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1.
Fourier transform Raman spectroscopy was employed for structural analysis of triacylglycerols and edible oils. Raman spectra sensitively reflected structural changes in oils. Even slight structural fluctuation between triacylglycerols and free fatty acids led to obvious differences in Raman bands as shown by C-O-C stretching from 800 to 1000 cm(-1) and the band at 1742 cm(-1). Structural difference in geometric isomers was easily distinguished as proved by C = C stretching at 1655 cm(-1) (cis) shifting to 1668 cm(-1) (trans) and by =C-H in-plane bending at 1266 cm(-1) in cis disappearing in the trans isomer. Raman intensity at 1266, 1302, and 1655 cm(-1) changed concomitantly with the change of double-bond content in oils. It showed that FT-Raman was capable of precisly reflecting the content of double bonds in oils. A linear correlation with high consistency between the Raman intensity ratio (v1655/v1444) and the iodine value was obtained for commercial oils. Based on the results, FT-Raman spectroscopy proved itself a simple and rapid technique for oil analysis since each measurement could be directly completed in 3 min without any sample modifications. 相似文献
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Quantitative determination of moisture in lubricants by Fourier transform infrared spectroscopy 总被引:1,自引:0,他引:1
van de Voort FR Sedman J Yaylayan V Saint Laurent C Mucciardi C 《Applied spectroscopy》2004,58(2):193-198
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. 相似文献
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Conventional Raman measurements of dyes in the visible region exhibit resonant effects which enhance the Raman scattering cross-section of the chromophores by several orders of magnitude but make scattering from other parts of the molecules, such as the hydrocarbon chains, unobservable. Taking advantage of the benefits inherent to Fourier transform (FT) spectroscopy, Raman spectra can now be measured routinely with an FT IR spectrometer and a continuous wave Nd:YAG laser. By coupling the laser excitation into a thin film waveguide, we have recently observed FT Raman spectra of a thin film of polystyrene. The advantages of using integrated optics with FT Raman spectroscopy for Langmuir-Blodgett films of dye molecules are also discussed. 相似文献
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The benefits of Raman signal enhancement and improved measurement precision are demonstrated using 180° backscattering Fourier transform Raman (FT-Raman) spectroscopy from drilled cylindrical-conical holes within pharmaceutical tablet cores. Multiple scattering of the incident laser light within the holes results in an increased Raman signal due to the larger Raman sampling volume. This is important for overcoming typical sub-sampling issues encountered when employing FT-Raman backscattering of heterogeneous pharmaceutical tablets. Hole depth and diameter were found to be important experimental parameters and were optimized to yield the greatest signal enhancement. The FT-Raman spectra collected using backscattering from cylindrical-conical holes is compared to typical 180° backscattering from flat surfaces using tablet cores of Excedrin? and Vivarin?. Raman chemical images are used to establish a representative sampling area. We observe a three- to five-fold increase in the Raman intensity and a two-fold improvement in the measurement precision when sampling from cylindrical-conical holes rather than classic backscattering from flat tablet cores. Self-absorption effects on analyte band ratios are negligible in the fingerprint region but are more significant at the higher near-infrared (NIR) absorbances found in the C-H/O-H/-N-H stretching region. The sampling technique will facilitate developing quantitative FT-Raman methods for application to pharmaceutical tablets using the fingerprint spectral region. 相似文献
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Quantitative analysis of pharmaceutical formulations using the new approach of transmission Raman spectroscopy has been investigated. For comparison, measurements were also made in conventional backscatter mode. The experimental setup consisted of a Raman probe-based spectrometer with 785 nm excitation for measurements in backscatter mode. In transmission mode the same system was used to detect the Raman scattered light, while an external diode laser of the same type was used as excitation source. Quantitative partial least squares models were developed for both measurement modes. The results for tablets show that the prediction error for an independent test set was lower for the transmission measurements with a relative root mean square error of about 2.2% as compared with 2.9% for the backscatter mode. Furthermore, the models were simpler in the transmission case, for which only a single partial least squares (PLS) component was required to explain the variation. The main reason for the improvement using the transmission mode is a more representative sampling of the tablets compared with the backscatter mode. Capsules containing mixtures of pharmaceutical powders were also assessed by transmission only. The quantitative results for the capsules' contents were good, with a prediction error of 3.6% w/w for an independent test set. The advantage of transmission Raman over backscatter Raman spectroscopy has been demonstrated for quantitative analysis of pharmaceutical formulations, and the prospects for reliable, lean calibrations for pharmaceutical analysis is discussed. 相似文献
