Improved methods for fluorescence background subtraction from Raman spectra

Raman spectroscopy has attracted interest as a non‐invasive optical technique to study the composition and structure of a wide range of materials at the microscopic level. The intrinsic fluorescence background can be orders of magnitude stronger than the Raman scattering, and so, background removal is one of the foremost challenges for quantitative analysis of Raman spectra in many samples. A range of methods anchored in instrumental and computational programming approaches have been proposed for removing fluorescence background signals. An enhanced adaptive weighting scheme for automated fluorescence removal is reported, applicable to both polynomial fitting and penalized least squares approaches. Analysis of the background fitting results for ensembles of simulated spectra suggests that the method is robust and reliable and can significantly improve the background fit over the range of signal, shot noise and background parameters tested, while reducing the subjective nature of the process. The method was also illustrated by application to experimental data generated from aqueous solutions of bulk protein fibrinogen mixed with dextran. Copyright © 2013 John Wiley & Sons, Ltd.     

Emission background in the Raman spectra of barbituric acid and azobenzene

The suggestion that two photon absorption and reemission may contribute to the emission background observed in the Raman spectra of barbituric acid and azobenzene has been tested by a study of the anti-Stokes fluorescence and of the dependence of the emission on the incident laser intensity of these molecules. Both tests indicate that the two photon process is an insignificant factor in the background emission.     

Vibrational features of confined water in nanoporous TiO_2 by Raman spectra

Raman spectra of confined water adsorbed in nanoporous TiO_2 are obtained in experiment. TiO_2 samples with different pore diameters under different humidity conditions are investigated. The results indicate that the symmetric vibrational mode of water molecule is destroyed when relative humidity decreases. This indicates that the interaction between water molecules and surface of TiO_2 becomes stronger when the distance between water molecules and surface turns smaller, and the interaction plays a major role in depressing the symmetric vibrational peak. The spectra of confined water in TiO_2 and Vycor are compared. When filling fractions are the same, their spectra show distinctions no matter whether they are in partial filling condition or in full filling condition. The spectra of HDO confined in TiO_2 with different filling fractions are compared with each other. There is no clear distinction among their vibrational peaks, and the peaks mainly relate to asymmetric vibration. Therefore, the interaction between water molecules and the wall of pore decouples the symmetric vibrational mode only, and the influences on asymmetric vibrational mode show little differences among different filling fractions.     

1.0～4.4GPa下奥长石拉曼光谱特征的变化

常温、1.0～4.4GPa下,利用激光拉曼光谱研究了奥长石晶体结构随压力的变化。发现,压力为2.9GPa时,517cm-1附近出现新的谱峰,奥长石开始相变。3.4GPa时,源于奥长石结构中M—O伸缩振动的288cm-1拉曼谱峰频移发生突变,517cm-1附近谱峰消失,奥长石由三斜晶系完全相变为单斜晶系(P1-I1)。随压力增加,归属于奥长石四面体结构中Si—O—Si弯曲振动的458及516cm-1谱峰随压力增加有规律地向高频方向偏移,斜率分别是1.667cm-1/GPa和3.560cm-1/GPa,而源于Al—O—Al弯曲振动的480cm-1谱峰与压力没有明显的线性变化关系。卸压过程中,288cm-1拉曼谱峰频移保持不变,458,480及516cm-1谱峰向低频偏移。长石类矿物的相变压力与结构中八元环所含阳离子种类有关。     

Raman spectra of different carbonaceous materials of astrophysical interest

We present here the Raman spectra of 9 different carbonaceous materials of astronomical relevance, including single polycyclic aromatic hydrocarbons and mixtures. Eight of 9 samples show two main bands falling respectively at around 1600 and 1350 cm⁻¹ which imply that all the materials are composed by randomly oriented structural units varying from 50 to 80 Å in size. Further bands and/or shoulders appear in some cases between 800 and 1700 cm⁻¹ (6 and 12 μm) and are attributed to CC or CH_n (n = 1,2,3) functional groups. The coronene spectrum is the only one which does not present any significant band although it shows a very high level of fluorescence. These results provide information about candidate materials which may account for unidentified IR bands observed in astronomical sources.     

