Determination of solid fat index by fourier transform infrared spectroscopy

A unique and rapid Fourier transform infrared (FTIR) spectroscopic method for the determination of solid fat index (SFI) of fats and oils was developed, which is capable of predicting the SFI profile of a sample in approximately two minutes, without the need for tempering. Hydrogenated soybean oil samples (n=72), pre-analyzed for SFI by dilatometry, were melted and their FTIR spectra acquired using a 25 μm NaCl transmission flow cell maintained at 80°C. Approximately half the samples were used for calibration, with the balance used as validation samples. Partial least squares (PLS) calibrations were developed from selected spectral regions that are associated with thecis, trans, ester linkage and fingerprint regions of the spectrum and related to the dilatometric SFI values obtained at 50, 70, 80, and 92°F. The calibrations were initially optimized and cross-validated by using the “leave one out” approach, with the accuracy and reproducibility of the calibration models assessed by predicting the validation samples. The overall cross validation accuracy of the PLS calibration models was in the order of ±0.71 SFI units over the four temperatures. Week-to-week validation accuracy and reproducibility was determined to be ±0.60 and ±0.38 SFI units, respectively, the reproducibility being within the specifications associated with the dilatometric reference method. To facilitate routine “on-line” FTIR analyses, a Visual Basic program was written to drive the spectrometer, prompt the user to load the sample, calculate, and print the SFI values determined from the PLS calibrations. As structured, the FTIR method has the potential to serve as a viable substitute for the traditional dilatometric SFI method, with the elimination of the tempering step reducing analysis time from hours to minutes. The FTIR approach should also be applicable to the determination of solid fat content if calibrated against solids data obtained by nuclear magnetic resonance.     

Stoichiometric determination of hydroperoxides in fats and oils by fourier transform infrared spectroscopy

A primary Fourier transform infrared (FTIR) spectroscopic method for the determination of peroxide value (PV) in edible oils was developed based on the stoichiometric reaction of triphenylphosphine (TPP) with hydroperoxides to produce triphenylphosphine oxide (TPPO). Accurate quantitation of the TPPO formed in this reaction by measurement of its intense absorption band at 542 cm⁻¹ provides a simple means of determining PV. A calibration was developed with TPPO as the standard; its concentration, expressed in terms of PV, covered a range of 0–15 PV. The resulting calibration was linear over the analytical range and had a standard deviation of ±0.05 PV. A standardized analytical protocol was developed, consisting of adding ∼0.2 g of a 33% (w/w) stock solution of TPP in hexanol to ∼30 g of melted fat or oil, shaking the sample, and scanning it in a 100-μm KCI IR transmission cell maintained at 80°C. The FTIR spectrometer was programmed in Visual Basic to automate scanning and quantitation, with the reaction/FTIR analysis taking about 2 min per sample. The method was validated by comparing the analytical results of the AOCS PV method to those of the automated FTIR procedure by using both oxidized oils and oils spiked with tert-butyl hydroperoxide. The two methods correlated well. The reproducibility of the FTIR method was superior (±0.18) to that of the standard chemical method (±0.89 PV). The FTIR method is a significant improvement over the standard AOCS method in terms of analytical time and effort and avoids solvent and reagent disposal problems. Based on its simple stoichiometry, rapid and complete reaction, and the singular band that characterizes the end product, the TPP/TPPO reaction coupled with a programmable FTIR spectrometer provides a rapid and efficient means of determining PV that is especially suited for routine quality control applications in the fats and oils industry.     

