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.     

Determining cement composition by Fourier transform infrared spectroscopy

A diffuse reflectance mid-infrared Fourier transform spectroscopy (DRIFTS) method is described for obtaining high quality Fourier transform infrared (FTIR) spectra of cements. DRIFT spectra of synthetic C₃S, C₂S, C₃A, and C₄AF and of pure gypsum, bassanite, anhydrite, syngenite, and calcite are shown. Typical spectra of American Petroleum Institute class G and class A cements display characteristic features which can be related qualitatively to variations in the constituent minerals. For quantitative analysis, the FTIR spectra of 156 cements of varied origin and known elemental composition have been used to construct multivariate calibration models. These relate the spectrum to composition (expressed in terms of nine mineral components and five minor oxides) and allow the composition of unknown cements to be determined rapidly from the FTIR spectrum alone. Error estimates are given.     

Characterization of magnetic paper using Fourier transform infrared spectroscopy

Magnetic papers were prepared by using the co-precipitation method. The spectral data of the magnetic fibres were obtained by using the photoacoustic Fourier transform infrared spectroscopy (FTIR-PAS) and attenuated total reflection (ATR). It was found that the elevated loading degree increased the IR absorption and reduced the tensile strength of the paper. The partial-least-squares analyses showed that the FTIR-ATR data were strongly correlated with the degree of loading and the correlation obtained was better than that of the FTIR-PAS spectral data.     

Application of Fourier transform infrared spectroscopy in cement Alkali quantification

Alkali in cement is responsible for the Alkali–silica-reaction phenomenon that manifests itself in the form of premature cracking in concrete structures such as bridge decks and concrete pavements. X-ray fluorescence spectroscopy (XRF) is commonly used for cement Alkali quantification but a simpler and faster analytical procedure based on Fourier transform infrared spectroscopy (FTIR) has been expanded for this purpose. An analytical absorption band at 750 cm^?1 in the FTIR spectra of cement samples belonging to Alkali solid solution of tricalcium aluminate [C₃A(ss)] is used for Alkali quantification. Regression analysis of a plot correlating FTIR absorption band area ratio (750/923 cm^?1) to equivalent Alkali Na₂O _e (Na₂O _e  = % Na₂O + 0.658 × % K₂O) measured by XRF shows a linear correlation coefficient, R ², of 0.97. High Alkali cement samples show a higher microstructural disorder coefficient, C _d, which is a reactivity criterion introduced by Bachiorrini and co-authors (Proceedings of the seventh international conference on concrete alkali-aggregate reactions? 1986) for ASR-susceptible aggregates. Results of this research indicate applicability of FTIR technique to quantitatively predict cement vulnerability to ASR through the \( A_{{750\,{\text{cm}}^{ - 1} }} \) to \( A_{{923\,{\text{cm}}^{ - 1} }} \) band area ratio and the magnitude of the disorder coefficient (C _d).     

Quantitative determination of moisture in lubricants by Fourier transform infrared spectroscopy

This paper describes the development of a practical Fourier transform infrared (FT-IR) method for the determination of moisture in lubricants through the combined use of signal transduction and differential spectroscopy to circumvent matrix effects. The acid-catalyzed stoichiometric reaction of 2,2-dimethoxypropane (DMP) with moisture to produce acetone was used to provide IR signals proportional to the amount of moisture present in oils. Calibration standards were prepared by spiking polyalphaolefin (PAO) gravimetrically with water using dioxane as a carrier. For FT-IR analysis, standards and samples were diluted with acidified isooctane and then split, with one aliquot treated with DMP and the other with a blank reagent. The spectra of the two aliquots were collected, and a differential spectrum was obtained so as to ratio out the invariant spectral contributions from the sample. Quantitation for moisture was based on measurement of the peak height of the nu(C=O) absorption of acetone at 1717 cm(-1), yielding a standard error of calibration of approximately 40 ppm H2O. The method was validated by standard addition of water in dioxane to PAO containing added base as well as to new and used oils. In all cases the method responded quantitatively to standard addition, the average standard error of prediction being approximately 80 ppm, with the results showing only a minor dependence on the oil formulation. From an analytical perspective, the FT-IR method is both more reproducible and more accurate than Karl Fischer methods and has advantages in terms of environmental considerations, sample size, and speed of analysis as well as the variety of oil types that can be handled. Signal transduction/differential spectroscopy may have broader utility as an alternative means for the determination of low levels of moisture in complex matrices.     

