基于拉曼光谱鉴定黑色签字笔笔迹的种类与书写时间

黑色签字笔字迹种类与书写时间的鉴定一直是国内外法庭科学研究领域的热点问题。基于拉曼光谱法的分辨率高、稳定性好、效率高以及无损检测等优点,对收集的16种品牌或牌号的黑色签字笔字迹样本进行测试。完成同一品牌或牌号同一时间在不同存储条件(暗室和光照)与不同纸张本底(复印纸和笔记本)字迹样本的制备。将样本字迹剪裁,双面胶固定在载玻片上,放入储存箱内避光保存,间隔一段时间对样品进行测试,测试工作共持续1年,形成图谱数据库。在考察实验条件如测量点、激光功率及共焦类型等因素影响的基础上,筛选出最佳条件。在此条件基础上,检测黑色签字笔在不同书写时间、储存环境、纸张本底等条件下的字迹样本。实验结果表明:(1)存储条件(暗室和光照)、纸张本底(复印纸和笔记本)等不同条件下,同种黑色签字笔字迹的拉曼位移相同,重复性好,受水和纸张等本底的干扰较小。(2)根据拉曼位移的差异可将16种黑色签字笔分成5类。(3)以2#样本为例, 1 140 cm^-1处拉曼光谱特征峰,归属为酯类化合物的C-O伸缩振动ν(CO)。酯类化合物的含量随着时间延长而不断减少,因此随着书写时间越久远,特征峰的相对强度越大(8→1)。通过拟合后计算出相对面积数值I,样本书写时间越早,I值越大,反之I值越小。研究结果可用于快速、准确、无损判定黑色签字笔字迹的种类和推断其相对书写时间。     

Liquid hydridosilane precursor prepared from cyclopentasilane via sonication at low temperatures without the action of light

We report on a liquid hydridosilane precursor ink prepared via the ultrasonically induced ring-opening polymerisation of cyclopentasilane (Si₅H₁₀) without irradiation by ultraviolet light. The sonication is carried out in N₂ atmosphere at temperatures between 20 and 75 °C. We use size exclusion chromatography (SEC) to show polymer growth and estimate molecular mass with increasing sonication time. In combination with UV–vis transmission measurements, further SEC analysis is used to compare solutions subjected to either purely thermal or ultrasonic treatment at the same process temperature and for the same duration. Our findings provide strong evidence showing that the initiation of the polymerisation is sonocatalytic in nature and not thermic due to the macroscopic temperature of the solution. The liquid precursor is used to produce homogeneous hydrogenated amorphous silicon (a-Si:H) thin films via spin coating and pyrolytic conversion. The optoelectronic properties of the films are subsequently improved by hydrogen radical treatment. Fourier transform infrared spectroscopy (FTIR) is used to determine a compact film morphology and electrical conductivity measurements show that the layers attain a light-to-dark photosensitivity ratio of 2 × 10³ making them suitable for application in optoelectronic devices.     

一个新的非常规各向异性元的收敛性分析

构造了一个新的非常规各向异性Hermite型矩形单元并据此对二阶椭圆问题提出了一个混合元格式,同时给出了该格式的收敛性分析.     

车辆天窗气动噪声的数值分析与实验研究

本文从汽车天窗气动噪声的机理入手,利用与实车几何尺寸为1:5的简化模型进行了空腔绕流的数值计算,分析了其流场结构及气动噪声产生的原因.在低速静音风洞中进行了不同流速下的流场和声场实验研究,研究了天窗不同位置的速度剪切层变化,以及不同流速下的声压级变化,发现了除了特征频率下的风振噪声,还存在较大频率范围的气动噪声,其随着...     

外场作用下C12H4Cl4O2的分子结构和电子光谱研究

各种环境毒物危害着人类的生产生活,二噁英更是严重危害人类的健康.C₁₂H₄Cl₄O₂（2,3,7,8-tetrachlorodibenzo-p-dioxin,TCDD）是二噁英中毒性最强的化合物,也是目前已知毒性最强的污染物.为研究TCDD外场效应,采用密度泛函理论方法优化了不同静电场0–0.025 a.u.（0–1.2856×10¹⁰ V/m）作用下TCDD分子的基态几何结构,得到了分子总能量;在此基础上,采用含时密度泛函理论方法对TCDD分子的紫外-可见（UV-Vis）吸收光谱在不同外电场下的变化进行了研究.结果表明：分子几何构型与电场大小呈现强烈的依赖关系,分子总能量随着外电场的增强而减小;伴随着外电场的增强,分子激发态的摩尔吸收系数逐渐减小,UV-Vis吸收峰显著红移.     