Upgrading the AOCS infrared trans method for analysis of neat fats and oils by fourier transform infrared spectroscopy

An automated protocol for the direct, rapid determination of isolated trans content of neat fats and oils by Fourier transform infrared (FTIR) spectroscopy was devised, based on a simple modification of the standard AOCS trans method, eliminating the use of CS₂ and methylation of low trans samples. Through the use of a commercially available, heated transmission flow cell, designed specifically for the analysis of neat fats and oils, a calibration (0–50%) was devised with trielaidin spiked into a certified, trans-free soybean oil. The single-beam spectra of the calibration standards were ratioed against the single-beam spectrum of the base oil, eliminating the spectral interference caused by underlying triglyceride absorptions, facilitating direct peak height measurements as per the AOCS IR trans method. The spectrometer was preprogrammed in Visual Basic to carry out all spectral manipulations, measurements, and calculations to produce trans results directly as well as to provide the operator with a simple interface to work from. The derived calibration was incorporated into the software package, obviating the need for further calibration because the program includes an automatic recalibration/standardization routine that automatically compensates for differences in optical characteristics between instruments, instrument drift over time, and cell wear. The modified AOCS FTIR analytical package was evaluated with Smalley check samples for repeatability, reproducibility, and accuracy, producing SD of ± 0.07, 0.13, and 0.70 trans, respectively, the FTIR predictions being linearly related to the Smalley means (r=0.999; SD=± 0.46), and well within one SD of the Smalley sample means. Calibration transfer was assessed by implementing the calibration on a second instrument and reanalyzing the Smalley check samples in cells of two different pathlengths (25- and 50-μm). There were no statistically significant differences between the FTIR trans predictions obtained for the Smalley samples from the two instruments and two cells, indicating that the software was able to adjust the calibrations to compensate for differences in instrument response and cell pathlength. The FTIR isolated trans analysis protocol developed by the McGill IR Group has the benefit of being based on the principles of an AOCS-approved method, matches its accuracy, and allows the analysis to be performed on both neat fats and oils, producing trans predictions in less than 2 min per sample. It is suggested that this integrated approach to trans analysis, which requires a minimum level of sample manipulation and operator skill, be considered as a modification of the proposed Recommended Practice CD14b-95.     

Determination of iodine value of palm oil by fourier transform infrared spectroscopy

A rapid method for the quantitative determination of iodine value (IV) of palm oil products by FTIR transmission spectroscopy is described. A calibration standard was developed by blending palm stearin and superolein in specific ratios that covered a range of 27.9 to 65.3 IV units. The spectra of these standards was measured in the range between 3050 and 2984 cm⁻¹, corresponding to the absorption band of=C-H cis stretching vibration. A partial least squares calibration model for the prediction of IV was developed to quantify the IV of palm oil products. A validation approach was used to optimize the calibration with a correlation coefficient of R ²=0.9995 and a standard error of prediction of 0.151. This study concludes that the FTIR transmission approach can be used to determine the IV of palm oil products with a total analysis time per sample of less than 2 min for liquid samples.     

Trans fatty acid determination in fats and margarine by fourier transform infrared spectroscopy using a disposable infrared card

The use of a disposable polyethylene infrared (IR) card as a sample carrier for the quantitative determination of trans content of fats and oils and margarine by Fourier transform IR spectroscopy was investigated. Standards prepared by dissolving trielaidin in a zero-trans oil were used to develop partial least squares (PLS) calibrations for both the IR card and a 100-μm transmission flow cell. These calibrations were then used to predict a series of gas chromatographically-preanalyzed unknowns, the trans predictions obtained using the card being comparable to those obtained with the transmission flow cell. Somewhat improved performance could be obtained when the spectral data from the card were normalized to compensate for inherent variations in path length and variability in sample loading. Both IR methods tracked the gas chromatographic reference trans values very well. A series of margarine samples was also analyzed by the card method, producing results similar to those obtained using a flow cell. For the analysis of margarines, the card method has the advantage that the trans analysis can be performed directly on microwave melted emulsions because moisture is not retained on the card. Overall, the disposable IR card was shown to work well and has the benefit of allowing trans analyses to be carried out without requiring investment in a heated flow cell or attenuated total reflectance accessory.     

