Vibrational circular dichroism in general anisotropic thin solid films: measurement and theoretical approach

In this study, the measurement of the true vibrational circular dichroism (VCD) spectrum is considered from an experimental and theoretical approach for any general anisotropic thin solid sample exhibiting linear as well as circular birefringence (LB, CB) and dichroism (LD, CD) properties. For this purpose, we have made use of a simple model alpha-helix polypeptide, namely, the poly(gamma-benzyl-L-glutamate) or PBLG, reference sample possessing a well-known VCD spectrum and giving rise to slightly oriented films by deposition onto a solid substrate. Also, we have used a different Fourier transform infrared modulation of polarization (PM-FTIR) optical setup with two-channel electronic processing in order to record the PM-VLD and PM-VCD spectra for various sample orientations in its film plane. All the corresponding general relations of the expected intensities in these experiments and the related properly designed calibration measurements were established using the Stokes-Mueller formalism; in addition, the residual birefringence of the optical setup and the transmittance anisotropy of the detector were estimated. From a comparative study of the results obtained in solution and in the solid state, we then propose a simple new experimental procedure to extract the true VCD spectrum of an oriented PBLG thin film: its consists of calculating the half-sum of two spectra recorded at theta and at theta +/- 90 degrees sample orientations. Moreover, the complete linear and circular birefringence and dichroism properties of the ordered PBLG thin film are estimated in the amide I and amide II vibrational regions. This allows us to establish for any sample orientation various theoretical simulations of the VCD spectra that agree nicely with the observed experimental results; this confirms that the measurement of LD and LB is in this case a prerequisite in simulating the true VCD spectrum of a partly oriented anisotropic sample. This validates our combined experimental and theoretical approach and opens the route to promising future vibrational CD studies on other macroscopic anisotropic thin film samples.     

Theoretical simulation of a polarization modulator based on mechanical rotation of a polarizing element

The properties of three alternative designs for a polarization modulator of potential use for the measurement of vibrational circular dichroism (VCD) are evaluated and compared by use of Mueller calculus. The analysis shows that the combination of a fixed polarizer plus either a photoelastic modulator or a rotating quarter-wave plate possesses nearly the same capability for generation of time-varying, circularly polarized light. However, a modulator composed of a rotating polarizer plus a fixed birefringent plate entails considerable theoretical and experimental difficulties for use in the measurement of VCD spectra. While VCD spectra obtained with the rotating devices can be calibrated in the same manner as spectra obtained with a photoelastic modulator, Mueller analysis shows that the form of the resultant calibration signal will have a different shape. The relevant expressions for VCD and linear dichroism as well as the calibration signals are presented, and consequences for practical realization of these experiments are discussed.     

Observation of Fourier transform near-infrared vibrational circular dichroism to 6150 cm-1

We report here the first measurement of near-infrared (NIR) vibrational circular dichroism (VCD) with Fourier transform (FT) instrumentation. The measurements were carried out using a commercial rapid-scan FT-IR VCD spectrometer modified for operation in the NIR region between 3750 and 6150 cm-1. Overtone and combination band VCD intensities, first reported by Keiderling and Stephens using dispersive VCD instrumentation in 1976, were reproduced with equivalent signal quality and spectral resolution using collection times of only a few minutes. These results offer substantial promise for the routine use of rapid-scan FT instrumentation for the measurement of overtone and combination band VCD spectra in the NIR region.     

Extension of fourier transform vibrational circular dichroism into the near-infrared region: continuous spectral coverage from 800 to 10 000 cm(-1)

