双傅氏变换核磁共振波谱学

二维NMR波谱是近十年来核磁共振领域内的重要新发展之一。本文综述了实现二维谱的五种可能性。给出双傅氏变换核磁共振谱的基本原理及实验的一般方法。讨论了这类谱的两个主要分支即:二维分谱解及二维相关谱。     

Near-Infrared Spectroscopy: Effective Tool for Screening of Polymorphs in Pharmaceuticals

Abstract

Near-infrared (NIR) spectroscopy has emerged as an important technique for the screening and characterization of polymorphs in pharmaceuticals. Polymorphism, the ability of a substance to exist in two or more crystalline phases having different physicochemical and biopharmaceutical parameters, has attracted pharmaceutical scientists due to the patentability of new forms. Transformation of the solid phase due to polymorphic changes during manufacturing and storage may lead to formulation hurdles. Vibrational spectroscopy, particularly NIR spectroscopy, is a widely used technique for polymorphs screening in drug development processes and has emerged as a process analytical technology tool. In this review, a brief overview of NIR spectroscopy, chemometric tools, and polymorphs screening of pharmaceuticals using NIR spectroscopy is presented. Recent developments in NIR spectroscopy instrumentation are also discussed.     

激光稳频中的高灵敏度光谱技术

高灵敏度谱分析技术是激光稳频系统的关键。通过系统的理论分析,结合国内外研究的稳频系统,详尽介绍了导数谱和ＦＭ 光谱激光稳频技术,并对其进行了分析、比较。两者的根本区别在于ＦＭ 光谱技术具有相对较大的调制频率,这是它们在应用中各具特点的根源：ＦＭ 光谱技术具有更高的灵敏度和噪声抑制能力,可以探测到０－００５ ％ 的微小吸收,而导数谱技术对未知的超精细谱线结构具有较好的兼容性。     

时间分辨偏振红外光谱及其应用

时间分辨偏振红外光谱已被广泛应用于研究光化学过程中的分子结构动力学. 通过测定瞬态物质跃迁偶极矩之间的角度等结构信息,可以提供光化学过程中伴随的电荷分布、分子结构和构象变化等动态信息. 包括简要介绍时间分辨偏振红外光谱技术的原理和应用：(i) 时间分辨偏振红外光谱概述;(ii) 时间分辨偏振红外光谱的原理及其优势;(iii) 利用时间分辨偏振红外光谱探测多种化学动力学过程,例如蛋白质构象动力学、激发态的电子局域化和光致异构化等;(iv) 时间分辨偏振红外光谱的局限和发展前景.     

Applications of Raman spectroscopy in herbal medicine

Raman spectroscopic techniques are a group of chemical fingerprint detection methods based on molecular vibrational spectroscopy. They are compatible with aqueous solutions and are time saving, nondestructive, and highly informative. With complementary and alternative medicine (CAM) becoming increasingly popular, more people are consuming natural herbal medicines. Thus, chemical fingerprints of herbal medicines are investigated to determine the content of these products. In this study, I review the different types of Raman spectroscopic techniques used in fingerprinting herbal medicines, including dispersive Raman spectroscopy, resonance Raman spectroscopy, Fourier transform (FT)–Raman spectroscopy, surface-enhanced Raman scattering (SERS) spectroscopy, and confocal/microscopic Raman spectroscopy. Lab-grade Raman spectroscopy instruments help detect the chemical components of herbal medicines effectively and accurately without the need for complicated separation and extraction procedures. In addition, portable Raman spectroscopy instruments could be used to monitor the health and safety compliance of herbal products in the consumer market.     

二维傅里叶变换光谱实验方法简介

二维傅里叶变换光谱是近几十年来发展起来的一种先进光谱技术. 与其他超快光谱方法相比,它具有许多优点,并且为研究各种复杂系统提供了巨大的机会. 然而,二维傅里叶变换光谱的系统搭建、实验测量和理论描述仍面临许多挑战,从而限制了其广泛应用. 近年来,随着超快激光等各种相关技术的发展和革新,二维傅里叶变换光谱方法也逐渐发展成熟,进而大大降低了进行二维傅里叶变换光谱实验的技术壁垒. 对于二维傅里叶变换光谱实验装置的光学设计,目前存在许多不同的方法,每种方法都有其自身的优点和局限性. 但是目前还没有一个简单的教程可以帮助实验工作者选择搭建其第一套二维傅里叶变换光谱实验装置. 因此,本文旨在为计划搭建其第一套二维傅里叶变换光谱实验装置的初学者提供一个简短的介绍.     

Structure, phase composition, and optical properties of silicon nanopowders

The nanopowders obtained by sputtering of silicon with a high-power electron beam in nitrogen and argon atmospheres have been investigated by transmission electron microscopy, Raman spectroscopy, photoluminescence spectroscopy, ultrasoft X-ray emission spectroscopy, and X-ray absorption near-edge structure spectroscopy. The sizes of particles and their phase composition have been determined. A mechanism is proposed, which explains the visible photoluminescence of nanopowders.     