Quantitative analysis of palm carotene using fourier transform infrared and near infrared spectroscopy

β-Carotene content is usually determined by using ultraviolet (UV)-visible spectrophotometry at 446 nm. In this study, two spectroscopic techniques, namely, Fourier transform infrared (FTIR) and near infrared (NIR) spectroscopy, have been investigated and compared to UV-visible spectrophotometry to measure the β-carotene content of crude palm oil (CPO). Calibration curves ranging from 200 to 800 ppm were prepared by extracting β-carotene from original CPO using open-column chromatography. Separate partial least squares calibration models were developed for predicting β-carotene based on the spectral region from 976 to 926 cm⁻¹ for FTIR spectroscopy and 546 to 819 nm for NIR spectroscopy. The correlation coefficient (R ²) and standard error of calibration obtained were 0.972 and 25.2 for FTIR and 0.952 and 23.6 for NIR techniques, respectively. The validation set gave R ² of 0.951 with standard error of performance (SEP) of 25.78 for FTIR technique and R ² of 0.979 with SEP of 19.96 for NIR technique. The overall reproducibility and accuracy did not give comparable results to that of spectrophotometric method; however, the standard deviation of prediction was still within ±5% β-carotene content over the range tested. Because of their rapidness and simplicity, both FTIR and NIR techniques provide alternative means of measuring β-carotene content in CPO. In addition, these two spectroscopic techniques are environmentally friendly since no solvent is involved.     

Characterization of semisolid fats and edible oils by Fourier transform infrared photoacoustic spectroscopy

The potential of Fourier transform infrared photoacoustic spectroscopy (FTIR-PAS) for the analysis of semisolid fat and edible oil was demonstrated with butter, soybean oil, and lard as representative materials. Results of Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy analysis was compared with FTIR-PAS results. The PAS technique is simple and requires no sample preparation unlike ATR. Optimal PAS instrumental parameters for obtaining quality spectra are a scanning speed of 5 kHz, number of scans of 256 scans/sample, and a resolution of 4 cm⁻¹. The PAS spectra of soybean oil and lard are similar because they have similar functional groups. Results for soybean oil compare well with those available in the literature. The ATR spectra of butter were better than those from its PAS counterpart. Functional groups corresponding to vibration mode and intensity are provided for soybean oil and lard.     

Characterization of edible oils and lard by fourier transform infrared spectroscopy. Relationships between composition and frequency of concrete bands in the fingerprint region

Fourteen samples of edible oils and lard have been studied by means of Fourier transform infrared spectroscopy. The spectra were recorded from a film of pure oil or lard between two discs of KBr. The bands of the spectra were assigned to different functional group vibrations. The frequencies of some bands have constant values, independent of the nature of the sample. However, frequencies of other bands, some of them in the fingerprint region, depend greatly on the sample composition. Equations obtained from frequency of these bands and composition data are valuable to predict the proportions of saturated, monounsaturated and polyunsaturated acyl groups in oils and lard.     

The determination of peroxide value by fourier transform infrared spectroscopy

A rapid method for the quantitative determination of peroxide value (PV) of vegetable oils by Fourier transform infrared (FTIR) transmission spectroscopy is described. Calibration standards were prepared by the addition oft-butyl hydroperoxide to a series of vegetable oils, along with random amounts of oleic acid and water. Additional standards were derived through the addition of mono- and diglyceride spectral contributions, as well as zero PV spectra obtained from deuterated oils. A partial least squares (PLS) calibration model for the prediction of PV was developed based on the spectral range 3750–3150 cm⁻¹. Validation of the method was carried out by comparing the PV of a series of vegetable oils predicted by the PLS model to the values obtained by the American Oil Chemists Society iodometric method. The reproducibility of the FTIR method [coefficient of variation (CV)=5%)] was found to be better than that of the chemical method (CV =9%), although its accuracy was limited by the reproducibility of the chemical method. The method, as structured, makes use of a 1-mm CaF₂ flow cell to allow rapid sample handling by aspiration. The spectrometer was preprogrammed in Visual Basic to guide the operator in performing the analysis so that no knowledge of FTIR spectroscopy is required to implement the method. The method would be suitable for PV determinations in the edible oil industry and takes an average of three minutes per sample.     