We report the first vibrational circular dichroism (VCD) spectra with continuous coverage from 800 cm(-1) in the mid-infrared (MIR) region to 10 000 cm(-1) in the near-infrared (NIR) region. This coverage is illustrated with MIR and NIR absorbance and VCD spectra of 2,2-dimethyl-dioxolane-4-methanol (DDM), alpha-pinene, and camphor that serve as calibration samples over this entire region. Commercially available, dual-source Fourier transform (FT) MIR and NIR VCD spectrometers were equipped with appropriate light sources, optics, and detectors, and were modified for dual-polarization-modulation (DPM) operation. The combination of liquid-nitrogen- and thermoelectric-cooled HgCdTe (MCT) detectors, as well as InGaAs and Germanium (Ge) detectors operating at room temperature, permitted collection of the desired absorbance and VCD spectra across the range of vibrational fundamental, combination band, and overtone frequencies. The spectra of DDM and alpha-pinene were measured as neat liquids and recorded for both enantiomers in the various spectral regions. Spectra for camphor were all measured in CCl(4) solution at a concentration of 0.6 M, except for the carbonyl-stretching region, where a more dilute concentration was used. The typical anisotropy ratios (g) of the three molecules were estimated with respect to their strongest VCD bands in each spectral region. It was found that for all three molecules in the spectral regions above 2000 cm(-1), anisotropy ratios are approximately the same order (10(-5)) of magnitude. However, in the MIR region, the typical anisotropy ratios are significantly different for the three molecules. This study demonstrates that with modern FT-VCD spectrometers modified for DPM operation, VCD spectra can be measured continuously across a wide spectral range from the MIR to nearly the visible region with an unsurpassed combination of signal-to-noise ratio and spectral resolution.     

Vibrational circular dichroism of matrix-assisted amino acid films in the mid-infrared region

Vibrational circular dichroism (VCD) spectra in the mid-infrared region of amino acid films are reported here for the first time. Amino acid films are formed from aqueous solutions with alpha-cyclodextrin (CD) serving as the matrix to facilitate the film formation. This film method eliminates the strong interfering water absorption seen in the solution study and makes it easier to measure the VCD in the 1800-1200 cm-1 region. VCD spectra for films of six amino acids, L-alanine, L-proline, L-methionine, Lhistidine, L-phenylalanine, and L-tryptophan, are obtained. For amino acids with low solubility (L-phenylalanine and L-tryptophan), VCD could not be measured in solution, so the film method is the only means of obtaining the VCD spectra for such amino acids. For amino acids with moderate solubility (L-alanine, L-proline, L-methionine, and L-histidine), VCD spectra are also obtained in the solution state and compared with their corresponding spectra in the film state. A good correlation is found between the film and solution spectra for both absorption and VCD. The VCD spectra of L-methionine, L-histidine, L-phenylalanine, and Ltryptophan are reported here in the mid-infrared region for the first time. The present study broadens the application range of the VCD technique and enhances its role in the detection and analysis of biologically important compounds.     

Quantification and identification of components in solution mixtures from 1D proton NMR spectra using singular value decomposition

One-dimensional proton NMR spectra of complex solutions provide rich molecular information, but limited chemical shift dispersion creates peak overlap that often leads to difficulty in peak identification and analyte quantification. Modern high-field NMR spectrometers provide high digital resolution with improved peak dispersion. We took advantage of these spectral qualities and developed a quantification method based on linear least-squares fitting using singular value decomposition (SVD). The linear least-squares fitting of a mixture spectrum was performed on the basis of reference spectra from individual small-molecule analytes. Each spectrum contained an internal quantitative reference (e.g., DSS-d6 or other suitable small molecules) by which the intensity of the spectrum was scaled. Normalization of the spectrum facilitated quantification based on peak intensity using linear least-squares fitting analysis. This methodology provided quantification of individual analytes as well as chemical identification. The analysis of small-molecule analytes over a wide concentration range indicated the accuracy and reproducibility of the SVD-based quantification. To account for the contribution from residual protein, lipid or polysaccharide in solution, a reference spectrum showing the macromolecules or aggregates was obtained using a diffusion-edited 1D proton NMR analysis. We demonstrated this approach with a mixture of small-molecule analytes in the presence of macromolecules (e.g., protein). The results suggested that this approach should be applicable to the quantification and identification of small-molecule analytes in complex biological samples.     

A new method for the time-resolved analysis of structure and orientation: polarization modulation infrared structural absorbance spectroscopy

Polarization modulation infrared linear dichroism (PM-IRLD) is often used for measurements of molecular orientation with high sensitivity and good time resolution. However, PM-IRLD is unable to provide the structural absorbance spectrum because it does not measure separately the parallel and perpendicular spectra. Here we propose a new method, named polarization modulation infrared structural absorbance spectroscopy (PM-IRSAS), to overcome this limitation of PM-IRLD. PM-IRSAS measures the dichroic difference and structural absorbance spectra simultaneously and, therefore, allows quantitative analysis of molecular orientation and conformation with 200 ms time resolution. The PM-IRSAS method was first validated through comparison with conventional polarized FT-IR spectroscopy using drawn polymer films. Second, it was demonstrated that the PM-IRSAS method can provide a quantitative analysis of dynamic orientation and conformation changes in PET films during deformation and crystallization processes.     

