Quantitative characterisation of historic paper using THz spectroscopy and multivariate data analysis

THz spectroscopy in the time domain was explored in combination with multivariate data analysis, for quantitative determination of chemical and mechanical properties of historic paper, such as lignin content, tensile strength, and ash content. Using partial least squares (PLS) regression, it was shown that quantitative prediction of the material properties is possible, which indicates the potential of THz spectroscopy for chemical characterisation of complex organic materials of natural origin. In addition, the results demonstrate that THz spectra and PLS loading weights for lignin content differ significantly, which leads to the conclusion that THz spectra of composite macromolecular materials do not represent sums of spectra of the individual components. This supports the premise that THz spectra reflect intermolecular interactions. The study was carried out using 250 historical paper samples from the sixteenth century to present. Although the measurements were performed in vacuum to improve the quality of spectra, THz spectroscopy is in principle non-destructive. This research therefore reinforces the role of THz spectroscopy in characterisation of valuable historic materials, where invasive analysis is often not possible.     

基于多尺度加权主成分分析的SF6红外光谱分析

利用红外光谱法分析SF6气体及其衍生物是判断气体绝缘组合电器(GIS)运行状态和故障的一种重要手段。传统的诊断方法过程繁琐、效率低下,而且受主观因素的影响较大。本文指出可以采用机器学习的方法实现GIS设备的故障诊断,并提出了多尺度加权主成分分析的特征提取方法。多尺度加权主成分分析结合了主成分分析和多尺度分解的特点,保证了尺度特征信息的最大化,并且修正了特征向量在数据分类时的权重。通过对广西电力研究院提供的SF6及其衍生物的红外光谱进行分析,证明了多尺度加权主成分分析算法对训练样本的分类效果要比标准的主成分分析算法好3～4倍。     

Approximate chemical analysis of volcanic glasses using Raman spectroscopy

The effect of chemical composition on the Raman spectra of a series of natural calcalkaline silicate glasses has been quantified by performing electron microprobe analyses and obtaining Raman spectra on glassy filaments (~450 µm) derived from a magma mingling experiment. The results provide a robust compositionally‐dependent database for the Raman spectra of natural silicate glasses along the calcalkaline series. An empirical model based on both the acquired Raman spectra and an ideal mixing equation between calcalkaline basaltic and rhyolitic end‐members is constructed enabling the estimation of the chemical composition and degree of polymerization of silicate glasses using Raman spectra. The model is relatively insensitive to acquisition conditions and has been validated using the MPI‐DING geochemical standard glasses 1 as well as further samples. The methods and model developed here offer several advantages compared with other analytical and spectroscopic methods such as infrared spectroscopy, X‐ray fluorescence spectroscopy, electron and ion microprobe analyses, inasmuch as Raman spectroscopy can be performed with a high spatial resolution (1 µm²) without the need for any sample preparation as a nondestructive technique. This study represents an advance in efforts to provide the first database of Raman spectra for natural silicate glasses and yields a new approach for the treatment of Raman spectra, which allows us to extract approximate information about the chemical composition of natural silicate glasses using Raman spectroscopy. We anticipate its application in handheld in situ terrestrial field studies of silicate glasses under extreme conditions (e.g. extraterrestrial and submarine environments). © 2015 The Authors Journal of Raman Spectroscopy Published by John Wiley & Sons Ltd     

Practical method to estimate the standard deviation in absorption coefficients measured with THz time-domain spectroscopy

A model of standard deviation in the intensity spectrum of electric field observed with the terahertz time-domain spectroscopy (THz-TDS) is proposed to estimate the random error in the transmittance and absorption coefficients from a single or a few measurements of a sample. The proposed standard deviation which is derived on the basis of the statistical standard deviation and noise floor of intensity spectrum of reference fits well to the standard deviation of transmittance as well as absorption coefficient computed statistically. This study contributes the simple and computationally efficient method to demonstrate the accuracy in optical constants like imaginary part of refractive index and absorption coefficients measured using the THz-TDS.     

