介绍一个与材料相关的研究型综合化学实验——壳聚糖的制备与表征

在中国科学技术大学夏季学期的研究型实验课程"化学科研基础训练"中开设"壳聚糖的制备与表征"综合实验,以龙虾壳为原料,通过除蛋白、脱盐、脱色、脱乙酰等一系列反应,制备得到目标产物壳聚糖。运用红外光谱、核磁共振仪、黏度法、滴定等对产品的结构及性能进行表征。     

Setting local rank constraints by orthogonal projections for image resolution analysis: Application to the determination of a low dose pharmaceutical compound

Raman chemical imaging provides chemical and spatial information about pharmaceutical drug product. By using resolution methods on acquired spectra, the objective is to calculate pure spectra and distribution maps of image compounds. With multivariate curve resolution-alternating least squares, constraints are used to improve the performance of the resolution and to decrease the ambiguity linked to the final solution. Non negativity and spatial local rank constraints have been identified as the most powerful constraints to be used.     

Synthesis of partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions

Partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions (ps‐PES‐FPES), with ionic exchange capacity (IEC) ranging between 0.9 and 1.5 meq H⁺/g, are synthesized by regioselective bromination of partially fluorinated poly(arylene ether sulfone) multiblock copolymers (PES‐FPES), followed by Ullman coupling reaction with lithium 1,1,2,2‐tetrafluoro‐2‐(1,1,2,2‐tetrafluoro‐2‐iodoethoxy)ethanesulfonate. The PES‐FPES are prepared by aromatic nucleophilic substitution reaction by an original approach, that is, “one pot two reactions synthesis.” The chemical structures of polymers are analyzed by ¹H and ¹⁹F NMR spectroscopy. The resulted ionomers present two distinct glass transitions and α relaxations revealing phase separation between the hydrophilic and the hydrophobic domains. The phase separation is observed at much lower block lengths of ps‐PES‐FPES as compared with the literature. AFM and SANS observations supported the phase separation, the hydrophilic domains are well dispersed but the connectivity to each other depends on the ps‐PES block lengths. The thermomechanical behavior, the water up‐take, and the conductivity of the ps‐PES‐FPES membranes are compared with those of Nafion 117^® and randomly functionalized polysulfone (ps‐PES). Conductivities close or higher to those of Nafion 117^® are obtained. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1941–1956     

Thermally induced solid-state transformation of cimetidine. A multi-spectroscopic/chemometrics determination of the kinetics of the process and structural elucidation of one of the products as a stable N3-enamino tautomer

Exposure of cimetidine (CIM) to dry heat (160–180 °C) afforded, upon cooling, a glassy solid containing new and hitherto unknown products. The kinetics of this process was studied by a second order chemometrics-assisted multi-spectroscopic approach. Proton and carbon-13 nuclear magnetic resonance (NMR), as well as ultraviolet and infrared spectroscopic data were jointly used, whereas multivariate curve resolution with alternating least squares (MCR-ALS) was employed as the chemometrics method to extract process information. It was established that drug degradation follows a first order kinetics.     

焦炉上升管内壁结焦炭层的光谱学分析及结焦机理研究

以焦炉上升管内壁结焦炭层块为研究对象，采用X射线荧光光谱仪（XRF）、X射线衍射仪（XRD）、傅里叶红外光谱仪（FTIR）和激光共聚焦拉曼光谱仪（Raman）对结焦炭层的元素组成，以及各结焦炭层的矿物组成、组成结构和分子结构进行测试。分析从结焦炭层块外表面向内表面过渡的各结焦炭层的差异性，揭示焦炉上升管内壁结焦机理。结果表明焦炉上升管内粉尘中Fe，S和Cr极易催化荒煤气中蒽、萘等稠环芳烃化合物成炭，在焦炉上升管内壁形成炭颗粒沉积，为焦油凝结挂壁提供载体，在荒煤气温度降至结焦温度时易结焦积碳。结焦炭层均含有芳香层结构，随着结焦炭层从外表面向内表面过渡，各结焦炭层的面层间距(d₀₀₂)逐渐降低、层片直径(L_a)先降低后增加、层片堆砌高度(Lc)和芳香层数(N)先稳定后增加。结焦炭层石墨化过程是由结焦炭层内表面向外表面进行，主要包括其片层外缘的羧基和部分C-O结构的降解剥离，从而形成高度规整的共轭结构。结焦炭层块中C元素是以结晶碳与无定型碳的混合物形式存在。以上研究为解决焦炉上升管内壁结焦及腐蚀问题，提高换热器换热效率，有效回收焦炉荒煤气显热，降低焦化企业能耗提供实验基础和理论依据。     

