Nanomechanics of single keratin fibres: A Raman study of the α‐helix →β‐sheet transition and the effect of water

The use of micro‐Raman spectroscopy, through chemical‐bond, nano‐scale probes, allows the changes in conformations (α‐helix →β‐sheet), chain orientation, breakage of disulfide bonds (20%) and the increase of intra‐ and inter‐chain distances during the application of stress to be distinguished. The combination of micro‐Raman spectroscopy and a Universal Fibre Tester allows a quantitative measurement of the extension of chemical bonds in the peptide chain during loading. The nano‐structural transformations of keratin during strain of human hair in a dry environment (40–60% relative humidity) and saturated with water have been studied. Water permits the sliding of the chains and decreases the bond energy of the hair. Spectral analyses and 2D correlation are two coherent and independent methods to follow the structural nano‐mechanical (Raman) and micro‐mechanical (strain/stress) analyses, and confirm the validity of the experimental results, tools and principles used, as well as the agreement with the structural model of keratin fibres described by Chapman and Hearle. Copyright © 2006 John Wiley & Sons, Ltd.     

Vibrational and surface‐enhanced Raman spectra of vanillic acid

The 3‐methoxy‐4‐hydroxybenzoic acid or vanillic acid (VA) is a naturally occurring molecule important in winemaking. The spectral fingerprints of VA observed in the infrared and Raman spectra are assigned to fundamental vibrational wavenumbers supported by quantum chemical computations. The surface‐enhanced Raman scattering (SERS) of the VA has been obtained in silver colloidal solutions making possible analytical applications for detection of VA at picomole concentrations. Copyright © 2008 John Wiley & Sons, Ltd.     

Ascorbic acid vibrational spectra in sulfoxide solvents

Ascorbic acid in dimethyl-and diethylsulfoxide solutions has been studied using vibrational (Fourier transform IR and Raman) spectroscopy. Noticeable changes observed in the range of S=O-group vibrations can be explained by the presence of a hydrogen bond between ascorbic acid and sulfoxides. Various types of ascorbic acid/sulfoxide hydrogen-bonded complexes were revealed based on spectral analysis data. The results showed that the ascorbic acid/dimethylsulfoxide system has predominantly one type of complexes whereas the ascorbic acid/diethylsulfoxide system can contain three types of complexes. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 653–658, September–October, 2008.     

Iron oxide nanoparticles modified with oleic acid: Vibrational and phase determination

A simple path methodology to detect the phase composition of iron oxide nanoparticles modified with oleic acid based on vibrational spectroscopy is present here and applied on three different nanoparticles prepared by co-precipitation method. Firstly, the phase composition, magnetite, maghemite, and hematite, is determined using a reference intensity ratio methodology on X-ray diffraction pattern. Also, the size of each sample was calculated by Scherrer equation. Scanning, transmission electron microscopy, microanalysis and electron diffraction show a core magnetite particles size of around 10 nm for all particles. Based on lattice vibrations, we find a concentration of around 80% of magnetite and a hematite phase lower than 5%. Whereas, the magnetite composition from X-ray diffraction shows 76%. We also investigate the metal-organic interaction and disorder degree of organic molecule conformation by infrared and Raman spectroscopy analysis. Hematite lattice vibrations show more alterations as it interacts with the organic acid. Finally, magnetic measurements at room temperature of the modified particles, suggest a superparamagnetic behavior and high saturation magnetization.     

丁基苯酞衍生物的红外与拉曼光谱研究

丁基苯酞是我国脑血管领域第一个拥有自主知识产权的一类新药,常温下为一种淡黄色或者无色粘稠油状液体,具有众多优点,但在临床使用中会出现转氨酶升高、肝功能异常和消化道反应等不良反应。将卤素原子引入到丁基苯酞的6位,获得了3个固态的丁基苯酞类似物,并对其进行了IR和Raman光谱测定。两种光谱提供了互为补充的信息,引入卤原子后,双取代苯环的特征峰消失,出现了三取代苯环的特征峰。在红外中比较弱甚至检测不到的3位C—H伸缩振动在Raman中非常明显,在Raman的低波数区间检测到了可被指认为—C—C—C—C—的变形振动。根据这两种光谱的研究结果确认了所合成化合物的结构。     

DFT study of the hydrogen bond strength and IR spectra of formic,oxalic, glyoxylic and pyruvic acids in vacuum,acetone and water solution

