UV‐resonance Raman micro‐spectroscopy to assess residual chromophores in cellulosic pulps

Ultraviolet‐resonance Raman (UV‐RR) micro‐spectroscopy is an appropriate and sensitive tool to assess the chromophore structures in bleached cellulosic pulps used for papermaking. The particular selectivity in detection and identification of chromophores in pulps is achieved by acquiring the UV‐RR spectra in the solid state with laser excitation at 325 nm. This wavelength corresponds to absorption of poly‐unsaturated chromophore structures in partially bleached/fully bleached pulps, and linearly correlated with the signal at ca 1600 cm⁻¹ in the UV‐RR spectra. The characteristic vibrations from particular pulp chromophore structures have been assigned from experiments with model compounds, thus allowing the establishment of a UV‐RR database. Among the components of bleached pulp, the xylan–lignin complex was suggested to be an important source of chromophores. The monitoring of pulp bleaching by UV‐RR allowed us to suggest that it is the formation of new polysaccharide‐derived chromophores upon bleaching that hinders development of further brightness and is co‐responsible for the brightness reversion of fully bleached pulps. Copyright © 2010 John Wiley & Sons, Ltd.     

基于小波包能量熵和Fisher判别的油纸绝缘老化拉曼光谱诊断

准确诊断油纸绝缘材料的老化程度是保证油纸绝缘设备安全运行的重要技术手段。拉曼光谱在物质成分分析及状态诊断领域已经普遍应用。结合实验室搭建的油纸绝缘拉曼光谱分析平台，根据绝缘纸的平均聚合度将加速热老化实验获得的油纸样本分为四个老化阶段。通过对不同老化样本拉曼光谱所包含的能量信息分析，运用小波包能量熵提取特征量，结合Fisher判别法构造判别函数，建立基于拉曼光谱老化特征量的油纸绝缘老化诊断模型，并收集现场变压器油样验证诊断模型的泛化能力。结果表明，两个判别函数能区分不同老化阶段的绝缘油样，对于老化样本的判别正确率达到84.2%。拉曼光谱结合小波包能量熵和Fisher判别分析法能够有效地对油纸绝缘老化状态进行诊断。     

Evaluating paper degradation progress. Cross-linking between chromatographic, spectroscopic and chemical results

The study presents an overview of the chromatographic (SEC), spectroscopic (FTIR, UV/VIS), viscometric (DP) and chemical methods (titration, pH) used for the evaluation of the degradation progress of various kinds of paper under various conditions. The methods were chosen to follow different routes of paper degradation. Model paper samples represented boundary paper types from pure cellulose cotton paper, through softwood to low quality acidic, sized groundwood paper The accelerated ageing conditions were adjusted to achieve maximum effect (climatic chamber RH 59%, 90^oC) and also to mimic the environment inside books (closed vials). The results were settled on the literature data on the degradation mechanisms and compared in terms of the paper types and ageing conditions. The estimators of coupled de-polymerisation and oxidation have been proposed based on the correlation between SEC, UV/VIS and titrative coppper number determination. The overall oxidation index derived from FTIR results was shown to correlate with the summary –CHO and –COOH concentration determined by titrative methods.     

Gamma ray interactions with MoO3-doped lead phosphate glasses

The UV–Visible, Fourier transform infrared (FTIR) and Raman and electron spin resonance (ESR) spectra of undoped lead phosphate and MoO₃-doped glassy samples have been investigated. The UV–VIS absorption spectra were re-measured after successive gamma irradiation. Before irradiation, undoped sample exhibited strong ultraviolet absorption, which was attributed to co-absorption due to trace iron impurities (mainly Fe³⁺ ions) and lead Pb²⁺ ions. With the introduction of MoO₃ in progressive amounts, extra visible bands were recorded at about 400–440, 540, 750 and 870?nm. These bands are most likely correlated with the presence of Mo³⁺, Mo⁴⁺ and Mo⁵⁺ ions in the host glass. In the undoped specimen, gamma irradiation produced UV absorption bands that increased slightly with irradiation but no visible bands were recorded. Samples containing high MoO₃ content showed some resistance to irradiation with no bands in the visible region being observed. FTIR absorption spectra of the undoped and MoO₃-doped samples revealed the formation of metaphosphate and pyrophosphate structural units. Highly MoO₃-doped samples exhibited additional bands due to molybdate groups. Raman and ESR spectra were in agreement with UV–VIS and IR data, indicating the presence of molybdenum ions in lead phosphate glass, as Mo³⁺, Mo⁴⁺ and Mo⁶⁺ with different ratios. However, such glassy systems favor the trivalent species.     

