Uso da espectroscopia de reflectância do infravermelho próximo (NIRS) para previsão da composição bromatológica de vagens de algaroba e palma forrageira.

Espécies forrageiras adaptadas às condições semiáridas são uma alternativa para reduzir os impactos negativos na cadeia produtiva de ruminantes da região Nordeste brasileira devido à sazonalidade na oferta de forragem, além de reduzir custo com o fornecimento de alimentos concentrados. Dentre as espécies, a vagem de algaroba (Prosopis juliflora SW D.C.) e palma forrageira (Opuntia e Nopalea) ganham destaque por tolerarem o déficit hídrico e produzirem em períodos onde a oferta de forragem está reduzida, além de apresentam bom valor nutricional e serem bem aceitas pelos animais. Porém, devido à variação na sua composição, seu uso na alimentação animal exige o conhecimento profundo da sua composição para a elaboração de dietas balanceadas. No entanto, devido ao custo e tempo para análise, os produtores não fazem uso da prática de análise da composição químico-bromatológica dos alimentos. Por isto, a espectroscopia de reflectância no infravermelho próximo (NIRS) representa uma importante alternativa aos métodos tradicionais. Objetivou-se com este estudo desenvolver e validar modelos de predição da composição bromatológica de vagem de algaroba e palma forrageira baseados em espectroscopia NIRS, escaneadas em dois modelos de equipamentos e com diferentes processamentos da amostra. Foram coletadas amostras de vagem de algaroba nos estados do Ceará, Bahia, Paraíba e Pernambuco, e amostras de palma forrageira nos estados do Ceará, Paraíba e Pernambuco, frescas (in natura) ou pré-secas e moídas. Para obtenção dos espectros utilizaram-se dois equipamentos NIR, Perten DA 7250 e FOSS 5000. Inicialmente os alimentos foram escaneados in natura em aparelho do modelo Perten, e, com o auxílio do software The Unscrambler 10.2 foi selecionado um grupo de amostras para o banco de calibração. As amostras selecionadas foram secas e moídas, e escaneadas novamente em equipamentos Perten e FOSS. Os valores dos parâmetros de referência foram obtidos por meio de metodologias tradicionalmente aplicadas em laboratório de nutrição animal para matéria seca (MS), matéria mineral (MM), matéria orgânica (MO), proteína bruta (PB), estrato etéreo (EE), fibra solúvel em detergente neutro (FDN), fibra solúvel em detergente ácido (FDA), hemicelulose (HEM) e digestibilidade in vitro da matéria seca (DIVMS). O desempenho dos modelos foi avaliado de acordo com os erros médios de calibração (RMSEC) e validação (RMSECV), coeficiente de determinação (R2 ) e da relação de desempenho de desvio dos modelos (RPD). A análise exploratória dos dados, por meio de tratamentos espectrais e análise de componentes principais (PCA), demonstraram que os bancos de dados eram similares entre si, dando segurança de desenvolver os modelos com todas as amostras selecionadas em um único modelo para cada alimento, algaroba e palma. Na avaliação dos resultados de referência, observou-se que a variação dos resultados para cada parâmetro corroboraram com os descritos na literatura. No desempenho dos modelos, aqueles desenvolvidos com pré-processamento da amostra (pré-secagem e moagem) se mostraram mais robustos do que aqueles construídos com amostras in natura. O aparelho NIRS Perten apresentou desempenho semelhante ao equipamento FOSS, apesar desse último cobrir uma faixa espectral maior e com intervalos de leituras menores. A técnica NIR, associada ao método de calibração multivariada de regressão por meio de quadrados mínimos (PLS), mostrou-se confiável para prever a composição químico-bromatológica de vagem de algaroba e da palma forrageira. Abstract: Forage species adapted to semi-arid conditions are an alternative to reduce the negative impacts in the feed supply for ruminants in the Brazilian Northeast region, due to seasonality in forage availability, as well as in the reducing of cost by providing concentrated feedstuffs. Among the species, mesquite pods (Prosopis juliflora SW DC) and spineless cactus (Opuntia and Nopalea) are highlighted for tolerating the drought and producion in periods where the forage is scarce, and have high nutritional value and also are well accepted by the animals. However, its use in animal diets requires a knowledge about its composition to prepare balanced diets. However, farmers usually do not use feed composition analysis, because their high cost and time-consuming. Thus, the Near Infrared Reflectance Spectroscopy in the (NIRS) is an important alternative to traditional methods. The objective of this study to develop and validate predictive models of the chemical composition of mesquite pods and spineless cactus-based NIRS spectroscopy, scanned in two different spectrometers and sample processing. Mesquite pods samples were collected in the states of Ceará, Bahia, Paraiba and Pernambuco, and samples of forage cactus in the states of Ceará, Paraíba and Pernambuco. In order to obtain the spectra, it was used two NIR equipment: Perten DA 7250 and FOSS 5000. sSpectra of samples were initially obtained fresh (as received) using Perten instrument, and with The Unscrambler software 10.2, a group of subsamples was selected to model development, keeping out redundant ones. The selected samples were dried and ground, and scanned again in both Perten and FOSS instruments. The values of the reference analysis were obtained by methods traditionally applied in animal nutrition laboratory to dry matter (DM), mineral matter (MM), organic matter (OM), crude protein (CP), ether extract (EE), soluble neutral detergent fiber (NDF), soluble acid detergent fiber (ADF), hemicellulose ( HEM) and in vitro digestibility of dry matter (DIVDM). The performance of the models was evaluated according to the Root Mean Square Error of Calibration (RMSEC) and cross-validation (RMSECV), coefficient of determination (R2 ) and the deviation of Ratio of performance Deviation of the models (RPD). Exploratory data analysis through spectral treatments and principal component analysis (PCA), showed that the databases were similar to each other, and may be treated asa single model for each feed - mesquite pods and cactus. Evaluating the reference results, it was observed that the variation were similar to those reported in the literature. Comparing the preprocessing of samples, the performance ofthose developed with preprocessing (dried and ground) of the sample were more robust than those built with fresh samples. The NIRS Perten device performance similar to FOSS equipment, although the latter cover a larger spectral range and with lower readings intervals. NIR technology associate do multivariate techniques is reliable to predict the bromatological composition of mesquite pods and cactus.

