显微共聚焦拉曼光谱结合群分析的黑色直液笔墨迹鉴别研究

黑色直液笔是一种新型书写工具,目前对该种笔墨迹的相关研究较少。为给文件检验工作中墨迹的分析提供新的参考依据,本实验使用显微共聚焦拉曼光谱技术,采集了30支不同品牌、型号的黑色直液笔墨迹光谱数据,进行Savitzky-Golay卷积平滑处理后,依据光谱图的拉曼位移及拉曼谱峰差异对墨迹进行初步分析。设置聚类方法为组间联接,区间距离测量方式为平方欧式距离,对采集的光谱数据进行群分析,将30支黑色直液笔墨迹样本分成了3类,并与品牌建立了相关联系;同时通过主成分分析验证了群分析的可靠性和准确性。研究表明,显微共聚焦拉曼光谱技术结合群分析方法可实现对黑色直液笔墨迹的无损分析及有效鉴别,该方法操作简便、结果准确,适用于法庭科学文件检验。     

Depth profiling of polymer films by confocal Raman spectroscopy

Confocal Raman microspectroscopy has many potential applications in the study of polymer-solvent interactions, including the determination of solvent and polymer-solvent complex depth profiles. This contribution focuses on preventing the formation of polymer-solvent complexes, using surface chemical modification of PVC films. While the surface-specific nature of the film modification is easily demonstrated,^[1] confocal Raman measurements clearly show the effects of film refractive index: the modifier depth profile shows a lack of symmetry and the film thickness is underestimated. A spectral normalisation method is described, and this is shown to result in a modifier depth profile which is in good agreement with data obtained by Raman microspectroscopy following physical cross-sectioning of a sample. Alternative techniques for Raman depth profiling are also discussed.     

Site distribution in resin beads as determined by confocal Raman spectroscopy

Scanning confocal Raman spectroscopy was used to study the distribution of reactive sites within a resin bead used for solid-phase synthesis. The distribution of NH2 groups in aminomethylated polystyrene resin (APS) was determined by doping with varying amounts of 4-cyanobenzoic acid. The extent of loading was determined by both elemental analysis and ninhydrin assays. The spatial distribution of the coupled 4-cyanobenzamide within the bead was determined to an in-plane resolution of 1 microm and depth resolution of about 4 microm, using the strong Raman CN stretching vibrational transition at 2230 cm(-1). Dry and swollen beads were studied and the distribution was found to be essentially uniform throughout the bead in all cases.     

On optical depth profiling using confocal Raman spectroscopy

Until 2006 the performance of confocal Raman spectroscopy depth profiling was typically described and modeled through the application of geometrical optics, including refraction at the surface, to explain the degree of resolution and the precise form of the depth profile obtained from transparent and semicrystalline materials. Consequently a range of techniques, physical and analytical, was suggested to avoid the errors thus encountered in order to improve the practice of Raman spectroscopy, if not the understanding of the underlying mechanisms. These approaches were completely unsuccessful in accounting for the precise form of the depth profile, the fact that spectra obtained from laminated samples always contain characteristic peaks from all materials present both well above and below the focal point and that spectra can be obtained when focused some 40 μm above the sample surface. This paper provides further evidence that the physical processes underlying Raman spectroscopy are better modeled and explained through the concept of an extended illuminated volume contributing to the final Raman spectrum and modeled through a photon scattering approach rather than a point focus ray optics approach. The power of this numerical model lies in its ability to incorporate, simultaneously, the effects of degree of refraction at the surface (whether using a dry or oil objective lens), the degree of attenuation due to scatter by the bulk of the material, the Raman scattering efficiency of the material, and surface roughness effects. Through this we are now able to explain why even removing surface aberration and refraction effects through the use of oil immersion objective lenses cannot reliably ensure that the material sampled is only that at or close to the point of focus of the laser. Furthermore we show that the precise form of the depth profile is affected by the degree of flatness of the surface of the sample. Perhaps surprisingly, we show that the degree of flatness of the material surface is, in fact, more important than obtaining a precise refractive index match between the immersion oil and the material when seeking a high-quality depth profile or Raman spectrum from within a transparent or semicrystalline material, contrary to accepted norms that samples for interrogation by Raman spectroscopy require little preparation.     

