含未知干扰物体系的多元光度分析的化学计量学算法

基于投影矩阵算法和最小熵概念,本文提出了处理含部份未知成份体系的定性定量分析新方法。将此法应用于金属离子及多环芳烃混合物体系测定,获得了满意的结果。     

Modified indirect hard modeling for non-invasive Raman measurements containing surface interference

Non-invasive Raman spectroscopy has been used in an increasing number of applications in recent years. However, in situations where surface signal is excessive, the acquired spectrum of probed sample suffers from surface interference in either conventional backscattering Raman or specially designed Raman methods. A computational method for Raman spectral recovery is required. Strong overlapping of Raman bands and intense fluorescence are the main obstacles that hinder the spectral recovery. In this paper, we present a modified version of an indirect hard modeling algorithm to extract the true Raman spectrum of the probed sample in a two-layer system. The proposed algorithm requires two spectra. By an iterative stepwise optimization, it models one spectrum as a combination of a scaling of the other spectrum, a polynomial baseline and the Raman peaks of the probed sample. It addresses the issue of Raman bands overlapping as well as intense fluorescence interference. The performance of the algorithm is evaluated on experimental Raman spectra. Comparative studies show that the proposed algorithm provides better results for Raman spectral recovery.     

Effect of Atmospheric Interfering Absorption on Measurement of BTX by DOAS

It was reported on the elimination of interfering absorption of BTX. the absorption of O2 includes different absorption bands, which change differently when the partial pressure of oxygen is varied. These cause the nonlinear absorption of O2 and the observed band shape to vary with the column density of O2. The absorption ratios of molecular absorption in each of the Herzberg bands and dimer absorptions, as well as the contribution to the correction error of molecular absorption, are studied based on the characteristic of these absorption bands. The optimized way to eliminate the interfering absorption is obtained in the end and the effectiveness of using interpolation proposed by Volkamer et al. to remove O2 absorption is proved again. As to O3 and SO2, the effect of the thermal effect of characteristic spectra on the elimination error of their absorption is studied. Solutions to these problems are discussed and demonstrated together with methods to optimize the interpolation of spectra. As a sample application, differential optical absorption spectroscopy (DOAS) measurements of BTX are carried out. Results show a low detection limit and the good correlation with point instruments are achieved. All these prove the feasibility of using spectral interpolation to improve the accuracy of DOAS measurements of aromatic hydrocarbons for practical purposes.     

Spectroscopic studies of rhodamine 6G dispersed in polymethylcyanoacrylate

We report here electronic absorption, fluorescence and resonance Raman studies of rhodamine 6G laser dye dispersed in the polymethylcyanoacrylate matrix. In the electronic absorption and fluorescence spectra of dispersed rhodamine 6G, band maxima are red shifted compared to solution. Raman spectra show some new bands. These spectral changes arise due to matrix effect and interaction between rhodamine 6G and the host material involving amine group of rhodamine.     

Infrared spectra of the CF3I dimer: a concurrent application of matrix-isolation spectroscopy and cavity ring-down spectroscopy

We have observed infrared spectra of the CF(3)I dimer produced in a supersonic jet by matrix-isolation Fourier transform infrared spectroscopy and infrared cavity ring-down (IR-CRD) spectroscopy. In the matrix-isolation experiments, the dimer was isolated in an Ar matrix by the pulse-deposition method. The recorded spectral range covers the symmetric (nu(1)) and doubly degenerate (nu(4)) C-F stretching regions. From the concentration dependence of the matrix-isolation spectra we have assigned one dimer band for each fundamental region. It was not easy to identify the dimer band for the nu(4) band because of the multiplet feature of the monomeric nu(4) band caused by the site symmetry breaking. The spectra of (CF(3)I)(2) in the nu(4) band region were thus also measured in the gas phase by IR-CRD spectroscopy, where we detected two dimer bands. Comparing the observed band positions with the results of quantum chemical calculations, we have assigned the observed dimer bands to the head-to-head isomer. The structure of (CF(3)I)(2) and its photochemical implications are discussed, in comparison with methyl iodide dimer reported previously [Ito et al., Chem. Phys. Lett. 343, 185 (2001)].     

