CBS还原合成手性1-苯乙醇实验设计*

将学科热点之一催化不对称合成策略引入实验教学中,通过CBS还原制备手性醇。实验以苯乙酮为原料,还原得到粗产物手性1-苯乙醇,经制备色谱仪分离提纯,气相色谱和自动旋光仪表征产物的光学性质。实验为综合型有机化学实验,通过此实验,学生在掌握手性醇合成原理与方法的同时,进一步学习手套箱、气相色谱、制备色谱仪、自动旋光仪等新技术,以提升学生综合科研素质。     

QuEChERS/高效液相色谱-串联质谱法测定柑橘中7种酚类环境激素

建立了QuEChERS/高效液相色谱－串联质谱（QuEChERS/HPLC－MS/MS）同时检测柑橘中7种酚类环境激素的分析方法。柑橘样品均质粉碎后采用乙腈（含0.1%甲酸）超声提取,氯化钠盐析,经N-丙基乙二胺（PSA）+C18粉末吸附剂净化,目标化合物经Waters ACQUITY UPLC BEH C18柱（50 mm × 2.1 mm,1.7 μm）分离,以水（含0.5 mmol/L乙酸铵）和甲醇为流动相进行梯度洗脱。考察了不同提取溶剂、提取时间、提取溶剂体积、吸附剂种类和用量对目标化合物回收率的影响。结果表明：在最佳条件下,双酚A（BPA）、壬基酚（NP）、双酚F（BPF）在0.5～100 μg/L范围内线性关系良好,双酚B（BPB）、双酚S（BPS）、4-n-壬基酚（4-n-NP）、4-n-辛基酚（4-n-OP）在0.2～100 μg/L范围内线性关系良好,相关系数（r2）均不小于0.994 1,检出限（LOD）为0.2～0.5 μg/L,定量下限（LOQ）为0.5～1.5 μg/L。在10、250、500 μg/kg 3个加标水平下,目标化合物的回收率为88.5%～109%,相对标准偏差（RSD）为1.2%～9.0%。应用该方法对市售的8种柑橘样品进行检测,BPA在7种柑橘中均检出,4-n-OP在5种柑橘中检出,NP和4-n-NP在3种柑橘中检出,BPB在1种柑橘中检出,BPF、BPS在所有样品中均未检出。该方法操作简单、快速灵敏、定量准确、精密度高,适用于柑橘中7种酚类环境激素的测定。     

Cationic Nonporous Macrocyclic Organic Compounds for Multimedia Iodine Capture

Over the past two decades, progress in chemistry has generated various types of porous materials for removing iodine (¹²⁹I or ¹³¹I) that can be formed during nuclear energy generation or nuclear waste storage. However, most studies for iodine capture are based on the weak host-guest interactions of the porous materials. Here, we present two cationic nonporous macrocyclic organic compounds, namely, MOC-1 and MOC-2 , in which 6I^- and 8I⁻ were as counter anions, for highly efficient iodine capture. MOC-1 and MOC-2 were formed by reacting 1,1′-diamino-4,4′-bipyridylium di-iodide with 1,2-diformylbenzene or 1,3-diformylbenzene, respectively. The presence of a large number of I⁻ anions results in high I₂ affinity with uptake capacities up to 2.15 g ⋅ g⁻¹ for MOC-1 and 2.25 g ⋅ g⁻¹ for MOC-2 .     

pH‐controlled reaction divergence of decarboxylation versus fragmentation in reactions of dihydroxyfumarate with glyoxylate and formaldehyde: parallels to biological pathways

