脉冲阳极电沉积制备锰氧化物涂层电极

采用脉冲阳极电沉积工艺制备掺杂的锰氧化物涂层电极, 并利用FESEM、SEM、XRD及电化学等方法研究了涂层电极的形貌、相结构及性能. 结果表明, 该方法通过脉冲参数的调整, 可获得优异的电催化性能与稳定性能的涂层电极. 当脉冲频率(f)为90 Hz, 脉冲通断比为1:2时, 具有较大的镀速, 获得较厚的涂层; 氧化物为独特的纳米线与近球状纳米颗粒共聚的网络结构, 不仅增加了电极的电催化活性, 而且有效提高了电极的使用寿命,加速寿命达到1635 h, 比直流阳极电沉积提高55.3%.     

Cytochrome P450 Mediated Cyclization in Eunicellane Derived Diterpenoid Biosynthesis**

Terpene cyclization, one of the most complex chemical reactions in nature, is generally catalyzed by two classes of terpene cyclases (TCs). Cytochrome P450s that act as unexpected TC-like enzymes are known but are very rare. In this study, we genome-mined a cryptic bacterial terpenoid gene cluster, named ari, from the thermophilic actinomycete strain Amycolatopsis arida. By employing a heterologous production system, we isolated and characterized three highly oxidized eunicellane derived diterpenoids, aridacins A−C ( 1 – 3 ), that possess a 6/7/5-fused tricyclic scaffold. In vivo and in vitro experiments systematically established a noncanonical two-step biosynthetic pathway for diterpene skeleton formation. First, a class I TC (AriE) cyclizes geranylgeranyl diphosphate (GGPP) into a 6/10-fused bicyclic cis-eunicellane skeleton. Next, a cytochrome P450 (AriF) catalyzes cyclization of the eunicellane skeleton into the 6/7/5-fused tricyclic scaffold through C2−C6 bond formation. Based on the results of quantum chemical computations, hydrogen abstraction followed by electron transfer coupled to barrierless carbocation ring closure is shown to be a viable mechanism for AriF-mediated cyclization. The biosynthetic logic of skeleton construction in the aridacins is unprecedented, expanding the catalytic capacity and diversity of P450s and setting the stage to investigate the inherent principles of carbocation generation by P450s in the biosynthesis of terpenoids.     

边界对石墨烯量子点非线性光学性质的影响

石墨烯作为一种新型非线性光学材料,在光子学领域具有重要的应用前景,引起研究人员的极大兴趣.本文运用量子化学计算方法研究了边界引入碳碳双键(C=C)和掺杂环硼氮烷(B₃N₃)环对石墨烯量子点非线性光学性质和紫外-可见吸收光谱的影响.研究发现,扶手椅边界上引入C=C双键后,六角形石墨烯量子点分子结构对称性降低,电荷分布对称性发生破缺,导致分子二阶非线性光学活性增强.石墨烯量子点在从扶手椅型边界向锯齿型边界过渡的过程中,随着边界C=C双键数目的增加,六角形石墨烯量子点和B3N3掺杂六角形石墨烯量子点的极化率和第二超极化率分别呈线性增加.此外,边界对石墨烯量子点的吸收光谱也有重要影响.无论是石墨烯量子点还是B₃N₃掺杂石墨烯量子点,扶手椅型边界上引入C=C双键导致最高占据分子轨道能级升高,最低未占分子轨道能级的降低,前线分子轨道能级差减小,因而最大吸收波长发生了红移.中心掺杂B₃N₃环后会增大石墨烯量子点的分子前线轨道能级差,导致B3N3掺杂后的石墨烯量子点紫外-可见吸收光谱发生蓝移.本文研究为边界修饰调控石墨烯量子点非线性光学响应提供了一定的理论指导.     