Some aspects of the scope and limitations of derivative spectroscopy

Synthesised spectra are used to illustrate discussion of some relationships between recorded absorption profiles and their second and fourth derivative spectra. Limitations arising from the fortuitous overlap of a derivative peak with a neighbouring wing, and the possibilities of resolving spectra into their overlapping bands are also considered. The combined use of second and fourth derivative spectra to ascertain the correct number of bands within an observed profile is described. It is suggested that the practice of computing a least-squares fit of overlapping bands to a spectral profile be changed, because the minimisation achieved often produces a result involving excessive or negative absorbances: the spectral profile should be regarded as a boundary limit and any unaccounted (positive) absorbance then assessed as possible evidence for an additional band. An example is given, concerning the resolution of the spectrum of a thin, single crystal of uranium(IV) oxide at 77 K superimposed on an absorption edge. A comparison of the difference between the observed spectrum and the sum of its resolution into twelve overlapping bands, plus a similar comparison of their fourth derivative spectra, reveals a thirteenth band.     

四苯基卟啉镁的合成、表征及光化学性质

提出一种以乙酸镁和乙酸钠为原料合成四苯基卟啉镁(MgTPP)的新方法, 合成样品以柱层析法进行分离纯化. 分离产物经UV-Vis、1H-NMR、MALDI-TOF-MS(基质辅助激光解吸电离飞行时间质谱)等技术表征, 确定为MgTPP. UV-Vis光谱分析结果表明, 四苯基卟啉镁的Soret 吸收带为424 nm, Q 吸收带为563 nm 和602 nm. 此外, 光照对MgTPP的二氯甲烷溶液光谱性质的影响结果表明, 经光照射后MgTPP的UV-Vis光谱的Soret吸收带吸收强度明显降低, 同时, 经550 nm的光激发产生的荧光有明显的猝灭. 对光照后的MgTPP样品进行MALDI-TOF-MS分析, 发现有新的质核比(m/z)出现, 其为668, 这一结果表明, 在光照条件下, MgTPP分子可能与氧分子发生光化学作用, 形成MgTPP与氧的复合物MgTPP-O2.     

The detection of drugs of abuse in fingerprints using Raman spectroscopy II: cyanoacrylate-fumed fingerprints

This paper describes the application of Raman spectroscopy to the detection of exogenous substances in cyanoacrylate-fumed fingerprints. The scenario considered was that of an individual handling a substance and subsequently depositing a contaminated fingerprint. These fingerprints were enhanced by cyanoacrylate fuming, a process in which a layer of white cyanoacrylate polymer is deposited on the fingerprint material, enabling visual detection. Five drugs of abuse (codeine phosphate, cocaine hydrochloride, amphetamine sulphate, barbital and nitrazepam) and five non-controlled substances of similar appearance, which may be used in the adulteration of drugs of abuse (caffeine, aspirin, paracetamol, starch and talc), were used. The substances studied could be clearly distinguished using their Raman spectra and were all successfully detected in cyanoacrylate-fumed fingerprints. Photobleaching was necessary to reduce the fluorescence background in the spectra of some substances. Raman spectra obtained from the substances in cyanoacrylate-fumed fingerprints were of a similar quality to spectra obtained from the substances under normal sampling conditions, however, interfering Raman bands arising from the cyanoacrylate polymer were present in the spectra. In most cases the only interfering band was the C triple bond N stretching mode of the polymer, and there were no cases where the interfering bands prevented identification of the substances. If necessary, the interfering bands could be successfully removed by spectral subtraction. The most difficult aspect of the detection of these substances in cyanoacrylate-fumed fingerprints was visually locating the substance in the fingerprint beneath the polymer layer in order to obtain a Raman spectrum.     