Detection of biologically active diterpenoic acids by Raman Spectroscopy

Three poorly detectable, biologically active diterpenoic acids, kaurenoic, abietic, and gibberellic acid, were studied by using different modes of Raman spectroscopy. Because of their structural similarities, in the absence of strongly polarizable groups, conventional Raman spectroscopy is not suitable for their unambiguous identification, especially not in solution. We attempted to increase the sensitivity by applying UV‐resonance Raman spectroscopy and surface‐enhanced Raman spectroscopy (SERS) techniques. The UV‐Raman spectra of the three compounds in ethanol/water 50:50 showed only very few enhanced Raman lines. SERS spectra with 514‐nm excitation with Ag colloids were also relatively weak. The best SERS spectra were obtained with 785‐nm excitation on a novel nanostructured substrate, ‘black silicon’ coated with a 400‐nm gold layer. The spectra showed clear differences, and these ‘fingerprints’ would be suitable for the unambiguous identification of these diterpenoic acids. Copyright © 2009 John Wiley & Sons, Ltd.     

Optical investigation of CdS quantum dots in Langmuir–Blodgett films

Structures with CdS quantum dots produced by the Langmuir–Blodgett (LB) technique were investigated by Raman, IR, and UV spectroscopies. The confinement effect of longitudinal optical (LO) phonons in CdS quantum dots was investigated by Raman spectroscopy. Surface vibrational modes of CdS quantum dots were observed in IR spectra. It was shown experimentally that the frequency of the surface vibrational modes depends on the properties of the surrounding media. An average size of CdS quantum dots of about 3–6.4 nm was obtained from the analysis of UV measurements. Received: 1 February 1999 / Accepted: 1 April 1999 / Published online: 19 May 1999     

Raman spectroscopy of sol–gel derived titanium oxide thin films

Raman spectra of TiO₂ films prepared via the sol–gel process were studied by UV and visible Raman spectroscopy. The evolution of the phases of TiO₂ films during annealing was investigated, and the relative intensities of the Raman bands excited with 325 nm were found to be distinct from those of the bands excited with 514 nm. The transmittance and FTIR spectra of the films annealed at different temperatures were characterized. The crystallization process of the powders and thin films treated by different annealing methods were also studied with Raman spectroscopy. The results show that the change in the relative intensities is caused by the resonance Raman effect. The anatase to rutile transition of the powder occurs at 700 °C, while that of the thin film occurs at 800 °C. The analysis of Raman band shape (peak position and full width at half‐maximum) after conventional furnace annealing and rapid thermal annealing indicates the influence of the non‐stoichiometry and phonon confinement effect. Copyright © 2011 John Wiley & Sons, Ltd.     

Tailoring chemical and physical properties of graphene-added DNA hybrid thin films

While the characteristics of DNA and graphene are well studied, the chemical and physical properties of graphene-embedded DNA and cetyltrimethyl-ammonium chloride-modified DNA (CT-DNA) hybrid thin films (HTFs) have been rarely discussed due to the limited development of fabrication methodologies. Herein, we developed a simple drop-casting method for constructing DNA and CT-DNA HTFs added with graphene nanopowder (GNP). Additionally, we demonstrated their distinct characteristics, such as their structure, elemental composition, spin states and chemical functional groups, binding interactions, vibration/stretching modes by UV–Vis absorption, PL, and electrical measurements. The EDS spectra of GNP-added DNA HTFs showed C, N, O, Na, and P peaks at characteristic energies. Because of the physical adsorption of GNP on DNA, the peak shifts and suppression of the core spectra of O 1s and P 2p were observed by XPS. The intensity variation of Raman and FTIR bands indicated hybrid formation of GNP in DNA and CT-DNA through adsorption, electrostatic interaction, and π–π stacking. UV–Vis absorption and PL spectra showed the considerable influence of GNP in DNA and CT-DNA HTFs. DNA and CT-DNA HTFs with relatively higher [GNP] showed significant increases of current due to the formation of interconnected networks of GNP in the DNA and CT-DNA HTFs.     