Quantitative determination of hydroperoxides by fourier transform infrared spectroscopy with a disposable infrared card

Disposable polyethylene infrared cards (3M IR cards) were investigated for their suitability for the quantitative determination of peroxide value (PV) in edible oils relative to a conventional transmission flow cell. The analysis is based on the stoichiometric reaction of triphenylphosphine (TPP) with hydroperoxides to produce triphenylphosphine oxide (TPPO). Preliminary work indicated that the cards, although relatively consistent in their pathlength (±1%), had an overall effective pathlength variation of ±∼5%, caused by variability in loading of the oil onto the cards. This loading variability was reduced to <0.5% by developing a normalization protocol that is based on the peak height of the ester linkage carbonyl overtone band at 3475 cm⁻¹, which allowed one to obtain consistent and reproducible spectra. The standard PV calibration approach, based on the TPPO peak height at 542 cm⁻¹, failed because of unanticipated card fringing in the region where the measurements were being made. However, the development of a partial-least-squares (PLS) calibration provided a means of eliminating the interfering effect of the fringes and allowed the TPPO band to be measured accurately. An alternate approach to the standardized addition of TPP reagent to the oil was also investigated by impregnating the 3M IR cards with TPP, thus allowing the reaction to take place in situ. The spectral analysis protocols developed (normalization/calibration) were programmed to automate the PV analysis completely. The 3M card-based Fourier transform infrared PV methods developed were validated by analyzing oxidized oils and comparing the PV predictions obtained to those obtained in a 100-μm KCI flow cell. Both card methods performed well in their ability to predict PV. The TPP-impregnated 3M card method reproduced the flow cell PV data to within ±1.12 PV, whereas the method with an unimpregnated card was accurate to ±0.92 PV over the calibrated range (0–25 PV). Our results indicate that, with spectral normalization and the use of a PLS calibration, quantitative PV data, comparable to those obtained with a flow cell, can be provided by the 3M IR card. With the analytical protocol preprogrammed, the disposable 3M card provides a simple, rapid and convenient means of carrying out PV analyses, suitable for quality control laboratories, taking about 2–3 min per analysis.     

A rapid,automated method for the determination ofcis andtrans content of fats and oils by fourier transform infrared spectroscopy

A rapid Fourier transform infrared (FTIR) method was developed to simultaneously determine percentcis andtrans content of edible fats and oils. A generalized, industrial sample-handling platform/accessory was designed for handling both fats and oils and was incorporated into an FTIR spectrometer. The system was calibrated to predict thecis andtrans content of edible oils by using pure triglycerides as standards and partial least squares as the chemometric approach. The efficacy of the calibration was assessed by triglyceride standard addition, by mixing of oils with varyingcis/trans contents, and by analyzing fats and oils of known iodine value. Each of the approaches verified that the FTIR method measured thecis andtrans content in a reproducible (±0.7%) manner, with the measured accuracies being 1.5% for standard addition and 2.5% for the chemically analyzed samples. Comparisons also were made to the conventional American Oil Chemists’ Society (AOCS) method for the determination oftrans isomers by IR spectroscopy. The FTIR-partial least squares approach worked well over a wide range oftrans contents, including those between 0 and 15%. The sample-handling accessory designed for this application is robust, flexible, and easy to use, being particularly suited for quality-control applications. In addition, the analysis was automated by programming the spectrometer in Visual Basic (Windows), to provide a simple, prompt-based user interface and to allow an operator to carry outcis/trans analyses without any knowledge of FTIR spectroscopy. A typical analysis requires less than two minutes per sample. The derived calibration is transferable between instruments, eliminating the need for recalibration. The integrated analytical system provides a sound basis for the implementation of FTIR methods in place of a variety of AOCS wet chemical methods when analytical speed, cost, and environmental concerns are issues.     

