Quantitative Medium-Resolution NMR Spectroscopy Under Non-Equilibrium Conditions,Studied on the Example of an Esterification Reaction

Medium-resolution nuclear magnetic resonance spectroscopy is a promising tool for the monitoring of liquid reactions. For process analytical applications, the requirements of robustness and insensitivity of the spectrometer in relation to high temperatures and pressures are challenging. Within this study, a flow probe using a glass dewar is presented. Temperatures of flowing samples up to 130 °C and pressures up to 40 bar were successfully applied, and the corresponding temperature loss of the flowing sample at 2 ml min^?1 was <2.4 °C at 130 °C. Furthermore, if the process requires a measurement in a non-equilibrium state of magnetization, a comprehensive data treatment is given. For this purpose, the influences of the flow and T ₁ of the substances under investigation are studied in detail on the example of a homogeneously catalyzed esterification. In addition, data analysis schemes were designed such that the experiments directly revealed mole fractions from the spectra. Limited spectral resolutions and low signal-to-noise ratio still did not obstruct quantitative interpretation of the experiments.     

芯片级硅基光谱仪研究进展

光谱仪作为光谱分析不可或缺的工具,在生物传感、食药检测、医疗、环境监测等领域有着广泛的用途。传统的光谱仪体积大、功耗高、价格昂贵和难以二次开发,应用范围受到了极大地限制。随着微型加工工艺的发展,微型化的光谱仪逐渐出现。相较于传统的大型光谱仪,微型光谱仪不仅成本低、体积小、功耗低,而且便于二次开发,扩展了光谱仪的应用范围。但是,微型光谱仪通常是基于分立的光学器件,通过将光学器件的小型化而实现的,集成度和灵活性不高。随着对便携性的要求越来越高,光谱仪的进一步小型化和集成化已成趋势,出现了芯片级的光谱仪。芯片级光谱仪具有明显的尺寸、重量和功耗的优势,将对光谱仪在无人设备、智能平台等新兴领域中的应用产生重要影响。在芯片级光谱仪的实现过程中,硅基光子技术因其成熟的加工工艺和良好的集成性能,为光谱仪的芯片化提供了一种集成化、低成本的解决方案,国内外研究人员针对芯片级硅基光谱仪展开了大量的研究,取得了丰富的成果。文章分析了硅基片上光谱仪的工作原理,将目前的芯片级硅基光谱仪分成了色散型和傅里叶变换型两大类进行介绍,分析了这两类光谱仪的主要特点和典型实现方式。文中给出了刻蚀衍射光栅、波导阵列光栅、多模波导等色散型硅基片上光谱仪和空间外差、驻波式、热调、数字以及基于微机电系统的傅里叶变换型硅基片上光谱仪的最新研究进展,分析了各种光谱仪的性能特点和适用范围。在此基础上,展示了本组的最新研究成果,通过创造性地将基于马赫曾德尔干涉仪的空间外差傅里叶变换型光谱仪结构和波导阵列光栅的色散型光谱仪结构相结合,可同时实现较大的光谱范围和较高的光谱分辨率,为硅基片上光谱仪的应用打下了较好的基础。最后,论述了硅基片上光谱仪的发展趋势与应用前景,为芯片级硅基光谱仪的研究提供了参考。     

A REVIEW OF RECENT APPLICATIONS OF NEAR INFRARED SPECTROSCOPY,AND OF THE CHARACTERISTICS OF A NOVEL PbS CCD ARRAY-BASED NEAR-INFRARED SPECTROMETER

ABSTRACT

Near-infrared spectroscopy (NIRS) has been gaining popularity as an analytical tool due to advances in the power of personal computers, which allow the extraction of chemical and physical information about a sample, and the utilization of cost efficient and robust CCD array-based spectrometers. In this review, applications of NIRS are explored, within various fields of analytical chemistry, which take advantage of the inherent rapid analysis time and minimal sample preparation that is possible. For the purposes of illustration, the usefulness and limitations of a novel, PbS array-based spectrometer are described in the context of its application to the analysis of a variety of samples.     

