第12届全国大学生化学实验邀请赛物理化学实验试题解析

对第12届全国大学生化学实验邀请赛物理化学实验操作考试试题命题、考试情况进行了总结,并对实验竞赛过程中反映出的当前实验教学所存在的问题进行了分析。     

对映体选择性化学传感器与手性识别载体研究

对映体选择性化学传感器的研究是化学传感器研究领域新的重要课题。本文作为作者关于这一课题研究报道的开篇,综述了具有手性识别功能的对映体选择性化学传感器和作为其敏感材料的手性识别载体的研究概况,概述了其发展方面及有关问题,收引参考文献67篇。     

1,1′-二硒取代二茂铁衍生物的合成

由1,2,3-三硒[3]桥二茂铁(Ferrocenophane)经LiAlH_4还原生成二硒酚,不经分离直接与一亲电试剂在三乙胺存在下反应,得到7种1,1′-二硒醚二茂铁,4种1,n-二硒[n]桥二茂铁(n=3～5)和1种螺形化合物[Fe(C_5H_4Se)_2]_2Sn。这12种化合物中有7种尚未见文献报道,对其中几种产物进行了~(77)Se NMR谱及质谱分析。讨论了影响产率的因素和核磁共振图谱。     

Photocrosslinked methacrylated chitosan-based nanofibrous scaffolds as potential skin substitute

Nanofibers based on natural polymers have recently been attracting research interest as promising materials for use as skin substitutes. Here, we prepared photocrosslinked nanofibrous scaffolds based on methacrylated chitosan (MACS) by photocrosslinking electrospun methacrylated chitosan/poly (vinyl alcohol) (PVA) mats and subsequently removing PVA from the nanofibers. We comprehensively investigated the solution properties of MACS/PVA precursors, the intermolecular action between MACS and PVA components, and the morphology of MACS/PVA nanofibers. Results indicated that the fiber diameter and morphology of the photocrosslinked methacrylated chitosan-based nanofibrous scaffolds were controlled by the MACS/PVA mass ratio and showed highly micro-porous structures with many fibrils. In vitro cytotoxicity evaluation and cell culture experiments confirmed that MACS-based mats with micro-pore structure were biocompatible with L929 cells and facilitated cellular migration into the 3D matrix, demonstrating their potential application as skin replacements for wound repair.     

Bimetallic nanoclusters with strong red fluorescence for sensitive detection of hypochlorite in tap water

Gold-silver nanoclusters (Au-AgNCs) were synthesized by simultaneous chemical reduction of Au(III) and Ag(I) ions in one pot, using bovine serum albumin as both a template and a reductant. The Au-AgNCs have an average size of 2.4 nm and display strong red fluorescence (with an emission peak at 610 nm on excitation at 360 nm). The fluorescence quantum yield can reach 18.6%. Fluorescence is strongly quenched by hypochlorite, while other common anions have minor (or no) effects on fluorescence. Based on these findings, a fluorometric method was developed for the determination of hypochlorite. The method has a linear response in the 0.7 to 15 μM concentration range, with a limit of detection as low as 80 nM. It was successfully applied to the determination of hypochlorite in (spiked) tap water.

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Graphical abstract Gold-silver nanoclusters with strong red fluorescence were synthesized by simultaneous chemical reduction of Au(III) and Ag(I) ions in one pot, and a sensitive and selective method for the detection of hypochlorite was developed based on the quenching of the fluorescence of the nanoclusters.

     

HZSM-5/SAPO-11复合分子筛的制备、 表征及在异丁烷芳构化反应中的催化性能

将经聚二烯丙基二甲基氯化铵(PDDA)预处理的HZSM-5分子筛置于SAPO-11分子筛的合成母液中, 在水热体系中原位制备了一系列HZSM-5/SAPO-11复合分子筛, 并对分子筛的结构、 形貌及酸性进行了表征, 考察了其在异丁烷芳构化反应中的催化性能. 结果表明, 所得复合分子筛由HZSM-5表面包覆约20 nm的SAPO-11微晶组成, 且通过调变SAPO-11的Si含量可以有效调变复合分子筛的酸性, 提高芳构化强弱酸协同催化作用, 有效抑制裂解副反应. 结合异丁烷芳构化转化率及液体收率结果可知, 当SAPO-11合成溶胶中硅铝摩尔比为0.6时, HZSM-5/SAPO-11复合分子筛的芳构化活性及稳定性最佳.     

基于一种广义梁理论的弹性地基FGM简支梁自由振动解析解

基于一种扩展的n阶广义剪切变形梁理论(n-GBT),应用Hamilton原理,建立了以轴向位移、横向位移及转角为未知函数的Winkler-Pasternak弹性地基功能梯度材料(FGM)梁的自由振动方程,采用Navier法获得了弹性地基FGM简支梁自由振动的精确解。与多种梁理论预测结果进行比较,讨论并给出了GBT阶次n的理想取值;分析了梯度指标、跨厚比及地基刚度对FGM梁频率的影响。结果表明:本文方法有效且适用范围广,若采用高阶剪切梁理论模型,宜取n≥3的奇数;FGM梁的自振频率随材料梯度指标的增大而减小;随跨厚比的增加而增大,但当跨厚比大于20,跨厚比增加对频率的影响很小;随地基刚度的增加而增大,地基刚度足够大时,频率趋于收敛。     

非均匀关联径向偏振部分相干光的产生

从理论和实验两方面对非均匀关联径向偏振部分相干光的产生进行了研究.理论上,基于相位关联与相干度的联系,推导出了非均匀关联径向偏振部分相干光的2×2阶交叉谱密度矩阵及相干度分布.实验上,利用一个相位型液晶空间光调制器的不同区域,对入射的完全相干的径向偏振光的两个正交偏振分量分别加载随机相位调制,并实验测量了这种光束的相干度分布及其对光强分布的影响.实验结果验证了光束相干度的非均匀关联结构,并且通过改变随机相位的高斯调制半宽可以改变光束的相干性分布.研究表明,随着随机相位的高斯调制半宽的增加,光束中两点间的相干度逐渐减小,其光强分布由圆环状逐渐变化为类平顶的光强分布.这种非均匀关联的径向偏振部分相干光在激光微操纵和材料加工等领域具有一定的潜在应用价值.     

Al等离子体类锂伴线的布居机制分析及实验应用

基于K壳层稳态碰撞辐射模型的程序,详细分析Al等离子体类锂伴线的主要布居机制,分别给出1s2p^{2 2}P-1s²2p²P,1s2s2p(¹S)²P-1s²2s²S与1s2p^{2 2}D-1s²2p² 关键词： 碰撞辐射模型 类锂伴线 线强比 激光等离子体     

Lens axicon illuminated by polychromatic Gaussian beams for generating uniform focal segments

In this paper, we investigate a lens axicon, which actually is a lens with spherical aberration, illuminated by a polychromatic Gaussian beam for producing an extended axial line image of a desired length and nearly uniform intensity. A numerical calculation is performed to investigate the dependence of the axial intensity distribution of the focal segment on the parameters of the incident polychromatic Gaussian beam. It is shown that, compared with monochromatic Gaussian beam illumination, the illumination of the polychromatic Gaussian beam may improve the uniformity of the distribution of the axial intensity, and this improvement in the uniformity of the axis intensity is strongly dependent on the spectral width of the incident Gaussian beam. Moreover, apodization with annular super-Gaussian amplitude distribution is employed to reduce the undesired oscillation of the axial intensity.