用局部拟合主成分回归计算光度分析法测定黄连生物碱

针对具有样本数据非无匀分布和非线性特点的光度分析问题，提聘种局部拟合 主成分回归法，用于中药多组分计算测定。该方法根据待测样本与各已知样本光度 分析数据的欧式距离确定相应的权值，将部分权值较大的样本组成校正集，并用分 段线性拟合算法建立待测样本的校正预测模型，将其用于分析黄连的药根碱、巴巴 亭和小檗碱等三种生物碱，所得预测均方根误差分别为0.023,0.0400和0.052，优 于主成分回归法、偏最小二乘法以及人工神经元网络法所得结果。这表明，本方法 用于中药光度分析能获得较为准确的计算分析结果。     

Spectral density calculation by using the Chebyshev expansion

A method to calculate the spectral density of any state vectors with respect to a set of eigenstates of a Hamiltonian is presented. A spectral density operator, whose expectation value on the state vector gives the spectral density, is evaluated indirectly by using the Chebyshev expansion method. A spectral transformation function is introduced to improve resolution at the low energy region, at the expense of the one at the higher region. The predissociation spectrum of CO+ is calculated to demonstrate the method.     

电感耦合等离子体发射光谱中的光谱干扰

光谱干扰是电感耦合等离子体发射光谱(ICP-AES)中的主要干拢。已有不少文献作了报道。CIP发射光谱的波长表,为研究光谱干扰提供了可靠的数据和资料。本文试对这方面的文献进行了归纳和分析。光谱干扰包括光谱线的重叠和背景。在ICP-AES中,有以下几种类型的光谱干扰不可忽视:     

三线性分解方法用于光谱数据中背景漂移的扣除

在光谱测量中, 通常会发生光谱背景漂移现象. 引起光谱背景漂移的因素有很多, 如仪器的背景噪声变化, 测量时环境温度的变化, 光源如氙灯的使用时间等等. 针对三维光谱数阵, 发展了一种基于交替三线性分解(ATLD)算法的化学计量学方法用来处理光谱背景漂移问题. 该方法在进行三线性分解时, 对待光谱背景漂移与感兴趣组分一样, 将其单独当作一个组分或因子来考虑, 并将其从分解得到的相应矩阵中提取出来, 构建一个光谱背景漂移阵, 然后从三维原始响应数阵中将其减掉, 从而达到成功扣除光谱背景漂移的目的. 采用发展的方法处理2组模拟数据和2组实验数据, 都获得了满意的结果. 另外, 对于非线性较严重的背景漂移, 通过再进行一次扣除, 即“二次扣除”, 也达到了理想的效果. 该方法有望发展成为一种很有潜力的光谱预处理技术.     

对DEPT实验技术的一点改进

将DEPT -1 3 5实验的 1 3 5° -脉冲分成一个 90°脉冲和一个 4 5°脉冲 ,通过相位循环 ,设计了两个新的DEPT实验分别称为DEPT-90 -4 5和DEPT -90 +4 5。DEPT -90 -4 5谱中只有 -CH3的吸收峰。DEPT -90 +4 5谱中没有 >CH -的吸收峰 ,其 -CH3为正信号 ,-CH2 -为负信号。实验结果显示 ,对比DEPT -90谱 ,这两个新的DEPT谱中完全没有所选基团之外的残余干扰信号 ,而且DEPT -90 -4 5谱比DEPT-90 +4 5谱更好。     

原子光谱项的矢量求算法

在Ｐａｕｌｉ原理的基础上,分别求出轨道磁量子数和自旋磁量子数所对应的矢量,通过矢量的标量积求出微观状态数,进一步求出原子光谱项。     

Photochromism and the spectral properties of bispiroanthro-bis-oxazine

The spectral and photochromic properties of bispiroanthro-bis-oxazine (bis-SAO) in toluene, DMF, and polystyrene films were investigated in the 77–300 K interval. It is shown that the long-wave part of the absorption spectrum of the starting form of the molecule is formed by three-electron transitions localized in the anthro-bis-oxazine fragment. The directions of the oscillators of these transitions relative to the nuclear. backbone of the molecule are proposed on the basis of luminescence polarization data. It is proposed that the photochromic properties of the solutions are determined by the existence of bis-SAO molecules in dimer form.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. Institute of Solid State and Semiconductor Physics, Academy of Sciences of Belarus, 210023 Vitebsk. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2718–2725, December, 1992.     

