Excitation Dependence of Dipole-Dipole Broadening in Selective Reflection Spectroscopy

We investigate the dipole-dipole broadened selective reflection spectrum with the Cs atomic aensity of 10^14- 10^15 cm^-3. The dipole-dipole broadening is reduced and the hyperfine splitting is well resolved when the ground state atoms are excited by a detuned pump beam. The dependences of dipoleMipole broadening of Cs atoms in the 6S1/2（F= 3） → 6P3/2（F＇= 4） hyperfine transition line on atomic density and the excitation factor are studied. It is found that the reduction of the dipole-dipole broadening is dependent on the pump beam power and is independent of the atomic density in this density range. These results are useful for understanding of the dynamical process in this range of atomic density.

Measurement of the wavelength modulation indices with selective reflection spectroscopy

The wavelength modulation indices are measured based on harmonic amplitude ratio of 4famp/6famp (4famp and 6famp are the 4- and 6-th harmonic central peak amplitudes correspondingly) with the Doppler-free selective reflection modulation spectroscopy. The experiments for the 6S1/2(F = 4) → 6P3/2(F' = 5) transition of cesium D2 line with 30-MHz linewidth were carried out. The 4f- and 6f-harmonic signals were detected with two digital lock-in amplifiers separately. The maximum error for modulation indices measurement was ±0.1 within the range of m from 3 to 6. The non-linear modulation behaviour of an external cavity diode laser induced by voltage tuning was studied with this method. The method for modulation indices measurement does not require a solid etalon as usual for measuring the wavelength modulation depth and the absorption linewidth correspondingly.

Quantifying the chemical composition of weathering products of Hainan basalts with reflectance spectroscopy and its implications for Mars

With the development of the hyperspectral remote sensing technique,extensive chemical weathering profiles have been identified on Mars.These weathering sequences,formed through precipitation-driven leaching processes,can reflect the paleoenvironments and paleoclimates during pedogenic processes.The specific composition and stratigraphic profiles mirror the mineralogical and chemical trends observed in weathered basalts on Hainan Island in south China.In this study,we investigated the laboratory reflectance spectra of a 53-m-long drilling core of a thick basaltic weathering profile collected from Hainan Island.We established a quantitative spectral model by combining the genetic algorithm and partial least squares regression(GA-PLSR)to predict the chemical properties(SiO2,Al2O3,Fe2O3)and index of laterization(IOL).The entire sample set was divided into a calibration set of 25 samples and a validation set of 12 samples.Specifically,the GA was used to select the spectral subsets for each composition,which were then input into the PLSR model to derive the chemical concentration.The coefficient of determination(R2)values on the validation set for SiO2,Al2O3,Fe2O3,and the IOL were greater than 0.9.In addition,the effects of various spectral preprocessing techniques on the model accuracy were evaluated.We found that the spectral derivative treatment boosted the prediction accuracy of the GA-PLSR model.The improvement achieved with the second derivative was more pronounced than when using the first derivative.The quantitative model developed in this work has the potential to estimate the contents of similar weathering basalt products,and thus infer the degree of alteration and provide insights into paleoclimatic conditions.Moreover,the informative bands selected by the GA can serve as a guideline for designing spectral channels for the next generation of spectrometers.

Construction of universal quantitative models for the determination of cefoperazone sodium/sulbactam sodium for injection from different manufacturers using near-infrared reflectance spectroscopy

To develop near-infrared （NIR） reflectance spectroscopic methods for the quantitative analysis of cefoperazone sodium/ sulbactam sodium from different manufacturers for injection powder medicaments. Various powders of cefoperazone sodium/ sulbactam sodium were directly analyzed by non-destructive NIR reflectance spectroscopy using the spectrometer EQUINOX55. Two quantitative methods via integrating sphere （IS） and fiberoptic probe （FOP） models were explored from 6 batches of commercial samples and 42 batches of laboratory samples at a content ranging from 30% to 70% for cefoperazone and 60% to 20% for sulbactam. The root mean square errors of cross validation （RMSECV） and the root mean square errors of prediction （RMSEP） of IS were 1.79% and 2.85%, respectively, for cefoperazone sodium, and were 1.86% and 3.08%, respectively, for sulbactam sodium; and those of FOP were 2.93% and 2.92%, respectively, for cefoperazone sodium, and were 2.23% and 3.01%, respectively, for sulbactam sodium. Based on the ICH guidelines and Ref. 12, the quantitative models were then evaluated in terms of specificity, linearity, accuracy, precision, robustness and model transferability. The non-destructive quantitative NIR methods used in this study are applicable for rapid analysis of injectable powdered drugs from different manufacturers.

