

Recent advances in material design for organic solar cells(OSCs) are primarily focused on developing near-infrared nonfullerene acceptors, typically A-DA′D-A type acceptors(where A abbreviates an electron-withdrawing moiety and D, an electron-donor moiety), to achieve high external quantum efficiency while maintaining low voltage loss. However, the charge transport is still constrained by unfavorable molecular conformations, resulting in high energetic disorder and limiting the device performance. Here, a facile design strategy is reported by introducing the "wing"(alkyl chains) at the terminal of the DA′D central core of the A-DA′D-A type acceptor to achieve a favorable and ordered molecular orientation and therefore facilitate charge carrier transport. Benefitting from the reduced disorder, the electron mobilities could be significantly enhanced for the"wing"-containing molecules. By carefully changing the length of alkyl chains, the mobility of acceptor has been tuned to match with that of donor, leading to a minimized charge imbalance factor and a high fill factor(FF). We further provide useful design strategies for highly efficient OSCs with high FF.     

Magnetron sputtering deposition of silicon nitride on polyimide separator for high-temperature lithium-ion batteries

To date,lithium-ion batteries are becoming increasingly significant in the application of portable devices and electrical vehicles,and revolutionary progress in theoretical research and industrial application has been achieved.However,the commercial polyolefin separators with unsatisfying electrolytes affinity and poor thermal stability have extremely restricted the further application of lithium-ion batteries,especially in the high-temperature fields.In this work,magnetron sputtering deposition technique is employed to modify the commercial polyimide separator by coating silicon nitride on both sides.Magnetron sputtering deposition modified polyimide(MSD-PI)composite separator shows high thermal stability and ionic conductivity.More importantly,compared with the cells using Celgard separator,the cells with MSD-PI separator exhibit superior electrochemical performance,especially long-term cycle performance under high temperature environment,owing to the high thermal conductivity of surface Si3 N4 particles.Hence,lithium-ion batteries with MSD-PI separator are capable of improving thermal safety and capacity retention,which demonstrates that magnetron sputtering deposition technique could be regarded as a promising strategy to develop advanced organic/inorganic composite separators for high-temperature lithium-ion batteries.     

Screening of Plant Pollen Sources,Polyphenolic Compounds,Fatty Acids and Antioxidant/Antimicrobial Activity from Bee Pollen

In this study, the botanical origin, total flavonoid and phenolic content, antioxidant activity, phenolic profile and fatty acid composition of mixed bee pollen loads collected in Bayburt, Turkey, were determined. In addition to these assays, antibacterial activity of bee-collected pollen extract (BCPE) against a variety of food-borne pathogenic bacteria was determined in vitro. Pollen loads were classified into five botanical families based on their color: Asteraceae, Fabaceae, Campanulaceae, Cistaceae and Rosaceae. Total flavonoid, total phenolic, CUPRAC and CERAC concentrations were 173.52 mg GAE/g, 79.21 mg QE/g, 85.59 mg Trolox/g and 118.13 mg Trolox/g, respectively. Twenty-three phenolic compounds were scanned in bee pollen extract by LC-MS/MS, with rutin being the most abundant. Cis-4,7,10,13,16,19 docosahexaenoic acid was the predominant fatty acid, followed by cis-11-eicosenoic acid, palmitic acid, and alfa linolenic acid. In addition, the agar well diffusion (AWD) and micro-broth dilution methods were used to determine of the antibacterial activity of the BCPE sample. MIC values were observed to vary between 2.5–5 mg/mL for Gram-positive bacteria and 5–10 mg/mL for Gram-negative bacteria. These findings indicate that bee pollen could be a potential source of antioxidants and antimicrobials.     

血清中葡萄糖含量CCQM-K11.1国际比对

研究利用同位素稀释质谱法测定血清中的葡萄糖含量,并利用该方法参加国际物质量咨询委员会（CCQM）2005年组织的关键比对CCQM—K11．1,我国国家标准物质研究中心（NRCCRM）的测定结果与韩国（KRISS）和墨西哥（CENAM）的测定结果非常接近,日本（NMIJ）的测定结果离群偏高。