基于扩散强化的Pickering界面生物催化系统构建及CO2矿化过程研究

CO₂的有效利用有助于解决环境和生态问题.碳酸酐酶(CA)等酶分子可精准活化CO₂分子以降低反应能垒,为CO₂的高效和高选择性转化提供了一种有前景的途径.然而,酶离开生物体后易失活,且难以重复利用.目前,包埋型固定化酶是常用且有效的提高酶稳定性与回用率的方法之一,但载体的存在会造成反应物CO₂内扩散阻力增加,降低反应活性.此外,CO₂酶促转化是一个气-液-固三相反应过程,反应体系中CO₂的外扩散性能也需要加强.金属有机骨架(MOFs),特别是咪唑酯骨架(ZIFs),常被用作酶固定化的载体.ZIFs的拓扑结构可被设计成不同形貌,进而通过ZIFs的结构工程来加强分子向其中的内扩散.Pickering乳液是指以固体颗粒代替常规表面活性剂而稳定的乳液.当固体颗粒具有催化活性时,催化剂颗粒会扩大液-液-固或气-液-固三相接触面积,从而有效协调反应物在不同相中的扩散时间.如果酶被用作这些颗粒的活性中心,所制备的Pickering乳液也可能具备类似的特性,可加强底物分子向酶的外扩散.本文选择两种具有不同结构的ZIFs(ZIF-L和ZIF-8),原位包埋CA后形成CA@ZIFs颗粒以稳定Pickeirng乳液.ZIF-L和CA@ZIF-L颗粒显示出独特的二维层状堆叠结构.ZIF-8和CA@ZIF-8颗粒呈棱角清晰的十二面体结构.与CA@ZIF-8颗粒相比,CA@ZIF-L颗粒显示出更大的孔径和更宽的孔径分布,这有助于CO₂从CA@ZIF-L颗粒表面扩散至酶活性中心.利用酶活测试来研究内扩散是否通过结构工程得到了加强,发现CA@ZIF-L颗粒的活性比CA@ZIF-8颗粒高22.3%,推测这是由于CA@ZIF-L颗粒特殊的十字花状结构会缩短CO₂从颗粒表面扩散至酶活性中心的距离.同时,十字花状结构可暴露更多的酶活性位点(CA@ZIF-L颗粒的暴露面积是CA@ZIF-8颗粒的~8倍),从而提升了反应物浓度并显示出更高的催化活性.本文还设计了吸附实验来进一步验证上述假设,发现BSA@ZIF-L颗粒对香豆素的吸附率远高于BSA@ZIF-8颗粒,说明与ZIF-8相比,酶包埋于ZIF-L具有更强的捕获小分子的能力,表明CO₂分子向CA@ZIF-L的扩散速度更快,即CA@ZIF-L的十字花状结构可强化系统的内扩散过程.进一步比较了PIBS和游离多酶体系的催化活性,将CO₂通入每个系统,在反应前20 min,PIBS的pH值下降速度比游离体系快得多,说明PIBS通过在气相和液相间构建更大的界面,缩短了CO₂向CA的扩散距离,从而提高了催化效率,促进了CO₂转化.上述假设也通过扩散动力学的计算得到了验证.为进一步研究PIBS的CO₂矿化能力,本文开展了CaCO₃矿化反应,发现PIBS的CaCO₃产量远高于游离多酶体系,表明构建的PIBS在强化内外扩散方面具有显著优势.最后,评估了PIBS在工业应用中的性能,由CA@ZIF-L和CA@ZIF-8颗粒构建的PIBS显示出较好的可回收性,在第8个循环后,PIBS仍可保持8.9 mg/5 min的CaCO₃产量.综上,PIBS可为CO₂的酶促转化和框架提供一个新方法和新平台.     

多层栅介质层有机薄膜晶体管的存储与光响应特性

在真空室内一次性制备了具有多层栅介质层结构的有机薄膜晶体管(OTFTs).结果表明,制备的OTFTs具有电控开关、存储和光敏多重功能特性.分析认为,存储特性归功于器件的结构,采用了分离的CaF2纳米粒子岛作为电荷俘获中心.在光照环境下,观察到了两种不同类型的光响应特性.快速的光响应来自于有源层吸收了能量大于带隙的光子所...     

