移动窗口二维相关光谱技术

移动窗口二维相关光谱是一种新的二维相关分析方法,它将移动窗口的概念和二维相关分析方法有效地结合在了一起,利用移动窗口将庞大的光谱数据按矩阵分割成若干个便于操作的子矩阵,用二维相关光谱分别处理,将得到的结果综合分析,用以光谱变量和扰动变量为坐标的等高图表现出来,从中可以非常直观地观察出光谱强度在扰动变量方向上的变化,进而找出引起光谱强度突变的特征扰动点。本文主要介绍了移动窗口二维相关光谱的计算方法、基本特征、影响因素和实际应用,同时还详细介绍了以它为基础改进得到的扰动相关移动窗口二维相关光谱。扰动相关移动窗口二维相关光谱包括同步图和异步图,它不仅能很好地反映出引起光谱强度突变的特征扰动,还能详尽地描述出光谱强度在扰动过程中的变化情况。     

激光诱导击穿光谱技术/多元二次非线性回归分析土壤中的铬元素

利用激光诱导击穿光谱(LIBS)技术对土壤中铬元素的含量进行了定量分析研究.由于土壤成分复杂,光谱谱线存在较严重的重叠干扰,若采用一元回归方法分析常得不到理想结果.为了更充分有效地利用光谱中信息,以土壤中Cr Ⅰ 425.43 nm和Fe Ⅰ 425.07 nm谱线的积分强度为自变量,Cr元素浓度为因变量,建立交叉降维近似多元非线性回归、多元二次非线性回归和平方降维近似多元非线性回归模型.对比分析表明,当添加Cr和Fe元素特征谱线强度交叉项影响时,所建立的多元二次非线性回归模型效果最佳,预测浓度与实际参考浓度之间线性关系达到0.9943,预测4个验证样品的相对误差分别为3.57％,0.76％,7.66％和2.24％.     

飞秒受激拉曼光谱技术

飞秒受激拉曼光谱（femtosecond stimulated raman spectroscopy,FSRS）是一种新型的非线性振动光谱技术.它使用两束重叠的窄带拉曼泵浦和宽带探测脉冲激光束,利用外差式检波方法在探测光方向上进行信号探测.FSRS既可以用来探测分子电子基态的振动动力学,也可以用来探测分子电子激发态的振动动力学,比如同质异构类反应.即使荧光背景很强的分子,也可以用FSRS来研究.FSRS可以用三阶微扰的波包图像来描绘.单从相位匹配条件出发,共有48项对应于FSRS过程,但是其中只有8项满足共振条件.可以用3种方法来描述这8项：双时间线拉曼图、封闭时间路径环路图和四波混频的能级图.进一步分析表明,这8项可以分成4类,即SRS（I）,SRS（II）,IRS（I）和IRS（II）,其中SRS代表受激拉曼散射,IRS代表反转拉曼散射.SRS（I）可以用来解释自发拉曼散射,但是其余的SRS（II）、IRS（I）和IRS（II）三项只在受激拉曼光谱中存在.FSRS光谱中SRS（I）过程产生的是斯托克斯拉曼谱线,而IRS（I）过程则产生的是反斯托克斯谱线.其余的两项SRS（II）和IRS（II）只是产生很宽的背景基线,基本和我们感兴趣的观测量不相关.使用简谐振动模型,我们可以得到三阶微扰极化率的四时间相关函数的解析表达式.我们讨论了FSRS光谱之所以能够得到高时间分辨率和高频率分辨率的物理原理.在文章中,我们还就以下研究做了计算与实验结果的比较：（a）荧光性罗丹明6G的共振FSRS谱和（b）CDCl3分子非共振脉冲泵浦光制备的相干振动态的二维FSRS谱.计算得到的结果与实验十分吻合,同时在理论上证明了CDCl3二维FSRS光谱中级联效应是占主导作用的.     

分子聚集体的光谱模拟

采用Frenkel激子理论研究了一维线性和二维人字形分子聚集体的吸收和发射光谱.通过引入激子离域长度的概念,将聚集体与单分子的光谱线形函数联系起来.计算的光谱结果表明,聚集体的光谱与分子在聚集体中的排列紧密相关.分析了一维J聚集光谱发生红移以及二维人字形分子聚集体吸收光谱形成J和H激子谱带的内在原因.模拟得到的聚集体的...     

