Near-infrared excited Raman optical activity

Measurements of near-infrared scattered circular polarization Raman optical activity (SCP-ROA) are presented using laser excitation at 780 nm for samples of S-(-)-alpha-pinene and L-alanyl-L-alanine. These are the first measurements of ROA outside the blue-to-green visible region between 488 and 532 nm. Comparison of Raman and ROA intensities measured with excitation at 532 and 780 nm demonstrate that the expected frequency to the fourth-power dependence for Raman scattering and the corresponding fifth-power dependence for ROA are observed. It can be concluded that, to within this frequency dependence, the same level of efficiency of Raman and ROA measurements using commercial instrumentation with 532 nm excitation is maintained with the change to near-infrared excitation at 780 nm.     

非线性光学晶体三硼酸铋的拉曼光散射

结构分析表明非线性光学晶体三硼酸铋BiB3 O6的晶胞参数为a1=0 .7116nm ,a2 =0 .4993nm ,a3 =0 .65 0 8nm ,β =10 5 .62° ,每个初基晶胞含有二个分子。在不同几何配置下的激光拉曼光谱观察到了晶体中硼氧四面体和硼氧三角形的特征晶格振动和振动模的分裂。拉曼光谱表明晶体的内部结构有很强的各向异性 ,这就是晶体非线性光学性质的来源     

Vibrational spectra and surface-enhanced vibrational spectra of 1-nitropyrene

The present report on the vibrational spectra of 1-nitropyrene (1NP) describes the infrared and Raman spectra; their interpretation is aided by local density functional theory (DFT) calculations at the B3LYP/6-311G(d, p) level of theory and by the surface-enhanced vibrational spectra (SEVS) with the final objective of trace organic analytical applications. The surface-enhanced Raman scattering (SERS) on silver island films and mixed silver/gold island films was investigated with several laser lines in the visible region. Surface-enhanced infrared absorption (SEIRA) was attempted on silver and gold island films. The interface of the organic 1-NP with smooth metal surfaces of silver and copper was also probed using reflection-absorption infrared (RAIRS) spectra that, in conjunction with the transmission spectra, allow one to extract the molecular orientation in vacuum evaporated thin solid films. Chemical adsorption of 1-NP on silver and further photochemical decomposition of the 1-NP-metal adsorbates was detected with all visible laser lines. Resonance Raman scattering (RRS) using UV-laser excitation at 325 nm was also recorded.     

Phosphorylation detection and characterization in ribonucleotides using Raman and Raman optical activity (ROA) spectroscopies

Raman and Raman optical activity (ROA) spectra are presented for adenosine and seven of its derivative ribonucleotides. Both of these spectroscopic techniques are shown to be sensitive to the site and degree of phosphorylation, with a considerable number of marker bands being identified for these ribonucleotides. ROA spectra are shown to provide the most sensitive diagnostic tool for phosphorylation characterization and quantification.     

The importance of protonation in the investigation of protein phosphorylation using Raman spectroscopy and Raman optical activity

The effect of protonation on amino acid monomers and protein phosphorylation was studied by means of a combination of Raman scattering and Raman optical activity (ROA). In the past, identifying spectral variations in phosphorylated proteins arising from either the phosphate stretch or amide vibrational modes has proven to be challenging mainly due to the loss of amide and P═O band intensity in the presence of phosphate. By contrast, we have developed a novel strategy based on the careful monitoring of the sample pH and thereby modified the protonation state, such that these difficulties can be overcome and phosphate-derived vibrations are readily visualized with both Raman and ROA. Variations in pH-dependent spectral sets of phosphorylated amino acid monomers serine and threonine demonstrated that the protonation state could be determined by the intensity of the monobasic (-OPO(3)H(-)) phosphate stretch band occurring at ~1080 cm(-1) versus the dibasic (-OPO(3)(2-)) band measured at ~980 cm(-1) in both Raman and ROA. Furthermore, by adjustment of the pH of aqueous samples of the phosphoprotein α-casein and comparing this result with dephosphorylated α-casein, spectral variations in phosphate stretch bands and amide bands could be easily determined. Consequently, structural variations due to both protonation and dephosphorylation could be distinguished, demonstrating the potential of Raman and ROA for future investigations of phosphoprotein structure and interactions.     