Quantitative determination of hydroperoxides by fourier transform infrared spectroscopy with a disposable infrared card

Disposable polyethylene infrared cards (3M IR cards) were investigated for their suitability for the quantitative determination of peroxide value (PV) in edible oils relative to a conventional transmission flow cell. The analysis is based on the stoichiometric reaction of triphenylphosphine (TPP) with hydroperoxides to produce triphenylphosphine oxide (TPPO). Preliminary work indicated that the cards, although relatively consistent in their pathlength (±1%), had an overall effective pathlength variation of ±∼5%, caused by variability in loading of the oil onto the cards. This loading variability was reduced to <0.5% by developing a normalization protocol that is based on the peak height of the ester linkage carbonyl overtone band at 3475 cm⁻¹, which allowed one to obtain consistent and reproducible spectra. The standard PV calibration approach, based on the TPPO peak height at 542 cm⁻¹, failed because of unanticipated card fringing in the region where the measurements were being made. However, the development of a partial-least-squares (PLS) calibration provided a means of eliminating the interfering effect of the fringes and allowed the TPPO band to be measured accurately. An alternate approach to the standardized addition of TPP reagent to the oil was also investigated by impregnating the 3M IR cards with TPP, thus allowing the reaction to take place in situ. The spectral analysis protocols developed (normalization/calibration) were programmed to automate the PV analysis completely. The 3M card-based Fourier transform infrared PV methods developed were validated by analyzing oxidized oils and comparing the PV predictions obtained to those obtained in a 100-μm KCI flow cell. Both card methods performed well in their ability to predict PV. The TPP-impregnated 3M card method reproduced the flow cell PV data to within ±1.12 PV, whereas the method with an unimpregnated card was accurate to ±0.92 PV over the calibrated range (0–25 PV). Our results indicate that, with spectral normalization and the use of a PLS calibration, quantitative PV data, comparable to those obtained with a flow cell, can be provided by the 3M IR card. With the analytical protocol preprogrammed, the disposable 3M card provides a simple, rapid and convenient means of carrying out PV analyses, suitable for quality control laboratories, taking about 2–3 min per analysis.     

Rapid quantitative determination of free fatty acids in fats and oils by fourier transform infrared spectroscopy

Rapid direct and indirect Fourier transform infrared (FTIR) spectroscopic methods were developed for the determination of free fatty acids (FFA) in fats and oils based on both transmission and attenuated total reflectance approaches, covering an analytical range of 0.2–8% FFA. Calibration curves were prepared by adding oleic acid to the oil chosen for analysis and measuring the C=O band @ 1711 cm^–1 after ratioing the sample spectrum against that of the same oil free of fatty acids. For fats and oils that may have undergone significant thermal stress or extensive oxidation, an indirect method was developed in which 1% KOH/methanol is used to extract the FFAs and convert them to their potassium salts. The carboxylate anion absorbs @ 1570 cm^–1, well away from interfering absorptions of carbonyl-containing oxidation end products that are commonly present in oxidized oils. Both approaches gave results comparable in precision and accuracy to that of the American Oil Chemists’ Society reference titration method. Through macroprogramming, the FFA analysis procedure was completely automated, making it suitable for routine quality control applications. As such, the method requires no knowledge of FTIR spectroscopy on the part of the operator, and an analysis takes less than 2 min.     

Diffuse reflectance fourier transform infrared spectroscopy of triacylglycerol and oleic acid adsorption on synthetic magnesium silicate

Diffuse reflectance fourier transform infrared (FTIR) was used to observe adsorption complexes of triacylglycerol and oleic acid on silica gel and synthetic magnesium silicate. The spectra provide evidence of the nature of the surface interaction. Triacylglycerol was shown to be physically adsorbed to both adsorbents. Oleic acid was physically adsorbed to the silica gel, but both physically and chemically adsorbed to the magnesium silicate. The FTIR spectrum of magnesium silicate that was used to treat a degraded frying oil was similar to that of oleic acid adsorbed on magnesium silicate.     