Detection and quantification of multiple molecular species in mainstream cigarette smoke by continuous-wave terahertz spectroscopy

Continuous-wave terahertz spectroscopy by photomixing is applied to the analysis of mainstream cigarette smoke. Using the wide tunability of the source, spectral signatures of hydrogen cyanide (HCN), carbon monoxide (CO), formaldehyde (H2CO), and water (H2O) have been observed from 500 to 2400 GHz. The fine spectral purity allows direct concentration measurement from the pure rotational transitions of HCN and CO. The quantification of the measurement was validated by the means of a calibration gas containing CO. The potential of this technique for trace gas detection is demonstrated with an estimated detection limit of HCN equal to 9 parts in 10(6).     

Direct-comb molecular spectroscopy with accurate, resolved comb teeth over 43 THz

We demonstrate a dual-comb spectrometer using stabilized frequency combs spanning 177 to 220 THz (1360 to 1690 nm) in the near infrared. Comb-tooth-resolved measurements of amplitude and phase generate over 4×10(5) individually resolved spectral elements at 100 MHz point spacing and kilohertz-level resolution and accuracy. The signal-to-noise ratio is 100 to 3000 per comb tooth. Doppler-broadened phase and amplitude spectra of CO(2), CH(4), C(2)H(2), and H(2)O in a 30 m multipass cell agree with established spectral parameters, achieving high-resolution measurements with optical bandwidth generally associated with blackbody sources.     

Chemical analysis of surgical smoke by infrared laser spectroscopy

The chemical composition of surgical smoke, a gaseous by-product of some surgical devices??lasers, drills, vessel sealing devices??is of great interest due to the many toxic components that have been found to date. For the first time, surgical smoke samples collected during routine keyhole surgery were analyzed with infrared laser spectroscopy. Traces (ppm range) of methane, ethane, ethylene, carbon monoxide and sevoflurane were detected in the samples which consisted mostly of carbon dioxide and water vapor. Except for the anaesthetic sevoflurane, none of the compounds were present at dangerous concentrations. Negative effects on the health of operation room personnel can be excluded for many toxic compounds found in earlier studies, since their concentrations are below recommended exposure limits.     

Quantitative analysis of surface amine groups on plasma-polymerized ethylenediamine films using UV-visible spectroscopy compared to chemical derivatization with FT-IR spectroscopy, XPS and TOF-SIMS

A quantitative analysis of the surface density of amine groups on a plasma-polymerized ethylenediamine thin film deposited on a platinum surface using inductively coupled plasma chemical vapor deposition method is described. UV-visible spectroscopy together with a chemical derivatization technique using Fourier transform infrared (FT-IR) spectroscopy was used to obtain the quantitative information. Chemical tags of pentafluorobenzaldehyde were hybridized with the surface amine groups and were easily detected due to the characteristic absorption bands of C-F stretching, aromatic ring and CN stretching vibrations in the reflection-absorption FT-IR spectra. The surface amine density was reproducibly controlled as a function of deposition plasma power and quantified using UV-visible spectroscopy. A good linear correlation was observed between the FT-IR intensities of the characteristic absorption bands and the surface amine densities, suggesting the possibility of using this chemical derivatization technique to quantify the surface densities of specific functional groups on an organic surface. Chemical derivatization was also used with X-ray photoelectron spectroscopy on the same samples, and the results were compared with those obtained from FT-IR and time-of-flight secondary ion mass spectrometry. Although each analysis technique has different probing depths from the surface, the three different data sets obtained from the chemical tags correlated well with each other since each analysis technique measured the chemical tags on the sample surface.     

Application of electron spectroscopy to chemical analysis

The capacity of the electron spectroscopic method for performing qualitative and quantitative analyses of the elements in chemical compounds is demonstrated. Applications are made to elements of low atomic number, such as carbon and oxygen.     

Analysis of explosives using chemical ionization mass spectroscopy

Methane chemical ionization (MeCI) mass spectra of several explosives, including nitrate esters, nitramines, nitroaromatics, and stabilizers, are presented. The predominance of the pseudomolecular ion (M+H)⁺ greatly facilitates identification of these temperature-sensitive compounds. Structural effects and mechanistic pathways rationalizing formation of the major ions are included. Gas chromatographic (GC) separation of selected explosive formulations are shown. GC chemical ionization mass spectra response factors for ethylene glycol dinitrate, nitroglycerin, 2,4-dinitrotoluene, and 2,4,6-trinitrotoluene show nanogram sensitivity of this technique.     