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.     

Fluorescence lifetime imaging and Fourier transform infrared spectroscopy of Michelangelo's David

We developed a combined procedure for the analysis of works of art based on a portable system for fluorescence imaging integrated with analytical measurements on microsamples. The method allows us to localize and identify organic and inorganic compounds present on the surface of artworks. The fluorescence apparatus measures the temporal and spectral features of the fluorescence emission, excited by ultraviolet (UV) laser pulses. The kinetic of the emission is studied through a fluorescence lifetime imaging system, while an optical multichannel analyzer measures the fluorescence spectra of selected points. The chemical characterization of the compounds present on the artistic surfaces is then performed by means of analytical measurements on microsamples collected with the assistance of the fluorescence maps. The previous concepts have been successfully applied to study the contaminants on the surface of Michelangelo's David. The fluorescence analysis combined with Fourier transform infrared (FT-IR) measurements revealed the presence of beeswax, which permeates most of the statue surface, and calcium oxalate deposits mainly arranged in vertical patterns and related to rain washing.     

Study of dilution of Spin-On Glass by Fourier transform infrared spectroscopy

In this work, we study the dilution of Spin-On Glass (SOG) in order to obtain high quality SiO₂ films at 200 °C, with optical and electrical characteristics similar to those of the thermally grown SiO₂. For the production of SiO₂ films we used 2-propanol and deionized water (DI) as diluents for the SOG and we compared the electrical and optical film properties with those of the films obtained from undiluted SOG. From Fourier transform infrared spectroscopy we observed a considerable reduction of SiOH (920 cm^− 1), OH (3490 cm^− 1) and CH, CO bonds (1139 cm^− 1) in the films produced from SOG diluted with DI. Besides the above, the insulator breakdown field was approximately 21 MV/cm, the refractive index and the dielectric constant were close to those of the thermally grown SiO₂. Our results suggest that the film produced from SOG diluted with DI and cured at 200 °C is an excellent candidate to be used as insulator on flexible and large-area electronics.     

Prion protein alpha-to-beta transition monitored by time-resolved Fourier transform infrared spectroscopy

The conformational change of the recombinant, murine prion protein (PrP) from an alpha-helical to a beta-sheet enriched state was monitored by time-resolved Fourier transform infrared (FT-IR) spectroscopy. The alpha-to-beta transition is induced by reduction of the single disulfide bond in PrP. This transition is believed to generate the scrapie form PrP(Sc), the supposed infectious agent of transmissible spongiform encephalopathies. We followed the kinetics of this conformational change using a novel method for amide I band analysis of the infrared (IR) spectra. The amide I analysis provides the secondary structure. The amide I decomposition was calibrated with the three dimensional structure of cellular PrP solved by nuclear magnetic resonance (NMR). The novel secondary structure analysis provides a root mean squared deviation (RMSD) of only 3% as compared to the NMR structure. Reduction of alpha-helical PrP caused the transient accumulation of a partially unfolded intermediate, followed by formation of a state with higher beta-sheet than alpha-helical structure contents. The novel approach allows us to now determine the secondary structure of the beta-sheet conformation. This was not determined by either NMR or X-ray. The experiments were performed in a double-sealed security cuvette developed for IR analysis of potentially infectious PrP samples outside the biosafety laboratory.     

Fourier transform infrared spectroscopy of size-segregated aerosol deposits on foil substrates

A method based on Fourier transform infrared (FTIR) double-pass transmittance spectroscopy was developed for determining functional group loading in size-segregated ambient aerosol deposits. The impactor employed for sample collection utilized rotating stages, which produced uniform particulate matter (PM) deposits on standard Al foil substrates. Each sample was analyzed without extraction using an FTIR spectrometer equipped with a reflectometer accessory. The use of the reflectometer obviated the need for infrared window materials as substrates. (NH(4))(2)SO(4) aerosol generated under laboratory conditions were used to calibrate deposit mass to the band strength of the relatively isolated nu(4) bending mode of SO(2-)(4) centered near 620 cm(-1). Atmospheric PM was sampled during the summer of 2004 in Huntsville, Ala. Sulfate concentrations determined in this initial study correlated well with measurements made by collocated EPA air samplers.     

