紫外辐射对牛血清白蛋白影响的拉曼光谱分析

检测了牛血清白蛋白粉末和水溶液及其经过40min、3h、5h和8h紫外辐射的拉曼光谱图。实验结果表明紫外辐射改变了牛血清白蛋白中硫硫键的几何构型,40min的紫外辐射使牛血清白蛋白粉末中一半以上的硫硫键由“扭式-扭式-扭式”构型变成了“反式-扭式-扭式”构型,经过3h和5h的紫外辐射,从拉曼谱图上已看不到表征硫硫键几何构型的谱峰。40min和3h的紫外辐射使牛血清白蛋白水溶液中部分硫硫键由“扭式-扭式-扭式”构型变成了“反式-扭式-扭式”构型,但当紫外辐射时间长达5h时,硫硫键又只有“扭式-扭式-扭式”一种构型。经过紫外辐射,牛血清白蛋白粉末中酪氨酸残基有由“暴露”式向“埋藏”式转变的趋势;水溶液中一部分酪氨酸残基经紫外辐射后由“暴露”式变成了“埋藏”式。紫外辐射对粉末状态牛血清白蛋白主链构象影响要比溶液状态大。     

热处理和紫外辐射对DNA影响的拉曼光谱研究

检测了鲕鱼精ＤＮＡ纤维和经过４０℃，９１℃，２００℃加热处理的拉曼光谱。研究结果表明，在熔融温度以下热处理对ＤＮＡ构象的影响是轻微的，在熔融温度以上则随温度的升高，对ＤＮＡ分子结构的影响有破坏也逐渐加剧，首先受影响的是腺嘌呤和脱氧核糖。     

UV-A区段紫外辐射对DNA影响的拉曼光谱研究

检测了小牛胸腺 DNA水溶液经 2 h和 16 h UV- A区段紫外辐射的拉曼光谱。实验结果表明 ,该区段紫外辐射对 DNA的影响要比全波段紫外辐射的影响小得多。主链构象基本上没有受到影响。经过较长时间的 UV- A区段紫外辐射后 ,DNA受到了较轻的损伤。 80 3— 816 cm-1间峰的变化表明 DNA链不同区段的构型处于不断的变化之中。脱氧核糖的特征峰 ,或强度有所下降 ,或峰发生了位移 ,或者两种变化皆有 ,表明 A区段紫外辐射对 DNA的脱氧核糖有所损伤。胸腺嘧啶的 6 81cm-1、75 2 cm-1和 1177cm-1谱线都发生了变化 ,表明胸腺嘧啶也受到了影响。但嘌呤碱基和胞嘧啶基本上没有受到影响。     

紫外辐射对小牛胸腺DNA水溶液影响的拉曼光谱研究

报道了小牛胸腺DNA水溶液经9,20,40min紫外辐射的拉曼光谱图,紫外线的辐射照度为1868W·m-2。实验结果表明波长为2537nm的紫外光在起主要作用的紫外辐射对DNA的损伤是严重的,短短10min的紫外辐射就使1094cm-1这个强峰分裂成几个小峰,说明DNA的构象受到破坏,DNA的构型发生变化,部分单双键发生了断裂,出现了各种各样由于DNA键断裂产生的多核苷酸;4种碱基均受到不同程度的影响,碱基间的氢键造成断裂,其中嘧啶、嘌呤碱基受到的损伤较为严重;紫外辐射对脱氧核糖也产生了破坏。另外,该实验也表明,在水溶液中,DNA以B型结构为主,局部的A型结构仍然存在。     

油酸和亚油酸的激光拉曼光谱

不同的不饱和脂肪酸各自具有其不同的生理功能,但常见的不饱和脂肪酸产品大部分为几种脂肪酸的混合物,故在应用前对不纯的脂肪酸产品进行组成分析是必须的。测量了不饱和脂肪酸产品组分中最常见的油酸和亚油酸的拉曼光谱,确定了各拉曼谱线的振动模归属,分析了其分子的构象特征。该结果为研究长链不饱和脂肪酸的振动能级结构及能级间跃迁等做了基础工作,丰富了有机物分子的价键数据和性质。同时详细分析比较了油酸和亚油酸拉曼光谱的差异,为定性鉴别脂肪酸产品的成分提供了一种简便有效的方法,对拉曼光谱在地沟油检测方面的应用具有重要的指导意义。     