Multiple frequency stabilization of lasers using double saturation spectroscopy

We have developed a method of stabilizing multiple lasers based on double saturation spectroscopy. Compared with other laser-stabilization methods based on conventional saturation spectroscopy, ours provides numerous reference spectra constructed with several velocity groups of atoms. Two independent laser sources can be simultaneously stabilized by using combined optical-pumping processes associated with a single Rb reference. We analyzed the stability of the feedback loop taking the correlation effect of the saturation spectra into consideration. We experimentally demonstrated two stabilized laser sources with a frequency difference of 6,109 MHz in the ⁸⁷Rb D₂ line. The results were in good agreement with theory within errors in measurement.     

荧光探针检测香烟主流烟雾活性氧的机理研究

不具有荧光的探针双氢罗丹明6G被氧化后可以生成具有荧光特性的罗丹明6G。反应中,一个双氢罗丹明分子能够与2个活性氧发生作用。借助衍生荧光检测技术,可以将该探针用于香烟主流烟雾活性氧含量的检测实验。利用探针在该实验条件下检测市场上4种品牌香烟的主流烟雾中活性氧的含量,含量分别为：(59.93±5.32)nmol,(55.98±6.17)nmol,(54.78±7.82)nmol,(40.87±6.43)nmol。实验结果表明,香烟主流烟雾中活性氧的含量与烟草品种及制作工艺存在密切的联系。借助荧光特性进行主流烟雾活性氧含量近实时检测的方法具有灵敏度高与检测速度快的特点。     

Phase identification of microfeatures using EPMA methods,especially high-resolution X-ray spectroscopy

Methods of electron-probe microanalysis (EPMA), with some input from scanning and transmission electron microscopy (SEM/TEM), are applied for the identification of micro-scale constituents in a solid matrix. The subject of the study is a magnesium alloy composite, which contains silicon carbide-based fibres made by a liquid metal infiltration process. Backscattered electron imaging of the composite in the SEM showed that during composite manufacture, fibres were chemically attacked by the metal, many of the fibres exhibiting three distinct grey levels, indicative of different reaction zones, and others appearing uniformly black. EPMA measurements showed that each region contained ∼12 wt.% oxygen and that penetration of the fibre by magnesium was accompanied by a reduction in the concentration of silicon and carbon. From studying the position and shape of specific X-ray lines it was shown that magnesium penetration involved a chemical reaction with silicon oxycarbide, established in earlier EPMA studies as one of the fibre constituents. Also, in the outermost region, aluminium in the alloy reacted with free carbon in the fibre to form aluminium carbide and with magnesium to produce a Mg–Al intermetallic. The composition of black fibres was quite different from the grey ones, with negligible silicon and only a small amount of aluminium. Oxygen levels in black fibres were consistent with complete oxidation, indicating these fibres were subjected, locally, to severe oxidising conditions during composite manufacture. In the metal matrix itself, particles of a mixed magnesium/aluminium oxide, silicon carbide and magnesium silicide were observed, the latter two phases forming as silicon and carbon were ejected from fibres.     

Interaction of the docetaxel with human serum albumin using optical spectroscopy methods

Docetaxel is a semi-synthetic product derived from the needles of the European yew. It is an antineoplastic agent belonging to the taxoid family. The interaction between docetaxel and human serum albumin (HSA) has been investigated systematically by the fluorescence quenching technique, synchronous fluorescence spectroscopy, ultraviolet (UV)-vis absorption spectroscopy, circular dichroism (CD) spectroscopy and Fourier transform infrared (FT-IR) under physiological conditions. Our fluorescence data showed that HSA had only one docetaxel binding site and the binding process was a static quenching procedure. According to the Van’t Hoff equation, the thermodynamic parameters standard enthalpy (ΔH⁰) and standard entropy (ΔS⁰) were calculated to be −41.07 KJ mol⁻¹ and −49.72 J mol⁻¹ K⁻¹. These results suggested that hydrogen bond was the predominant intermolecular force stabling the docetaxel-HSA complex. The data from the CD, FT-IR and UV-vis spectroscopy supported the change in the secondary structure of protein caused by the interaction of docetaxel with HSA.     

