Attenuated total reflection Fourier transform infrared spectroscopy analysis of human hair fiber structure

The structure of human hair was studied by attenuated total reflection Fourier transform infrared (ATR-FT-IR) spectroscopy. The use of Ge, ZnSe, and Si internal reflection elements, various incident light angles, and difference spectra allowed detailed analysis of the cuticle, cortex, and cuticle-cortex intercellular regions without physically or mechanically removing the cuticle of the hair fiber. The ATR-FT-IR data showed the cuticle to be composed of protein having predominantly beta-sheet and disorder and beta-turn configurations. In contrast, the cortex spectra showed alpha-helical structures due to the presence of intermediate filaments of alpha keratin plus beta-sheet, beta-turn and disorder structures. In the cuticle-cortex interface region the protein structures were primarily disorder and beta-turn with small amounts of beta-sheet configurations. The spectral analyses are consistent with the general information on hair fiber structure proposed in the literature.     

Fourier transform infrared attenuated total reflection and transmission spectra studied by dispersion analysis

Fourier transform infrared transmission (FT-IR) and attenuated total reflection (ATR) spectra of water-ethanol mixtures are recorded and reconstructed thanks to a causal dispersion analysis technique. As expected, the Beer's law technique is an empirical approximate method that cannot account for complex spectral features. On the other hand, a rigorous analysis performed by using the theoretical optical paths for both experimental techniques and Gaussian dispersion analysis (GDA) allows the dielectric functions of the pure liquids to be calculated. Simulations of the whole mid-infrared spectra in the range 500-4000 cm(-1) match the experimental data very well, whatever the water-ethanol mixtures. This method is a powerful tool to quantify such model mixtures and more generally could be the first step toward software for assistance to the FT-IR spectrum analysis.     

Analysis of fiber blends using horizontal attenuated total reflection Fourier transform infrared and discriminant analysis

We have investigated the utility of a horizontal attenuated total reflection Fourier transform infrared spectrometer (HATR/FT-IR) for the analysis of fiber and textile blends. The identification of a blended textile can be accomplished by subtracting a reference spectrum of the textile's most abundant component, leading to a difference spectrum that infers the identity of the second constituent of the blended textile. Mathematical post-processing of the spectra employing discriminant analysis provided a useful statistical tool to confirm the fiber blend components.     

Single-pass attenuated total reflection Fourier transform infrared spectroscopy for the analysis of proteins in H2O solution

The application of single-pass attenuated total reflection Fourier transform infrared (ATR-FT-IR) microscopy was investigated for secondary structure analysis of 15 representative proteins in H2O solution. This is the first reported application of single-pass ATR-FT-IR for protein analysis; thus, the method was validated using transmission FT-IR and multipass ATR-FT-IR as referee methods. The single-pass ATR-FT-IR technique was advantageous since the single-pass geometry permits rapid secondary structure analysis on small volumes of protein in H2O solution without the use of demountable thin path length sample cells. Moreover, the fact that H2O backgrounds were small allowed the simultaneous observation of the amide I-III, A, and B regions without having to perform H2O subtraction. A comparison of replicate protein spectra indicated that the single-pass ATR-FT-IR method yields more reproducible data than those acquired by transmission FT-IR. The observed trends for the amide I-III and A bands obtained by single-pass ATR-FT-IR agreed with those in the literature for conventional transmission FT-IR.     

Fourier transform infrared analysis of gas composition in low-volume light bulbs

Fourier transform infrared spectroscopy has been used for in situ analysis of HBr, CH3Br, and CO within light bulbs at different stages of burning time. The interference fringes originated in the quartz walls of the bulbs have been eliminated by different methods. The NIPALS procedure yielded higher S/N ratio than the fringe-elimination method applied. The CO and HBr showed time-dependent concentration changes during the burning period. The maximum CO concentration (approximately 6 ppm) was detected after 30-50 s of burning time, and then it practically burned out after 5 h. The HBr concentration increased in the first 3 min of burning, and then its concentration stabilized at a 10-15 ppm level. After 5 s of illumination, the CH3Br concentration became undetectable.     