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The potential application of Fourier transform (FT) Raman spectroscopy to predict the bitterness of peptides was investigated. FT-Raman spectra were measured for the amino acid Phe and 9 synthetic di-, tri-, and tetra peptides composed of Phe, Gly, and Pro. Partial least squares regression (PLS)-1 analysis was applied to correlate the FT-Raman spectra with bitterness intensity values (R(caf) and log 1/T) reported in the literature. Using full cross-validation, Model 1 based on the single spectral data set for the nine peptides yielded a high correlation coefficient for calibration (R = 0.99), but a low correlation coefficient for prediction (R = 0.56). Two models were constructed using the data sets including replicate spectra for the calibrations and were validated using full cross-validation. Using leave-one-sample-set-out calibrations, Model 2, which was developed with the data for the peptides as well as Phe, yielded a low correlation coefficient (R = 0.533) for the prediction of the bitterness, while Model 3 developed with only the peptide data provided better correlation coefficients (R = 0.807 and 0.724 for R(caf) and log 1/T values, respectively). The correlation coefficients for prediction were 0.975 (R(caf) values) and 0.874 (log 1/T values) for Model 4, which was developed using subtracted spectral data (spectra of peptides with higher R(caf) values minus spectra of peptides with lower R(caf) values). Examination of the PLS regression coefficients at wavenumbers most highly correlated with bitterness revealed the importance of hydrophobicity and peptide length on bitterness. This study indicates the potential of FT-Raman spectroscopy as a useful tool for predicting bitterness of peptides and amino acids. 相似文献
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The ideal quality control method for pharmaceutical products should be capable of rapid nondestructive testing of intact tablets or capsules. Raman spectroscopy using near-infrared excitation is shown to be capable of obtaining useful spectral data directly from drug formulations in gel capsules and from the gel capsules inside blister packs. The Raman data collected from the capsules inside blister packs containing 0-100 mg of the active ingredient (bucindolol), when coupled with multivariate calibration, resulted in a calibration SEP of 3.36 mg. The largest source of error was found to be due to sample inhomogeneity. Even so, the method is shown to have significant potential as a rapid nondestructive quality control method for pharmaceutical samples. 相似文献
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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. 相似文献
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The transfer of multivariate calibration models is investigated between a primary (A) and two secondary Fourier transform near-infrared (near-IR) spectrometers (B, C). The application studied in this work is the use of bands in the near-IR combination region of 5000-4000 cm(-)(1) to determine physiological levels of glucose in a buffered aqueous matrix containing varying levels of alanine, ascorbate, lactate, triacetin, and urea. The three spectrometers are used to measure 80 samples produced through a randomized experimental design that minimizes correlations between the component concentrations and between the concentrations of glucose and water. Direct standardization (DS), piecewise direct standardization (PDS), and guided model reoptimization (GMR) are evaluated for use in transferring partial least-squares calibration models developed with the spectra of 64 samples from the primary instrument to the prediction of glucose concentrations in 16 prediction samples measured with each secondary spectrometer. The three algorithms are evaluated as a function of the number of standardization samples used in transferring the calibration models. Performance criteria for judging the success of the calibration transfer are established as the standard error of prediction (SEP) for internal calibration models built with the spectra of the 64 calibration samples collected with each secondary spectrometer. These SEP values are 1.51 and 1.14 mM for spectrometers B and C, respectively. When calibration standardization is applied, the GMR algorithm is observed to outperform DS and PDS. With spectrometer C, the calibration transfer is highly successful, producing an SEP value of 1.07 mM. However, an SEP of 2.96 mM indicates unsuccessful calibration standardization with spectrometer B. This failure is attributed to differences in the variance structure of the spectra collected with spectrometers A and B. Diagnostic procedures are presented for use with the GMR algorithm that forecasts the successful calibration transfer with spectrometer C and the unsatisfactory results with spectrometer B. 相似文献