双峰倍增配平导数—同步荧光法同时测定苯酚和间苯二酚的研究

本文提出用双峰倍增配平法计算解析苯酚和间苯二酚混合体系的一阶导数－同步荧光光谱，测定结果的回收率，精密度和两组分间浓度比范围均统一阶导数－同步荧光法优方法用于雷琐辛涂剂和水样中苯酚与间苯二酚的测定，结果令人满意。     

A simple method to extract spectral parameters using fractional derivative spectrometry

The nonlinear fitting method, based on the ordinary least squares approach, is one of several methods that have been applied to fit experimental data into well-known profiles and to estimate their spectral parameters. Besides linearization measurement errors, the main drawback of this approach is the high variance of the spectral parameters to be estimated. This is due to the overlapping of individual components, which leads to ambiguous fitting. In this paper, we propose a simple mathematical tool in terms of a fractional derivative (FD) to determine the overlapping band spectral parameters. This is possible because of several positive effects of FD connected with the behavior of its zero-crossing and maximal amplitude. For acquiring a stable and unbiased FD estimate, we utilize the statistical regularization method and the regularized iterative algorithm when a priori constraints on a sought derivative are available. Along with the well-known distributions such as Lorentzian, Gaussian and their linear combinations, the Tsallis distribution is used as a model to correctly assign overlapping bands. To demonstrate the power of the method, we estimate unresolved band spectral parameters of synthetic and experimental infra-red spectra.     

基于多阶导数拉曼光谱组合技术的矿物油模式分类

为了实现对法庭科学领域重质矿物油物证的快速、准确、无损的鉴定,该文基于光谱分析技术提出了一种多阶导数光谱数据组合分析的方法。收集了80种不同型号、不同厂家的重质矿物油样本,利用傅里叶变换拉曼光谱分析法采集样本的原始光谱数据和导数光谱数据,并通过结合化学计量学构建分类模型。在构建的主成分分析(PCA)结合径向基函数神经网络(RBF)分类模型中,对单独的原始光谱、一阶导数谱和二阶导数谱数据的训练集准确率分别为80.0%、86.7%和86.2%,测试集准确率分别为73.3%、80.0%和72.7%;对组合后的原始光谱+一阶导数谱、原始光谱+二阶导数谱和一阶导数谱+二阶导数谱数据的分类中,训练集准确率分别为97.0%、96.7%和100%,测试集准确率分别为85.7%、90.0%和100%。结果表明,对组合后的导数光谱与原始光谱构建分类模型,准确率更高。其中,基于一阶导数谱+二阶导数谱数据构建的PCA结合RBF分类模型的结果最为理想,准确率达100%。而K最近邻算法模型由于受到样本不均匀的影响,整体分类准确率均较低。利用组合的导数光谱与原始光谱数据构建分类模型能够实现对重质矿物油样本的快速、准确、无损鉴别,可为光谱组合技术在法庭科学及其他分析测试领域的应用提供一定的借鉴和参考。     

Synthesis,characterization and fluorescence behavior of new fluorescent probe phthalocyanines bearing coumarin substituents

In this study, we report a new ligand, 6-hexyloxy-3-[p-(3′,4′-dicyanophenoxy)phenyl]coumarin, and its fluorescent tetrasubstituted phthalocyanines {M[Pc(OBzCou)₄], M = 2H, Zn(II), Co(II); Bz: Benzene}. The effect of the coumarin derivative on the intensity of the fluorescence spectra of the metal-free (H₂Pc) and zinc phthalocyanine (ZnPc) derivatives was investigated. The change of the emission properties of both the coumarin moieties and the phthalocyanine core in the presence of the metal ion and the ring-opening reaction of the coumarin were studied by means of steady-state fluorescence spectroscopy. The radiative decay of the Pcs and the treated coumarin substituents bound to the Pcs was examined. The novel chromogenic compounds were characterized by elemental analysis, ¹H NMR, ¹³C NMR, Maldi-TOF, IR and UV–Vis spectral data. The photophysical properties of the Pcs are extensively affected by their state of aggregation: in particular, dimerization and aggregation result in a remarkable modification of the absorption and emission bands and may induce significant quenching of the usually strong Pc fluorescence. The electronic spectra exhibit a band of coumarin identity together with characteristic Q and B bands of the phthalocyanine core.     