生活用水的拉曼光谱分析

为了进行水质分析,运用激光拉曼光谱方法测量了自来水和白开水的拉曼光谱,分析了其振动方式归属与光谱强度。结果表明,3200～3400cm-1较强的拉曼谱带(伸缩振动)是水分子的振动拉曼特征峰,水中杂质尤其是钙镁离子含量是影响拉曼特征峰强度的主要因素。     

长波紫外辐射对Ⅰ型胶原损伤的拉曼光谱研究

应用拉曼光谱技术研究了长波紫外(Ultraviolet-A,UV-A)辐射对Ⅰ型胶原的损伤,检测了Ⅰ型胶原及其经过90min的UV-A辐射后的拉曼光谱,得到了一个较完整的Ⅰ型胶原紫外损伤机制。实验结果表明:90min的UV-A辐射导致Ⅰ型胶原分子内氢键断裂、氢键体系发生变化,肽链的螺旋度减少,逐渐解螺旋,无规卷曲等无序构象增加。此外,UV-A辐射使Ⅰ型胶原分子内脯氨酸的羟基化程度降低。这些变化必然会引起Ⅰ型胶原三螺旋结构的损伤,并导致皮肤光老化过程中组织内胶原纤维的破坏。     

聚合物分散液晶的制备及拉曼光谱分析

用溶致相分离的方法制备了以PMMA为基体的四种不同配比的聚合物分散液晶(PDLC),四氢呋喃为引发剂,并且通过傅立叶拉曼光谱仪对其进行检测,分析其光谱,观察各单体混合前后性质的变化,鉴别聚合物分散液晶的物质构成。此外,在指定的组分前提下,根据液晶最强峰与PMMA特征峰的相对强度拟合曲线得出PDLC中液晶与PMMA的质量百分比,为下一步研究聚合物分散液晶系统的光折变特性提供指导。     

内分泌干扰物三苯基锡的激光拉曼光谱分析

三苯基锡(TPhT)是目前已知的内分泌干扰物中唯一的两种金属化合物之一,被广泛应用于工业、农业和交通领域,其大量使用会对土壤、海洋和内陆淡水环境造成不同程度的影响。本实验采用激光共聚焦拉曼光谱采集固体TPhT的拉曼光谱信号,尝试将该方法用于TPhT检测,探索该方法的可行性,并进行检测参数的优化选择。将拉曼光谱分析检测方法与TPhT的物性研究相结合,根据TPhT分子中不同官能团振动模式的不同,将拉曼谱图分为高、中、低3个波数区(1 500～3 200,900～1 500和100～900 cm-1)进行拉曼谱峰的归属与分析,得到了TPhT的特征振动模式和拉曼特征峰,并建立一套TPhT的标准拉曼图谱库,光谱范围在100～3 200 cm-1之间。结果表明,当激光功率选择为衰减到原激光功率(500 mW)的0.5%、曝光10 s、累积2次时,得到的拉曼谱图信噪比高且检测时间短。在212,332,657,997和1 577 cm-1处出现的信号强度较高的拉曼峰,可作为固体TPhT拉曼检测的特征峰,657和997 cm-1处拉曼特征峰的同时出现即可认为复杂的环境样品中存在TPhT。实验结果给出了辨别TPhT存在的标志,这些结果将为拉曼光谱用于实际环境样品中TPhT的残留检测提供理论依据和数据基础。     

The autooxidation process in linoleic acid screened by Raman spectroscopy

The chemical changes associated to the autooxidation process of linoleic acid (LA) were detected by Raman spectroscopy and interpreted in the light of density functional theory (DFT) calculations performed for both the fatty acid and its main oxidation products. The present methodology, applied for a six‐day period upon induction of oxidation (through heating), allowed to understand the chemical modifications occurring during the oxidation process. Raman spectroscopy was shown to be a suitable and reliable technique for assessing the oxidation degree of fatty acid samples, particularly pure fatty acids, mainly when computational methods are used alongside to predict the spectral features of the distinct chemical entities involved. Screening of the oxidation process was mostly based on the loss of intensity of the bands assigned to LA cis‐double bonds. Copyright © 2012 John Wiley & Sons, Ltd.     