Doppler spectroscopy of zero-phonon lines

Narrow profiles of purely electronic zero-phonon lines open up attractive possibilities for spectral investigation with the use of the Doppler effect (Doppler spectroscopy). It is established that, for a 10-MHz-wide zero-phonon line to shift to a new position, the velocity of motion of a receiver with respect to a source needs to be only ～10 m/s. It is shown that the narrower the line or the spectral hole (its negative image), the more efficient the Doppler spectroscopy. The possibility of measuring the shape of spectral holes with the use of Doppler spectroscopy is demonstrated, and the potentialities of supersensitive Doppler spectroscopy are considered. The specific feature revealed in the frequency modulation by Doppler spectroscopy is that it occurs without a perturbation of the internal states of the emitter and absorber. The conclusion is drawn that there is a need to study the interference of a photon with itself when the frequency of “one-half of it” changes with the use of Doppler spectroscopy.     

Spectroscopy on a modulated magneto-optical trap

We demonstrate a new type of high-resolution two-photon frequency modulation (FM) spectroscopy with cold atoms in a magneto-optical trap. Instead of modulating the probe as in ordinary FM spectroscopy, we modulate the trap itself by FM of the trapping beams. We present theoretical as well as experimental results for both absorption and polarization rotation spectroscopy. Finally, we demonstrate two-photon FM spectroscopy, using the intrinsic phase noise of the trapping diode lasers.     

Elements of Mechanics,by P.F. Kelly

Applications of optogalvanic spectroscopy developed since the resurgence of interest in optogalvanic detection are reviewed. The optogalvanic effect is a change in the electrical properties of a discharge caused by illuminating the discharge with radiation having a wavelength corresponding to an atomic or molecular transition in the discharge. The general scheme of optogalvanic spectroscopy is presented, followed by a discussion of the gas discharge physics of the optogalvanic effect. Applications of optogalvanic detection in moderate resolution spectroscopy, in Doppler-free spectroscopy, and in analytic studies are discussed.     

光声光谱气体传感技术研究进展

光声光谱是通过光声效应把样品吸收光谱转换成声波探测,实现样品成分、浓度分析检测的一种光谱传感技术,是光谱学的一个重要分支。光声光谱除了具有吸收光谱的高选择性、高灵敏度外,还具有信号只跟样品光吸收有关,不受散射光影响,零背景, 信号与光功率成正比以及信号探测器不受光波长影响等诸多优点。在环境监测、工业过程控制与检测、医学诊断和国防危化品检测等领域得到了越来越多的应用,呈现出快速发展的趋势。除了传统的共振光声光谱技术,近年来先后出现了悬臂增强型光声光谱、石英音叉谐振增强型光声光谱、多通道光声光谱等各具特色的新技术。对光声光谱气体传感技术的研究进展进行了介绍,并分析了其应用前景和未来发展趋势。     

New developments in nuclear magnetic resonance using noise spectroscopy

In the 30 years since Ernst and Kaiser introduced the idea of incoherent radiation fields and their application to NMR spectroscopy, relatively few researchers have exploited the advantages of noise spectroscopy. Some recent applications of one-dimensional noise spectroscopy in NMR are presented which display a versatility which commonly is not appreciated. Excitation schemes are discussed which demonstrate both broadband and narrowband features, and demonstrate both theoretically and experimentally how noise spectroscopy allows for the observation of distortion-free broadline spectra in solids whichmay not be amenable to techniques more traditionally used in pulsed NMR experiments. It is argued that these applications of noise spectroscopy deserve a more common place in the experimentalists arsenal.     

Technical Development of Raman Spectroscopy: From Instrumental to Advanced Combined Technologies

Abstract

Raman-based techniques have developed into excellent analytical tools in various research fields, primarily due to their noninvasive sampling capability, minimal sample preparation, and short analysis time. Major improvements in lasers, spectrometers, detectors, and holographic optical components have made Raman spectroscopy an effective tool for analyzing natural and synthetic materials. This article presents a short introduction to Raman spectroscopy and several recently related advances, including, Fourier transform (FT) Raman spectroscopy, micro-Raman spectroscopy, Raman sensing, and stand-off Raman spectroscopy techniques. Other topics discussed in this article are the importance of its combination with laser-induced breakdown spectroscopy (LIBS) and laser-induced fluorescence (LIF).     