Density functional theory calculations and vibrational spectra of 2‐bromo‐4‐chloro phenol and 2‐chloro‐4‐nitro phenol

FTIR and FT Raman spectra of 2‐bromo‐4‐chloro phenol (BCP) and 2‐chloro‐4‐nitro phenol (CNP) were recorded in the region 4000–400 and 4000–50 cm⁻¹, respectively. The molecular structure, geometry optimization, and vibrational wavenumbers were investigated. The spectra were interpreted with the aid of normal coordinate analysis based on density functional theory (DFT) using the standard B3LYP/6‐31G** method and basis set combination and was scaled using multiple scale factors, which yield good agreement between the observed and calculated wavenumbers. The results of the calculations are applied to simulate the infrared and Raman spectra of the title compounds, which showed excellent agreement with the observed spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

4-乙烯基联吡啶金属配合物的光谱研究

采用水热合成法以4-乙烯基联吡啶（dpe）为有机配体与铜,锌和镉的硫酸盐合成了三种金属有机配合物,利用红外、拉曼、紫外-可见光谱对dpe及合成的配位化合物进行了对比研究,对主要红外和拉曼谱带进行了归属,讨论了配体dpe和配合物的特征谱带与其结构间的关系。红外吸收光谱上,dpe中C—C伸缩和C—N面内弯曲的复合振动,在Cu-dpe,Zn-dpe和Cd-dpe配合物中分别位移到较高的波数处。在拉曼光谱中,对于相应的C—N,CC, C—C和C—H键的振动频率也看到了相同的变化规律。在紫外-可见光谱中,Zn-dpe,Cd-dpe分别只有一个配体本身的跃迁吸收峰,而配合物Cu-dpe由于发生了d—d电子跃迁,产生两个吸收峰,分别归属为配体本身的跃迁吸收谱带和配位体场吸收谱带,可见同一种配体与不同的金属离子合成的配位化合物,由于金属离子核外电子分布的不同,其紫外-可见光谱有很大变化。     

Raman spectroscopy of a-C:H:N films deposited using ECR-CVD with mixed gas

Ultraviolet (UV) and visible Raman spectroscopy were used to study a-C:H:N films deposited using ECR-CVD with a mixed gas of CH₄ and N₂. Small percentage of nitrogen from 0 to 15% is selected. Raman spectra show that CN bonds can be directly observed at 2220 cm⁻¹ from the spectra of visible and UV Raman. UV Raman enhances the sp¹ CN peak than visible Raman. In addition, the UV Raman spectra can reveal the presence of the sp³ sites. For a direct correlation of the Raman parameter with the N content, we introduced the G peak dispersion by combining the visible and UV Raman. The G peak dispersion is directly relative to the disorder of the sp² sites. It shows the a-C:H:N films with higher N content will induce more ordered sp² sites. In addition, upper shift of T position at 244 nm excitation with the high N content shows the increment of sp² fraction of films. That means the films with high N content will become soft and contain less internal stress. Hardness test of films also confirmed that more N content is with less hardness.     

DFT simulations and vibrational analysis of FTIR and FT‐Raman spectra of 2‐amino‐4,6‐dihydroxypyrimidine

This work deals with the vibrational spectroscopy of 2‐amino‐4,6‐dihydroxy pyrimidine (ADHP) by means of quantum chemical calculations. The mid‐ and far FTIR and FT‐Raman spectra were measured in the condensed state. The fundamental vibrational wavenumbers and intensity of vibrational bands were evaluated using density functional theory (DFT) with the standard B3LYP/6‐311 + G** methods and basis set combinations, and were scaled using various scale factors, which yielded good agreement between the observed and calculated wavenumbers. The vibrational spectra were interpreted with the aid of normal coordinate analysis based on the scaled density functional force field. The results of the calculations were applied to simulate the infrared and Raman spectra of the title compound, which showed excellent agreement with the observed spectra. Copyright © 2008 John Wiley & Sons, Ltd.     