Detection of lard and randomized lard as adulterants in refined-bleached-deodorized palm oil by differential scanning calorimetry

A study was conducted to assess the use of differential scanning calorimetry (DSC) for detecting the presence of lard/randomized lard as adulterants in refined-bleached-deodorized (RBD) palm oil. Lard extracted from the adipose tissues of pig was chemically interesterified using sodium methoxide as catalyst. DSC thermal profiles of both genuine lard and randomized lard were compared with those of other common animal fats such as beef tallow, mutton tallow, and chicken fat. Lard and randomized lard were then blended with RBD palm oil in two series, in proportions ranging from 0.2 to 20%, and DSC analyses were obtained. The DSC cooling profiles of adulterated RBD palm oil samples showed an adulteration peak corresponding to lard/randomized lard in the low-temperature region. This peak was confirmed as an indicator of the presence of lard in RBD palm oil since similar experiments carried out using other common animal fats such as mutton tallow, beef tallow, and chicken fat showed that the lard adulteration peak could be distinctly identified. Using this method, a detection limit of 1% lard/randomized lard was reached (P<0.0001).     

Determination of phospholipids in vegetable oil by fourier transform infrared spectroscopy

A method was developed to determine the total phospholipid content in vegetable oil by Fourier transform infrared spectroscopy (FTIR). Calibration curves of I-α-phosphatidylcholine (PC), I-α-phosphatidylethanolamine (PE), and I-α-phosphatidylinositol (PI) in hexane were generated at different concentrations. The optimal phospholipid absorption bands between 1200–970 cm⁻¹ were identified and used for quantitative determination. High R ²≥0.968 were observed between band areas and phospholipid standard concentrations. Phospholipids from crude soybean oil were obtained by water degumming, and purification was performed on a silicic acid column. The phospholipid contents of purified phospholipid extract, degummed and crude soybean oil determined from calibration equations were >90, 0.0113, and 1.77%, respectively. High correlations of determination (R ²≥0.933) were observed between the FTIR method and thin-layer chromatography-imaging densitometry method for the determination of phospholipid content. FTIR was found to be a useful analytical tool for simple and rapid quantitative determination of phospholipids in vegetable oil.     

Determination of olive oil free fatty acid by fourier transform infrared spectroscopy

A new procedure for determining free fatty acids (FFA) in olive oil based on spectroscopic Fourier transform infrared-attenuated total reflectance spectroscopy measurements is proposed. The range of FFA contents of samples was extended by adding oleic acid to several virgin and pure olive oils, from 0.1 to 2.1%. Calibration models were constructed using partial least-squares regression (PLSR). Two wavenumber ranges (1775–1689 cm⁻¹ and 1480–1050 cm⁻¹) and several pretreatments [first and second derivative; standard normal variate (SNV)] were tested. To obtain good results, splitting of the calibration range into two concentration intervals (0.1 to 0.5% and 0.5 to 2.1%) was needed. The use of SNV as a pretreatment allows one to analyze samples of different origins. The best results were those obtained in the 1775–1689 cm⁻¹ range, using 3 PLSR components. In both concentration ranges, at a confidence interval of α = 0.05, no significant differences between the reference values and the calculated values were observed. Reliability of the calibration vs. stressed oil samples was tested, obtaining satisfactory results. The developed method was rapid, with a total analysis time of 5 min; it is environment-friendly, and it is applicable to samples of different categories (extra virgin, virgin, pure, and pomace oil).     