The molecular geometries of the possible conformations of formic, oxalic, glyoxylic and pyruvic acids have been fully optimized at DFT B3LYP/6‐311++G(d,p) levels of calculation in vacuum as well as in water and acetone solution. Solutions were treated according to the SCRF PCM approach but some formic acid–water and formic acid–acetone clusters as well as adducts of oxalic acid with two or four water molecules were also taken into account for testing the importance of specific solute–solvent effects. All the most stable isomers of the title compounds are characterized by weak intramolecular hydrogen bonds, whose strengths (E_HB) cannot be correctly estimated as stability difference between the open and chelate forms since the energy of the former isomer is, in turn, stabilized by a weak hydrogen bridge due to the formic acid moiety. Following the Rotation Barrier Method (RBM), proposed some years ago, E_HB in the examined molecules (gas phase) falls in the range of 18–22 kJ/mol for oxalic acid (9.6 kJ/mol for the c‐C‐t isomer), 16.8 kJ/mol for glyoxylic acid and 19.8 kJ/mol for pyruvic acid. Most of them disappear at all, or nearly at all, both in acetone and aqueous solution, in consequence of the solvent effect. The frequencies of the OH and C?O stretching modes, calculated according to the anharmonic oscillator model, are in very good agreement with the experimental literature data, where available. Copyright © 2009 John Wiley & Sons, Ltd.     

Density functional and experimental studies on the FT‐IR and FT‐Raman spectra and structure of benzoic acid and 3,5‐dichloro salicylic acid

FT‐IR and FT‐Raman spectra of benzoic acid (BA) and 3,5‐dichloro salicylic acid (SA) have been recorded in the regions of 4000–400 and 4000–50 cm⁻¹ respectively. The spectra were interpreted with the aid of normal coordinate analysis following the full structure optimizations and force field calculations based on density functional theory (DFT) using standard B3LYP6‐31G** method and basis set combinations. The DFT force field transformed to natural internal coordinates was corrected by a well‐established set of scale factors that were found to be transferable to the title compounds. The infrared and Raman spectra were also predicted from the calculated intensities. Comparison of the simulated spectra with the experimental spectra provides important information about the ability of the computational method to describe the vibrational modes. Copyright © 2008 John Wiley & Sons, Ltd.     

Vibrational assignment of isoxazole aided by rovibrational data and density functional theory

IR and Raman spectra of isoxazole and D₃-isoxazole are reassigned with the aid of density functional theory calculations at the B3LYP/6-311+G(d,p) level. Harmonic wavenumber values of all non-CH stretch modes give an r.m.s. deviation from experimental values of 3 cm⁻¹ when they are uniformly scaled by 0.9818. Anharmonic values obtained using a second-order perturbative approach show an r.m.s. deviation of 7.6 cm⁻¹. Results of equal quality are obtained for D₃-isoxazole. Predicted Raman and IR band strengths match experimental spectra very closely. Detailed re-examination of rovibrational constants and inertial defect data from high resolution IR spectra, in comparison with values from the anharmonic frequency calculation, provides confirmation of the vibrational assignments. ‘Dark state’ fundamentals ν₁₂ (900.2 cm⁻¹) and ν₁₅ (866 cm⁻¹) are detected through the perturbations they cause in nearby bands.     

Vibrational spectroscopy and DFT calculations of N,N′‐dicyclohexylcarbodiimide

Infrared (IR) and Raman spectra were obtained for N,N′‐dicyclohexylcarbodiimide (DCC) in the solid state and in CHCl₃ solution. Structures and vibrational spectra of isolated, gas‐phase DCC molecules with C₂ and C_i symmetries, computed at the B3‐LYP/cc‐pVTZ level, show that the IR and Raman spectra provide convincing evidence for a C₂ structure in both the solid state and in CHCl₃ solution. Using a scaled quantum‐chemical force field, these density functional theory calculations have provided detailed assignments of the observed IR and Raman bands in terms of potential energy distributions. Comparison of solid‐state and solution spectra, together with a Raman study of the melting behaviour of DCC, revealed that no solid‐state effects were evident in the spectra. Copyright © 2010 John Wiley & Sons, Ltd.     

振动光谱法研究布洛芬及其固体分散体

将拉曼光谱法与红外光谱法相结合,以期获得布洛芬更全面的结构信息.另外,为了验证Raman光谱法验证固体分散体的可行性,采用熔融法制备布洛芬固体分散体,并用Raman光谱法和红外光谱法研究其分散性.两种鉴别方法得到一致的结果——布洛芬与载体之间不存在相互作用,以微晶状态分散在固体分散体中,且拉曼光谱法简单易行、快速直接、...     

