Comparing Near-infrared Conventional Diffuse Reflectance Spectroscopy And Hyperspectral Imaging For Determination Of The Bulk Properties Of Solid Samples By Multivariate Regression: Determination Of Mooney Viscosity And Plasticity Indices Of Natural Rubber.

Conventional reflectance spectroscopy (NIRS) and hyperspectral imaging (HI) in the near-infrared region (1000-2500 nm) are evaluated and compared, using, as the case study, the determination of relevant properties related to the quality of natural rubber. Mooney viscosity (MV) and plasticity indices (PI) (PI0 - original plasticity, PI30 - plasticity after accelerated aging, and PRI - the plasticity retention index after accelerated aging) of rubber were determined using multivariate regression models. Two hundred and eighty six samples of rubber were measured using conventional and hyperspectral near-infrared imaging reflectance instruments in the range of 1000-2500 nm. The sample set was split into regression (n = 191) and external validation (n = 95) sub-sets. Three instruments were employed for data acquisition: a line scanning hyperspectral camera and two conventional FT-NIR spectrometers. Sample heterogeneity was evaluated using hyperspectral images obtained with a resolution of 150 × 150 μm and principal component analysis. The probed sample area (5 cm(2); 24,000 pixels) to achieve representativeness was found to be equivalent to the average of 6 spectra for a 1 cm diameter probing circular window of one FT-NIR instrument. The other spectrophotometer can probe the whole sample in only one measurement. The results show that the rubber properties can be determined with very similar accuracy and precision by Partial Least Square (PLS) regression models regardless of whether HI-NIR or conventional FT-NIR produce the spectral datasets. The best Root Mean Square Errors of Prediction (RMSEPs) of external validation for MV, PI0, PI30, and PRI were 4.3, 1.8, 3.4, and 5.3%, respectively. Though the quantitative results provided by the three instruments can be considered equivalent, the hyperspectral imaging instrument presents a number of advantages, being about 6 times faster than conventional bulk spectrometers, producing robust spectral data by ensuring sample representativeness, and minimizing the effect of the presence of contaminants.

Simultaneous FT-NIR and ESR analyses to yield propagation rate coefficients for polymerization of methyl methacrylate based monomers

A hyphenated instrumental approach has been used to obtain reliable values for the propagation rate coefficients as a function of conversion for polymerizations of methyl methacrylate (MMA) and a mixture of MMA and ethyleneglycol dimethacrylate (EGDMA) with a 1:1 concentration of double bonds, from near the onset of the Trommsdorf region into the glass region. ESR spectroscopy was used to measure the radical concentration while FT-NIR fibre-optic spectroscopy was employed to measure instantaneously the double-bond concentration within the temperature-controlled cavity of the ESR instrument during polymerization. The advantage of this approach to the measurement of the rate coefficient is that it is equally applicable to branching and linear polymerizations. For the polymerization of methyl methacrylate, the values of the rate coefficient at the lowest conversions at which reliable values could be obtained were in agreement with recently reported values obtained by the PLP-SEC method. For the lowest conversions, the values obtained were 403 1 mol(-1) s(-1) at 306 K for MMA and 5201 mol(-1) s(-1) at 310 K for a 1:1 mixture of MMA and EGDMA. (C) 2003 Society of Chemical Industry.

Comparative analysis of near and mid-infrared spectroscopy to monitor recombinant cyprosin production

Infrared spectroscopy, either in the near and mid (NIR/MIR) region of the spectra, has gained great acceptance in the industry for bioprocess monitoring according to Process Analytical Technology, due to its rapid, economic, high sensitivity mode of application and versatility. Due to the relevance of cyprosin (mostly for dairy industry), and as NIR and MIR spectroscopy presents specific characteristics that ultimately may complement each other, in the present work these techniques were compared to monitor and characterize by in situ and by at-line high-throughput analysis, respectively, recombinant cyprosin production by Saccharomyces cerevisiae. Partial least-square regression models, relating NIR and MIR-spectral features with biomass, cyprosin activity, specific activity, glucose, galactose, ethanol and acetate concentration were developed, all presenting, in general, high regression coefficients and low prediction errors. In the case of biomass and glucose slight better models were achieved by in situ NIR spectroscopic analysis, while for cyprosin activity and specific activity slight better models were achieved by at-line MIR spectroscopic analysis. Therefore both techniques enabled to monitor the highly dynamic cyprosin production bioprocess, promoting by this way more efficient platforms for the bioprocess optimization and control.