二维红外光谱研究聚碳酸酯薄膜中水的扩散

利用二维衰减全反射红外光谱方法,研究了水在聚碳酸酯(PC)薄膜中的扩散过程,发现水的羟基弯曲振动谱带中可以分辨出分别位于1672、1646和1621 cm-1的吸收峰,而羟基伸缩振动谱带中可以分辨出分别位于3560、3425和3255 cm-1的吸收峰,由此可知水分子在聚碳酸酯薄膜中存在3种状态,分别为与羰基形成强、中强氢键作用的水分子和进入PC微孔中的弱氢键作用的水分子。 经过二维相关分析得到水分子进入PC薄膜的顺序为首先形成中等强度的氢键,然后形成弱和强2种强度的氢键。     

分子动态模拟与分子振动光谱——Ⅰ.内坐标相关法与谱带的归属

分子动态模拟法的发展为从理论上模拟真实的分子体系的振动光谱打开了方便之门。该法不但可以预报分子的振动频率,谱带的强度,还有能力模拟谱带的形状。该法在这方面发展中的不足之处是振动谱带归属不清晰。本研究提出了一个新的方法,“内坐标相关法”,来克服这一缺点。文中对“内坐标相关法”模拟振动光谱的合理性做出了理论上的解释。并指出用这一方法模拟的光谱与传统的简正坐标分析方法得到的结果的关联。对用“内坐标相关法”模拟的孤立分子的振动光谱,在有序的晶体中分子链的振动光谱,以及振动谱带对温度响应情况进行了简要的讨论。     

激光功率和积分时间对表面增强拉曼光谱的影响EI北大核心CSCD

表面增强拉曼光谱(SERS)技术能够有效增强低浓度样品的拉曼光谱强度,然而由于SERS的结构、材质等工艺原因,SERS实际应用中往往由于未能正确选择激光功率与积分时间而导致测量效果显著下降。本文以浓度为2,0.08μg/mL的三聚氰胺溶液样品、Au@Ag NPs纳米柱结构固态SERS基底为例,使用自主搭建的便携式拉曼光谱仪,采集不同激光功率和积分时间下的SERS光谱,使用算法平滑光谱、计算光谱基线,得到样品SERS光谱强度和SERS光谱基线强度变化趋势。实验表明,激发光源功率和积分时间改变时,SERS光谱基线强度在不同光谱区域变化幅度不同,部分光谱区域基线强度的变化幅度远大于样品光谱强度,导致使用拉曼光谱仪进行光谱测量时极易造成光谱强度饱和,影响低浓度样品的测量。临时更换样品试剂或SERS基底又会增加成本,且操作繁琐。研究发现,通过控制激光功率和积分时间这2个简单可控的变量,可以在一定程度上抑制SERS光谱基线、提高样品光谱强度,从而避免因光谱强度易饱和而无法测得低浓度样品光谱信号的问题。     

二维相关振动光谱技术

从发展历史、计算方程、性质规则等方面系统地介绍了近年来发展起来的二维相关光谱技术.结合各种常见的一维振动光谱, 如红外、拉曼、荧光、近红外-红外等光谱举例阐述了二维振动光谱的优势及其普适性.介绍了在广义二维相关光谱理论上最新延伸发展起来的二维样品-样品相关技术和二维杂化相关技术的基本理论, 并将之与传统的二维变量-变量相关技术(广义二维相关光谱)进行了比较.     

聚甲基丙烯酸正丁酯的核磁共振异核相关二维谱

<正> 核磁共振二维谱是研究高聚物分子结构的有力工具.有时一张谱图,就能得到高聚物序列结构或共聚物构型的直接证据.对高聚物结构分析有重要意义.自1983年Brown首次报道聚氯乙烯的二维J谱以来.美国Macromolecules等杂志竟相报道各种聚合物的二维谱图.目前已经报道过的聚合物核磁共振二维谱有二维J谱、~(19)F-~1H异核相关谱、~(13)C-~1H异核相关谱、~1H COSY谱、~(19)F COSY谱、NOESY     

红外光谱法对肉苁蓉径向不同部位的分析与评价

采用傅里叶变换红外光谱、二阶导数谱和二维相关红外光谱技术对肉苁蓉由表及里3个部位的药材粉末及其水提物和醇提物进行了分析与评价研究.结果表明,肉苁蓉不同部位的一维光谱非常相似,三者相似系数分别为0.9605,0.944和0.976;二阶导数谱中峰位和峰强的差异明显.1430～1700 cm-1范围内的二维相关谱中皮部自动峰有3个,而中部及髓部均为4个,更直观的反映出三者的差异.不同部位水提物和醇提物的分析结果进一步明确了肉苁蓉皮部芳香类、环烯醚萜类及糖苷类物质与中部和髓部存在明显不同,而髓部的水溶性多糖、半乳糖醇和苯乙醇苷类物质均高于其它部位.可见红外光谱法结合二维相关红外光谱技术为同种药材不同部位的细微差异分析和评价提供了一种快速、全面和客观的方法和手段.     