Raman micro-spectroscopic analysis of cultured HCT116 colon cancer cells in the presence of roscovitine

Raman micro-spectroscopic analysis of cultured HCT116 colon cancer cells in the presence of roscovitine, [seliciclib, 2-(1-ethyl-2-hydroxy-ethylamino)-6-benzylamino-9-isopropylpurine], a promising drug candidate in cancer therapy, has been performed for the first time. The aim of this study was to investigate modulations in colon cancer cells induced by roscovitine. Raman spectra of the cultured HCT116 colon cancer cells treated with roscovitine at different concentrations (0, 5, 10, 25 and 50 μM) were recorded in the range 400-1850 cm(-1). It was shown that the second derivative profile of the experimental spectrum gives valuable information about the wavenumbers and band widths of the vibrational modes of cell components, and it eliminates the appearance of false peaks arising from incorrect baseline corrections. In samples containing roscovitine, significant spectral changes were observed in the intensities of characteristic protein and DNA bands, which indicate roscovitine-induced apoptosis. Roscovitine-induced apoptosis was also assessed by flow cytometry analysis, and analysis of propidium iodide staining. We observed some modifications in amide I and III bands, which arise from alterations in the secondary structure of cell proteins caused by the presence of roscovitine.     

Different level of fluorescence in Raman spectra of montmorillonites

The paper presents the study of selected montmorillonite standards by Raman spectroscopy and microscopy supported by elemental analysis, X-ray powder diffraction analysis and thermal analysis. Dispersive Raman spectroscopy with excitation lasers of 532 nm and 780 nm, dispersive Raman microscopy with excitation laser of 532 nm and 100× magnifying lens, and Fourier Transform-Raman spectroscopy with excitation laser of 1064 nm were used for the analysis of four montmorillonites (Kunipia-F, SWy-2, STx-1b and SAz-2). These mineral standards differed mainly in the type of interlayer cation and substitution of octahedral aluminium by magnesium or iron. A comparison of measured Raman spectra of montmorillonite with regard to their level of fluorescence and the presence of characteristic spectral bands was carried out. Almost all measured spectra of montmorillonites were significantly affected by fluorescence and only one sample was influenced by fluorescence slightly or not at all. In the spectra of tested montmorillonites, several characteristic Raman bands were found. The most intensive band at 96 cm⁻¹ belongs to deformation vibrations of interlayer cations. The band at 200 cm⁻¹ corresponds to deformation vibrations of the AlO₆ octahedron and at 710 cm⁻¹ can be assigned to deformation vibrations of the SiO₄ tetrahedron. The band at 3620 cm⁻¹ corresponds to the stretching vibration of structural OH groups in montmorillonites.     

Synchronous fluorescence and excitation emission characteristics of transformer oil ageing

This paper describes the evaluation of synchronous fluorescence spectroscopy (SFS) and excitation emission matrix fluorescence (EEMF) spectroscopy as means of monitoring transformer oil degradation. When accelerated thermal ageing method is used, the onset of degradation of transformer oil on 17th day and transformer oil with polypropylene and cellulosic paper on 23rd and 27th days is sensitively reflected in the SFS and EEMF fluorescence spectral characteristics.     

Fluorescence spectra measurement of olive oil and other vegetable oils

Fluorescence spectra of some common vegetable oils, including olive oil, olive residue oil, refined olive oil, corn oil, soybean oil, sunflower oil, and cotton oil, were examined in their natural state, with a wavelength of 360 nm used as excitation radiation. All oils studied, except extra virgin olive oil, exhibited a strong fluorescence band at 430-450 nm. Extra virgin olive oil gave a different by interesting fluorescence spectrum, composed of 3 bands: one low intensity doublet at 440 and 455 nm, one strong at 525 nm, and one of medium intensity at 681 nm. The band at 681 nm was identified as the chlorophyll band. The band at 525 nm was at least partly derived from vitamin E. The low intensity doublet at 440 and 455 nm correlated with the absorption intensity at 232 and 270 nm of olive oil. The measurements of these fluorescence spectra were quick (about 5 min) and easy and could possibly be used for authentification of virgin olive oil.     