溴化银晶体光谱敏化光电流的研究和染料增感性能的判据

本文以AgBr晶体和菁染料为对象,对AgBr晶体的光电流进行了研究。实验发现,AgBr晶体经其本征吸收波长的光辐照后,可产生新的诱导吸收带。用诱导吸收带波长范围内的光辐照AgBr晶体,在非本征吸收区可测量到自敏化光电流。若染料吸附在AgBr晶体片上,则其敏化光电流将叠加在自敏化光电流上。增感染料对AgBr晶体的阳极和阴极光电导均有不同程度的敏化作用。本文在实验研究的基础上,提出了对染料增(减)感性能的判据S_D,比现有的一些判据更具有综合性。利用S_D—λ曲线可以较直观地对染料的增(减)感性能做出预测。本文利用S_D判据对一些实用增感染料及其组合作了分析。     

微型CCD光谱仪在光谱分析中的应用

现代分析仪器的一个重要发展趋势是仪器的小型化（miniaturization）、微型化（microminiaturiza．ion），甚至于芯片实验室（lab-on-a-chip；或称微全分析系统，micro total analysis system，μ-TAS）。因此，许多科学工作者在提高光谱分析仪器的基本部件——辐射源、样品室、分光元件和检测器的性能和减小其体积方面做了大量的研究工作。半导体检测器在光谱分析中的应用越来越广泛，在实验室和实际工作中常常会接触到摄谱仪、光电倍增管（photomultiplier tube，PMT）和电荷耦合器件（charge coupled device，CCD）等，本文介绍微型CCD光谱仪在本科教学中的一些应用。     

食品安全速测设备光谱标定仪的研制

对没有光谱测量功能的分光光度计类测量设备的光谱分析问题进行系统研究,研制成可自校准并有效溯源的食品安全速测设备光谱标定仪,解决了设备光源标定问题,为食品安全速测设备的准确测量提供可靠技术保证。     

LiNbO3晶体中Yb3+的配位场能级分析

０引言自从上世纪６０年代LiNbO３晶体合成以来，人们对这种材料的兴趣越来越大。它的优良的非线性特征使LiNbO３晶体成为用于光电装置的最好的物质之一，也是信息贮存和全息照相的很好材料。稀土离子可以很容易地掺杂到该晶体中，用频率自动加倍、自猝灭开关和自动密封等方式来发展微激光。在这种意义上，Yb３＋成为主要的激光材料掺杂离子，它的光谱特征在大量体系中已有研究，已经获得了不同基质中的激光犤１～５犦。由于Yb３＋的谱带积分面积较大，所以，Yb３＋已被用作其它稀土离子的敏化剂，用以提高它们的激发效率，如：Yb－Er…     

不同电荷基团修饰环糊精与离子型表面活性剂的键合行为研究

采用紫外-可见光谱和荧光光谱滴定的方法测定了单(6-脱氧-6-苯胺)-β-环糊精(1)、单(6-脱氧-6-乙二胺-β-环糊精(2)和单[6-氧-(4-苯甲酸)β-环糊精(3)在磷酸缓冲溶液中分别与阴离子表面活性剂十二烷基硫酸钠(SDS)和阳离子表面活性剂十二烷基三甲基溴化铵(DTAC)包结配位的稳定常数,并通过二维核磁等手段研究了主-客体之间的键合模式.结果表明,在环糊精的小口端修饰带有不同电荷的取代基,引入静电相互作用的识别位点,能够有效地改变环糊精对于离子型表面活性剂的键合能力,从而实现主体环糊精对于客体分子的选择性识别.     

[T（P—NO2）PP]Fe（Ⅱ）（NO）配合物的制备与光谱性质研究

70年代以来,金属卟啉无机小分子配合物日益受到重视。NO可以与金属卟啉形成配合物,并且自身被活化。目前关于原卟啉Ⅸ二甲酯铁、四苯基卟啉铁和八乙基卟啉铁的NO配合物研究已有一些报道,但有取代基的四苯基卟啉体系研究甚少。为深入考察不同取代基活化NO的规律,我们合成了五配位的四(对-硝基苯基)卟啉铁-氧化氮配合物[简称[T(p-NO_2)PP]Fe(Ⅱ)(NO)],并研究了它的光谱性质。     

新型香豆素N-取代-1,3,4-噻二唑基酰胺类化合物的合成及其光学性能

8-甲氧基香豆素-3-甲酰氯(1)与5-取代-2-氨基-1,3,4-噻二唑经取代反应合成了9个新型的香豆素N-取代-1,3,4-噻二唑基酰胺类化合物(3a~3i),其结构经1H NMR,IR和HR-MS表征。UV-Vis和FL研究表明,3较1的λmax红移,吸收强度增强;3较1有更强的荧光性能。     