激光诱导击穿光谱定量分析中的分析线自动选择方法

为了实现激光诱导击穿光谱分析中的分析线自动选择,定义了元素发射谱线的相对强度比(RDTIR)、波长偏差(WDDT)两个参数,并据此对检测谱线进行筛选,通过设定合理的阈值,剔除自吸收和干扰严重的谱线。通过对高合金钢(GBW01605)实验数据的分析,分别选定了样品中主要元素铁、铬、镍、锰、铜的分析线,选线结果符合谱线的选取原则。     

Particle-size measurements in flames using light scattering; comparison with diffusion-broadening spectroscopy

Particle-size measurements have been performed above a flat-flame burner using CH₄/O₂ mixtures. Size estimates were made on the assumption that particle sizes are defined by the self-preserving distribution (s.p.d.). Desymmetry ratios were measured for parallel and perpendicularly polarized argonion-laser radiation at 4880 A. These ratios for the assumed s.p.d. yield mean radii when the Mie theory is applied to spherical particles for a known value of the complex index of refraction (m = 1.57-0.44 i).The measured results are found to be in good agreement with our earlier studies using diffusion-broadening spectroscopy.     

Validation of protein structural models using THz spectroscopy: a promising approach to solve three-dimensional structures

Terahertz (THz) spectroscopy is a promising technique for the study of protein structure and internal flexibility. Here, we used THz spectroscopy and molecular modeling for bovine serum albumin (BSA) structure investigation. BSA molecule was built using homology modeling methods and 30 different more relaxed models were obtained by molecular dynamics simulations of the hydrated protein. As the experimental and simulated THz spectra are linear, we compared them by comparing the slopes of the lines that fit them. Six BSA structures had slope values in the range given by the slope of the experimental spectrum $\pm $  0.2 and a total of sixteen BSA structures had slope values in the 0.6 interval near the experimental slope value. BSA average structures were calculated over the six and the sixteen identified BSA molecules. Based on the similarity with the crystal structure of BSA, we validated the average structure calculated over the sixteen BSA conformations. The comparison with the crystal structure showed that the structure validated using THz spectroscopy is a coarse model of BSA, as its root-mean-square deviation relative to the crystal structure is 1.9 Å. The regions from our model that present the highest deviation from the crystal structure are exterior loops. The results presented here show that using THz spectroscopy and molecular modeling is a promising approach to determine the structure of proteins.     

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.     

Real-time monitoring the formation and decomposition processes of methane hydrate with THz spectroscopy

<正>Gas hydrates are crystalline clathrate compounds comprised of hydrogen-bonded water cavities,consisting of guest molecules trapped in a lattice of polyhedral water cages under elevated pressures and low temperatures[1].The structures of the gas hydrates are closely related to the types and sizes of the guest species,and three distinct structures,including cubic structure-Ⅰ(sⅠ),cubic structure-Ⅱ(sⅡ),and hexagonal structure-H(sH),are known to form[2].Being expected as a kind of future energy resource,natural gas     

材料化学分析的物理方法(Ⅰ)

材料的化学信息是理解科学、工程与技术领域各种过程、机制和材料行为的最基本要素，材料研究的第一步是要确定材料的化学，包括构成材料的原子的种类、分布以及具体的化学态等内容，任何具有元素特征的物理信息，包括原子量、电子的能级、原子核自旋，甚至局域的电子态密度等都可以用来做材料的化学分析，化学信息由来自材料本身的或用作探针的电子、光子、离子或中性原子携带，相应的分析技术包括X射线光电子能谱、俄歇电子谱、核磁共振、特征X射线分析、二次离子质谱、能量损失谱、溅射中性粒子质谱，各类离子散射谱以及扫描隧道显微学方法等等，文章对上述各种分析方法的物理原理、仪器以及应用等逐一做扼要的介绍。