原位液相透射电子显微镜及其在 纳米粒子表征方面的应用

近年来,基于透射电子显微技术、微纳加工技术和薄膜制造技术的发展,原位液相透射电子显微技术产生,为构建多种纳米级分辨率尺度下的微实验平台,发展新型纳米表征技术和众多领域的相关研究提供了途径.本文首先介绍了应用于原位液相透射电子显微技术的液体腔设计要求,然后介绍了液体腔的发展和典型的制备工艺,最后综述了近年来液体腔透射电子显微镜在纳米粒子成核和生长方面的应用研究,并探讨了该技术前沿发展面临的机遇和挑战.本文将为提高我国先进纳米表征技术和原子精准构筑技术提供相关讨论和支持.     

Reducing Huge Gyroscopic Eigenproblems by Automated Multi-level Substructuring

Simulating numerically the sound radiation of a rolling tire requires the solution of a very large and sparse gyroscopic eigenvalue problem. Taking advantage of the automated multi-level substructuring (AMLS) method it can be projected to a much smaller gyroscopic problem, the solution of which however is still quite costly since the eigenmodes are non-real and complex arithmetic is necessary. This paper discusses the application of AMLS to huge gyroscopic problems and the numerical solution of the AMLS reduction. A numerical example demonstrates the efficiency of AMLS.     

胆绿素及其铜配合物的表面增强拉曼光谱研究

本文研究了胆绿素的表面增强拉曼光谱。结果表明，在溶液酸度不同时，拉曼光谱特征频率的变化表现出胆绿素的质子化。铜离子与胆绿素的相互作用实验结果说明金属铜离子可与胆绿素生成金属配合物。     

355nm Nd∶YAG激光在H_2中的高效一级斯托克斯转换

对脉冲Nd∶YAG激光(355 nm)在H2和H2∶He-Ar混合气体中的受激拉曼散射(SRS)进行了研究。在0.5 MPa的氢气中,同时测量到从二级反斯托克斯到三级斯托克斯的多波长输出,其总转化效率达88%;而高压下只剩下一级和二级斯托克斯输出,其中二级斯托克斯最大能量转化效率达44%(对应量子效率为63%)。由于高级斯托克斯的竞争,纯氢气中一级斯托克斯的最大能量转换效率不超过43%。通过向3 MPa氢气中掺入2 MPaAr气后,很好地抑制了二级斯托克斯的产生,从而获得了能量转换效率高达71%(对应量子效率为83%)的一级斯托克斯输出。对四波混频和级联受激拉曼散射在氢气多级斯托克斯产生中的作用以及惰性气体对它们的影响进行了讨论。     

High pressure X-ray diffraction study of CdAl2Se4 and Raman study of AAl2Se4 (A=Hg, Zn) and CdAl2X4 (X=Se, S)

We report the results of an X-ray diffraction study of CdAl₂Se₄ and of Raman studies of HgAl₂Se₄ and ZnAl₂Se₄ at room temperature, and of CdAl₂S₄ and CdAl₂Se₄ at 80 K at high pressure. The ambient pressure phase of CdAl₂Se₄ is stable up to a pressure of 9.1 GPa above which a phase transition to a disordered rock salt phase is observed. A fit of the volume pressure data to a Birch-Murnaghan type equation of state yields a bulk modulus of 52.1 GPa. The relative volume change at the phase transition at ∼9 GPa is about 10%. The analysis of the Raman data of HgAl₂Se₄ and ZnAl₂Se₄ reveals a general trend observed for different defect chalcopyrite materials. The line widths of the Raman peaks change at intermediate pressures between 4 and 6 GPa as an indication of the pressure induced two stage order-disorder transition observed in these materials. In addition, we include results of a low temperature Raman study of CdAl₂S₄ and CdAl₂Se₄, which shows a very weak temperature dependence of the Raman-active phonon modes.