Microwatt shot-noise measurement

We report a simple scheme for sensitive measurements of optical-noise spectra. Optical noise is separated from electronic noise when the output of an analog spectrum analyzer is real-time squared and then lock-in detected. This method directly yields the desired mean-square noise voltage, i.e., the power spectrum of the optical noise on a linear scale. To demonstrate this technique, the mean-square shot noise of a laser beam is measured and found to vary linearly with the laser power from several milliwatts down to one microwatt, in excellent quantitative agreement with predictions.     

Electronic spectra of the crystalline polymers of C60: photoluminescence study at high pressure

Specific details of the electronic spectra of perfect crystalline polymers of C60 were studied by means of the photoluminescence spectra measurements at normal conditions and at high pressure up to 4 GPa. The structure of the photoluminescence spectra, the intensity distribution between the principal bands and the pressure-induced shift of the bands differ considerably among the pristine C60, linear orthorhombic and planar tetragonal and rhombohedral polymeric phases of C60. Unlike the planar polymers of C60, the linear orthorhombic polymer exhibits irreversible changes in the photoluminescence spectrum under simultaneous application of high pressure and laser irradiation. The changes observed in the photoluminescence spectra of the planar polymeric phases of C60, as compared to the pristine material, are discussed in relation to the corresponding changes in the calculated electronic structure of the pristine C60 and its polymeric phases. The observed photoluminescence spectral structure along with the pressure behavior of the photoluminescence spectra are very sensitive to the structure of the polymers as well as to the C60 cage deformations and can be used to effectively characterize the various polymeric phases of C60.     

Reduction of chemical formulas from the isotopic peak distributions of high-resolution mass spectra

A method has been developed for the reduction of the chemical formulas of compounds in complex mixtures from the isotopic peak distributions of high-resolution mass spectra. The method is based on the principle that the observed isotopic peak distribution of a mixture of compounds is a linear combination of the isotopic peak distributions of the individual compounds in the mixture. All possible chemical formulas that meet specific criteria (e.g., type and number of atoms in structure, limits of unsaturation, etc.) are enumerated, and theoretical isotopic peak distributions are generated for each formula. The relative amount of each formula is obtained from the accurately measured isotopic peak distribution and the calculated isotopic peak distributions of all candidate formulas. The formulas of compounds in simple spectra, where peak components are fully resolved, are rapidly determined by direct comparison of the calculated and experimental isotopic peak distributions. The singular value decomposition linear algebra method is used to determine the contributions of compounds in complex spectra containing unresolved peak components. The principles of the approach and typical application examples are presented. The method is most useful for the characterization of complex spectra containing partially resolved peaks and structures with multiisotopic elements.     

CO的第二泛频(3←0)跃迁谱线线形强度测量研究

CO分子是监测大气污染气体的优异示踪气体,要实现对CO分子实时监控就需要做到对气体浓度的精确快速测量。气体分子浓度测量可以利用测量吸收光谱和谱线线形强度得到,CO的(3←0)泛频谱带是吸收较弱的跃迁波段,利用以干空气为缓冲气体的200μmol/mol的CO混合物,基于稳频的光腔衰荡装置测量了在温度293K、压力13~93kPa下的CO分子R支3条跃迁谱线的吸收光谱。HTP(Hartmann-Tran profile)线形被用来获得这些谱线的线形强度,测量结果的相对标准不确定度优于1%,与国际HITRAN、HITEMP和GEISA光谱数据库比较,相对偏差小于4%。     

Accurate modeling of spectral fine-structure in Earth radiance spectra measured with the Global Ozone Monitoring Experiment