Surface-enhanced Raman optical activity on adenine in silver colloidal solution

We report the collection of Raman optical activity (ROA) spectra of adenine in silver colloidal solution, that is, surface-enhanced Raman optical activity (SEROA) using considerably shorter data acquisition times, reduced excitation power, and lower concentration, as compared to classical ROA measurements on molecules of biological interest so far reported in the literature. These improvements in experimental parameters for ROA measurements can be explained by enhanced Raman signals in the local optical fields of the silver nanoparticles and by at least 1 order of magnitude higher values for circular intensity differences (CIDs), as compared to classical ROA that has been suggested before and theoretically discussed in terms of large field gradients near a metal surface. The measured ROA effect for adenine can be understood in terms of adsorption-induced chirality in the prochiral molecules on the silver nanoparticles. Surface-enhanced Raman optical activity offers potential capabilities for sensitive, rapid, stereochemical characterization of basic building blocks of biopolymers, such as amino acids and nucleosides, as well as biologically active molecules, in particular, also for probing organization and self-assembling of such molecules on metal surfaces.     

Automated method for subtraction of fluorescence from biological Raman spectra

One of the challenges of using Raman spectroscopy for biological applications is the inherent fluorescence generated by many biological molecules that underlies the measured spectra. This fluorescence can sometimes be several orders of magnitude more intense than the weak Raman scatter, and its presence must be minimized in order to resolve and analyze the Raman spectrum. Several techniques involving hardware and software have been devised for this purpose; these include the use of wavelength shifting, time gating, frequency-domain filtering, first- and second-order derivatives, and simple curve fitting of the broadband variation with a high-order polynomial. Of these, polynomial fitting has been found to be a simple but effective method. However, this technique typically requires user intervention and thus is time consuming and prone to variability. An automated method for fluorescence subtraction, based on a modification to least-squares polynomial curve fitting, is described. Results indicate that the presented automated method is proficient in fluorescence subtraction, repeatability, and in retention of Raman spectral lineshapes.     

Raman and infrared spectra of SmAsO4

SmAsO₄ crystals were grown by the high-temperature flux method. Raman and infrared spectra of the crystals have been taken in the frequency region of 20–4000 and 300–4000 cm⁻¹ respectively. Assignments and correlations have been made for the observed bands. The results obtained were compared with those of some other compounds of the rare-earth arsenates.     

Influence of Si doping level on the Raman and IR reflectivity spectra and optical absorption spectrum of GaN

The optical absorption (hν) and Raman and Infra Red (IR) spectra of Si doped GaN layers deposited on sapphire through buffer layers have been recorded for electron concentrations from 5×10¹⁷ to 5×10¹⁹ cm⁻³. The (hν) values deduced from photothermal deflection spectroscopy (0.5–3.5 eV) and IR absorption (0.15–0.5 eV) vary between 50 and 10⁴ cm⁻¹ showing doping dependant free electron absorption at low energy, doping independant band gap at high energy, and slowly doping dependant defect absorption in the medium energy range. In our micro Raman geometry, maxima appear or can be deduced near the frequency expected for either the A₁(LO⁻) or the A₁(LO⁺) modes split from the A₁(LO) mode by plasmon phonon interaction. There is a large systematic evolution in the expected way for the IR reflectivity.     

Retrieval of linear optical functions from finite range spectra

There are many experimental situations in which infrared reflectivity spectra can be acquired only over a limited spectral range. It is therefore necessary to find computing procedures that allow the efficient analysis of such data. In this paper, we propose a new procedure labeled constrained finite range correction (CFRC) that can be advantageously substituted to multiply subtractive Kramers-Kronig relations. The constrained finite range correction is able to produce realistic results even when very little supplementary information is available. For semitransparent crystals, the hypothesis of the phase spectrum positiveness alone is often sufficient to compute satisfactory approximations of the optical functions. The efficiency of the new method is shown through the analysis of several synthetic and experimental spectra.     

Fe@洋葱状富勒烯的拉曼特征

采用化学气相沉积方法制备了Fe@洋葱状富勒烯并采用高分辨透射电镜（HRTEM）、拉曼（Raman）分析对其进行了表征。结果表明：产物粒径稳定在50nm左右，拉曼特征峰相对于HOPG发生了软化，这是由于其特殊的弯曲层状结构造成。     

Raman spectra of iron-modified amorphous carbon

Raman spectra of amorphous carbon films containing encapsulated iron (a-C:Fe) have been measured in the frequency range 200–1000 cm⁻¹. The concentration of encapsulated iron atoms (3, 26, 38, and 54 at. %) was controlled by changing the relative areas of iron and graphite targets during the film deposition by RF magnetron sputtering and checked by Rutherford backscattering. The Raman spectra of a-C:Fe films display a series of almost equidistant bands spaced by approximately 110 cm⁻¹. This character of the spectrum is explained in terms of the atomic vibrations in short carbon nanotubes formed during the introduction of iron into an amorphous carbon matrix.     