Polymorphism of 4-Fluorophenylpyruvic Acid Studied by X-Ray Crystallography and Vibrational Spectroscopy

Two polymorphic forms (I and II) of 4-fluorophenylpyruvic acid (F-PPA) were obtained by crystallization from different solvents, showing a melting point at 163.2 and 171.0 °C. Crystal structures of polymorphs I and II were determined by X-ray crystallography. IR and Raman spectra of the two polymorphs were measured and the spectral characteristics were compared with those of phenylpyruvic acid. the two polymorphs show similar molecular and crystal structures to each other, except for the molecular geometries of the enol and the carboxylic acid moieties. Distinct IR spectral differences which result from the crystal field splitting were observed between the two polymorphs.     

Structural conformations and electronic interactions of the natural product,oroxylin: a vibrational spectroscopic study

The oroxylin, 5,7‐dihydroxy 6‐methoxy flavone is a potent natural product extracted from ‘Vitex peduncularis’. Density functional theory (DFT) at B3LYP/6‐311G(d,p) level has been used to compute energies of different conformers of oroxylin to find out their stability, the optimized geometry of the most stable conformer and its vibrational spectrum. The conformer ORLN‐1 with torsion angles 0, 180, 180 and 0 degrees, respectively, for H₁₃ O₁₂ C₆ C₅, H₁₄ O₁₀ C₄ C₅, H₁₃ O₁₂ C₆ C₅ and H₁₄ O₁₀ C₄ C₅ is found to be most stable. The optimized geometry reveals that the dihedral angle φ between phenyl ring B and the chrome part of the molecule in − 19.21° is due to the repulsive force due to steric interaction between the ortho‐hydrogen atom H₂₉ of the B ring and H₁₈ of the ring C (H₂₉·H₁₈ = 2.198 Å). A vibrational analysis based on the near‐infrared Fourier transform(NIR‐FT) Raman, Fourier transform‐infrared (FT‐IR) and the computed spectrum reveals that the methoxy group is influenced by the oxygen lone pair‐aryl p_z orbital by back donation. Hence the stretching and bending vibrational modes of the methoxy group possess the lowest wavenumber from the normal values of methyl group. The carbonyl stretching vibrations have been lowered due to conjugation and hydrogen bonding in the molecules. The intramolecular H‐bonding and nonbonded intramolecular interactions shift the band position of O₁₀ H₁₄ and O₁₂ H₁₃ stretching modes, which is justified by DFT results. Copyright © 2008 John Wiley & Sons, Ltd.     

田黄的红外与拉曼光谱研究

对中国寿山田黄石进行了X射线粉晶衍射(XRD)、红外光谱和拉曼光谱测试, 以获得田黄的谱学特征。研究表明田黄有地开石质、珍珠陶石质和伊利石质三类,其红外特征吸收峰分别为3 621,3 629和3 631 cm-1,拉曼特征峰分别为3 626,3 627和3 632 cm-1,3 550～3 750 cm-1间OH振动所致拉曼谱峰与红外结果一致。地开石质田黄含无序、有序两类,无序地开石OH3振动吸收峰相对有序地开石向低波数方向移动8 cm-1,相对强度增强,无序结构可能与高含量的Fe有关。3 550～3 750 cm-1间地开石OH振动红外吸收峰强于珍珠陶石,表现为珍珠陶石质田黄的红外光谱明显叠加有副矿物地开石的强吸收峰。伊利石质田黄主要为2M₁型伊利石,并含有少量1M型伊利石。这些特征为科学鉴定田黄提供了理论依据。     

Experimental and theoretical study of the structure and vibrational spectra of valpromide,C7H15CONH2

In this work, we present results of the conformational and vibrational properties of valpromide (Vpd), an amide with antiepileptic activity, studied by IR and Raman spectroscopy at 300 and 77 K, and 300 K, respectively. Experimental data are compared against ab initio calculations performed at B3LYP level with the inclusion of solvatation effects. Experimental results, reinforced by theoretical calculations, point out that Vpd has three conformers on the potential energy surface, with different structures that can be identified in the CO and NH spectral regions. These conformers are defined by different angular arrays of the dihedral angles formed with the CO, C N and C〈 H, C C of the aliphatic chain bonds. The existence of different conformations and structures are discussed on the basis of results derived from electronic localization function (ELF) and natural orbital bond (NBO) analysis. Copyright © 2008 John Wiley & Sons, Ltd.     