蒸镀法制备全有机并五苯薄膜场效应晶体管

以全蒸镀方法在真空室内一次性制备了正装结构的全有机并五苯薄膜场效应晶体管。正装结构全蒸镀法有利于简化工艺制备程序,缩小器件尺寸,提高集成度。制备的绝缘层厚度仅为50nm的全有机薄膜场效应晶体管,器件的工作电压降至10V,相同电压下饱和输出电流有了明显提高。筛选适当的有机绝缘材料,改善全有机薄膜场效应晶体管有源层/绝缘层的界面性能,使阈值电压几乎降至0V,场效应迁移率提高了3倍多,输出饱和电流也有了明显的提高。     

并五苯同质异相体中分子间势能与能带计算

采用Born-Mayer-Haggins对势模型，分析了并五苯分子间势能及其相互作用. 用紧束缚模型计算了两种并五苯同质异相体结构的能带宽度. 计算带宽随温度升高减小8%—14%. 关键词： 并五苯 同质异相体 分子间势能 能带计算     

理科教师教学反思实证研究特点与展望

教师加强教学反思是基础教育改革的时代要求,也是教师专业发展的重要途径。通过对近10年理科教师教学反思实证研究的梳理与分析,把脉当前国内外研究进展,厘定我国理科教师教学反思实证研究发展方向,即理科教师教学反思的范式研究、基于学生视角的教学反思研究、理科教师教学反思的跟进研究、职前理科教师教学反思培养研究,以期为当前理科教师教学反思研究提供参考。     

Dependence of Junction Voltage Saturation on Uniformity and Quality of Laser Diode Bars

The dependence of the sinkage at the threshold of the electric derivative curve （IdV/dI-I） on the uniformity and the quality of the laser diode bar is analyzed. By using the equations derived from the equivalent circuits of the bars, the influence of the bar uniformity on the depth of the dip is investigated in theory under certain conditions. Furthermore, the experimental results based on the presented technique indicate that the depth of the dip is interrelated to the uniformity and the quality of the corresponding bar. The present technique can be used conveniently and effectively to measure the laser diode bars in practice.     

High-sensitivity Bloch surface wave sensor with Fano resonance in grating-coupled multilayer structures

A new type of device consisting of a lithium niobate film coupled with a distributed Bragg reflector (DBR) was theoretically proposed to explore and release Bloch surface waves for applications in sensing and detection. The film and grating made of lithium niobate (LiNbO₃) were placed on both sides of the DBR and a concentrated electromagnetic field was formed at the film layer. By adjusting the spatial incidence angle of the incident light, two detection and analysis modes were obtained, including surface diffraction detection and guided Bloch detection. Surface diffraction detection was used to detect the gas molecule concentrations, while guided Bloch detection was applied for the concentration detection of biomolecule-modulated biological solutions. According to the drift of the Fano curve, the average sensor sensitivities from the analysis of the two modes were 1560 °/RIU and 1161 °/RIU, and the maximum detection sensitivity reached 2320 °/RIU and 2200 °/RIU, respectively. This study revealed the potential application of LiNbO₃ as a tunable material when combined with DBR to construct a new type of biosensor, which offered broad application prospects in Bloch surface wave biosensors.     

苯乙烯/聚氯乙烯接枝膜的热稳定性研究

用自由基悬浮聚合法合成了苯乙烯 /聚氯乙烯接枝膜 ,并对产物热处理 ,然后进行紫外 -可见光谱 ,红外光谱 ,热失重分析。结果表明接枝苯乙烯后的聚氯乙烯膜热稳定性得到了提高。同时 ,讨论了热稳定性机理。     

聚(对-苯撑乙烯)衍生物蓝色发光二极管及平面显示

成功地合成了柔性脂肪链段和刚性发光链段相互交替的共聚物,并对其进行了表征.发现该聚合物的荧光随柔性链段的增长而增强的实验结果.用所合成的共聚物作发光层,研制出了发光亮度可达190cd/m~2,最小开启电压为15V的发蓝色光的聚合物发光二极管及平板显示屏.讨论了(口恶)二唑衍生物(PBD)和8-羟基喹淋铝(Alq_3)电子输运层的引入对器件的发光亮度和稳定性的影响.     

Improved Performance by a Double-Insulator Layer in Organic Thin-Film Transistors

Organic thin film transistors based on pentacene are fabricated by the method of full evaporation. The thickness of insulator film can be controlled accurately, which influences the device operation voltage markedly. Compared to the devices with a single-insulator layer, the electric performance of devices by using a double-insulator as the gate dielectric has good improvement. It is found that the gate leakage current can be reduced over one order of magnitude, and the on-state current can be enhanced over one order of magnitude. The devices with double-insulator layer exhibit field-effect mobility as large as 0.14cm^2/Vs and near the zero threshold voltage. The results demonstrate that using a proper double insulator as the gate dielectrics is an effective method to fabricate OTFTs with high electrical performance.