Recent developments in two-dimensional (2D) correlation spectroscopy

Recent noteworthy developments in the field of two-dimensional(2D) correlation spectroscopy are reviewed.2D correlation spectroscopy has become a very popular tool due to its versatility and relative ease of use.The technique utilizes a spectroscopic or other analytical probe from a number of selections for a broad range of sample systems by employing different types of external perturbations to induce systematic variations in intensities of spectra.Such spectral intensity variations are then converted into2 D spectra by a form of correlation analysis for subsequent interpretation.Many different types of 2D correlation approaches have been proposed.In particular,2D hetero-correlation and multiple perturbation correlation analyses,including orthogonal sample design scheme,are discussed in this review.Additional references to other important developments in the field of 2D correlation spectroscopy,such as projection correlation and codistribution analysis,were also provided.     

二维相关分析光谱技术

给出推导二维相关光谱和推广至普遍意义上的数学过程,其物理含义和二维相关光谱的性质及其解释规则。以应用实例给出了该光谱技术在分析结构、相互作用等相关性方面的独特性质。还给出紫外可见二维相关光谱。     

Application of two-dimensional near-infrared correlation spectroscopy to protein research

The purpose of the present paper is to demonstrate the potential of generalized two-dimensional (2D) near-infrared (NIR) correlation spectroscopy in studies of hydration and structure of proteins. We describe here two examples. The first example is concerned with heat denaturation process of ovalbumin in aqueous solutions and the second one deals with isomerizations with varying pH of serum albumin. New insight has been obtained into the hydration and unfolding process of secondary structures of ovalbumin and serum albumin by studying temperature- or pH-dependent correlation patterns in 2D synchronous and asynchronous spectra. Generalized 2D NIR correlation spectroscopy emphasizes spectral features not readily observable in conventional one-dimensional spectra, enabling to extract subtle but valuable structural changes concerning with the protein denaturation.     

Determination of relative rate of spectral events by novel modification of two-dimensional correlation spectroscopy

Sign of two-dimensional (2D) correlation peaks provides information on sequence of spectral events. This information is related to molecular mechanism of changes in a given system. Recently, few papers addressing the problems with interpretation of the sign of 2D correlation peaks have been published. To overcome these problems, a modification of the generalized 2D correlation method has been proposed. This method compares variations in the dynamic spectrum with a linear change at a reference point. The rates of spectral responses at individual wavenumbers are proportional to magnitudes of the peaks in the slice of asynchronous spectrum at the reference point. This way, analysis of complex 2D contour plots is replaced by a simple examination of one-dimensional (1D) slice spectrum. In spite of reduced ability of the resolution enhancement, in special cases the proposed method provides information not accessible from the classical 2D correlation analysis. At first, the principles of this method are shown with the synthetic data. Next, the influence of spectral separation, band width and position changes on the slice spectrum is evaluated. Finally, the proposed approach is applied to the experimental spectra of two hydrogen-bonded systems.     

Two-dimensional infrared spectroscopy study on phase transition and structural variations of a hydrogen-bonded liquid crystal

Infrared (IR) spectra have been measured for a liquid crystal (LC) consisting of one trans-butene diacid (BD) molecule as a proton donor and two 4-(2,3,4-tridecyloxybenzoyloxy)-4'-stilbazoles (DBS) molecules as a proton acceptor (DBS:BD:DBS) linked together with each other by inter-molecular hydrogen bonds over a temperature range from 20 to 120 degrees C to explore its phase transition and heat-induced structural variations. The temperature-dependent IR spectra have shown that the inter-molecular hydrogen bonds are stable in the liquid crystalline phase but become slightly decoupled with temperature increasing. Two kinds of two-dimensional (2D) correlation spectroscopy, variable-variable (VV) and sample-sample (SS) 2D spectroscopy, have been employed to analyze the observed temperature-dependent spectral variations more efficiently. The SS 2D correlation analysis in the spectral range of 2700-1800 cm(-1) has demonstrated that a change in hydrogen bonds in the LC starts from 40 degrees C, which is not clarified by differential scanning calorimetry (DSC) and conventional IR and Raman spectroscopic analyses. On the other hand, the phase transition of LC revealed by SS 2D spectroscopy in the specific spectral regions of 1750-1650 and 3000-2700 cm(-1) is in a good agreement with that revealed by DSC for the heating process. The VV 2D correlation spectroscopy analysis has provided information about the structural variations of inter-molecular hydrogen bonds. The different species of hydrogen-bonded and free -COOH and -COO- groups in the LC have been clarified by the VV 2D correlation analysis. It has also elucidated the specific order of the temperature-induced structural changes in the intra- and inter-molecular hydrogen bonds concerning with the -COOH and/or -COO- groups in the LC.     