Identification of ultra-thin layers by cross-sectional Raman spectroscopy

 Micro-Raman spectroscopy measurements in a cross-sectional sample geometry were performed for three heterosystems (3C-SiC/Si(100), diamond/Si(100), and ZnS_xSe_1-x/GaAs(100)). Using an automated xy-stage with a minimum step width of 100 nm one-dimensional scans across the interface were taken. It is demonstrated that sufficient sensitivity for the detection of ultra-thin layers with thicknesses in the nanometer range can be achieved. Thus surface and interface layers not accessible in a plane-view geometry can be identified. In addition, the depth-resolved variation of sample properties like interfacial reactions, stress, and stoichiometry will be discussed. Received: 24 June 1996/Revised: 9 December 1996/Accepted: 13 December 1996     

Identification of pharmaceutical tablets by Raman spectroscopy and chemometrics

Raman spectroscopy has become an attractive tool for the analysis of pharmaceutical solid dosage forms. In the present study it is used to ensure the identity of tablets. The two main applications of this method are release of final products in quality control and detection of counterfeits. Twenty-five product families of tablets have been included in the spectral library and a non-linear classification method, the Support Vector Machines (SVMs), has been employed. Two calibrations have been developed in cascade: the first one identifies the product family while the second one specifies the formulation. A product family comprises different formulations that have the same active pharmaceutical ingredient (API) but in a different amount. Once the tablets have been classified by the SVM model, API peaks detection and correlation are applied in order to have a specific method for the identification and allow in the future to discriminate counterfeits from genuine products. This calibration strategy enables the identification of 25 product families without error and in the absence of prior information about the sample. Raman spectroscopy coupled with chemometrics is therefore a fast and accurate tool for the identification of pharmaceutical tablets.     

Elucidating interactions of ionic liquids with polymer films using confocal Raman spectroscopy

We report on the molecular interactions between room-temperature ionic liquids (RTILs) and Nafion and PDMS membranes, proving that in contact with these polymers RTILs behave like electrolytes rather than solvents.     

Structure of polypropylene/polyethylene blends assessed by polarised PA-FTIR spectroscopy,polarised FT raman spectroscopy and confocal Raman microscopy

Physical structure and morphology of differently prepared and treated bulk specimens of isotactic polypropylene, linear polyethylene and their blend was studied by polarised FT Raman spectroscopy, polarised FTIR spectroscopy with photoacoustic detection, and by confocal Raman microscopy. The specimens differed in preparation technique, mechanical and thermal history. The orientation and reorientation of molecular chains of individual blend components, their crystallinity and the size and structure of the microdomains both in the skin and in the core of the specimens were correlated with the preparation conditions, mechanical treatment and thermal history. The possibilities and limitations of each method were discussed.     

Label free non-invasive imaging of topically applied actives in reconstructed human epidermis by confocal Raman spectroscopy

Raman spectroscopy has become a versatile tool for the in vivo characterization of skin. Here we describe use of Raman spectroscopy for high resolution optical cross sectioning to resolve skin constituents and administered drugs at the cellular level. Percutaneous penetration is typically studied using permeation cells with biopsies of animals or human skin. Although this technique provides valuable clinical data, little insight is gained in the microstructure of drug penetration (intercellular or transcellular) or in the mode of action of applied vehicles or penetration enhancers. Therefore, a Raman microspectroscopic method was combined with a confocal scanning setup to image the microstructure of commercially available skin models (SkinEthic^®) and the spatial distribution of penetrated actives. The models’ microstructure was scanned without any special treatment or environment such as cutting, staining, freezing, or application of vacuum. The non-invasive Raman images reveal the layered structure of stratum corneum. This in particular for lipids while water tends to be more evenly distributed. When penetration of the hydrophilic active glycerol and the lipophilic octyl methoxycinnamate, OMC, was studied, a strong correlation between the local distribution of skin constituents and the hydrophilic/lipophilic character of the active was observed.     

Dynamics of phase transitions in a liquid crystal probed by Raman spectroscopy

Raman spectra of the Schiff 's base liquid crystalline compound 5O5, N-(4- n-pentyloxybenzylidene)-4'-n-pentylaniline, have been recorded as a function of temperature from 22 to 80°C in the 1140-1220 cm^-1 and 1550-1640 cm^-1 spectral regions. From careful deconvolution of the spectral features using Lorentzian profiles, precise values of peak positions, integrated intensities and linewidths of some selected Raman bands were obtained. The variations of the Raman spectral parameters with temperature are discussed in terms of changes in the molecular alignment and its effect on intra-/inter-molecular interactions at the Cr-G, G-SmF, SmF-SmC and SmA-N phase transitions. From a detailed study, it is inferred that the increased orientational/vibrational freedom of the alkyl chains, as well as the delocalization of the electron clouds, is responsible for the spectral anomalies at the Cr-G transition. Loss of positional ordering and twist around the -C₆H₄-N= bond takes place at the SmF-SmC transition. In the SmA-N transition, some evidence for the formation of cybotactic clusters was obtained.     