Multipurpose High-Frequency ESR Spectrometer for Condensed Matter Research

We describe a multifrequency quasi-optical electron spin resonance (ESR) spectrometer operating in the 75–225 GHz range and optimized at 222.4 GHz for general use in condensed matter physics and chemistry. The quasi-optical bridge detects the change of millimeter wave polarization at the ESR condition. A controllable reference arm maintains a millimeter wave bias at the detector. The sensitivity of 2 × 10¹⁰ spin/(G Hz^0.5), measured on a dilute Mn:MgO sample in a non-resonant probe head at 222.4 GHz and 300 K, is comparable to that of commercial high-sensitive X-band spectrometers. The spectrometer is robust, easy to use and may be operated by undergraduate students. Its performance is demonstrated by examples from various fields of condensed matter physics.     

A Sensitive Isotope Selective Nondispersive Infrared Spectrometer for 13CO2 and 12CO2 Concentration Measurements in Breath Samples

We present a nondispersive infrared spectrometer (NDIRS) for the measurement of the ¹³CO₂/¹²CO₂-ratio in breath samples. A commercial NDIR spectrometer for CO₂ concentration measurements in industrial process control was modified using two separate optical channels for the ¹³CO₂ and ¹²CO₂ detection. Cross interference due to overlapping absorption lines of both isotopic gases was successfully eliminated. The sensitivity of this device is ± 0.4‰ of the ¹³CO₂/¹²CO₂-ratio in a range of 2.5 to 5% of total CO₂. This is sufficient for biomedical applications. Our spectrometer is small in size, cheap and simple to operate and thus a true alternative to isotope ratio mass spectrometers (IRMS). Several biomedical applications with breath samples were demonstrated and were compared in very good agreement with IRMS.     

基于支持向量机的模型传递方法研究

模型传递是以数学方法通过在2台不同仪器之间寻求一种变换关系来增强光谱仪数据通用性、可比性的一种基本途径。由于实际测量数据具有非线性特征,加上校正样本集合的有限性,使得解决小样本条件下非线性关系的模型传递问题显得尤为重要。文章在概述支持向量机基本原理的基础上,探讨了支持向量机方法在光谱仪的模型传递问题中的应用,提出了基于支持向量机的分段直接校正方法,最后采用计算机模拟的方式对该方法进行了举例说明,并和人工神经网络方法进行了相应的比较。     

X‐ray fluorescence analysis with a pyroelectric x‐ray generator

Several types of handy x‐ray fluorescence spectrometers are presented. The results obtained with a Niton spectrometer are presented as a goal to develop a laboratory‐made spectrometer using an Amptek Cool‐X pyroelectric x‐ray generator. A small and cheap charge‐up x‐ray emitting device and its spectrum are also presented. Handy x‐ray spectrometers are now progressing rapidly and the detection limits are in the range of a few ppm for certain elements. Copyright © 2005 John Wiley & Sons, Ltd.     

Ex vivo assessment of polyol coated-iron oxide nanoparticles for MRI diagnosis applications: toxicological and MRI contrast enhancement effects

Polyol synthesis is a promising method to obtain directly pharmaceutical grade colloidal dispersion of superparamagnetic iron oxide nanoparticles (SPIONs). Here, we study the biocompatibility and performance as T2-MRI contrast agents (CAs) of high quality magnetic colloidal dispersions (average hydrodynamic aggregate diameter of 16-27 nm) consisting of polyol-synthesized SPIONs (5 nm in mean particle size) coated with triethylene glycol (TEG) chains (TEG-SPIONs), which were subsequently functionalized to carboxyl-terminated meso-2-3-dimercaptosuccinic acid (DMSA) coated-iron oxide nanoparticles (DMSA-SPIONs). Standard MTT assays on HeLa, U87MG, and HepG2 cells revealed that colloidal dispersions of TEG-coated iron oxide nanoparticles did not induce any loss of cell viability after 3 days incubation with dose concentrations below 50 μg Fe/ml. However, after these nanoparticles were functionalized with DMSA molecules, an increase on their cytotoxicity was observed, so that particles bearing free terminal carboxyl groups on their surface were not cytotoxic only at low concentrations (<10 μg Fe/ml). Moreover, cell uptake assays on HeLa and U87MG and hemolysis tests have demonstrated that TEG-SPIONs and DMSA-SPIONs were well internalized by the cells and did not induce any adverse effect on the red blood cells at the tested concentrations. Finally, in vitro relaxivity measurements and post mortem MRI studies in mice indicated that both types of coated-iron oxide nanoparticles produced higher negative T2-MRI contrast enhancement than that measured for a similar commercial T2-MRI CAs consisting in dextran-coated ultra-small iron oxide nanoparticles (Ferumoxtran-10). In conclusion, the above attributes make both types of as synthesized coated-iron oxide nanoparticles, but especially DMSA-SPIONs, promising candidates as T2-MRI CAs for nanoparticle-enhanced MRI diagnosis applications.     