Vibrational spectroscopy investigation using density functional theory on 7‐chloro‐3‐methyl‐2H‐1,2,4‐ benzothiadiazine 1,1‐dioxide

The solid phase Fourier transform infrared (FTIR) and Fourier transform (FT) Raman spectral analysis of 7‐chloro‐3‐methyl‐2H‐1,2,4‐benzothiadiazine 1,1‐dioxide (diazoxide), an antihypertensive agent was carried out along with density functional computations. The optimized geometry, wavenumber and intensity of the vibrational bands of diazoxide were obtained by DFT‐B3LYP level of theory with complete relaxation in the potential energy surface using 6‐31G(d,p) basis set. A complete vibrational assignment aided by the theoretical harmonic frequency analysis has been proposed. The harmonic vibrational wavenumbers calculated have been compared with experimental FTIR and FT Raman spectra. The observed and the calculated wavenumbers are found to be in good agreement. The experimental spectra coincide satisfactorily with those of calculated spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

Amorphous silicon carbide thin films doped with P or B for the photoelectrochemical water splitting devices

Photoelectrochemical water splitting devices require semiconductor photoelectrode material fulfilling a number of primary requirements such as band gap, band edge alignment and corrosion resistance to electrolyte. Amorphous silicon carbide films, undoped and doped (P or B), were deposited on Si substrates by PECVD technology. The concentration of elements in the films was determined by RBS and ERD analytical method. Raman spectroscopy study of the SiC films were performed by using a Raman microscope and chemical compositions were analyzed by FTIR, before and after immersion of samples to aqueous pH 2.0 and pH 1.0 sulphuric acid electrolyte. Electrical properties of SiC films before and after immersion of samples to aqueous pH 2.0 and pH 1.0 sulphuric acid electrolyte were studied by measurement of the I–V characteristics on structure Al/SiC/Si/Al. Differences between Raman spectra, FTIR spectra and I–V characteristics before and after immersion to electrolyte are discussed.     

Structure and vibrational analysis of 1‐hydroxy naphthalene based on density functional theory calculations

The solid phase mid‐FTIR and FT‐Raman spectra of 1‐hydroxy naphthalene (HNP) were recorded in the regions 4000–400 and 4000–50 cm, respectively. The spectra were interpreted with the help of normal coordinate analysis following full structure optimization and force field calculations based on the density functional theory (DFT) using the standard B3LYP/6‐31G** method and basis set combination. The results of the calculations were applied to simulate infrared and Raman spectra of the title compound which showed excellent agreement with the observed spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopy at different excitation wavelengths (1064, 785 and 532 nm) as a tool for diagnosis of colon cancer

Raman spectroscopy is structure sensitive non‐destructive method that allows observing the status of biological tissues with minimal impact. This method has a great potential in the diagnosis of various types of degenerative diseases including cancer damages. Near‐infrared Fourier transform (NIR‐FT)‐Raman (λ_ex ~1064 nm), NIR‐visible (Vis)‐Raman (λ_ex ~785 nm) and Vis‐Raman (λ_ex ~532 nm) spectra of normal and colorectal carcinoma colon tissue samples were recorded in macroscopic mode at 10–20 randomly chosen independent sites. In the cases of NIR‐Vis‐ and Vis‐Raman spectra, enhanced resonance effects were observed for tissue chromophores absorbing in the visible area. Evident spectral differences were noticed for Raman spectra of normal colon tissue samples in comparison with abnormal samples. The average Raman spectra of colon tissue samples were analysed by principal component analysis (PCA) to discriminate normal and abnormal tissues. PCA of combined dataset containing Raman intensities of chosen NIR‐FT, NIR‐Vis or Vis‐Raman bands led to discrimination of normal and abnormal colon tissue samples. Therefore, combination of these three Raman methods can be helpful for recognizing cancer lesions in colon for diagnostic purposes. Copyright © 2014 John Wiley & Sons, Ltd.     