Industrial validation of fourier transform infrared trans and lodine value analyses of fats and oils

A Fourier transform infrared (FTIR) edible oil analysis package designed to simultaneously analyze for trans content, cis content, iodine value (IV), and saponification number (SN) of neat fats and oils by using calibrations based on pure triglycerides and derived by application of partial-least-squares (PLS) regression was assessed and validated. More than 100 hydrogenated rapeseed and soybean samples were analyzed by using the edible oil analysis package as well as the newly proposed modification of the AOCS IR trans method with trielaidin in a trans-free oil as a basis for calibration. In addition, ∼1/3 of the samples were subsequently reanalyzed by gas chromatography (GC) for IV and trans content. The PLS approach predicted somewhat higher trans values than the modified AOCS IR method, which was traced to a combination of the inclusion of trilinolelaidin in the calibration set and the effects of baseline fluctuations. Eliminating trilinolelaidin from the triglyceride standards and the use of second-derivative spectra to remove baseline fluctuations produced excellent concurrence between the PLS and modified AOCS IR methods (mean difference of 0.61% trans). Excellent internal consistency was obtained between the IV and cis and trans data provided by the edible oil analysis package, and the relationship was close to that theoretically expected [IV=0.86 (cis + trans)]. The IV data calculated for the GC-analyzed samples matched the PLS IV predictions within 1 IV unit. The trans results obtained by both IR methods were linearly related to the GC data; however, as is commonly observed, the GC values were significantly lower than the IR values, the GC and IR data being related by a slope factor of ∼0.88, with an SD of ∼0.80. The concurrence between the trans data obtained by the two FTIR methods, and between the FTIR and GC-IV data, as well as the internal consistency of the IV, cis and trans FTIR predictions, provides strong experimental evidence that the edible oil analytical package measures all three variables accurately. Co-Director, McGill IR Group.     

Fourier transform infrared spectroscopy and chemometrics as a tool for the rapid detection of other vegetable fats mixed in cocoa butter

The Fourier transform infrared (FTIR) technique in combination with multivariate data evaluation was used to analyze a wide variety of cocoa butters (CB), cocoa butter equivalents (CBE), and mixtures thereof. The sample set consisted of 14 CB (10 pure from various geographical origins and 4 commercial mixtures), 18 CBE (12 mixtures and 6 pure CBE from kokum, illipé, and palm midfraction), and 154 mixtures of CB with CBE at various concentrations (ranging from 5 to 20%). A total of 192 samples were analyzed in triplicate. All CB and CBE were shown to have very characteristic FTIR spectra that gave highly reproducible fingerprints. The main vibrational modes were also elucidated. FTIR can easily be employed to distinguish between pure CB and pure CBE. With prior knowledge of which cocoa butter is present in mixtures, FTIR can be applied to distinguish between CB mixed with CBE at the 10 and 20% levels (corresponding to about 2 and 5% of CBE in chocolate). However, the study revealed that a single “global” statistical model (multilayer perceptron, radial basis functions, or partial least square regression) was not able to predict the precise level of addition. The FTIR approach detailed here shows great potential as a rapid screening method for distinguishing between pure vegetable fats and, we believe, could be extended to investigate mixtures of CB and CBE by the establishment of a database.     

Fourier transform Raman and Fourier transform infrared spectroscopy studies of silk fibroin

The chemical and conformational structures of Bombyx mori silk were studied with the complementary techniques of Fourier transform Raman spectroscopy and Fourier transform infrared spectroscopy. The Fourier transform Raman spectrum of silk showed strong bands for the photosensitive aromatic amino acids tyrosine, tryptophan, and phenylalanine. Intensive UV/ozone irradiation reduced the Raman intensities of the amide III band and the tyrosine signals due to peptide chain scission of the silk polymer and the photochemical changes in the tyrosine residues on the silk molecules. However, the Raman spectroscopy changes for tryptophan were less clearly defined because of peak overlapping with other amino acid signals and the low concentration of tryptophan. The Fourier transform infrared (attenuated total reflectance) technique, coupled with second‐derivative spectroscopy analysis, demonstrated a decrease in the crystallinity degree and tyrosine content of UV/ozone‐irradiated silk, as indicated by changes in the Fourier transform infrared bands of amide III doublet and tyrosine signals. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1999–2004, 2005