Classification of Guizhou Aspidistra Plants by Near-infrared Diffuse Reflectance Spectroscopy

[Objective] This study was conducted to establish a near-infrared diffuse reflectance spectroscopy of Guizhou Aspidistra plants. [Method] Twenty three batch- es of Guizhou Aspidistra plants including A. chishuiensis, A. spinula, A. Caespitosa, A. sichuanensis, A. ebianensis, A. retusa, A. guizhouensis and A. liboensis were subjected to drying, pulverization and sieving and then directly determined for near- infrared reflectance spectrums; and the plants in this genus were classified by clus- ter analysis and principal component analysis （PCA）. [Result] The near-infrared re- flectance spectrums of the 23 batches of Guizhou Aspidistra plants showed very high similarity. The spectrums were processed by first derivative method, and the spectral range of 4 000-7 500 cm-1 was selected as the analytical range. Cluster analysis and PCA were employed to mass spectrum variables of plants in Aspidis- tra, fewer new variables became the linear combination of primary variables, and small differences between different varieties were enlarged, thereby facilitating intu- itive classification of plants in this genus. [Conclusion] Near-infrared diffuse re- flectance spectroscopy is nondestructive and rapid for determination of solid sam- pies, and provides a new method for the classification of Guizhou Aspidistra plants combined by information processing techniques.

The Study of Using Near-infrared Diffuse Reflectance Spectroscopy Rapid Identify Wheat Drought Resistance-Ⅱ

[Objective] The aim was to build an evaluation method rapidly identifying wheat drought tolerance with near infrared diffuse reflectance spectroscopy. [Method] In the research, 36 wheat varieties in 2007-2009 were chosen and drought-tolerance degrees of wheat were graded and identified according to Winter-wheat Drought Tol- erance Evaluation Technical Standards （GB/T 21127-2007）, and harvest wheat grains underwent spectrum collection, with a full-spectrum analyzer, to establish a database. [Result] Based on qualitative analysis and full-spectrum correlation research, the coef- ficient of determination （RSQ） and cross-validation coefficient of determination （1-VR） were concluded at 0.697 5 and 0.600 2, showing near-infrared diffuse reflectance spectroscopy is of significant differences among wheat varieties and of significant or extremely significant correlation with drought-tolerance indices. [Conclusion] The re- search indicates that to evaluate drought-tolerance of wheat with near-infrared diffuse reflectance spectroscopy is a rapid and feasible way, which is simple, convenient without damages on grains, and of practical values for construction wheat drought-tol- erance evaluation index system and identification of breeding materials.

Determination of Active Components in a Natural Herb with Near Infrared Spectroscopy Based on Artificial Neural Networks

The non-linear relationships between the contents of ginsenoside Rg 1, Rb 1, Rd and Panax notoginseng saponins(PNS) in Panax notoginseng root herb and the near infrared(NIR) diffuse reflectance spectra of the herb were established by means of artificial neural networks(ANNs). Four three-layered perception feed-forward networks were trained with an error back-propagation algorithm. The significant principal components of the NIR spectral data matrix were utilized as the input of the networks. The networks architecture and parameters were selected so as to offer less prediction errors. Relative prediction errors for Rg 1, Rb 1, Rd and PNS obtained with the optimum ANN models were 8.99%, 6.54%, 8.29%, and 5.17%, respectively, which were superior to those obtained with PLSR methods. It is verified that ANN is a suitable approach to model this complex non-linearity. The developed method is fast, non-destructive and accurate and it provides a new efficient approach for determining the active components in the complex system of natural herbs.

Discrimination of Transgenic Rice Based on Near Infrared Reflectance Spectroscopy and Partial Least Squares Regression Discriminant Analysis

Near infrared reflectance spectroscopy （NIRS）, a non-destructive measurement technique, was combined with partial least squares regression discrimiant analysis （PLS-DA） to discriminate the transgenic （TCTP and mi166） and wild type （Zhonghua 11） rice. Furthermore, rice lines transformed with protein gene （OsTCTP） and regulation gene （Osmi166） were also discriminated by the NIRS method. The performances of PLS-DA in spectral ranges of 4 000-8 000 cm-1 and 4 000-10 000 cm-1 were compared to obtain the optimal spectral range. As a result, the transgenic and wild type rice were distinguished from each other in the range of 4 000-10 000 cm-1, and the correct classification rate was 100.0% in the validation test. The transgenic rice TCTP and mi166 were also distinguished from each other in the range of 4 000-10 000 cm-1, and the correct classification rate was also 100.0%. In conclusion, NIRS combined with PLS-DA can be used for the discrimination of transgenic rice.