We present what we believe to be a novel approach to simulating the spectral fine structure (<1 nm) in measurements of spectrometers such as the Global Ozone Monitoring Experiment (GOME). GOME measures the Earth's radiance spectra and daily solar irradiance spectra from which a reflectivity spectrum is commonly extracted. The high-frequency structures contained in such a spectrum are, apart from atmospheric absorption, caused by Raman scattering and by a shift between the solar irradiance and the Earth's radiance spectrum. Normally, an a priori high-resolution solar spectrum is used to simulate these structures. We present an alternative method in which all the required information on the solar spectrum is retrieved from the GOME measurements. We investigate two approaches for the spectral range of 390-400 nm. First, a solar spectrum is reconstructed on a fine spectral grid from the GOME solar measurement. This approach leads to undersampling errors of up to 0.5% in the modeling of the Earth's radiance spectra. Second, a combination of the solar measurement and one of the Earth's radiance measurement is used to retrieve a solar spectrum. This approach effectively removes the undersampling error and results in residuals close to the GOME measurement noise of 0.1%.     

High precision in Raman frequency achieved using real-time calibration with a neon emission line: application to three-dimensional stress mapping observations

A three-dimensional (3D) Raman mapping system with a real-time calibration function was developed for detecting stress distributions in solid materials from subtle frequency shifts in Raman spectra. An atomic emission line of neon at 918.3 cm(-1) when excited at 514.5 nm was used as a wavenumber standard. An emission spectrum of neon and a Raman spectrum from a sample were introduced into a single polychromator using a bifurcated optical fiber. These two spectra were recorded simultaneously on a charge-coupled device (CCD) detector using double-track mode. Energy deviation induced by the fluctuation of laboratory temperature, etc., was removed effectively using the neon emission line. High stability during long measurements was achieved. By applying curve fitting, positions of the Raman line were determined with precision of about 0.05 cm(-1). The present system was applied to measurements of residual pressure around mineral inclusions in a natural diamond: 3D stress mapping was achieved.     

Resonant two-photon ionization mass spectrometry of jet-cooled phenolic acids and polyphenols

A method for analyzing phenolic acids and polyphenols by means of resonant two-photon ionization (R2PI) mass spectrometry coupled with laser desorption and supersonic jet cooling is described. The R2PI spectra of gallic acid, 3-O-methylgallic acid, protocatechuic acid, syringic acid, vanillic acid, and trans-resveratrol are vibronically resolved and distinct to allow for unambiguous identification. For vanillic acid, its R2PI spectrum can be separated into contributions of two rotational isomers based on UV-UV and IR-UV double-resonance spectroscopy. Since R2PI spectra display sharp and well-resolved peaks, the laser wavelength can be tuned for selective ionization of targeted molecules. The mass spectrum recorded under jet-cooled conditions and at the resonant wavelength displays only the molecular ion peak with no fragmentation or background peaks. Picogram sensitivity and linear response over a nanogram range allows trace quantitative measurements of target molecules in complex matrixes. These techniques were applied to detect syringic acid in a model archaeological wine vessel.     

Shift-invariant,DWT-based "projection" method for estimation of ultrasound pulse power spectrum

An approach to computing estimates of the ultrasound pulse spectrum from echo-ultrasound RF sequences, measured from biological tissues, is proposed. It is computed by a "projection" algorithm based on the Discrete Wavelet Transform (DWT) using averaging over a range of linear shifts. It is shown that the robust, shift invariant estimate of the ultrasound pulse power spectrum can be obtained by the projection of RF line log spectrum on an appropriately chosen subspace of L2(R) (i.e., the space of square-integrable functions) that is spanned by a redundant collection of compactly supported, scaling functions. This redundant set is formed from the traditional (in Wavelet analysis) orthogonal set of scaling functions and also by all its linear (discrete) shifts. A proof is given that the estimate, so obtained, could be viewed as the average of the orthogonal projections of the RF line log spectrum, computed for all significant linear shifts of the RF line log spectrum in frequency domain. It implies that the estimate is shift-invariant. A computationally efficient scheme is presented for calculating the estimate. Proof is given that the averaged, shift-invariant estimate can be obtained simply by a convolution with a kernel, which can be viewed as the discretized auto-correlation function of the scaling function, appropriate to the particular subspace being considered. It implies that the computational burden is at most O(n log2 n), where n is the problem size, making the estimate quite suitable for real-time processing. Because of the property of the wavelet transform to suppress polynomials of orders lower than the number of the vanishing moments of the wavelet used, the presented approach can be considered as a local polynomial fitting. This locality plays a crucial role in the performance of the algorithm, improving the robustness of the estimation. Moreover, it is shown that the "averaging" nature of the proposed estimation allows using (relatively) poorly regular wavelets (i.e., short filters), without affecting the estimation quality. The latter is of importance whenever the number of calculations is crucial.     