The reactions of dihydroxyfumarate with glyoxylate and formaldehyde exhibit a unique pH‐controlled mechanistic divergence leading to different product suites by two distinct pathways. The divergent reactions proceed via a central intermediate (2,3‐dihydroxy‐oxalosuccinate, 3 , in the reaction with glyoxylate and 2‐hydroxy‐2‐hydroxymethyl‐3‐oxosuccinate, 14 , in the reaction with formaldehyde). At pH 7–8, products ( 7 , 8 , and 15 ) exclusively from a decarboxylation of the intermediate are observed, while at pH 13–14, products ( 9 , 10 , and 16 ) solely derived from a hydroxide‐promoted fragmentation of the intermediate are formed. The decarboxylative and fragmentation pathways are mutually exclusive and do not appear to coexist under the range of pH (7–14) conditions investigated. Herein, we employ a combination of quantitative ¹³C NMR measurements and density functional theory calculations to provide a rationale for this pH‐driven reaction divergence. These rationalizations also hold true for the reactions of dihydroxyfumarate produced in situ by the catalytic cyanide‐mediated dimerization of glyoxylate. In addition, the non‐enzymatic decarboxylation and fragmentation transformations of these central intermediates ( 3 and 14 ) appear to have intriguing parallels to the enzymatic reactions of oxalosuccinate and formation of glyceric acid derivatives in extant metabolism – the high and low pH mimicking the precise control exerted by the enzymes over reaction pathways. Copyright © 2016 John Wiley & Sons, Ltd.     

基于光导微探针的近场/远场可扫描太赫兹光谱技术

太赫兹技术已经成为涉及公共安全、军事国防和国民经济等国家核心利益的前沿研究领域.以往太赫兹测量技术中通常以远场测量为主,如常用的太赫兹时域光谱仪.近年来太赫兹近场技术得到了迅猛的发展,特别是基于光导天线的探针技术的发展,为可扫描的太赫兹近场测量提供了可能.本文详细报道了我们近期在可扫描太赫兹近场光谱仪研究中的进展.采用光纤耦合的光导微探针实现了方便灵活的太赫兹近场/远场三维扫描,并同时获得振幅和相位信息.该系统将有可能广泛应用于人工微结构、石墨烯、表面等离子激元、波导传输、近场成像、生物样品检测、芯片检测等研究领域.     

富勒烯C20四聚体的结构与性能研究

采用密度泛函理论(DFT)中的杂化密度泛函(B3LYP)方法, 在6-31 G基组水平上对C₂₀四聚体进行了几何参数全优化, 得到了基态构型, 并对其稳定性、电子结构、极化率和芳香性进行了计算研究. 结果表明: C₂₀碳笼以[2+2]加成方式结合形成C₂₀四聚体, 具有良好的热力学稳定性; C原子内部以sp²的方式杂化, C原子之间有少量电荷转移; C₂₀ 四聚体的IR和Raman光谱都有较多的振动峰; 随碳笼数的增加, C₂₀聚合物中原子间的成键相互作用随之增强; C₂₀四聚体具有芳香性.     

On the correlation of the local OVII and OVI absorption lines in the spectra of active galactic nuclei

正Dear Editors,Active Galactic Nuclei(AGNs)are very effective tools to study the environment both intrinsic to the central black holes of galaxies[1],or absorbing gas distributed along the sight lines.Recently,numerous highly ionized,local(z=0)metal absorption lines were detected in the X-ray spectra of background AGNs[2],providing an important method in probing hot gas and its content in and around our Galaxy.Of particular     

Photoacoustic Doppler effect from flowing small light-absorbing particles

From the flow of a suspension of micrometer-scale carbon particles, the photoacoustic Doppler shift is observed. As predicted theoretically, the observed Doppler shift equals half of that in Doppler ultrasound and does not depend on the direction of laser illumination. This new physical phenomenon provides a basis for developing photoacoustic Doppler flowmetry, which can potentially be used for detecting fluid flow in optically scattering media and especially low-speed blood flow of relatively deep microcirculation in biological tissue.     

Enhanced superprism effect based on positive/negative lateral shift of reflective beam in a Fabry-Perot filter

It is found that when a light beam is incident obliquely on a thin film Fabry-Perot filter (FPF) from different incident media (air or substrate), the reflective beam will be shifted in both the forward and the backward directions. Based on this inverted spatial dispersion effect, two thin film FPFs with different directional lateral shifts are assembled to get a thin film superprism with a wider dispersion band. The thin film samples are fabricated as well as tested, and the results are in approximate agreement with numerical simulation.