Quantitative analysis of polyethylene blends by Fourier transform infrared spectroscopy

The quantitative analysis of binary polyethylene (PE) blends by Fourier transform infrared (FT-IR) spectroscopy has been achieved based on the ratio of two absorbance peaks in an FT-IR spectrum. The frequencies for the absorbance ratio are selected based on structural entities of the PE components in the blend. A linear relationship between the absorbance ratio and the blend composition was found to exist if one of the absorbance peaks is distinct to one of the components and the other peak is common to both components. It was also found that any peak resulting from short-chain branching in copolymers (such as linear low-density polyethylene (LLDPE) or metallocene-catalyzed LLDPE (mLLDPE)), is suitable for use as the peak that is designated as being distinct to that component. In order to optimize the linearity of the equation, however, the selection of the second common peak is the most important and depends on the blend system studied. Indeed, under certain circumstances peaks that are not spectrally distinct can be used successfully to apply the method. The method exhibits potential for the routine analysis of PE blends that have been calibrated prior to its application.     

Time-resolved Fourier transform infrared spectroscopic imaging

Fourier transform infrared (FT-IR) imaging allows simultaneous spectral characterization of large spatial areas due to its multichannel detection advantage. The acquisition of large amounts of data in the multichannel configuration results, however, in a poor temporal resolution of sequentially acquired data sets, which limits the examination of dynamic processes to processes that have characteristic time scales of the order of minutes. Here, we introduce the concept and instrumental details of a time-resolved infrared spectroscopic imaging modality that permits the examination of repetitive dynamic processes whose half-lives are of the order of milli-seconds. As an illustration of this implementation of step-scan FT-IR imaging, we examine the molecular responses to external electric-field perturbations of a microscopically heterogeneous polymer-liquid crystal composite. Analysis of the spectroscopic data using conventional univariate and generalized two-dimensional (2D) correlation methods emphasizes an additional capability for accessing of simultaneous spatial and temporal chemical measurements of molecular dynamic processes.     

Characterization of infrared matrix-assisted laser desorption ionization samples by Fourier transform infrared attenuated total reflection spectroscopy

Fourier transform infrared attenuated total reflection (FT-IR ATR) spectroscopy was used to characterize thin films of succinic acid, a matrix compound commonly used with infrared matrix-assisted laser desorption ionization (IR-MALDI) mass spectrometry. IR spectra of succinic acid thin films deposited alone and in combination with the analyte biomolecules insulin and cytochrome c were obtained by FT-IR ATR spectroscopy. Spectra of analyte and matrix alone were similar to those obtained previously from KBr pellets, Nujol mull, or thin-film absorption, although the ATR spectra have significantly lower background interferences. Thin films deposited from mixtures of water and methanol have additional peaks compared to films deposited from a methanol solution. These additional peaks are attributed to carboxylate groups stabilized by residual water molecules. No evidence was found to suggest that residual water absorption contributes to absorption at wavelengths typically used for IR-MALDI. Absorption of energy by analyte vibrational modes with rapid energy transfer to the matrix is suggested as a contributor to desorption and ionization consistent with the FT-IR ATR results.     

Single-pass attenuated total reflection Fourier transform infrared spectroscopy for the prediction of protein secondary structure