The Discrimination of Colored Acrylic, Cotton, and Wool Textile Fibers Using Micro-Raman Spectroscopy. Part 1 : In Situ Detection and Characterization of Dyes

Raman spectroscopy has been applied to characterize fiber dyes and determine the discriminating ability of the method. Black, blue, and red acrylic, cotton, and wool samples were analyzed. Four excitation sources were used to obtain complementary responses in the case of fluorescent samples. Fibers that did not provide informative spectra using a given laser were usually detected using another wavelength. For any colored acrylic, the 633-nm laser did not provide Raman information. The 514-nm laser provided the highest discrimination for blue and black cotton, but half of the blue cottons produced noninformative spectra. The 830-nm laser exhibited the highest discrimination for red cotton. Both visible lasers provided the highest discrimination for black and blue wool, and NIR lasers produced remarkable separation for red and black wool. This study shows that the discriminating ability of Raman spectroscopy depends on the fiber type, color, and the laser wavelength.

Profiling of counterfeit medicines by vibrational spectroscopy

Counterfeit pharmaceutical products have become a widespread problem in the last decade. Various analytical techniques have been applied to discriminate between genuine and counterfeit products. Among these, Near-infrared (NIR) and Raman spectroscopy provided promising results.The present study offers a methodology allowing to provide more valuable information fororganisations engaged in the fight against counterfeiting of medicines.A database was established by analyzing counterfeits of a particular pharmaceutical product using Near-infrared (NIR) and Raman spectroscopy. Unsupervised chemometric techniques (i.e. principal component analysis - PCA and hierarchical cluster analysis - HCA) were implemented to identify the classes within the datasets. Gas Chromatography coupled to Mass Spectrometry (GC-MS) and Fourier Transform Infrared Spectroscopy (FT-IR) were used to determine the number of different chemical profiles within the counterfeits. A comparison with the classes established by NIR and Raman spectroscopy allowed to evaluate the discriminating power provided by these techniques. Supervised classifiers (i.e. k-Nearest Neighbors, Partial Least Squares Discriminant Analysis, Probabilistic Neural Networks and Counterpropagation Artificial Neural Networks) were applied on the acquired NIR and Raman spectra and the results were compared to the ones provided by the unsupervised classifiers.The retained strategy for routine applications, founded on the classes identified by NIR and Raman spectroscopy, uses a classification algorithm based on distance measures and Receiver Operating Characteristics (ROC) curves. The model is able to compare the spectrum of a new counterfeit with that of previously analyzed products and to determine if a new specimen belongs to one of the existing classes, consequently allowing to establish a link with other counterfeits of the database.

Prediction of crude protein and classification of the growth stage of wheat plant samples from NIR spectra

Near-infrared spectroscopy (NIRS) was used to analyse the crude protein content of dried and milled samples of wheat and to discriminate samples according to their stage of growth. A calibration set of 72 samples from three growth stages of wheat (tillering, heading and harvest) and a validation set of 28 samples was collected for this purpose. Principal components analysis (PCA) of the calibration set discriminated groups of samples according to the growth stage of the wheat. Based on these differences, a classification procedure (SIMCA) showed a very accurate classification of the validation set samples : all of them were successfully classified in each group using this procedure when both the residual and the leverage were used in the classification criteria. Looking only at the residuals all the samples were also correctly classified except one of tillering stage that was assigned to both tillering and heading stages. Finally, the determination of the crude protein content of these samples was considered in two ways: building up a global model for all the growth stages, and building up local models for each stage, separately. The best prediction results for crude protein were obtained using a global model for samples in the two first growth stages (tillering and heading), and using a local model for the harvest stage samples.