Range‐independent background subtraction algorithm for recovery of Raman spectra of biological tissue

An important requirement for the use of Raman spectroscopy for tissue diagnostic applications is an appropriate algorithm that can faithfully retrieve weak tissue Raman signals from the measured raw Raman spectra. Although iterative modified polynomial‐fitting‐based automated algorithms are widely used, these are sensitive to the choice of the fitting range, thereby leading to significantly different Raman spectra for different start and stop wavenumber selection. We report here an algorithm for automated recovery of the weak Raman signal, which is range independent. Given a raw Raman spectrum and the choice of the start and the stop wavenumbers, the algorithm first truncates the spectrum to include the raw data within this wavenumber range, linearly extrapolates the truncated raw spectrum beyond the points of truncation on the two sides by using coefficients of linear least‐square fit, adds two Gaussian peaks of appropriate height and width on the extrapolated linear wings on either side and then iteratively smoothens the data with all these add‐ons such that the smaller of the ordinate values of the smoothed and the starting raw data serve as the input to each successive round of iterative smoothing until the added Gaussian peaks are fully recovered. The algorithm was compared with the modified polynomial‐based algorithms using mathematically simulated Raman spectrum as well as experimentally measured Raman spectra from various biological samples and was found to yield consistently range‐independent and artifact‐free Raman signal with zero baseline. Copyright © 2012 John Wiley & Sons, Ltd.     

Slow variations of the electroconductivity of distilled water

The conductivity of distilled water with a slow change in temperature has been measured experimentally and studied. Periodic variations in the electrical conductivity of water have been found, which are observed at the rate of temperature change dT/dt < 0.1 K/h. The periods were longer than 24 h; the amplitudes of the variation ranged from +2.7% to–2.3%. The possible causes of the observed phenomena are discussed.     

Vibrational properties and Raman spectra of different edge graphene nanoribbons,studied by first-principles calculations

The vibrational properties and Raman spectra of graphene nanoribbons with six different edges have been studied by using the first-principles calculations. It is found that edge reconstruction leads to the emergence of localized vibrational modes and new topological defect modes, making the different edges identified by polarized Raman spectra. The radial breathing-like modes are found to be independent of the edge structures, while the G-band-related modes are affected by different edge structures. Our results suggest that the polarized Raman spectrum could be a powerful experimental tool for distinguishing the GNRs with different edge structures due to their different vibrational properties.     

用激光拉曼光谱研究液态乙醇的水合作用过程

为研究室温下乙醇-水二元混合物内部的分子间缔合情形,测得了不同体积配比溶液的拉曼光谱,发现位于2 800~3 050 cm-1波数区间的C—H伸缩振动频率随乙醇中加入水量的增加整体呈现蓝移趋势,而位于1 048 cm-1附近的CO伸缩振动频率的变化规律却与此相反。分析认为,这种现象主要由溶液内部分子间发生的不同水合作用所致,并据此阐明了液态乙醇的水合作用过程:水分子首先与纯乙醇中的自缔合短链发生氢键缔合作用,形成了含有较多乙醇分子数的乙醇水合团簇,直到溶液中水的体积含量达到50%时,乙醇的水合作用达到暂时饱和;而当水的体积含量继续增加到70%以后,水分子致使原有乙醇水合团簇解离形成较小尺寸的团簇,并与解离点位上的乙醇分子羟基发生进一步水合作用;而后,当水体积含量增至一定程度后,还会导致乙醇分子疏水基CH基团与水分子间形成弱氢键C—H…O。     

Spontaneous Raman scattering spectra of ADP and DADP crystals in different polarization schemes

Spontaneous Raman-scattering spectra of light in ADP and DADP crystals were obtained in four polarization schemes, the widths of some Raman lines were measured. The presence of a strong and sharp Raman line corresponding to the totally symmetric vibration of the phosphate group and a strong diffuse Raman satellite corresponding to the totally symmetric vibration of the ammonium group in the spontaneous scattering spectra of both (ADP and DADP) crystals was observed. According to the theory, such lines are preferable for the stimulated Raman scattering.     

Raman scattering of light by the electroactivated water

Raman spectra of the electroactivated water and its chemical analogs are studied. The substantial differences are found in the 700–2700-cm^?1 region, which are assumed to be related to the presence of a charged hydrogen bond in associates involving excessive H⁺ and OH^? ions.     