Conformational and phase transformations of chlorocyclohexane at high pressures by Raman spectroscopy

Pressure induced conformational and phase transformations of chlorocyclohexane (CCH) were investigated in a diamond anvil cell by Raman spectroscopy at room temperature. Pure CCH was compressed up to 20 GPa and then decompressed to ambient pressure. The conformational equilibrium was shifted by pressure from equatorial to axial conformers in the fluid phase below 0.7 GPa, consistent with previous observations. Upon further compression, several solid-to-solid phase transitions were identified by the observation of markedly different Raman patterns as well as different pressure dependences of characteristic Raman modes. The possible structures of these phases were analyzed in correlation with previously observed solid phases at low temperatures. Finally, CCH exhibits pressure hysteresis and partial reversibility upon decompression which result in the formation of the phases with different Raman patterns from those obtained upon compression. The difference can be interpreted as conformational contribution as well as the intrinsic plasticity of CCH crystals.     

Dynamics of phase transitions in a liquid crystal probed by Raman spectroscopy

Raman spectra of the Schiff 's base liquid crystalline compound 5O5, N-(4- n-pentyloxybenzylidene)-4'-n-pentylaniline, have been recorded as a function of temperature from 22 to 80°C in the 1140-1220 cm^-1 and 1550-1640 cm^-1 spectral regions. From careful deconvolution of the spectral features using Lorentzian profiles, precise values of peak positions, integrated intensities and linewidths of some selected Raman bands were obtained. The variations of the Raman spectral parameters with temperature are discussed in terms of changes in the molecular alignment and its effect on intra-/inter-molecular interactions at the Cr-G, G-SmF, SmF-SmC and SmA-N phase transitions. From a detailed study, it is inferred that the increased orientational/vibrational freedom of the alkyl chains, as well as the delocalization of the electron clouds, is responsible for the spectral anomalies at the Cr-G transition. Loss of positional ordering and twist around the -C₆H₄-N= bond takes place at the SmF-SmC transition. In the SmA-N transition, some evidence for the formation of cybotactic clusters was obtained.     

Identification and quantification of valuable plant substances by IR and Raman spectroscopy

This review presents various infrared and Raman spectroscopic methods applied to the analysis of valuable plant substances or quality parameters in horticultural and agricultural crops. In most cases, vibrational measurements can be performed directly on plant tissues as well as on fractions isolated from the plant material by hydro-distillation or solvent extraction. Generally, both spectroscopy techniques allow to obtain spectra which present some characteristic key bands of individual components. These bands provide information about the chemical composition, including both primary and secondary metabolites, of the investigated samples. Furthermore, based on such markers related to individual plant substances, spectroscopic analyses in principle allow the discrimination of different species, and even chemotypes among the same species. Combination of vibrational spectroscopy and hierarchical cluster analysis provides a fast, easy and reliable method for chemotaxonomy characterization. In most presented cases, determination of main plant components applying the PLS algorithm results in comparatively high R² and low SECV values. The ability to rapidly monitor various plant components makes it possible to efficiently select high-quality single plants from wild populations as well as progenies of crossing experiments. Furthermore, the vibrational spectroscopy methods can also be used by the processing industry in order to perform fast quality checks of incoming raw materials as well as continuous controlling of the production.     

基于显微共聚焦拉曼光谱技术快速检测3种梭菌中肉毒梭菌

提出了一种基于显微共聚焦拉曼光谱技术的肉毒梭菌快速鉴别方法.利用共聚焦显微拉曼光谱技术(CRM)采集了肉毒梭菌、艰难梭菌和产气荚膜梭菌的拉曼光谱,比较了3种梭菌的平均拉曼光谱,采用基线校正、标准正态变换、Savitzky-Golay 5点平滑和最大最小值归一化预处理后,借助主成分分析(PCA)降维并提取特征变量,对样本...     