Simulated radiance profiles for automating the interpretation of airborne passive multi-spectral infrared images

Methodology is developed for simulating the radiance profiles acquired from airborne passive multispectral infrared imaging measurements of ground sources of volatile organic compounds (VOCs). The simulation model allows the superposition of pure-component laboratory spectra of VOCs onto spectral backgrounds that simulate those acquired during field measurements conducted with a downward-looking infrared line scanner mounted on an aircraft flying at an altitude of 2000-3000 ft (approximately 600-900 m). Wavelength selectivity in the line scanner is accomplished through the use of a multichannel Hg:Cd:Te detector with up to 16 integrated optical filters. These filters allow the detection of absorption and emission signatures of VOCs superimposed on the upwelling infrared background radiance within the instrumental field of view (FOV). By combining simulated radiance profiles containing analyte signatures with field-collected background signatures, supervised pattern recognition methods can be employed to train automated classifiers for use in detecting the signatures of VOCs during field measurements. The targeted application for this methodology is the use of the imaging system to detect releases of VOCs during emergency response scenarios. In the work described here, the simulation model is combined with piecewise linear discriminant analysis to build automated classifiers for detecting ethanol and methanol. Field data collected during controlled releases of ethanol, as well as during a methanol release from an industrial facility, are used to evaluate the methodology.     

Multipoint temperature-independent fiber-Bragg-grating strain-sensing system employing an optical-power-detection scheme

A temperature-independent fiber-Bragg-grating strains-sensing system, based on a novel optical-power-detection scheme, is developed and analyzed. In this system a pair of fiber Bragg gratings with reflection spectra either partially or substantially overlapping is placed side by side to form a temperature-independent strain-sensor unit. Conventional wavelength-interrogation techniques are not used here, and instead an optical-power-detection scheme is proposed to directly calibrate the measurand, i.e., the strain. Unlike the conventional approach in a multiplexed sensing system, the presented power-detection-based interrogation method does not need the fiber-Bragg-grating sensors to be spectrally separate. The only requirement is that the spectra of the two fiber Bragg gratings of each sensor unit in a multiplexed system be identical or slightly separate (slightly overlapping spectra would also work in the sensing scheme) and the source's optical power be sufficient for sensitive measurement. Based on a three-sensor-unit system, we demonstrate simple strain measurements of high linearity (+/- 0.4%), good sensitivity [2 microstrains (microS)], high thermal stability (+/- 0.8%), and zero cross talk. The effects of light source spectral flatness and fiber bending loss on measurement accuracy are also discussed.     

Quantitative spectroscopic analysis of heterogeneous mixtures: the correction of multiplicative effects caused by variations in physical properties of samples

Spectral measurements of complex heterogeneous types of mixture samples are often affected by significant multiplicative effects resulting from light scattering, due to physical variations (e.g., particle size and shape, sample packing, and sample surface, etc.) inherent within the individual samples. Therefore, the separation of the spectral contributions due to variations in chemical compositions from those caused by physical variations is crucial to accurate quantitative spectroscopic analysis of heterogeneous samples. In this work, an improved strategy has been proposed to estimate the multiplicative parameters accounting for multiplicative effects in each measured spectrum and, hence, mitigate the detrimental influence of multiplicative effects on the quantitative spectroscopic analysis of heterogeneous samples. The basic assumption of the proposed method is that light scattering due to physical variations has the same effects on the spectral contributions of each of the spectroscopically active chemical components in the same sample mixture. On the basis of this underlying assumption, the proposed method realizes the efficient estimation of the multiplicative parameters by solving a simple quadratic programming problem. The performance of the proposed method has been tested on two publicly available benchmark data sets (i.e., near-infrared total diffuse transmittance spectra of four-component suspension samples and near-infrared spectral data of meat samples) and compared with some empirical approaches designed for the same purpose. It was found that the proposed method provided appreciable improvement in quantitative spectroscopic analysis of heterogeneous mixture samples. The study indicates that accurate quantitative spectroscopic analysis of heterogeneous mixture samples can be achieved through the combination of spectroscopic techniques with smart modeling methodology.