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Spruce thermomechanical pulp (TMP) was oxidized by the 2,2'azinobis-3-ethylbenzthiazoline-6-sulfonate cation radical (ABTS*+) in the presence and absence of oxygen. The pulp modification was monitored by Fourier transform (FT) Raman difference spectroscopy and other nondestructive spectroscopic methods. The ABTS*+ oxidative system resulted in modifications very similar to the laccase-ABTS-oxygen system, except for the FT-Raman results, which showed a difference in mechanisms attributed to a difference in produced Raman bands. Oxygen resulted in no oxygen-derived products, but only enhanced the production of a specific Raman band of several oxidation-produced bands. Detailed information on lignin reactions can be obtained from FT-Raman signals. 相似文献
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Xiaoqian Shan Ligen Chen Yuan Yuan Changsheng Liu Xiaolan Zhang Yan Sheng Feng Xu 《Journal of materials science. Materials in medicine》2010,21(1):241-249
Based on the penetrability of IR within the polymeric nanoparticles, a novel Fourier transform infrared spectroscopy (FTIR)
method, with polyacrylonitrile (PAN) as the internal reference standard, was developed to quantify the hemoglobin (Hb) content
in Hb-based polymeric nanoparticles (HbPN). The HbPN was fabricated by double emulsion method from poly(ethylene glycol)–poly(lactic
acid)–poly(ethylene glycol) triblock copolymers. Depending on the characteristic un-overlapped IR absorbances at 1540 cm−1 of Hb (amide II) and at 2241 cm−1 of PAN (–C≡N), calibration equations, presenting the peak height ratio of Hb and PAN as a function of the weight ratio of
Hb and PAN, were established. This new quantification method is validated and used to the determination Hb content in HbPN.
Due to the good results of this calibration strategy, the proposed simple FTIR approach with minimal sample-needed and solvent-free
makes it useful for routine analysis of protein content and could be also applied to any other drug/protein encapsulated particles. 相似文献
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The resolution of a grating polychromator for Raman spectroscopy has been simulated by measuring spectra on a Fourier transform (FT) Raman spectrometer and selecting the FT of the apodization function so that the instrument line shape function mimics the triangular spectral slit function of the polychromator. To this end, FT-Raman spectra measured with a nominal resolution of 0.5 cm-1 were modified through the application of sinc2 apodization functions of various widths to simulate spectra measured on a polychromator at lower resolution. The success of this approach was validated using the 1085 cm-1 band of calcite. When the modified FT-Raman spectra were compared with spectra measured on a grating polychromator equipped with slits of widths 100 and 150 microns, the resolution of the polychromator was estimated to be 6.3 and 7.8 cm-1, respectively. This conclusion was verified experimentally by measuring the separation of two bands in the Raman spectrum of BaSO4 at approximately 460 cm-1. 相似文献
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Chin H. Chia Sarani Zakaria Kien L. Nguyen Vinh Q. Dang Tuan D. Duong 《Materials Chemistry and Physics》2009,113(2-3):768-772
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. 相似文献
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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. 相似文献
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Epigallocatechin-3-gallate (EGCG) is credited with the majority of the health benefits associated with green tea consumption. It has a high economic and medicinal value. The feasibility of using different variable selection approaches in Fourier transform near-infrared (FT-NIR) spectroscopy for a rapid and conclusive quantitative determination of EGCG in green tea was investigated. Graphically oriented multivariate calibration modeling procedures such as interval partial least squares (iPLS), synergy interval partial least squares (siPLS), and genetic algorithm optimization combined with siPLS (siPLS-GA) were applied to select the most efficient spectral variables that provided the lowest prediction error. The performance of the final model was evaluated according to the root mean square error of prediction (RMSEP) and coefficient of determination (R(2)) for the prediction set. Experimental results showed that the siPLS-GA model obtained the best results in comparison to other models. The optimal models were achieved with R(2)(p) = 0.97 and RMSEP = 0.32. The model can be obtained with only 36 variables retained and it provides a robust model with good estimation accuracy. This demonstrates the potential of NIR spectroscopy with multivariate calibration methods to quickly detect the bioactive component in green tea. 相似文献
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The silanol concentration of quartz was determined by mixing 50 mg ground silica sample with 500 mg KBr followed by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and chemometric data analysis. Reference samples were prepared by blending ground quartz of different silanol content. Good correlation was achieved between 10 and 240 ppm Si-OH by mass. The chemometric model's quality is characterized by a correlation coefficient of 0.965 (cross-validation) using five latent variables (factors) and a root mean square error of calibration (RMSEC) of 7 ppm. Chemometric data is compared to results from univariate data analysis. The biggest impact on the reproducibility is due to sample preparation (grinding and blending), which is dependant on the operator involved. 相似文献