Optical system design of the Dyson imaging spectrometer based on the Fery prism

Imaging spectrometer has obtained wide development since rich feature information can be obtained by it; now, we focus on its high spectral resolution and miniaturization. In this paper, we design the Dyson imaging spectrometer system based on Fery prism. The average spectral resolution is 4.3 nm and the structure of the total length is 229 mm. It is a small, high-spectrometer imaging system. The front and rear surface of the traditional prism are plane, but the surfaces of the Fery prism are spherical, which can provide some optical power to realize imaging function and produce the dispersion effect. The Fery prism does not need to be placed in the parallel optical path, which simplifies the collimator lens and the imaging lens and are necessary in the prism spectrometer, making it possible to obtain a compact spectrometer. Full-spectrum transmittance of the prism is up to 94 %. Compared to the convex grating, the energy efficiency is greatly improved, and the free spectral range is wider, and its dispersion will not bring higher-order spectral aliasing problem. The small high spectrometer only includes two components. Its spectral range is from 400 to 1000 nm, covering the near-ultraviolet to near-infrared. The various aberrations of the typical spectrum are corrected. The spectrometer is excellent in performance.     

Comparison of two confocal micro‐XRF spectrometers with different design aspects

Two different confocal micro X‐ray fluorescence spectrometers have been developed and installed at Osaka City University and the Vienna University of Technology Atominstitut. The Osaka City University system is a high resolution spectrometer operating in air. The Vienna University of Technology Atominstitut spectrometer has a lower spatial resolution but is optimized for light element detection and operates under vacuum condition. The performance of both spectrometers was compared. In order to characterize the spatial resolution, a set of nine specially prepared single element thin film reference samples (500 nm in thickness, Al, Ti, Cr, Fe Ni, Cu, Zr, Mo, and Au) was used. Lower limits of detection were determined using the National Institute of Standards and Technology standard reference material glass standard 1412. A paint layer sample (cultural heritage application) and paint on automotive steel samples were analyzed with both instruments. The depth profile information was acquired by scanning the sample perpendicular to the surface. © 2013 The Authors. X‐Ray Spectrometry published by John Wiley & Sons, Ltd.     

结合SNV的分段直接标准化方法在拉曼光谱模型传递中的应用

为了实现拉曼光谱在不同仪器上的模型传递,文章提出了一种改进的分段直接标准化算法.该方法先利用标准正态变换法对光谱数据进行处理,以减少源机与目标机之间的光谱背景与强度影响,再采用分段直接标准化算法消除不同仪器间对样本信息反应差异,实现拉曼光谱的全谱传递.此外,还提出了传递误差率指标用于对光谱传递效果的定量评价.针对汽油拉...     

A Fourier transform Raman spectrometer with visible laser excitation

We present the development and performance of a Fourier transformation (FT)‐based Raman spectrometer working with visible laser (532 nm) excitation. It is generally thought that FT‐Raman spectrometers are not viable in the visible range where shot noise limits the detector performance and therein they are outperformed by grating based, dispersive ones. We show that contrary to this common belief, the recent advances of high‐performance interference filters makes the FT‐Raman design a valid alternative to dispersive Raman spectrometers for samples which do not luminesce. We critically compare the performance of our spectrometer to two dispersive ones: a home‐built single channel and a state‐of‐the‐art charge coupled device‐based instruments. We demonstrate a similar or even better sensitivity than the charge coupled device‐based dispersive spectrometer particularly when the laser power density is considered. The instrument possesses all the known advantages of the FT principle of spectral accuracy, high throughput, and economic design. We also discuss the general considerations, which helps the community reassess the utility of the different Raman spectrometer designs. Copyright © 2015 John Wiley & Sons, Ltd.     