Determination of the HMX and RDX content in synthesized energetic material by HPLC, FT-MIR, and FT-NIR spectroscopies

A new method has been developed for determining the content of mixtures of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), the HMX/RDX ratio, in explosive compositions by Fourier transform infrared spectroscopy (FT-IR), in the regions MIR (mid infrared) and NIR (near infrared) with reference values obtained by chromatographic analysis (HPLC). Plots of relative MIR (A917 / A783) or NIR absorbance values (A4412 / A4317) versus HMX/RDX ratio determined by HPLC analysis revealed good linear relationships.

LS-SVM: uma nova ferramenta quimiométrica para regressão multivariada. Comparação de modelos de regressão LS-SVM e PLS na quantificação de adulterantes em leite em pó empregando NIR

Least-squares support vector machines (LS-SVM) were used as an alternative multivariate calibration method for the simultaneous quantification of some common adulterants found in powdered milk samples, using near-infrared spectroscopy. Excellent models were built using LS-SVM for determining R², RMSECV and RMSEP values. LS-SVMs show superior performance for quantifying starch, whey and sucrose in powdered milk samples in relation to PLSR. This study shows that it is possible to determine precisely the amount of one and two common adulterants simultaneously in powdered milk samples using LS-SVM and NIR spectra.

Previsão das propriedades físicas do papel kraft por espectroscopia no infravermelho próximo (NIR) e regressão por mínimos quadrados parciais (PLS)

The main objective of the present work is represented by the characterization of the physical properties of industrial kraft paper (i.e. transversal and longitudinal tear resistance, transversal traction resistance, bursting or crack resistance, longitudinal and transversal compression resistance (SCT (Compressive Strength Tester) and compression resistance (RCT-Ring Crush Test)) by near infrared spectroscopy associated to partial least squares regression. Several multivariate models were developed, many of them with high prevision capacity. In general, low prevision errors were observed and regression coefficients that are comparable with those provided by conventional standard methodologies.

NIR-Vis Up-Conversion Luminescence in the Yb3+,Er3+ Doped Y2O2S, ZrO2, and NaYF4 Nanomaterials

Since the discovery of the up-conversion phenomenon, there has been an ever increasing interest in up-converting phosphors in which the absorption of two or more low energy photons is followed by emission of a higher energy photon. Most up-conversion luminescence materials operate by using a combination of a trivalent rare earth (lanthanide) sensitizer (e.g. Yb or Er) and an activator (e.g. Er, Ho, Tm or Pr) ion in a crystal lattice. Up-converting phosphors have a variety of potential applications as lasers and displays as well as inks for security printing (e.g. bank notes and bonds). One of the most sophisticated applications of lanthanide up-conversion luminescence is probably in medical diagnostics. However, there are some major problems in the use of photoluminescence based on the direct UV excitation in immunoassays. Human blood absorbs strongly UV radiation as well as the emission of the phosphor in the visible. A promising way to overcome the problems arising from the blood absorption is to use a long wavelength excitation and benefit from the up-conversion luminescence. Since there is practically no absorption by the whole-blood in the near IR region, it has no capability for up-conversion in the excitation wavelength region of the conventional up-converting phosphor based on the Yb3+ (sensitizer) and Er3+ (activator) combination. The aim of this work was to prepare nanocrystalline materials with high red (and green) up-conversion luminescence efficiency for use in quantitative whole-blood immunoassays. For coupling to biological compounds, nanometer-sized (crystallite size below 50 nm) up-converting phosphor particles are required. The nanocrystalline ZrO2:Yb3+,Er3+, Y2O2S:Yb3+,Er3+, NaYF4:Yb3+,Er3+ and NaRF4-NaR’F4 (R: Y, Yb, Er) materials, prepared with the combustion, sol-gel, flux, co-precipitation and solvothermal synthesis, were studied using the thermal analysis, FT-IR spectroscopy, transmission electron microscopy, EDX spectroscopy, XANES/EXAFS measurements, absorption spectroscopy, X-ray powder diffraction, as well as up-conversion and thermoluminescence spectroscopies. The effect of the impurities of the phosphors, crystallite size, as well as the crystal structure on the up-conversion luminescence intensity was analyzed. Finally, a new phenomenon, persistent up-conversion luminescence was introduced and discussed. For efficient use in bioassays, more work is needed to yield nanomaterials with smaller and more uniform crystallite sizes. Surface modifications need to be studied to improve the dispersion in water. On the other hand, further work must be carried out to optimize the persistent up-conversion luminescence of the nanomaterials to allow for their use as efficient immunoassay nanomaterials combining the advantages of both up-conversion and persistent luminescence.