Spectral and non-spectral interferences in inductively coupled plasma mass-spectrometry

Inductively coupled plasma mass spectrometry of environmental and biological samples is often hampered by spectral and non-spectral interferences. Spectral interferences, caused by the limited resolution of the quadrupole mass spectrometer, can be eliminated in a variety of ways. For their identification inspection of a signal versus carrier gas flowrate is useful. Anion exchange allows the removal of most S and Cl containing compounds, which are at the origin of the majority of spectral interferences. Matrix modification, for example the addition of ethanol and subsequent optimization of the gas flow rates in a number of cases enables the reduction of the interferences to insignificant values. Often a mathematical correction based on isotopic signal ratios can be applied. Non-spectral interferences can be divided in reversible, that is occurring while the sample is being measured, and irreversible matrix effects, that is clogging of the nebulizer and sampling orifices or deposition on the torch or in the ion lens stack. The errors associated with non-spectral interferences can be eliminated by appropriate calibration procedures, adapted sample preparation or limitation of the amount of sample delivered to nebulizer, plasma and sampling devices, for example by the application of flow injection. Applications of all the elimination procedures are described for the analysis of sea-water, estuarine water, soil and sewage extracts, percolate water, urine, serum and wine.     

新型多臂方酸菁化合物的合成及光谱性质

合成了引入多甘醇醚链的５－Ｎ，Ｎ－双（２－羟乙基）胺基－１，３－间苯二酚及其衍生物，使之与方酸发生缩合反应，获得了７种新型多臂方酸菁化合物，研究了它们的光谱性质     

Computer aided processing of laser microprobe mass spectra

This article describes the development and subsequent application of a computer aided method, based on the library search strategy, for the interpretation of laser microprobe mass analysis (LAMMA) spectra. Such a routine is essential whenever huge amounts of spectra are needed to obtain relevant results, as e.g. in environmental research. The main handicap for a straightforward automation is the poor reproducibility of the analytical technique.     

Improvement and application of two extrapolation methods to FT-IR data

The applicability of two non-parametric extrapolation methods to FT-IR absorptance spectra is investigated. The first method minimizes those parts of the spectrum which do not satisfy a given constraint, while the second one changes them in each iteration through the true values.     

卟啉-salen化合物的合成及谱学性质研究

合成了三种含羟基的salen化合物: salen-OH, Cl-salen-OH和t-Bu-salen-OH, 并用后两种羟基salen与5,10,15-三苯基-20-对羟基苯基卟啉(HPTPP)以烷烃链[O(CH)₆O及O(CH)₁₀O]相连合成四种卟啉-salen化合物: HPSC₆ (1), HPSC₁₀ (2), HPt-BuSC₆ (3), HPt-BuSC₁₀ (4)及其金属锌(II)化合物: ZnPSC₆ (Zn-1), ZnPSC₁₀ (Zn-2), ZnPt-BuSC₆ (Zn-3), ZnPt-BuSC₁₀ (Zn-4). 用元素分析、核磁共振、红外光谱、紫外-可见光谱等手段对其组成的结构进行表征, 并对其谱学性质进行了研究.     

Synthesis,Structure and Spectral Properties of a Novel Triaryl Substituted Triazole and Its Co(Ⅱ) Complex

The new compound 3-(2-pyridyl)-4-(p-methoxyphenyl)-5-(2-thienyl)-1,2,4-triazole L was synthesized and characterized by elemental analysis,IR,1H NMR,13C NMR,MS,UV and photoluminescent spectra.The complex CoL2(NCS)2 was prepared by the reaction of ligand L with Co(SCN)2,and its structure was characterized by single-crystal X-ray diffraction,IR,UV,elemental analysis and MS.The complex crystallizes in monoclinic,space group P21/n with a=13.7639(19),b=7.6641(11),c=18.409(3),β=101.549(3)o,V = 1902.6(5) 3,Z=2,C38H28CoN10O2S4,Mr=843.87,Dc=1.473 g/cm3,μ=0.720 mm-1,S=1.075,F(000)=866.0,the final R=0.0825 and wR=0.2149 for 2566 observed reflections(I2σ(I)).In the crystal structure,the cobalt atom adopts a distorted octahedral environment with two NCS-ions in the axial positions and two bidentate chelating L ligands in the equatorial plane.The extended 2D network of the complex is formed by intermolecular C-H…N hydrogen bonds together with π-π stacking interactions.