Double-beam fourier spectroscopy with two inputs and two outputs

A theoretical treatment of double-beam Fourier spectroscopy, with two inputs and two outputs measured by a single detector, is presented. One of the novel features is the use of the radiation that returns to the source in a conventional Fourier spectrometer, i.e., the anti-interferogram beam. The double beam feature allows simultaneous measurement of the difference in the spectra of the sample and a reference standard with optical cancellation of common features. Several versions of spectrometers suited for specific applications are discussed as special cases. Applications include the ability to measure small absorptivity or reflectivity against strong and varying background, to compare the emission spectra of two nearly equal sources, or the sensitivity of two different detectors. Moreover, by suitably chopping the input or output beams, the noise due to fluctuations in source intensity may be strongly reduced.     

计算层析成像光谱技术研究进展

从技术特点和研究热点的角度,综述了近些年来计算层析成像光谱技术的国内外进展,主要包括计算层析成像光谱仪的系统结构改进及与其他技术联用的新集成设计,新器件新设备的研发和应用,仪器定标技术和目标重建算法的优化与改进等;并按照应用范围的特点进行了分类,对在探测波段扩展和应用领域拓展等方面的应用现状进行了总结.介绍了光栅型和旋转棱镜型计算层析成像光谱技术的原理,并展望了计算层析成像光谱技术的发展趋势.     

Microbolometer imaging spectrometer

Newly developed, high-performance, long-wave- and mid-wave-IR Dyson spectrometers offer a compact, low-distortion, broadband, imaging spectrometer design. The design is further accentuated when coupled to microbolometer array technology. This novel coupling allows radiometric and spectral measurements of high-temperature targets. It also serves to be unique since it allows for the system to be aligned warm. This eliminates the need for cryogenic temperature cycling. Proof of concept results are shown for a spectrometer with a 7.5 to 12.0 μm spectral range and approximately 20 nm per spectral band (~200 bands). Results presented in this Letter show performance for remote hot targets (>200 °C) using an engineering grade spectrometer and IR commercial lens assembly.     

基于线阵CCD的小型光谱仪光度特性研究

基于线阵电荷耦合器件（CCD）的小型光谱仪具有便于携带和快速探测的优点，故特别适于现场检测应用。介绍一种自行研制的小型光栅光谱仪，它采用Czerny-Turner式光学结构，并用线阵CCD作为探测器。该光谱仪光度特性的实验检测结果证明：实验样机的光度精密度优于±0.04Abs，光度准确度为±0.04Abs（0Abs～1Abs）。实验分析了光谱仪的杂散光、光度噪声和基线平直度等指标对仪器光度准确度的影响。最后针对小型光谱仪的特点提出改善其光度特性的措施。     

In situ detection of cocaine hydrochloride in clothing impregnated with the drug using benchtop and portable Raman spectroscopy

This study describes the application of benchtop and portable Raman spectroscopy for the in situ detection of cocaine hydrochloride in clothing impregnated with the drug. Raman spectra were obtained from a set of undyed natural and synthetic fibres and dyed textiles impregnated with the drug. The spectra were collected using three Raman spectrometers: one benchtop dispersive spectrometer coupled to a fibre‐optic probe and two portable spectrometers. Despite the presence of some spectral bands arising from the natural and synthetic polymer and dyed textiles, the drug could be identified by its characteristic Raman bands. High‐quality spectra of the drug could be acquired in situ within seconds and without any sample preparation or alteration of the evidential material. A field‐portable Raman spectrometer is a reliable technique that can be used by emergency response teams to rapidly identify unknown samples. Copyright © 2009 John Wiley & Sons, Ltd.     