Resonance Raman spectra of carbon nanotubes by cross-polarized light

Resonance Raman studies on single wall carbon nanotubes (SWNTs) show that resonance with cross polarized light, i.e., with the E(mu,mu+/-1) van Hove singularities in the joint density of states needs to be taken into account when analyzing the Raman and optical absorption spectra from isolated SWNTs. This study is performed by analyzing the polarization, laser energy, and diameter dependence of two Raman features, the tangential modes (G band) and a second-order mode (G' band), at the isolated SWNT level.     

Determination of the tautomeric composition of adenine in the gas phase by vibrational spectroscopy methods: II. Analysis of resonance Raman spectra

The resonance Raman spectra of adenine in the gas phase under excitation with laser radiation at wavelengths of 266, 218, and 200 nm have been investigated experimentally. The quantum-mechanical calculations of the intensity distribution in the resonance Raman spectra of three adenine tautomers are performed in the Herzberg-Teller approximation with the inclusion of the Duschinsky and frequency effects. Conclusions regarding the tautomeric composition of adenine in the gas phase are drawn from comparison of the results of quantum-mechanical calculations with experimental data.     

Stimulated Raman spectra generated by ps-pulses in a single-mode fiber

Efficient frequency conversion of 5 ps-pulses from a cavity dumped Rh6G-dye laser by stimulated-Raman-scattering (SRS) into the first and second Stokes order has been achieved. The simulateneously produced asymmetric spectrical broadening of the pump pulses leads to double peaks in the Raman spectrum. By means of spectrally resolved cross-correlation measurements with 2 ps pulses from a second synchronized dye laser, the relative arrival time of the various spectral components is measured. Furthermore it is shown that the effect of a reduction of the pump peak power by SPM is partially compensated by the temporal broadening of the pump pulses leading to a longer interaction length for SRS.     

Fluctuation theory of hydrogen bonding applied to vibration spectra of HOD molecules in liquid water. I. Raman spectra

Statistical distributions of the frequencies of OH vibrations calculated from the experimental Raman spectra of HOD molecules over the temperature range of 10–200 C using the recently developed deconvolution technique have been analysed in the framework of fluctuation theory of hydrogen bonding. Two temperature independent functions that are the basis of the Zhukovsky theory for describing the temperature transformation of frequency distribution functions of OH vibrations in a statistical ensemble of O—H…O bonds were established and analytically approximated. This made it possible to reconstruct the entire set of initial spectra and to extrapolate their forms to a wider temperature range. These results support the continuum model of liquid water structure.     

Raman spectra of the high-Tc superconductor Y-Ba-Cu-O

The Raman scattering experiments on the high-T_c superconducting material Y-Ba-Cu-O have been performed at room temperature. Two strong lines at 600 and 1100 cm^-1 have been observed and discussed.     

李时珍石的红外与拉曼光谱

李时珍石是一种硫酸盐新矿物，理想分子式为：ＺｎＦｅ＿２（ＳＯ＿４）＿４·１４Ｈ＿（２）Ｏ。属三斜晶系。空间群Ｐ，Ｚ＝１。本文首次报导它的拉曼光谱，并结合红外光谱，以及与它的类质同象物─—粒铁矾的振动光谱对照，对李时珍石的振动光谱的主要谱带的归属作了探讨。     

n-SiC的电子拉曼散射及二级拉曼谱研究

研究了利用离子注入法得到的掺氮n-SiC拉曼光谱. 理论线形分析表明,与4H-SiC相比,6H-SiC中LO声子等离子体激元耦合模(LOPC模)拉曼位移随自由载流子浓度变化较小. 5145nm激发光下得到的电子拉曼散射光谱表明,k位处由1s(A₁)到1s(E)的能谷轨道跃迁带来的拉曼谱6H-SiC中有四条,4H-SiC中有二条;高频6303及635cm^-1处观察到的谱线被认为与深能级缺陷有关. 最后,利用纤锌矿型结构二级拉曼散射选择定则指认了6 关键词： 碳化硅 电子拉曼散射 轨道能谷分裂 倍频谱