Investigation of L(+)-Ascorbic acid with Raman spectroscopy in visible and UV light

Abstract: Raman spectroscopy investigations of l(+)-ascorbic acid and its mono- and di-deprotonated anions (AH^? and A^2?) are reviewed and new measurements reported with several wavelengths, 229, 244, 266, 488, and 532 nm. Results are interpreted, assisted by new DFT/B3LYP quantum chemical calculations with 6-311++G(d,p) basis sets for several conformations of ascorbic acid and the anions. Raman spectra were measured during titration with NaOH base in an oxygen-poor environment to avoid fluorescence when solutions were alkaline. The ultraviolet (UV) absorption band for ascorbic acid in aqueous solution at ～247 nm was found to cause strong resonance enhancement for the ring C?C stretching mode (called B) at ～1692 cm^?1. The ascorbate mono-anion absorbs at ～264.8 nm giving Raman resonance enhancement for the same ring C–C bond stretching, downshifted to ～1591 cm^?1. Finally, for the ascorbate di-anion, absorption was found at ～298.4 nm with molar absorptivity of ～7,000 L mol^?1 cm^?1 and below ～220 nm. With UV light (244 and 266 nm), strongly basic solutions gave pronounced Raman resonance enhancement at ～1556 cm^?1. Relatively weak preresonance enhancement was seen for A^2? when excitation was done with 229 nm UV light, allowing water bands to become observable as for normal visible light Raman spectra.     

Blood analysis by Raman spectroscopy

Concentrations of multiple analytes were simultaneously measured in whole blood with clinical accuracy, without sample processing, using near-infrared Raman spectroscopy. Spectra were acquired with an instrument employing nonimaging optics, designed using Monte Carlo simulations of the influence of light-scattering-absorbing blood cells on the excitation and emission of Raman light in turbid medium. Raman spectra were collected from whole blood drawn from 31 individuals. Quantitative predictions of glucose, urea, total protein, albumin, triglycerides, hematocrit, and hemoglobin were made by means of partial least-squares (PLS) analysis with clinically relevant precision (r(2) values >0.93). The similarity of the features of the PLS calibration spectra to those of the respective analyte spectra illustrates that the predictions are based on molecular information carried by the Raman light. This demonstrates the feasibility of using Raman spectroscopy for quantitative measurements of biomolecular contents in highly light-scattering and absorbing media.     

Raman spectroscopy of laser‐induced oxidation of titanomagnetites

Titanomagnetites are important carriers of magnetic remanence in nature and can track redox conditions in magma. The titanium concentration in magnetite bears heavily on its magnetic properties, such as saturation moment and Curie temperature. On land and in the deep ocean, however, these minerals are prone to alteration which can mask the primary magnetic signals they once recorded. Thus, it is essential to characterize the cation composition and oxidation state of titanomagnetites that record the paleomagnetic field. Raman spectroscopy provides a unique tool for both purposes. Nonetheless, the heat generated by the excitation laser can itself induce oxidation. We show that the laser power threshold to produce oxidation decreases with increasing titanium content. With confocal Raman spectroscopy and magnetic force microscopy (MFM) on natural and synthetic titanomagnetites, a non‐destructive Raman imaging protocol was established. We applied this protocol to map out the composition and magnetization state within a single ex‐solved titanomagnetite grain in a deep‐sea basalt. Copyright © 2011 John Wiley & Sons, Ltd.     

Monitoring deprotonation of gallic acid by Raman spectroscopy

Gallic acid (GA) is involved in many biochemical processes and reactions and is of great importance in environment thanks to its antioxidant and pro‐oxidant properties. We present in this paper a comprehensive study of GA deprotonation by means of Raman spectroscopy. In the Raman spectra, we identified the characteristic bands that were sensitive to the five pH‐dependent GA forms. From these results, we extracted the GA pKa values that are consistent with the reference values. These results permit the monitoring of GA forms for applications. Copyright © 2015 John Wiley & Sons, Ltd.     