Detection of dopamine at graphene-ZIF-8 nanocomposite modified electrode

A hybrid graphene-ZIF-8 (G-ZIF-8) nanocomposite modified electrode was prepared in our work. SEM characterization shows that nanocrystals of zeolitic imidazolate frameworks (ZIF-8) were homogeneously well-intergrown on the surface of graphene and thus the graphene sheets were refrained from restacking, which implies the high accessible surface area. The BET results further testifies that G-ZIF-8 composites had a larger surface area than 3D graphene. G-ZIF-8 modified electrode exhibited excellent electroanalytical performance for dopamine. The linear concentration range was from 3.0 μmol/L to 1.0 μmol/L with the detection sensitivity of 0.34 μA/μmol/L and the detection limit of 1.0 μmol/L was obtained. The interference study, electrode stability and reproducibility were carried out. In addition, the prepared sensor was applied to the detection of DA in serum sample with recoveries from 96.8% to 100.7%. It is believable that the structure characteristic of G-ZIF-8 nanocomposite is favorable for using MOFs to fabricate highly sensitive electrochemical sensor.     

基于前驱体Pb(OH)I溶液法制备FAPbI3太阳能电池

甲脒铅碘因具有高热稳定性和较窄的禁带宽度而受到广泛关注。本工作使用羟基碘化铅代替传统碘化铅、氯化铅,通过一步溶液法制备介孔甲脒铅碘钙钛矿太阳能电池,研究退火温度对材料的结晶性、覆盖层形貌和器件的效率等方面的影响。较之传统的溶液法工艺,基于羟基碘化铅制备的甲脒铅碘薄膜表现出更为优异的热稳定性能。最终在AM 1.5G一个太阳光照明下,得到了5.8%的光电转化效率,其中短路电流为18.6mA·cm^-2,开路电压为0.67V,填充因子为0.47。     

Diiron butane-2,3-dithiolate complexes with monophosphine coligands: synthesis,characterization, and electrochemistry

Transition Metal Chemistry - In this paper, three diiron butane-2,3-dithiolate complexes [Fe2(CO)5L{µ-SCH(CH3)CH(CH3)S}] [L?=?P(4-C6H4F)3, 2; P(4-C6H4OCH3)3, 3; P(3-C6H4Cl)3, 4]...     

手持技术数字化实验支持下的抽象化学概念学习*——以探究比较丁醇同分异构体的分子间作用力大小为例

根据TQVC概念认知模型设计手持技术数字化实验,比较丁醇同分异构体的分子间作用力大小,并应用“四重表征”理论对实验结果进行解释与分析。研究发现:蒸发时温度下降速度越快,同分异构体的空间位阻越大,其分子间作用力越小;同分异构体混合液的分子间作用力比任一组分的分子间作用力小。     

“化学教育技术”核心词汇及其研究进展*——基于对2006-2017年国内核心期刊文献的分析

信息技术和化学课程的整合给教育行业带来崭新的变化,涌现出“化学教育技术”等新领域,为该领域确定作为研究热点的15个核心词汇,简述其研究方法和选词原则,并对核心词汇的发展进行分类和统计分析,从侧面反映我国化学教育技术的研究现状和进展,并为该领域的发展提出相关建议。     

食品中富马酸二甲酯残留量的测定——气相色谱法

将食品样品经乙腈提取,石油醚净化后,用氢火焰离子化检测器进行检测.该方法可准确测定食品中的富马酸二甲酯且有很好的线性关系,相关系数为0.9998,检出限为4mg/kg,平均加标回收率在93.4%-100.9%之间,相对标准偏差(RSD)为2.5%-5.0%,可用于食品中富马酸二甲酯的检测.     

改进的反Stokes能量传递对ErP5O14非晶中荧光动力学研究的影响

本文通过建立不同浓度五磷酸盐非晶材料(Er_xLa_1-xP₅O₁₄)动力学过程的速率方程,特别是引入了改进系数exp{hc _k/kT}以区别能量传递Stokes过程和反Stokes过程,分别对Er_0.01La_0.99P₅O₁₄,Er_0.1La_{关键词： 反Stokes能量传递改进系数 动力学过程 五磷酸盐非晶 红外量子剪裁}