Principal component regression (PCR) was applied to a spectral library of proteins in H2O solution acquired by single-pass attenuated total reflectance (ATR) Fourier transform infrared (FT-IR) spectroscopy. PCR was used to predict the secondary structure content, principally alpha-helical and the beta-sheet content, of proteins within a spectral library. Quantitation of protein secondary structure content was performed as a proof of principle that use of single-pass ATR-FT-IR is an appropriate method for protein secondary structure analysis. The ATR-FT-IR method permits acquisition of the entire spectral range from 700 to 3900 cm(-1) without significant interference from water bands. An "inside model space" bootstrap and a genetic algorithm (GA) were used to improve prediction results. Specifically, the bootstrap was utilized to increase the number of replicates for adequate training and validation of the PCR model. The GA was used to optimize PCR parameters, particularly wavenumber selection. The use of the bootstrap allowed for adequate representation of variability in the amide A, amide B, and C-H stretching regions due to differing levels of sample hydration. Implementation of the bootstrap improved the robustness of the PCR models significantly; however, the use of a GA only slightly improved prediction results. Two spectral libraries are presented where one was better suited for beta-sheet content prediction and the other for alpha-helix content prediction. The GA-optimized PCR method for alpha-helix content prediction utilized 120 wavenumbers within the amide I, II, A, B, and IV and the C-H stretching regions and 18 factors. For beta-sheet content predictions, 580 wavenumbers within the amide I, II, A, and B and the C-H stretching regions and 18 factors were used. The validation results using these two methods yielded an average absolute error of 1.7% for alpha-helix content prediction and an average absolute error of 2.3% for beta-sheet content prediction. After the PCR models were developed and validated, they were used to predict the alpha-helix and beta-sheet content of two unknowns, casein and immunoglobulin G.     

Optimum condition of Fourier transform infrared multiple-angle incidence resolution spectrometry for surface analysis

A novel measurement technique of pure out-of-plane vibrational modes of thin films on a nonmetallic substrate has recently been proposed, which is named multiple-angle incidence resolution spectrometry (MAIRS). Since this technique could not be replaced by other conventional techniques, MAIRS was expected to be a promising tool for analysis of thin soft materials and surface adsorbates. Nevertheless, some experimental conditions have been found to be inappropriate for MAIRS, which yields incorrect results. In the present study, therefore, the problems in the technique have been investigated in terms of optics to improve the accomplishments of MAIRS. The problems have been found to have a strong relationship with optics in FT-IR, which is influenced by refractive index of the sample material and angle of incidence. In particular, optimization of the size matching of the detector surface and the infrared spot at the detector was a key to having MAIRS perform properly. It has been concluded that reliable MAIRS measurements require overfilling of the detector and a substrate with a high-refractive index.     

Calibration transfer algorithm for automated qualitative analysis by passive Fourier transform infrared spectrometry

The automated qualitative analysis of passive Fourier transform infrared (FT-IR) remote sensing data is made difficult by the presence in the data of background and instrument-specific variation. For data collected with a single instrument, variation in the data arises from changes in the infrared background radiance, changes in the atmospheric composition within the field-of-view of the spectrometer, and changes in the instrument response function arising from temperature variation in the spectrometer. When more than one spectrometer is used, the variation in detector responses and phase signatures between instruments serves to complicate further the task of implementing an automated processing algorithm for detecting the signature of a target compound. In this work, a combination of signal processing and pattern recognition methodology is applied directly to the interferogram data collected by the FT-IR spectrometer to implement an automated compound detection procedure that is independent of background and instrument-specific variation. The key to this algorithm is the use of highly attenuating digital filters to isolate in the interferogram the frequencies associated with an analyte absorption or emission band while suppressing information at other frequencies. For the test compounds, acetone and sulfur hexafluoride, it is demonstrated that when this digital filtering procedure is coupled with either piecewise linear discriminant analysis or a back-propagation neural network, an automated detection algorithm can be developed with data from a primary instrument and then subsequently used to predict the presence of analyte signatures in data collected with a secondary spectrometer. Correct classification rates in excess of 92% are obtained for both compounds when the algorithm is applied to data collected with the secondary instrument.     

Bilayer free-standing beam splitter for Fourier transform infrared spectrometry

We describe the design, fabrication, testing, and performance of a two-layer free-standing beam splitter for use in far-infrared Fourier transform infrared spectrometers. This bilayer beam splitter, consisting of a low-index polymer layer in combination with a high-index semiconductor layer, has an efficiency that is higher than that of the best combination of four single-layer Mylar beam splitters currently in use for spectrometry from 50 to 550 cm(-1).     

Fourier transform spectroscopy of LaS in the infrared

We recorded the emission spectrum of diatomic lanthanum sulfide on the Los Alamos Fourier transform spectrometer. In the region 7500-16,000 cm(-1), we identified over 120 bands and assigned them to the A(2)∏(r)-X(2)Σ(+) and B(2)Σ(+)-X(2)Σ(+) transitions. Each of these bands is four headed.     