The relation between zeolite framework structure and vibrational spectra

Using a general valence force field method, infrared and Raman spectra of pure silica zeolite crystals and molecular substructures of zeolites are calculated. Computed spectra of the substructures are directly compared with computed spectra of the crystal. Also, a comparison of the atomic displacement vectors of the vibrational modes is made. No general theoretical basis for a correlation between the presence of large structural elements and spectral features, sometimes reported, is found to exist. An extensive comparison between experimental and theoretical infrared and Raman spectra of the SiO₂ forms of sodalite and faujasite is made. Other applications of vibrational spectroscopy to zeolite structure research, such as the SiOSi angle distribution and the location of acid sites, are evaluated as well.     

Carbon films: Structure and microtexture (optical and electron microscopy,Raman spectroscopy)

Nearly pure carbon films (150 and 500 Å thick) were prepared by condensing carbon vapour in vacuum. They were then heat treated under an inert gas flow from 25 to 2700 °C. The samples were studied comparatively with (1) a conventional transmission electron microscope (structure and microtexture), (2) a Raman microprobe (for quantification of the different types of defect by Raman spectroscopy) and (3) an optical microscope (for determination of the optical indices). The carbon films were found to graphitize in five stages. Each stage is characterized by the release of a given type of defect. Crystal growth occurs first in thickness and then in diameter. Perfect aromatic layers are formed progressively and the three-dimensional order improves. Polycrystalline graphite is then obtained. The graphitization is faster and more complete for thick films (about 500 Å thick) than for thin films (about 150 Å).     

Shift-excitation Raman difference spectroscopy-difference deconvolution method for the luminescence background rejection from Raman spectra of solid samples

The feasibility of the shift-excitation Raman difference spectroscopy-difference deconvolution (SERDS-DDM) method for fluorescence suppression from Raman spectra of solid samples is discussed. For SERDS measurements a tunable diode laser source with an emission band centered at 684 nm is coupled to a conventional micro-Raman apparatus and a monochromator device is used for checking the excitation frequency stability. The shifted Raman spectra are then mathematically treated and a deconvolution procedure is used to reconstruct the Raman spectrum devoid of fluorescence. Two different cases are presented. In the first one, fluorescence is intrinsic to the sample and the Raman spectrum of cinnabar pigment is finally reconstructed. In the second, the presence of an external luminescence background in the spectrum of a pure sulfur crystal is considered. The SERDS-DDM reconstructed spectra are compared with spectra obtained via multi-point baseline subtraction and a significant improvement in the detection of weak bands is demonstrated. Practical insights for the application of this method are presented as well.     

The Raman spectra of high modulus polyethylene fibres by Raman microscopy

Raman-microscopy has been used to analyse a series of high modulus polyethylene fibres. The high degree of orientation within the material means that upon 90° rotation of the samples and/or polarisation analyser, marked variations in band intensities occur throughout the spectra. Measurements of the 1131 : 1064 cm–1 band intensity ratio of the fibres are made and related to their Young's modulus. This relationship is useful in morphological studies of polyethylene fibres.     

Retrieval of optical constants and thickness of thin films from transmission spectra

We discuss a new method to estimate the absorption coefficient, the index of refraction, and the thickness of thin films using optical transmission data only. To solve the problem we used a pointwise constrained optimization approach, defining a nonlinear programming problem, the unknowns of which are the coefficients to be estimated, with linear constraints that represent prior knowledge about the physical solution. The method applies to all kinds of transmission spectra and does not rely on the existence of fringe patterns or transparency. Results on amorphous semiconductor thin films and gedanken films are reported. They show that the new method is highly reliable.     

Structure refinement, infrared and Raman spectra of KDyP4O12

Crystals of KDyP₄O₁₂ have been grown by the flux technique and characterized by single-crystal X-ray diffraction. KDyP₄O₁₂ crystallizes in the monoclinic C2/c space group with lattice parameters: a=7.8158(3), b=12.3401(5), c=10.4382(3) Å, β=111.053°(2), V=939.6(4) Å³, Z=4. The crystal structure has been refined yielding a final R(F²)=0.034 and R_w(F²)=0.082 for 902 independent reflections (F_o²≥2σ(F_o²)). The structure of KDyP₄O₁₂ consists of DyO₈ polyhedra and cyclotetraphosphate P₄O₁₂ groups sharing oxygen atoms to form a three-dimensional framework, delimiting intersecting tunnels in which the potassium ion is located. Each K⁺ ion is bonded to 10 oxygen atoms. The energies of the vibrational modes of the crystal were obtained from measurements of the infrared and Raman spectra.