基于结构性思维的生物化学实验教学探索

为了多维度地培养学生的实践创新能力、终身学习能力及信息获取能力等核心素养,以具体实验为例,探讨结构性思维在生物化学实验教学中的综合应用。教学实践表明：结构性思维可使知识更有序、梯度更明确、更易表达,实验操作变得程序化,学生学习倾向主动,是一种多维度地培养学生核心素养的教学模式。     

Palladium catalysed mono-N-arylation of enantiopure diamines

The palladium catalysed arylation of amines is employed to prepare selectively a range of new, mono-N-arylated, enantiopure diamine ligands. The ligands were tested in the catalytic asymmetric transfer hydrogenation of acetophenone.     

光谱法和电化学法研究甲硫氨酸二肽与DNA的相互作用

利用紫外-可见光谱、荧光探针、循环伏安等方法研究了甲硫氨酸二肽(Met-Met)与DNA的相互作用.结果发现:加入甲硫氨酸二肽后,DNA-Met-Met体系的紫外光谱呈减色效应,同时甲硫氨酸二肽的加入使得EB-DNA荧光强度减弱;循环伏安法表明,DNA的加入使得甲硫氨酸二肽的峰电流减小,峰位负移;Stern-Volmer方程说明二肽对DNA-EB的作用属于静态猝灭.这几种方法的实验结果都表明两者的作用模式为静电结合,多种计算方法得到两者作用的结合常数达到103 L/mol.     

Kinetics of non-isothermal decomposition of cinnamic acid

The thermal stability and kinetics of decomposition of cinnamic acid were investigated by thermogravimetry and differential scanning calorimetry at four heating rates. The activation energies of this process were calculated from analysis of TG curves by methods of Flynn-Wall-Ozawa, Doyle, Distributed Activation Energy Model, ?atava-?esták and Kissinger, respectively. There are only one stage of thermal decomposition process in TG and two endothermic peaks in DSC. For this decomposition process of cinnamic acid, E and logA[s^?1] were determined to be 81.74 kJ mol^?1 and 8.67, respectively. The mechanism was Mampel Power law (the reaction order, n = 1), with integral form G(α) = α (α = 0.1–0.9). Moreover, thermodynamic properties of ΔH ^≠, ΔS ^≠, ΔG ^≠ were 77.96 kJ mol^?1, ?90.71 J mol^?1 K^?1, 119.41 kJ mol^?1.     

Surface-enhanced Raman scattering of 4-mercaptobenzoic acid and hemoglobin adsorbed on self-assembled Ag monolayer films with different shapes

Polyvinylpyrrolidone (PVP)-protected silver nanostructures of various shapes, including nanocubes, nanospheres, and hybrid shapes with nanospheres and nanorods, on the surface of glass or Si substrates (PVP-Ag films) are prepared by using electrostatic self-assembly. With 4-mercaptobenzoic acid (4-MBA) as a probe molecule, it is demonstrated that the PVP-protected silver nanocubes films (PVP-Ag NCs) have better surface-enhanced Raman scattering (SERS) activity with an order of magnitude larger enhancement factors (EF) than the PVP-protected silver nanospheres films and the PVP-protected silver hybrid shapes films, which is confirmed by our numerical simulations. The EF of 4-MBA on the PVP-Ag NCs film are up to ~5.38 × 10⁶, and the detection limit is at least down to ~10^?8 M. The uniformity and reproducibility of the SERS signals on PVP-Ag NCs film are tested by point-to-point and batch-to-batch measurements. Meanwhile, the PVP-Ag films are also shown to be an excellent SERS substrate with good biocompatibility for hemoglobin detection. It is shown that the PVP-Ag NCs films can be used as excellent SERS substrate with good activity, uniformity, reproducibility, and biocompatibility and are promising for a myriad of chemical and biochemical sensing applications.