Classification and identification of organic binding media in artworks by means of Fourier transform infrared spectroscopy and principal component analysis

Fourier transform infrared spectroscopy is a powerful analytical technique to study organic materials. However, in Cultural Heritage, since the sample under analysis is always a complicated matrix of several materials, data analysis performed through peak-by-peak comparisons of sample spectra with those of standard compounds is a tedious method that does not always provide good results. To overcome this problem, a chemometric model based on principal component analysis was developed to classify and identify organic binding media in artworks. The model allows the differentiation of five families of binders: drying oils, waxes, proteins, gums, and resins, taking into account the absorption bands in two characteristic spectral windows: C–H stretching and carbonyl band. This new methodology was applied in the characterization of binders in three kinds of artworks: papers of historical, archeological, and artistic value, easel paintings, and polychromed stone-based sculptures.     

ANALYSIS OF LASER-INDUCED FLUORESCENCE LINE SHAPE OF INTACT LEAVES: APPLICATION TO UV STRESS DETECTION

Abstract— In vivo laser-induced fluorescence spectra of intact leaves of healthy and UV-irradiated Salvia splendens plants excited at 337 nm by a nitrogen laser were recorded using an optical multichannel analyzer system. The spectra showed the typical fluorescence bands centered around 450, 530, 685 and 730 nm. Exposure to UV radiation changed the relative intensity values of these bands and their peak positions. The analysis of the acquired spectra in terms of a linear combination of Gaussian bands was carried out to determine accurately the peak positions and the relative intensity contribution of the various bands to the laser-induced fluorescence spectra on healthy and UV-treated plants of different age.
The results indicate that a curve-fitting analysis of the measured fluorescence spectra is a useful and sensitive method to discriminate the various band contribution to the whole leaf fluorescence spectrum. The comparison among blue-green and red-far-red fluorescence of leaves was also confirmed as an effective indicator of UV stress in plants.     

Deconvolution of fluorescence spectra: contribution to the structural analysis of complex molecules

Fluorescence spectroscopy is a sensitive analytical tool in the studies of both simple and complex molecular structures. In complex molecules, however, determining the number and position of components may give a specific insight into the structure, complementary to the other analytical techniques. We applied log–normal model to analyze fluorescence of simple monofluorophore molecule. In order to analyze spectra where both fluorophores and Raman emission bands were present, we developed a method obtained by combination of the symmetric, Gaussian, for Raman and asymmetric, log–normal model, for fluorescence, applicable to the molecules of different complexity. Technically, for each sample we varied excitation wavelength with 5 nm step and recorded the corresponding emission spectra. They were subsequently used for component analysis. Position of each component was plotted against the excitation wavelength. Applying this approach we could identify minimal number of components having stable positions, while their approximate probability density (APD) in a spectral series was correlated with the probable number of fluorophores in the molecule. The method was tested on molecules containing different number of fluorophores: monomers involved in the synthesis of plant polymer lignin—coniferyl alcohol (one fluorophore), ferulic acid (two fluorophores) and on lignin model compound produced from these monomers (many fluorophores). All investigated species belong to benzene-substituted class of compounds, and it is reasonable to assume that they have similar fluorescence band contour. We also report the results of environmental scanning electron microscopy (ESEM) studies showing multilayered dehydrogenative polymer (DHP) structure, in order to show complexity of the polymer. Our results present complementarity of these two approaches in the structural studies of the lignin model compound.     

基于近红外光谱技术与化学计量学的绿茶无损鉴别方法研究

该文利用近红外光谱技术结合化学计量学方法开发了不同品种绿茶的无损鉴别方法。通过近红外光谱技术得到了8个品种绿茶样品的近红外光谱,比较了单一以及优化组合光谱预处理方法对光谱的影响,利用无监督的主成分分析(PCA)与有监督的线性判别分析方法(LDA)分别构建了茶叶品种鉴别模型。结果表明：对比单一预处理方法,优化组合预处理具有更优的鉴别准确性。标准正态变量变换预处理消除了茶叶样品大小不均造成的光谱散射影响,一阶导数预处理实现了变动背景的消除,减少了基线漂移的影响,突出了图谱中的有效信息,采用二者相结合的预处理方式并结合无监督的主成分分析法可实现较为准确的绿茶样品种类鉴别分析,准确率达75.0%。此外,采用有监督的线性判别分析方法处理原始光谱数据,可达到100%的鉴别准确率,但该方法需提供类别的先验知识。因此,采用近红外光谱技术和化学计量学相结合的手段可实现不同品种绿茶的快速无损鉴别。