泾渭河交汇区域平水期水体和表层沉积物溶解性有机质的光谱性质

溶解性有机质是环境生态学者关注的典型对象,其对环境质量的指示作用以及修复策略的效果评价具有重要参考价值。现阶段,对于河流和沉积物DOM的研究略显不足,尤其考虑到目标组分的动态差异 (时空、水文、环境、尺度等),相关方面的精细化研究便显得尤为必要。以泾渭河交汇区域(陕西西安高陵段)水体和表层沉积物为研究对象,通过光谱联用技术(元素分析、UV、FTIR、Raman、3D-EEMs和NMR) 深度揭示其微观特征。研究表明：沉积物DOM的H/C和N/C比都高于水体DOM,说明沉积物DOM碳氢饱和度更高,同时含有更多含氮组分。DOM紫外吸光度随吸收波长的增加逐渐下降;水体DOM吸收平台极弱,但沉积物DOM发现较明显的吸收平台(240～310 nm)。DOM含有—OH,CC, C—O等基团,沉积物DOM官能团性质略为复杂,具体体现在峰形和峰强的局部差异上。水体和沉积物DOM的Raman图谱相似,基本无法给予有效的区别信息。水体DOM荧光峰归属为可见光区类色氨酸和紫外区类富里酸,以陆源有机质为主;沉积物DOM荧光峰均属于紫外区类富里酸荧光峰,没有发现类蛋白组分特征峰。水体和沉积物DOM具有类似的C骨架,但沉积物DOM的脂族特性更明显。1H NMR结果表明碳水化合物H含量较高,而芳香族H、γ-H等含量较低。总体认为水体DOM的陆源性更加明显,沉积物DOM组分更为复杂和“年轻”。相关结果有助于深度明晰典型环境体系DOM的微观性质和环境行为。     

紫外脉冲激光退火发次对KDP晶体抗损伤性能的影响

在R-on-1的辐照模式下, 利用355 nm的紫外脉冲激光以低于KH₂PO₄ (KDP)晶体零概率损伤阈值的通量对其进行不同发次的全域扫描, 目的是为了研究KDP晶体在接受不同发次的紫外激光辐照后其抗损伤能力的变化规律及机制. 辐照后的1-on-1损伤测试表明, 适当的紫外激光退火可以有效地提升KDP晶体的抗损伤能力, 提升的幅度与其接受激光扫描的次数有关. 通过荧光和紫外吸收检测深入探讨了晶体内缺陷对激光退火的影响, 结果表明: 紫外脉冲激光辐照后KDP 晶体内的氧空位电子缺陷的存在与否是导致其抗损伤能力变化的主要原因; 通过拉曼和红外光谱的测量表明, 辐照后KDP 晶体内的PO₄, P–OH和P＝O基团的极化变形也导致了其抗损伤能力的改变. 关键词： 激光退火 荧光 拉曼 红外     

Vibrational Spectroscopic Investigation,First Hyper Polarizability and Homo–Lumo Analysis of Tetrahydroxy-1,4Quinone Hydrate Using Density Functional Theory and Hartree-Fock Method

The FTIR and FT-Raman spectra of tetrahydroxy-1,4quinone hydrate have been recorded in the regions 4000–400 and 3500–50 cm^–1 respectively. Using the observed Fourier-transform infrared spectroscopy (FTIR) and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound has been carried out. The optimum molecular geometry, harmonic vibrational frequencies, infrared intensities and Raman scattering activities, were calculated by the density functional theory (DFT/B3LYP) and Hartree–Fock (HF) method with 6-311+G(d,p) basis set. The difference between the observed and scaled wavenumber values of most of the fundamental vibrations is very small. A detailed interpretation of the infrared and Raman spectra of tetrahydroxy-1,4quinone hydrate is also reported. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule.     

Modification of optical, chemical and structural response of CR-39 polymer by 50 MeV lithium ion irradiation

CR-39 polymer samples were irradiated with 50 MeV lithium ion beam; the fluence was varied in the range 10¹¹–10¹³ ionscm⁻². Irradiation effects were studied using UV–visible, FTIR spectroscopic and X-ray diffraction techniques. The observation of the recorded spectra shows that the detector is sensitive to swift ions irradiation and its UV absorption is influenced by the stopping power (dE/dx)_e. The FTIR spectra does not show any considerable changes due to the irradiation indicating that the detector is chemically stable. No appreciable change in the diffraction pattern of CR-39 polymer after irradiation upto the fluence level of 10¹³ ionscm⁻² is observed, showing its structural stability also.