Diffuse reflectance near infrared spectroscopy can distinguish normal from enzymatically digested cartilage

A non-destructive, diffuse reflectance near infrared spectroscopy (DR-NIRS)approach is considered as a potential tool for determining the component-level structural properties of articular cartilage. To this end, DR-NIRS was applied in vitro to detect structural changes, using principal component analysis as the statistical basis for characterization. The results show that this technique, particularly with first-derivative pretreatment, can distinguish normal, intact cartilage from enzymatically digested cartilage. Further, this paper establishes that the use of DR-NIRS enables the probing of the full depth of the uncalcified cartilage matrix, potentially allowing the assessment of degenerative changes in joint tissue, independent of the site of initiation of the osteoarthritic process.

Rapid quantification of methamphetamine: using Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR) and Chemometrics

In Australia and increasingly worldwide, methamphetamine is one of the most commonly seized drugs analysed by forensic chemists. The current well-established GC/MS methods used to identify and quantify methamphetamine are lengthy, expensive processes, but often rapid analysis is requested by undercover police leading to an interest in developing this new analytical technique. Ninety six illicit drug seizures containing methamphetamine (0.1% - 78.6%) were analysed using Fourier Transform Infrared Spectroscopy with an Attenuated Total Reflectance attachment and Chemometrics. Two Partial Least Squares models were developed, one using the principal Infrared Spectroscopy peaks of methamphetamine and the other a Hierarchical Partial Least Squares model. Both of these models were refined to choose the variables that were most closely associated with the methamphetamine % vector. Both of the models were excellent, with the principal peaks in the Partial Least Squares model having Root Mean Square Error of Prediction 3.8, R2 0.9779 and lower limit of quantification 7% methamphetamine. The Hierarchical Partial Least Squares model had lower limit of quantification 0.3% methamphetamine, Root Mean Square Error of Prediction 5.2 and R2 0.9637. Such models offer rapid and effective methods for screening illicit drug samples to determine the percentage of methamphetamine they contain.

Quantitative assessment of total phenol contents of European oak (Quercus petraea and Quercus robur) by diffuse reflectance NIR spectroscopy on solid wood surfaces