Digital filtering implementations for the detection of broad spectral features by direct analysis of passive Fourier transform infrared interferograms

Finite impulse response (FIR) filters and finite impulse response matrix (FIRM) filters are evaluated for use in the detection of volatile organic compounds with wide spectral bands by direct analysis of interferogram data obtained from passive Fourier transform infrared (FT-IR) measurements. Short segments of filtered interferogram points are classified by support vector machines (SVMs) to implement the automated detection of heated plumes of the target analyte, ethanol. The interferograms employed in this study were acquired with a downward-looking passive FT-IR spectrometer mounted on a fixed-wing aircraft. Classifiers are trained with data collected on the ground and subsequently used for the airborne detection. The success of the automated detection depends on the effective removal of background contributions from the interferogram segments. Removing the background signature is complicated when the analyte spectral bands are broad because there is significant overlap between the interferogram representations of the analyte and background. Methods to implement the FIR and FIRM filters while excluding background contributions are explored in this work. When properly optimized, both filtering procedures provide satisfactory classification results for the airborne data. Missed detection rates of 8% or smaller for ethanol and false positive rates of at most 0.8% are realized. The optimization of filter design parameters, the starting interferogram point for filtering, and the length of the interferogram segments used in the pattern recognition is discussed.     

Characterization of historic silk by polarized attenuated total reflectance Fourier transform infrared spectroscopy for informed conservation

When assessing historic textiles and considering appropriate conservation, display, and storage strategies, characterizing the physical condition of the textiles is essential. Our work has concentrated on developing nondestructive or micro-destructive methodologies that will permit this. Previously, we have demonstrated a correlation between the physical deterioration of unweighted and "pink" tin (IV) chloride weighted silk and certain measurable spectroscopic and chromatographic signatures, derived from polarized Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy (Pol-ATR) and high-performance liquid chromatography (HPLC) microsampling analyses. The application of the Pol-ATR technique to aged silk characterization has now been extended to include a more comprehensive range of weighting methods and aging regimes. This was intended to replicate the full spectrum of states of deterioration observed in silk textiles, from pristine to heavily degraded. Breaking strength was employed as a measure of the physical integrity of the fibers, and, as expected, decreased with aging. An orientational crystallinity parameter, reflecting the microstructural ordering of the fibroin polymer within the fibers, was derived from the Pol-ATR spectra. A good correlation was observed between the breaking strength of the variety of fibers and this parameter. This suggests that the physical state of historic silk fabrics might be adequately characterized for conservation purposes by such indirect micromethodology.     

Two-dimensional correlation analysis of polyimide films using attenuated total reflection-based dynamic compression modulation step-scan Fourier transform infrared spectroscopy

Attenuated total reflection (ATR)-based dynamic compression modulation two-dimensional (2D) correlation study of poly(p-phenylene biphenyltetracarboximide) film is carried out in combination with spectral simulation analysis by density functional theory (DFT). The dynamic 2D infrared (IR) correlation spectra in the region of imide I (C=O stretching mode) show three distinct correlation peaks located around 1777, 1725, and 1708 cm(-1). The band at 1708 cm(-1) is the lower wavenumber shift component of 1777 or 1735 cm(-1) peaks and is attributed to the results from intermolecular interactions, according to the DFT analysis. The 1708 cm(-1) band also shows the largest dynamic response, suggesting that these intermolecular interactions may enhance the dynamic response. The dynamic 2D IR correlation spectra in the region of imide II (C-N-C axial stretching mode) vibrations also show three correlation peaks located around 1335, 1355, and 1370 cm(-1), although the imide II band is shown to consist substantially of one component by the DFT analysis. These multiple peaks may be attributed to the compression-induced wavenumber shift of the band in the backbone structures. The sequential analysis of 2D correlation data show that, upon applying the dynamic compression, the response of the backbone regions (imide II) occurs first, followed by that of the side-chain regions (imide I, C=O).