Application of two‐dimensional near‐infrared (2D‐NIR) correlation spectroscopy to the discrimination of three species of Dendrobium

The objective of this paper was to apply two‐dimensional (2D) near‐infrared (NIR) correlation spectroscopy to the discrimination of three species of Dendrobium. Generalized 2D‐NIR correlation spectroscopy was able to enhance spectral resolution, simplify the spectrum with overlapped bands and provide information about temperature‐induced spectral intensity variations that was hard to obtain from one‐dimensional NIR spectroscopy. The FT‐NIR spectra were measured over a temperature range of 30–140°C. The 2D synchronous and asynchronous spectra showed remarkable differences within the range of 5600–4750 cm⁻¹ between different species of Dendrobium. Copyright © 2009 John Wiley & Sons, Ltd.     

Application of two-dimensional near-infrared correlation spectroscopy to the discrimination of Chinese herbal medicine of different geographic regions

Fructus Lycii is a traditional Chinese medicinal herb. The objective of this paper was to apply two-dimensional (2D) near-infrared (NIR) correlation spectroscopy to the discrimination of Fructus Lycii of four different geographic regions. Generalized 2D-NIR correlation spectroscopy was able to enhance spectral resolution, simplify the spectrum with overlapped bands, and provide information about temperature-induced spectral intensity variations that was hard to obtain from one-dimensional NIR spectroscopy. The 2D synchronous and asynchronous spectra showed remarkable differences within the range of 4950-5700cm(-1) between samples of different geographic regions. Using NIR instead of IR made the 2D approach more convenient and fast, and it can be applied to more area like process control. This approach can also be applied analogously to the discrimination of other Chinese herbal medicine of different geographic regions.     

New background correction approach based on polynomial regressions for on-line liquid chromatography–Fourier transform infrared spectrometry

In the present study a new approach for the chemometric background correction in on-line gradient LC–FTIR is introduced. For this purpose, the spectral changes of the elution mixture during gradient elution were analyzed applying 2D correlation spectroscopy. The fundamentals of the new background correction algorithm, based on polynomial fits calculated from a reference spectra matrix (Polyfit-RSM method) are explained. The Polyfit-RSM approach was applied on blank gradient runs as well as on LC–FTIR data obtained from the injection of a soft drink sample using acetonitrile:water as eluent. Results found were critically assessed and compared to those obtained by two previous background correction methods which are likewise based on the use of a reference spectra matrix (RSM). The Polyfit-RSM method provided lower noise levels throughout the whole spectral range than other alternative background correction methods, an excellent recovery of analyte spectra as well as chromatograms with a low noise level and also free from baseline shifts. A significant finding, which implies a major advantage for the practical applicability of the algorithm, is that the size of the RSMs can be reduced without affecting the accuracy of the correction method.     

Two-dimensional fluorescence correlation spectroscopy II: spectral analysis of derivatives of anthracene and pyrene in micellar solutions

Generalized two-dimensional (2D) correlation spectroscopy has been applied to the analysis of fluorescence spectra in two micellar systems: (1) a mixture of pyrene and 1,3,6,8-pyrenetetrasulfonic acid in the cationic micellar solutions of cetyltrimethylammonium chloride (CTAC) and (2) a mixture of pyrene and 9-anthracencepropionic acid in anionic micellar solutions of sodium dodecyl sulfate (SDS). Fluorescence quenching is employed as a perturbation mode for causing intensity changes in fluorescence bands (quenching perturbation). Iodide ion (I-) is used as a quencher in the former system, and cetyl pridinium chloride (CPC) is used in the latter. Vibronic bands in the complicated fluorescence spectra of the mixture of the analytes were successfully resolved. It is shown that asynchronous maps are especially useful for spectral resolution enhancement when the quenching perturbation is employed in 2D fluorescence correlation spectroscopy. Furthermore, the information about the order of response of the bands to quenching is obtained by comparing the signs of synchronous and asynchronous cross-peaks.     

Spec2D: a structure elucidation system based on 1H NMR and H-H COSY spectra in organic chemistry

A system for structure elucidation based on proton NMR spectra has been developed. The system, named Spec2D (system for spectra from 2D-NMR), incorporates 1H NMR and H-H correlation spectroscopy (COSY) spectral information obtained from 2D-NMR experiments. 2D-NMR is important for the structure elucidation because it provides information about the relationships among differently situated protons in the structures of unknown compounds. The system uses the concepts of molecular graphs. The improved representation of substructures as well as several novel algorithms for structure generation have been devised to solve the combinatorial problem and to reduce the processing time. Spec2D consists of a knowledge base, an analysis module, and a candidate structure generator module. Spec2D proposes candidate structures from only 1H NMR and H-H COSY spectral information of an unknown compound without any 13C NMR spectral or structural information, such as molecular formulas. Spec2D has the capability to propose the "new" structure of an unknown compound, if the corresponding substructures are included in the knowledge base.