Vibrational Spectroscopy of Phenols and Phenolic Polymers. Theory,Experiment, and Applications

In the first part of this review, the authors give a survey on the literature of vibrational spectroscopy of phenol, phenol derivatives, and other phenolic componds from the last decade of the last century through today. The classical and modern methods of vibrational spectroscopy are also introduced and a glossary is included to aid comprehension. The second part deals with the literature regarding the importance of vibrational spectroscopy in the investigation and identification of phenolic compounds in natural substances, the application of vibrational spectroscopy in composite and synthetic polymer chemistry, and following of chemical processes and investigating their resulting products. Vibrational spectroscopy is a very good tool for determination of molecular structures and is important in chemical analysis and in the chemical industry.     

Experimental comparison of two Doppler-free detection methods with a new technique: Differential saturation spectroscopy

Some Doppler-free detection techniques for the detection of small quantities of radioisotopes in the gas phase were tested. The techniques were applied to ²³Na (100%) at a density of (5.54 ± 0.05) x 10¹⁴ m^-3. For the same experimental condition of the sample the signal to noise ratio for saturation spectroscopy, FM spectroscopy and a new technique — differential saturation spectroscopy — were in the proportion 1 to 2.5 to 1.7. So the signal to noise ratio for saturation spectroscopy can be increased by the application of differential saturation spectroscopy but the best sensitivity is obtained for FM spectroscopy.     

Synthesis of germanium encapsulated fullerene

A method has been described for encapsulating Ge in a fullerene cage using GeO₂ and a graphite composite rod as anode and graphite as cathode. Annealing in an inert atmosphere before arcing, and the amount of GeO₂ in the rod determined the yield of Ge doped metallofullerene. Solvent extraction using soxlet in inert atmosphere followed by calcination in air was used to isolate metallofullerene from the soot. The insertion of Ge inside the fullerene was proven by ultra violet–visible absorption spectroscopy, matrix assisted laser desorption ionization-time of flight mass spectroscopy, Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy.     

一种实现光声光谱的导数光谱的新方法

提出了一种实现光声光谱的导数光谱的新方法,为了获得光声光谱的导数光谱,利用一台单色仪和一个分光棱镜研制成一个波长-光强分束器,并用这个波长-光强分束器同时获得两束光强相等而波长有微小差别的两束光,这两束光经过一个互补调制器调制后在光声探测器内叠加,可以实现光声信号的差分,扫描单色仪的波长,就可以获得光声吸收光谱的导数光谱。实验证明这种方法可以准确实现光声光谱的一阶导数光谱,而且导数光声光谱比光声吸收光谱具有更高的光谱分辨率。     

Spectroscopic techniques for the forensic analysis of textile fibers

A review has been conducted on the application of the spectroscopic techniques to the comparative study and identification of different textile fibers. Microspectrophotometry in the ultraviolet-visible range and Raman spectroscopy are the main techniques investigated with this aim in the forensic field. UV-Vis MSP is the first recommended technique, which is principally used to study the color of the fibers. A more complete approximation focused on determining the specific color of the fibers providing adding Raman spectroscopy to the analytical scheme. Sometimes, it also provided information about the polymeric nature of the fibers. Regarding FTIR spectroscopy, it is the recommended tool to determine the fiber nature. Raman and FTIR spectroscopy are complementary techniques and a frequent recommendation is a combination of both techniques, in order to get a comprehensive analysis of textile fibers. On the other hand, new and more informative analytical techniques are emerging to the analysis of textile fibers as traces related with criminal contacts, such as infrared chemical imaging spectroscopy and X-ray fluorescence spectroscopy.     

Laser spectroscopy : 1. Principal problems

Laser spectroscopy has made it possible to solve, or at least to begin solving, a number of important problems to which classical spectroscopy could not be applied. These problems are defined in this, the first in a series of articles reviewing the subject of laser spectroscopy. This is followed by an outline of the present status of tunable lasers — the basic instruments used in developing the techniques of laser spectroscopy.     

Laser induced breakdown spectroscopy for multielement analysis of powdered materials used in additive technologies

Additive manufacturing technologies utilizing metal parts production with layer by layer printing are of high demand for different fields of science and technology. Analytical chemistry is challenged to provide multielemental quantitative analysis of any metal powders within a few minutes and onsite to fulfil the requirements for high quality metal parts production. Powder materials utilized in additive technologies were quantitatively analyzed by laser induced breakdown spectroscopy for the first time. Laser induced breakdown spectroscopy mapping of loose metal powder attached to the double-sided adhesive tape provided high reproducibility of measurements even for powder mixtures with large difference of particles densities (tungsten carbide particles in nickel alloy powder). Laser induced breakdown spectroscopy analytical capabilities were estimated for tungsten and carbon analysis by calibration curve construction and accuracy estimation by leave-one-out cross-validation procedure. Laser induced breakdown spectroscopy and X-ray fluorescence spectroscopy techniques comparison revealed better results for laser induced breakdown spectroscopy analysis. Improved accuracy of analysis and capability to quantify light elements (carbon, etc.) demonstrated the potential of laser induced breakdown spectroscopy as a promising technique for express onsite multielement analysis of powder materials utilized in additive technologies.