Supercritical water syntheses of transition metal-doped CeO_2 nano-catalysts for selective catalytic reduction of NO by CO:An in situ diffuse reflectance Fourier transform infrared spectroscopy study

In the present study,we synthesized CeO2 catalysts doped with various transition metals(M=Co,Fe,or Cu)using a supercritical water hydrothermal route,which led to the incorporation of the metal ions in the CeO2 lattice,forming solid solutions.The catalysts were then used for the selective catalytic reduction(SCR)of NO by CO.The Cu‐doped catalyst exhibited the highest SCR activity;it had a T50(i.e.,50%NO conversion)of only 83°C and a T90(i.e.,90%NO conversion)of 126°C.Such an activity was also higher than in many state‐of‐the‐art catalysts.In situ diffuse reflectance Fourier transform infrared spectroscopy suggested that the MOx‐CeO2 catalysts(M=Co and Fe)mainly followed an Eley‐Rideal reaction mechanism for CO‐SCR.In contrast,a Langmuir‐Hinshelwood SCR reaction mechanism occurred in CuO‐CeO2 owing to the presence of Cu+species,which ensured effective adsorption of CO.This explains why CuO‐CeO2 exhibited the highest activity with regard to the SCR of NO by CO.

Application of Near Infrared Diffuse Reflectance Spectroscopy with Radial Basis Function Neural Network to Determination of Rifampincin Isoniazid and Pyrazinamide Tablets

Partial least squares（PLS）,back-propagation neural network（BPNN）and radial basis function neural network（RBFNN）were respectively used for estalishing quantative analysis models with near infrared（NIR）diffuse reflectance spectra for determining the contents of rifampincin（RMP）,isoniazid（INH）and pyrazinamide（PZA）in rifampicin isoniazid and pyrazinamide tablets.Savitzky-Golay smoothing,first derivative,second derivative,fast Fourier transform（FFT）and standard normal variate（SNV）transformation methods were applied to pretreating raw NIR diffuse reflectance spectra.The raw and pretreated spectra were divided into several regions,depending on the average spectrum and RSD spectrum.Principal component analysis（PCA）method was used for analyzing the raw and pretreated spectra in different regions in order to reduce the dimensions of input data.The optimum spectral regions and the models＇ parameters were chosen by comparing the root mean square error of cross-validation（RMSECV）values which were obtained by leave-one-out cross-validation method.The RMSECV values of the RBFNN models for determining the contents of RMP,INH and PZA were 0.00288,0.00226 and 0.00341,respectively.Using these models for predicting the contents of INH,RMP and PZA in prediction set,the RMSEP values were 0.00266,0.00227 and 0.00411,respectively.These results are better than those obtained from PLS models and BPNN models.With additional advantages of fast calculation speed and less dependence on the initial conditions,RBFNN is a suitable tool to model complex systems.

Determination of Protein and Starch Content in Whole Maize Kernel by Near Infrared Reflectance Spectroscopy

Using 128 bulk-kernel samples of inbred lines and hybrids, a study was conducted toinvestigate the feasibility and method of measuring protein and starch contents inintact seeds of maize by near infrared reflectance spectroscopy (NIRS). The chemometricalgorithms of partial least square (PLS) regression was used. The results indicated thatthe calibration models developed by the spectral data pretreatment of firstderivative+multivariate scattering correction within the spectral region of 10000-4000cm-1, and first derivative + straight line subtraction in 9000-4000cm-1 were thebest for protein and starch, respectively. All these models yielded coefficients ofdetermination of calibration (R2cal) above 0.97, while R2cv and R2val of cross and externalvalidation ranged from 0.92 to 0.95, respectively; however, the root of mean squareerrors of calibration, cross and external validation (RMSEE, RMSECV and RMSEP) werebelow 1(ranged 0.3-0.7),respectively. This study demonstrated that it is feasible touse NIRS as a rapid, accurate, and none-destructive technique to predict protein andstarch contents of whole kernel in the maize quality improvement program.