Pressure induced phase transitions of TTAB-micellar solutions studied by SANS and Raman spectroscopy

Using small angle neutron scattering in combination with optical Raman spectroscopy, phase transitions in the micellar system tetradecyl-trimethylammonium bromide (TTAB) have been investigated in a wide range of temperatures, pressures and surfactant concentrations. Allowing for the sluggish kinetics of crystallisation, the phase diagram in the p-T-c space could be determined that is dominated by a pronounced two-phase region of coexisting liquid and solid phases at elevated pressures.     

Role of hydration in the phase transition of polypeptides investigated by NMR and Raman spectroscopy

NMR, Raman spectroscopy and ab initio quantum-chemical calculations have been employed to investigate the role of the hydration water in the inverse temperature transition of elastin-derived biopolymers represented by poly(Gly-Val-Gly-Val-Pro) and poly(Ala-Val-Gly-Val-Pro). Temperature and concentration dependences of the Raman spectra measured for water solutions of polymers and of a low-molecular-weight model have been correlated with the vibrational frequencies calculated at the DFT (B3LYP) and MP2 levels for the peptide segment surrounded by a growing number of water molecules. The results indicate strong hydration before the transition that, in addition to water hydrogen-bonded to amide groups, includes hydrophobic hydration of non-polar groups by a dynamic cluster of several water molecules. According to ¹H longitudinal and transverse relaxation of HOD signals in D₂O solutions, the number of water molecules motionally correlated with the polymer is about 4 per one amino acid residue.     

High-pressure induced conformational and phase transformations of 1,2-dichloroethane probed by Raman spectroscopy

1,2-Dichloroethane (DCE) was loaded into diamond anvil cells and compressed up to 30 GPa at room temperature. Pressure-induced transformations were probed using Raman spectroscopy. At pressures below 0.6 GPa, fluid DCE exists in two conformations, gauche and trans in equilibrium, which is shifted to gauche on compression. DCE transforms to a solid phase with exclusive trans conformation upon further compression. All the characteristic Raman shifts remain constant in fluid phase and move to higher frequencies in the solid phase with increasing pressure. At about 4-5 GPa, DCE transforms from a possible disordered phase into a crystalline phase as evidenced by the observation of several lattice modes and peak narrowing. At 8-9 GPa, dramatic changes in Raman patterns of DCE were observed. The splitting of the C-C-Cl bending mode at 325 cm-1, together with the observation of inactive internal mode at 684 cm-1 as well as new lattice modes indicates another pressure-induced phase transformation. All Raman modes exhibit significant changes in pressure dependence at the transformation pressure. The new phase remains crystalline, but likely with a lower symmetry. The observed transformations are reversible in the entire pressure region upon decompression.     

差分拉曼光谱结合SVM对便签纸的鉴别分析

基于差分拉曼光谱技术与支持向量机(SVM)模型,提出了一种对便签纸类检材的快速可视化鉴别方法。实验获取了40组不同品牌便签纸样本的差分拉曼光谱数据,利用BP神经网络和差分技术完成谱图的除噪与基线校正后,借助F检验与主成分分析提取谱段信息,构建出SVM分类模型。实验结果表明,当设置Linear为SVM模型的核函数时,可以实现对样本测试集的完全准确划分,K折交叉验证的结果理想。相比于传统聚类分析手段,本方法可以在原始高维光谱数据中筛选出有效特征矩阵,且SVM模型兼具高效性和准确性,为公安实践中纸张类物证的区分鉴别提供一种新思路。     

Identification of peroxo groups in supramolecular layered structures as probed by Raman spectroscopy

Peroxide-containing supramolecular structures prepared by reacting lithium aluminum layered double hydroxides (Li-Al LDHs) with concentrated hydrogen peroxide solutions were characterized by Raman spectroscopy. These compounds were formulated as [LiAl₂(OH)₆](OH) · H₂O₂ · H₂O(I) and [LiAl₂(OH)₆](OOH) · H₂O₂ · H₂O(II). The frequencies 830 and 849 cm⁻¹ in the spectra of compounds I and II were assigned to O—C stretching vibrations in two nonequivalent peroxo groups. The band at 866 cm⁻¹ in compound II was assigned to O—O vibrations in the hydroperoxo group (OOH)⁻. Proceeding from calculated strength factors, we inferred that the O—O bond in the hydroperoxo group of compound II is stronger than in the H₂O₂ solvating group. Original Russian Text ? T.A. Tripol’skaya, I.V. Pokhabova, P.V. Prikhodchenko, G.P. Pilipenko, E.A. Legurova, N.A. Chumaevskii, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 3, pp. 513–515.