NIR Spectroscopic and Laser Induced Fluorescence studies of some organic molecules

Vibrational overtone spectroscopy of molecules containing X-H oscillators (X = C, N, O...) has become an effective tool for the study of molecular structure, dynamics, inter and intramolecular interactions, conformational aspects and substituent effects in aliphatic and aromatic compounds. In the present work, the author studied the NIR overtone spectra of some liquid phase organic compounds. The analysis of the CH, NH and OH overtones yielded important structural information about these systems. In an attempt to get information on electronic energy levels, we studied the pulsed Nd:YAG laser induced fluorescence spectra of certain organic compounds. The pulsed laser Raman spectra of some organic compounds are also studied. The novel high resolution technique of near infrared tunable diode laser absorption spectroscopy (TDLAS) is used to record the rotational structure of the second OH overtone spectrum of 2-propanol. The spectral features corresponding to the different molecular conformations could be identified from the high resolution spectrum. The whole work described in this thesis is divided into five chapters.

Determination of yield and quality parameters of energy crops applying laboratory and field spectroscopy

A real-time analysis of renewable energy sources, such as arable crops, is of great importance with regard to an optimised process management, since aspects of ecology and biodiversity are considered in crop production in order to provide a sustainable energy supply by biomass. This study was undertaken to explore the potential of spectroscopic measurement procedures for the prediction of potassium (K), chloride (Cl), and phosphate (P), of dry matter (DM) yield, metabolisable energy (ME), ash and crude fibre contents (ash, CF), crude lipid (EE), nitrate free extracts (NfE) as well as of crude protein (CP) and nitrogen (N), respectively in pretreated samples and undisturbed crops. Three experiments were conducted, one in a laboratory using near infrared reflectance spectroscopy (NIRS) and two field spectroscopic experiments. Laboratory NIRS measurements were conducted to evaluate to what extent a prediction of quality parameters is possible examining press cakes characterised by a wide heterogeneity of their parent material. 210 samples were analysed subsequent to a mechanical dehydration using a screw press. Press cakes serve as solid fuel for thermal conversion. Field spectroscopic measurements were carried out with regard to further technical development using different field grown crops. A one year lasting experiment over a binary mixture of grass and red clover examined the impact of different degrees of sky cover on prediction accuracies of distinct plant parameters. Furthermore, an artificial light source was used in order to evaluate to what extent such a light source is able to minimise cloud effects on prediction accuracies. A three years lasting experiment with maize was conducted in order to evaluate the potential of off-nadir measurements inside a canopy to predict different quality parameters in total biomass and DM yield using one sensor for a potential on-the-go application. This approach implements a measurement of the plants in 50 cm segments, since a sensor adjusted sideways is not able to record the entire plant height. Calibration results obtained by nadir top-of-canopy reflectance measurements were compared to calibration results obtained by off-nadir measurements. Results of all experiments approve the applicability of spectroscopic measurements for the prediction of distinct biophysical and biochemical parameters in the laboratory and under field conditions, respectively. The estimation of parameters could be conducted to a great extent with high accuracy. An enhanced basis of calibration for the laboratory study and the first field experiment (grass/clover-mixture) yields in improved robustness of calibration models and allows for an extended application of spectroscopic measurement techniques, even under varying conditions. Furthermore, off-nadir measurements inside a canopy yield in higher prediction accuracies, particularly for crops characterised by distinct height increment as observed for maize.