Near infrared spectroscopy (NIRS) combined with multivariate analysis techniques was applied to assess phenol content of European oak. NIRS data were firstly collected directly from solid heartwood surfaces: in doing so, the spectra were recorded separately from the longitudinal radial and the transverse section surfaces by diffuse reflectance. The spectral data were then pretreated by several pre-processing procedures, such as multiplicative scatter correction, first derivative, second derivative and standard normal variate. The tannin contents of sawmill collected from the longitudinal radial and transverse section surfaces were determined by quantitative extraction with water/methanol (1:4, by vol). Then, total phenol contents in tannin extracts were measured by the Folin-Ciocalteu method. The NIR data were correlated against the Folin-Ciocalteu results. Calibration models built with partial least squares regression displayed strong correlation - as expressed by high determination correlation coefficient (r2) and high ratio of performance to deviation (RPD) - between measured and predicted total phenols content, and weak calibration and prediction errors (RMSEC, RMSEP). The best calibration was provided with second derivative spectra (r2 value of 0.93 for the longitudinal radial plane and of 0.91 for the transverse section plane). This study illustrates that the NIRS technique when used in conjunction with multivariate analysis could provide reliable, quick and non-destructive assessment of European oak heartwood extractives.

Anisotropic exchange splitting of excitons in (001)GaAs/Al0.3Ga0.7As superlattice studied by reflectance difference spectroscopy

Anisotropic exchange splitting (AES) is induced by the joint effects of the electron-hole exchange interaction and the symmetry reduction in quantum wells and quantum dots. A model has been developed to quantitatively obtain the electron-hole exchange energy and the hole-mixing energy of quantum wells and superlattices. In this model, the AES and the degree of polarization can both be obtained from the reflectance difference spectroscopy. Thus the electron-hole exchange energy and the hole-mixing energy can be completely separated and quantitatively deduced. By using this model, a (001)5 nm GaAs/7 nm Al0.3Ga0.7As superlattice sample subjected to [110] uniaxial strains has been investigated in detail. The n=1 heavy-hole (1H1E) exciton can be analyzed by this model. We find that the AES of quantum wells can be linearly tuned by the [110] uniaxial strains. The small uniaxial strains can only influence the hole-mixing interaction of quantum wells, but have almost no contribution to the electron-hole exchange interaction. (c) 2008 American Institute of Physics.

Investigation of GaAs/AlGaAs interfaces by reflectance-difference spectroscopy

The in-plane optical anisotropy of several GaAs/AlGaAs quantum well samples with different well widths has been measured at room temperature by reflectance-difference spectroscopy (RDS). The RDS line shapes are found to be similar in all the samples examined here, which dominantly consist of two peak-like signals corresponding to 1HH-->1E and 1LH-->1E transition. As the well width is decreased, or the 1 ML InAs layer is inserted at one interface, the intensity of the anisotropy increases quickly. Our detail analysis shows that the anisotropy mainly arises from the anisotropic interface roughness. The results demonstrate that the RDS technique is sensitive to the interface structures.

Interface-related in-plane optical anisotropy of quantum wells studied by reflectance-difference spectroscopy

The in-plane optical anisotropy of three groups of GaAs/AlGaAs quantum well structures has been studied by reflectance-difference spectroscopy (RDS). For GaAs/Al0.36Ga0.64As single QW structures, it is found that the optical anisotropy increases quickly as the well width is decreased. For an Al0.02Ga0.98As/AlAs multiple QW with a well width of 20nm, the optical anisotropy is observed not only for the transitions between ground states but also for those between the excited states with transition index n up to 5. An increase of the anisotropy with the transition energy, or equivalently the transition index n, is clearly observed. The detailed analysis shows that the observed anisotropy arises from the interface asymmetry of QWs, which is introduced by atomic segregation or anisotropic interface roughness formed during the growth of the structures. More, when the 1 ML InAs is inserted at one interface of GaAs/AlGaAs QW, the optical anisotropy of the QW can be increased by a factor of 8 due to the enhanced asymmetry of the QW. These results demonstrate clearly that the RDS is a sensitive and powerful tool for the characterization of semiconductor interfaces.

Strain-induced in-plane optical anisotropy in (001) GaAs/AlGaAs superlattice studied by reflectance difference spectroscopy

In-plane optical anisotropy (IPOA) in (001) GaAs/AlGaAs superlattice induced by uniaxial strain has been investigated by reflectance difference spectroscopy (RDS). Uniaxial strain on the order of 10(-4) was introduced by bending a strip sample with a stress apparatus. The IPOA of all interband transitions shows a linear dependence on strain. The birefringence and dichroism spectra induced by strain are obtained by RDS on the basis of a three-phase model, which is in good agreement with the reported results. (c) 2006 American Institute of Physics.

Study on in-plane optical anisotropy of semiconductor materials by reflectance difference spectroscopy

In the present review, the measuring principle of reflectance difference spectroscopy (RDS) is given. As a powerful tool in the surface and interface analysis technologies, the application of RDS to the research on semiconductor materials is summarized. along with the origins of the in-plane optical anisotropy of semiconductors. And it is believed that RDS will play an important role in the electrooptic modification of Si-based semiconductor materials.