吡喃酮类化合物与镱配合物的红外和拉曼光谱研究

采用非水体系中牺牲金属阳极的电化学方法分别合成了稀土金属镱与 3 羟基黄酮及 3 羟基 2 甲基 γ 吡喃酮的配合物。对配合物进行了IR和Raman光谱测定。两种光谱提供了互为补充的信息 ,配体经配位后—OH的伸缩振动谱峰消失 ,部分相关的谱峰频率发生了明显位移 ,特别是羰基伸缩振动红移十分明显 ,在Raman光谱的低波数区间检测到可指认为金属和配体键合的伸缩振动。根据这两种光谱的研究结果推断了所得配合物的可能结构。     

Micro‐Raman spectroscopic study of artificially aged natural and dyed wool

The objective of this study was to evaluate the use of micro‐Raman spectroscopy as a non‐invasive vibrational spectroscopic technique applied to the examination of wool samples, which may be applied to textile materials of cultural heritage interest. In this work, a selection of wool materials were primarily investigated in their unaged states through the utility of a natural wool reference together with selected samples dyed with different natural colorants, namely woad, weld and madder. The identification of the main modes of vibration of the wool fibre keratin was assessed in all the samples, which aided the determination of the changes within the protein structure, in particular, through the cysteine and peptide cross‐linkages brought about by the addition of the dyes that can produce effects similar to degradation. The dye too was assessed importantly to enable its identification through its characteristic scattering or fluorescence emissions on a woollen matrix, as well as to ascertain whether a uniform covering across the surface of the wool was achieved or not. Regarding the artificial degradation of the samples it was possible to observe numerous modifications within the molecular structure of the wool, in particular, within the amide I, C H bending, amide III and S‐S stretchings along with the physical photo‐yellowing of fibres given by the presence of lipids dispersed across the surface of the wool. The effects of ageing on the dyed samples were also investigated, indicating that many of the bands relative to the colorants were still present, yet so too were numerous vibrations from the wool that also indicated a certain level of stress and degradation to the underlying wool. Copyright © 2008 John Wiley & Sons, Ltd.     

美国通用电气公司宝石级合成翡翠的振动谱学研究

对近来面市的美国通用电气公司的宝石级合成翡翠,使用傅里叶红外光谱仪、 激光拉曼光谱仪等谱学分析测试仪器进行测试,研究其振动光谱,试图从振动谱学的角度分析研究这种合成翡翠的特征,并比较它与天然翡翠的异同。研究结果表明： 在红外光谱方面： 美国通用电气公司宝石级合成翡翠的指纹区与天然翡翠的基本相同; 而在基团频率区,则有明显的不同： 在3 400～3 700 cm-1范围内显示一组由OH的伸缩振动导致的特征吸收谱带: 3 375,3 471和3 614 cm-1。揭示了合成翡翠中含有一定数量的羟基。在拉曼光谱方面,一组376,700,989和1 039 cm-1的尖锐吸收峰一方面显示了和天然翡翠的拉曼特征一致性,另一方面也显示其具有完好的结晶形态,红外光谱和拉曼光谱均显示了样品中重质量的阳离子的缺乏。     

Vibrational spectroscopy of perfluoropropionic acid in the region between 1000 and 11 000 cm

Fully fluorinated compounds, known as perfluorinated compounds, are widely used in industrial applications. Recently, some perfluorinated acids have been detected in the atmosphere and the tissues of animals. Some perfluorocarboxylic acids are emitted to the atmosphere from the thermolysis of fluoropolymers and the degradation of fluorotelomer alcohols. The gas phase vibrational spectrum of a representative perfluorocarboxylic acid in the region between 1000 and 11 000 cm⁻¹ has been investigated, with emphasis on the vibrational overtone spectrum in the near-IR region. The most intense transition in the fundamental spectrum is the CF₃ stretch while in the overtone region, the O-H stretch carries most of the intensity. A comparison of the perfluorocarboxylic acid vibrational spectrum with the hydrocarbon analog acid is discussed.     

A Review of the Vibrational Spectroscopic Studies of Arsenite,Antimonite, and Antimonate Minerals

Abstract

This review focuses on the vibrational spectroscopy of the compounds and minerals containing the arsenite, antimonite, and antimonate anions. The review collects and correlates the published data.     

Vibrational study,phase transitions and electrical properties of 4-benzylpyridinium monohydrogenselenate

The title compound C₆H₅CH₂C₅H₄NH⁺·HSeO₄⁻ crystallizes in the orthorhombic system with the space group Pbca and the following unit cell dimensions: a=27.449(5) Å; b=10.821(6) Å and c=8.830(1) Å.The structure consists of infinite parallel two-dimensional planes built of HSeO₄⁻ anions and C₆H₅CH₂C₅H₄NH⁺ cations mutually.Differential scanning calorimetry study on 4-benzylpyridinium monohydrogen-selenate was carried out. A high temperature second order phase transition at 363 K was found and characterized by electric measurements. The Raman of polycrystalline sample has been recorded at different temperature between 297 and 373 K.The conductivity relaxation parameters associated with some H⁺ conduction have been determined from an analysis of the M′′/M′′_max spectrum measured in a wide temperature range. An appearance of the superionic phase transition in 4-BSe is closely related to a liberation or even a rotation increase of HSeO₄⁻ groups with heating.