Near infrared reflectance spectroscopy (NIRS) to predict biological parameters of maize silage: effects of particle comminution, oven drying temperature and the presence of residual moisture

Maize silage nutritive quality is routinely determined by near infrared reflectance spectroscopy (NIRS). However, little is known about the impact of sample preparation on the accuracy of the calibration to predict biological traits. A sample population of 48 maize silages representing a wide range of physiological maturities was used in a study to determine the impact of different sample preparation procedures (i.e., drying regimes; the presence or absence of residual moisture; the degree of particle comminution) on resultant NIR prediction statistics. All silages were scanned using a total of 12 combinations of sample pre-treatments. Each sample preparation combination was subjected to three multivariate regression techniques to give a total of 36 predictions per biological trait. Increased sample preparations procedure, relative to scanning the unprocessed whole plant (WP) material, always resulted in a numerical minimisation of model statistics. However, the ability of each of the treatments to significantly minimise the model statistics differed. Particle comminution was the most important factor, oven-drying regime was intermediate, and residual moisture presence was the least important. Models to predict various biological parameters of maize silage will be improved if material is subjected to a high degree of particle comminution (i.e., having been passed through a 1 mm screen) and developed on plant material previously dried at 60 degrees C. The extra effort in terms of time and cost required to remove sample residual moisture cannot be justified. (c) 2005 Elsevier B.V. All rights reserved.

Synthesis, spectroscopy and spectroelectrochemistry of chlorocarbonyl {1,2-bis[(2,6-diisopropylphenyl)imino]-acenaphthene-kappa(2)-N,N '}rhodium (I)

Reaction of the dinuclear complex [{Rh(CO)(2)}(2) (mu-Cl)(2)]with an alpha-diimine ligand, 1,2- bis[(2,6-diisopropylphenyl) imino] acenaphthene (iPr(2)Ph-bian), produces square-planar [RhCl(CO)(iPr(2)Ph-bian)]. For the first time, 2: 1 and 1: 1 alpha-diimine/dimer reactions yielded the same product. The rigidity of iPr(2)Ph-bian together with its flexible electronic properties and steric requirements of the 2,6-diisopropyl substituents on the benzene rings allow rapid closure of a chelate bond and replacement of a CO ligand instead of chloride. A resonance Raman study of [RhCl(CO)(iPr(2)Ph-bian)] has revealed a predominant Rh-to-bian charge transfer (MLCT) character of electronic transitions in the visible spectral region. The stabilisation of [RhCl(CO)(iPr(2)Ph-bian)] in lower oxidation states by the pi-acceptor iPr(2)Ph-bian ligand was investigated in situ by UV-VIS, IR and EPR spectroelectrochemistry at variable temperatures. The construction of the novel UV-VIS-NIR-IR low-temperature OTTLE cell used in these studies is described in the last part of the paper.

Application of near and mid-infrared spectroscopy to determine cheese quality and authenticity

This paper reviews the current state of development of both near-infrared (NIR) and mid-infrared (MIR) spectroscopic techniques for process monitoring, quality control, and authenticity determination in cheese processing. Infrared spectroscopy has been identified as an ideal process analytical technology tool, and recent publications have demonstrated the potential of both NIR and MIR spectroscopy, coupled with chemometric techniques, for monitoring coagulation, syneresis, and ripening as well as determination of authenticity, composition, sensory, and rheological parameters. Recent research is reviewed and compared on the basis of experimental design, spectroscopic and chemometric methods employed to assess the potential of infrared spectroscopy as a technology for improving process control and quality in cheese manufacture. Emerging research areas for these technologies, such as cheese authenticity and food chain traceability, are also discussed.