Large g factors of higher-lying excitons detected with reflectance difference spectroscopy in GaAs-based quantum wells

Exciton g factors in GaAs-based quantum wells (QWs) were evaluated by reflectance difference spectroscopy (RDS) under a weak magnetic field. The well-width dependence of the n=1 heavy-hole exciton (1H1E) g factor agrees well with the reported results, demonstrating RDS as a sensitive tool for detection of g factor. By comparison, the n=1 light-hole exciton g factor increases with the well width, and shows a larger value than that of 1H1E. In a 20-nm-wide Al0.02Ga0.98As/AlAs multiple QW sample, the g factors of up to ten excitons are obtained, and the higher-lying exciton g factors are found to be one order larger than that of the 1H1E exciton.

Evolution of the amount of InAs in wetting layers in an InAs/GaAs quantum-dot system studied by reflectance difference spectroscopy

The wetting layer (WL) in InAs/GaAs quantum-dot systems has been studied by reflectance difference spectroscopy (RDS). Two structures related to the heavy-hole (HH) and light-hole (LH) related transitions in the WL have been observed. On the basis of a calculation model that takes into account the segregation effect and exciton binding energies, the amount of InAs in the WL (t(WL)) and its segregation coefficient ( R) have been determined from the HH and LH transition energies. The evolutions of tWL and R exhibit a close relation to the growth modes. Before the formation of InAs dots, t(WL) increases linearly from similar to 1 to similar to 1.6 monolayer (ML), while R increases almost linearly from similar to 0.8 to similar to 0.85. After the onset of dot formation, t(WL) is saturated at similar to 1.6 ML and R decreases slightly from 0.85 to 0.825. The variation of tWL can be interpreted by using an equilibrium model. Different variations of in-plane optical anisotropy before and after dot formation have been observed.

Evolution of wetting layer of InAs/GaAs quantum dots studied by reflectance difference spectroscopy

For the InAs/GaAs quantum-dot system, the evolution of the wetting layer (WL) with the InAs deposition thickness has been studied by reflectance difference spectroscopy (RDS) in combination with atomic force microscopy and photoluminescence. One transition related to the light hole in the WL has been observed clearly in RDS, from which its transition energy and in-plane optical anisotropy (OA) are determined. The evolution of WL with the InAs dot formation and ripening has been discussed. In addition, the remarkable changes in OA at the onsets of the dot formation and ripening have been observed, implying the mode transitions of atom transport between the WL and the dots.

Study on in-plane optical anisotropy of Si0.75Ge0.25/Si/Si0.5Ge0.5 asymmetric superlattice by reflectance difference spectroscopy - art. no. 071908

Si0.75Ge0.25/Si/Si0.5Ge0.5 trilayer asymmetric superlattices were prepared on Si (001) substrate by ultrahigh vacuum chemical vapor deposition at 500 degrees C. The nonlinear optical response caused by inherent asymmetric interfaces in this structure predicted by theories was verified by in-plane optical anisotropy in (001) plane measured via reflectance difference spectroscopy. The results show Si0.75Ge0.25/Si/Si0.5Ge0.5 asymmetric superlattice is optically biaxial and the two optical eigen axes in (001) plane are along the directions [110] and [-110], respectively. Reflectance difference response between the above two eigen axes can be influenced by the width of the trilayers and reaches as large as similar to 10(-4)-10(-3) in 15-period 2.7 nm-Si0.75Ge0.25/8 nm-Si/1.3 nm-Si0.5Ge0.5 superlattice when the normal incident light wavelength is in the range of 500-1100 nm, which is quite remarkable because the optical anisotropy does not exist in bulk Si.

Interface-related in-plane optical anisotropy in GaAs/AlxGa1-xAs single-quantum-well structures studied by reflectance difference spectroscopy

The in-plane optical anisotropies of a series of GaAs/AlxGa1-xAs single-quantum-well structures have been observed at room temperature by reflectance difference spectroscopy. The measured degree of polarization of the excitonic transitions is inversely proportional to the well width. Numerical calculations based on the envelope function approximation incorporating the effect of C-2v-interface symmetry have been performed to analyze the origin of the optical anisotropy. Good agreement with the experimental data is obtained when the optical anisotropy is attributed to anisotropic-interface structures. The fitted interface potential parameters are consistent with predicted values.