便携式拉曼光谱仪用于合成大麻素类物质快速定性分析探究

我国于2021年7月将合成大麻素类物质整类列入管制,在一线查缉现场对疑似合成大麻素样品进行快速定性分析是办案民警的迫切需求。研究系统考察了拉曼光谱对合成大麻素的整体区分能力,比较了四款手持式拉曼光谱仪分析实际缴获样品时的结果差异,探讨了制约拉曼光谱在一线查缉现场广泛应用的原因。ProTT-EZRaman-A7便携式拉曼光谱仪的整体性能介于台式拉曼和手持式拉曼之间,选用该仪器采集了90种合成大麻素对照品的拉曼光谱,并利用兼容性强的KnowItAll软件建立了90种合成大麻素通用拉曼光谱库。分析90种合成大麻素的拉曼光谱,结果表明,当不存在荧光干扰时,拉曼光谱可以区分所有合成大麻素物质,但对部分结构相差一个甲基、卤素原子等的结构类似物区分度欠佳。不同款拉曼光谱仪的性能差异大,为考察其原因,本研究选用了四款手持式拉曼光谱仪分别对120份实际缴获合成大麻素样品进行了测定,随后使用KnowItAll软件并选用包含90种合成大麻素的通用拉曼光谱库对每张光谱图进行谱库检索。四款手持式拉曼光谱仪的正确匹配率分别为71.7%, 68.3%, 46.7%和24.2%。抗荧光干扰能力和分辨率的不同是造成不同...     

Stable isotope deltas: tiny,yet robust signatures in nature

Although most of them are relatively small, stable isotope deltas of naturally occurring substances are robust and enable workers in anthropology, atmospheric sciences, biology, chemistry, environmental sciences, food and drug authentication, forensic science, geochemistry, geology, oceanography, and paleoclimatology to study a variety of topics. Two fundamental processes explain the stable isotope deltas measured in most terrestrial systems: isotopic fractionation and isotope mixing. Isotopic fractionation is the result of equilibrium or kinetic physicochemical processes that fractionate isotopes because of small differences in physical or chemical properties of molecular species having different isotopes. It is shown that the mixing of radioactive and stable isotope end members can be modelled to provide information on many natural processes, including ¹⁴C abundances in the modern atmosphere and the stable hydrogen and oxygen isotopic compositions of the oceans during glacial and interglacial times. The calculation of mixing fractions using isotope balance equations with isotope deltas can be substantially in error when substances with high concentrations of heavy isotopes (e.g. ¹³C, ²H, and ¹⁸O ) are mixed. In such cases, calculations using mole fractions are preferred as they produce accurate mixing fractions. Isotope deltas are dimensionless quantities. In the International System of Units (SI), these quantities have the unit 1 and the usual list of prefixes is not applicable. To overcome traditional limitations with expressing orders of magnitude differences in isotope deltas, we propose the term urey (symbol Ur), after Harold C. Urey, for the unit 1. In such a manner, an isotope delta value expressed traditionally as?25 per mil can be written as?25 mUr (or?2.5 cUr or?0.25 dUr; the use of any SI prefix is possible). Likewise, very small isotopic differences often expressed in per meg ‘units’ are easily included (e.g. either+0.015 ‰ or+15 per meg can be written as+15 μUr.     

Perturbed Angular Correlation of the stretched cascade in the decay of 180mHf using a digital spectrometer

We report on the measurement of the nuclear quadrupole interaction (NQI) at Hf sites using the nuclear probe ^180mHf in HfF₄·HF·2H₂O at 300 K by exploiting all possible start quanta in the stretched cascade with a digital Time Differential Perturbed Angular Correlation (TDPAC) spectrometer. With conventional spectrometers, multiple prompt start signals would paralyze the router. The gain in coincidence rate is about a factor of 5 compared to a conventional spectrometer using a single start only. With multiple starts ^180mHf is a promising new isomeric nuclear probe in TDPAC experiments. As an additional feature we implemented the possibility to measure up to four cascades simultaneously in order to save data collection time or to measure isobaric contaminations like ^111mCd and ¹¹¹In.