Dengue blood analysis by Raman spectroscopy

In this work Raman spectra of normal and dengue infected serum and whole blood were analyzed. In normal whole blood and serum characteristic peaks were observed when excited at 442 and 532 nm. In dengue whole blood and serum all peaks found to be blue shifted with reduced Raman intensity. Dengue whole blood and serum shows two peaks at 1614 and 1750 cm^?1 which are due to presence of Immunoglobulin antibodies IgG and IgM. Whole study provides a route of information for diagnosis of dengue viral infection.     

Simple and inexpensive instrument for deep‐UV Raman spectroscopy

Deep‐UV Raman spectroscopy is a powerful way to collect chemically specific information about complex samples. The availability of inexpensive and reliable light sources in the spectral region below 250 nm has been always considered a major bottleneck problem on the way of a widespread of this powerful spectroscopic technique. We report on the efficient fourth‐harmonic generation of a low‐power microchip Nd:YAG laser operating at 946 nm. High‐quality deep‐UV Raman spectra were collected using a newly developed laser source. Copyright © 2013 John Wiley & Sons, Ltd.     

In vivo Raman spectroscopic analysis of the influence of UV radiation on carotenoid antioxidant substance degradation of the human skin

It is well known from the literature that carotenoid antioxidant substances decrease after the irradiation of the skin with UV light. Available literature has shown no information about the response time and total dynamics of degradation of carotenoid antioxidants after UV irradiation. The measurements were made with the HPLC method, which is time-consuming and does not give relevant information about the dynamics of degradation of carotenoids in the skin after UV irradiation. With the introduction of new noninvasive spectroscopic methods, it became possible to measure in vivo the behavior of carotenoid antioxidant substances, such as betacarotene and lycopene in the skin after UV light exposure. In the present study, the resonance Raman spectroscopy method was used as a fast and noninvasive optical method to measure the dynamics of degradation of beta-carotene and lycopene in living human skin after UV exposure. It was found that the beta-carotene and lycopene concentration in the skin does not decrease immediately after UV irradiation. There is a time delay, which varies from 30 up to 90 min for beta-carotene and from 0 up to 30 min for lycopene. A strong nonlinear correlation between the individual antioxidant level of volunteers and the magnitude of destruction of antioxidants in the skin was found.     

Residual benzamide contamination in synthetic oligonucleotides observed using UV resonance Raman spectroscopy

Spectroscopic methods based on Raman scattering have for many years employed synthetic oligonucleotides in a broad range of applications, either as probes or as model analytes for biophysical investigations. Benzamide is commonly used as a protecting group in the phosphoramidite synthesis of oligonucleotides and, while standard desalting used after synthesis yields sufficiently pure reagents for most assay reactions or other routine uses of the oligomer, it does not completely remove benzamide. We show that the 1609 cm⁻¹ band of residual benzamide contamination can interfere with certain nucleic acid bands, particularly when using excitation wavelengths near 244 nm where the benzamide band is strongly enhanced. For example, the 1609 cm⁻¹ band of benzamide could obscure (or be mistaken as) a weak vibration attributed to an  NH₂ scissoring. The extent of benzamide contamination in desalted preparations varies considerably among different commercial sources, and hence caution is advised when making direct comparisons of ultraviolet Raman data of oligonucleotides from different sources. Copyright © 2010 John Wiley & Sons, Ltd.     

Structural changes in perylene from UV Raman spectroscopy up to 1 GPa

Vibrational properties and structural changes under pressure of a highly luminescent molecular organic crystal have been investigated by ultraviolet resonant Raman spectroscopy with a 244‐nm excitation. Resonant Raman modes of α‐perylene crystal up to 1GPa were followed under hydrostatic pressure in an anvil cell with a sapphire window transparent to ultraviolet light. Nonlinear evolution of intra‐molecular modes is induced by pressure. Abrupt shifts of Raman wavenumbers suggest structural and planar modifications of the molecules in the crystal. We interpret these shifts as a first‐order phase transition to a lower volume of unit cell. The luminescence of perylene crystal is gradually modified as a consequence of these structural changes. The present experimental setup allows investigating with Raman spectroscopy very luminescent molecules involved in chemical reactions and molecular organic crystals under relatively high pressure (up to 1GPa). Copyright © 2016 John Wiley & Sons, Ltd.