Identification of scrapie infection from blood serum by Fourier transform infrared spectroscopy

We describe a new Fourier transform infrared (FT-IR) spectroscopy-based diagnostic approach, which may provide for the first time a rapid, reliable, and inexpensive blood test for scrapie and related transmissible spongiform encephalopathies (TSE). Blood serum from 146 terminally ill Syrian hamsters infected with 263K scrapie via different routes of inoculation and from 166 healthy control animals was analyzed by FT-IR spectroscopy and artificial neural networks (ANN). This revealed characteristic molecular alterations in the serum of infected donors. Different ANN models were constructed and challenged with previously unknown samples in test runs in order to establish whether the new method is able to discriminate between normal and infected animals. Optimized ANNs consistently yielded test sensitivities and specificities of 97% and 100%, respectively. The predictive value of a positive (negative) test was 100% (98%). The proposed serum test circumvents substantial drawbacks of conventional TSE diagnostics and can be fully automated.     

Determination of acid number and base number in lubricants by Fourier transform infrared spectroscopy

This paper describes the development of practical Fourier transform infrared (FT-IR) methods for the determination of acid number (AN) and base number (BN) in lubricants through the combined use of signal transduction via stoichiometric reactions and differential spectroscopy to circumvent matrix effects. Trifluoroacetic acid and potassium phthalimide were used as stoichiometric reactants to provide infrared (IR) signals proportional to the basic and acidic constituents present in oils. Samples were initially diluted with 1-propanol, then split, with one half treated with the stoichiometric reactant and the other half with a blank reagent, their spectra collected, and a differential spectrum obtained to ratio out the invariant spectral contributions from the sample. Quantitation for AN and BN was based on measurement of the peak height of the v(C = O) or v(COO) absorptions, respectively, of the products of the corresponding stoichiometric reactions, yielding a standard error of calibration of < 0.1 mg KOH/g oil. The AN/BN FT-IR methods were validated by the analysis of a wide range of new and used oils supplied by third parties, which had been analyzed by ASTM methods. Good correlations were obtained between the chemical and FT-IR methods, indicating that the measures are on the whole comparable. From a practical perspective, these new FT-IR methods have significant advantages over ASTM titrimetric methods in terms of environmental considerations, sample size, and speed of analysis, as well as the variety of oil types that can be handled. FT-IR analysis combining stoichiometric signal transduction with differential spectroscopy may be of wider utility as an alternative to titration in the determination of acid or basic constituents in complex nonaqueous systems.     

Separation and on-line distinction of enantiomers: a non-aqueous capillary electrophoresis Fourier transform infrared spectroscopy study

We report on the separation and on-line distinction of (R,S)-3,5-dinitrobenzoyl leucine (DNB-Leu) enantiomers with non-aqueous capillary electrophoresis (CE) and Fourier transform infrared (FT-IR) spectroscopic detection using O-(tert-butyl carbamoyl) quinine (tBuCQN) as the chiral selector (CS). Due to stereoselective intermolecular interactions--particularly ionic interactions, hydrogen bonding, and pi-pi-interactions--the enantiomers undergo enantioselective complex and ion-pair formation, respectively, with the CS enabling CE separation and direct identification with FT-IR detection. Especially the (S)-enantiomer of the analyte shows significant changes in the mid-infrared region upon complexation, allowing for a clear spectral distinction between both enantiomers. In this way FT-IR spectroscopy represents a novel and attractive detection method for CE enantiomeric separations providing qualitative stereochemical information on the interactions between the chiral selector and the enantiomers, which is hardly accessible by other CE detection methods.     

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.     

Stability of Nextel fibres in aqueous environments detected by photoacoustic Fourier transform infrared spectroscopy

Photoacoustic Fourier transform infrared spectroscopy was utilized to monitor the effect of basic, acidic and neutral aqueous environments on the stability of Nextel ceramic fibres. Such treatments led to the removal of a residual hydrocarbon phase from the fibre and formation of boric acid. The presence of boric acid upon the treatment does not effect the stability of the fibre at high temperatures. At high temperatures, B(OH)₃ is apparently converted to B₂O₃, this process enhancing the surface stability and improving the adhesive properties of fibres to the polymer matrix.     

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.