Rapid Identification for Drought Resistance of Wheat Using Near-infrared Diffuse Reflectance Spectroscopy

[Objective] This study aimed to establish an identification system for drought-resistance in wheat by using near-infrared diffuse reflectance spectroscopy. [Method] In 2006-2007, 36 wheat varieties with different drought resistance were selected and were classified according to their drought resistance grades determined by the Technical Specification of Identification and Evaluation for Drought Resistance in Wheat （GB/T 21127-2007）. In addition, the harvested wheat seed samples were spectrally analyzed with FOSS NIRSystems5000 near-infrared spectrum analyzer for grain quality （full spectrum analyzer） and then the forecasted regression equations were established. [Result] After the establishment of a database and validation, dis- criminated functions were obtained. The determination coefficient （RSQ） and coeffi- cients of determination for cross validation （1-VR） in the discriminant function built with seed samples from water stress area were 0.846 0 and 0.781 8, respectively, which indicated that the consistency between drought resistance and spectral charac- teristics in wheat varieties was good, and there was high correlation between the near-infrared diffuse reflectance spectra of seeds and the drought resistance in wheat. [Conclusiou] Under water stress condition, it is feasible to establish a conve- nient, rapid and no-damage identification system for the drought resistance in wheat by using the near-infrared diffuse reflectance spectrum technique to scan wheat seeds.

Near-infrared spectroscopy method for rapid proximate quantitative analysis of nutrient composition in Pacific oyster Crassostrea gigas

Glycogen,amino acids,fatty acids,and other nutrient components affect the flavor and nutritional quality of oysters.Methods based on near-infrared reflectance spectroscopy(NIRS)were developed to rapidly and proximately determine the nutrient content of the Pacific oyster Crassostreagigas.Samples of C.gigas from 19 costal sites were freeze-dried,ground,and scanned for spectral data collection using a Fourier transform NIR spectrometer(Thermo Fisher Scientific).NIRS models of glycogen and other nutrients were established using partial least squares,multiplication scattering correction first-order derivation,and Norris smoothing.The R_(C) values of the glycogen,fatty acids,amino acids,and taurine NIRS models were 0.9678,0.9312,0.9132,and 0.8928,respectively,and the residual prediction deviation(RPD)values of these components were 3.15,2.16,3.11,and 1.59,respectively,indicating a high correlation between the predicted and observed values,and that the models can be used in practice.The models were used to evaluate the nutrient compositions of 1278 oyster samples.Glycogen content was found to be positively correlated with fatty acids and negatively correlated with amino acids.The glycogen,amino acid,and taurine levels of C.gigas cultured in the subtidal and intertidal zones were also significantly different.This study suggests that C.gigas NIRS models can be a cost-effective alternative to traditional methods for the rapid and proximate analysis of various slaughter traits and may also contribute to future genetic and breeding-related studies in Pacific oysters.

Use of near-infrared reflectance spectroscopy for the rapid determination of the digestible energy and metabolizable energy content of corn fed to growing pigs

Background： The ability of near-infrared reflectance spectroscopy（NIRS） to determine the digestible energy（DE）and metabolizable energy（ME） content of corn fed to growing pigs was tested. One hundred and seventeen corn samples, comprising different planting regions and varieties were collected from all over China in a three-year period. The samples were randomly split into a calibration set（n = 88） and a validation set（n = 29）. The actual and calculated DE and ME content of the corn samples was determined by digestion-metabolism experiments and the prediction equations of Noblet and Perez（J Anim Sci. 71：3389–98,1993）. The samples were then subjected to NIRS scanning and calibrations were performed by the modified partial least square（MPLS） regression method based on77 different spectral pre-treatments. The NIRS equations based on the actually determined and calculated DE and ME were built separately and then validated using validation samples.Results： The NIRS equations obtained from actually determined DE, the coefficient of determination for calibration（RSQcal）, cross-validation（R^2CV）, and validation（RSQv） were 0.89, 0.87 and 0.86, and these values for determined ME were 0.87, 0.86 and 0.86. For the NIRS equations built from calculated DE, the RSQcal, R^2CV, and RSQvvalues were 0.88, 0.85 and 0.84, and these values for calculated ME were 0.86, 0.84 and 0.82. Except for the equation based on calculated ME（RPD_v= 2.38, 〈 2.50）, the other three equations built from actually determined energy and calculated DE produced good prediction performance（RPD_vranging from 2.53 to 2.69, 〉 2.50） when applied to validation samples.Conclusion： These results indicate that NIRS can be used as a quantitative method for the rapid determination of the available energy in corn fed to growing pigs, and the NIRS equations based on the actually determined energy produced better predictive performance than those built from calculated energy values.

THE VARIATIONS OF WATER IN HUMAN TISSUE UNDER CERTAIN COMPRESSION:STUDIED WITH DIFFUSE REFLECTANCE SPECTROSCOPY

The reflectance spectrun has been widely adopted to extract diagnosis information of human tissue because it possesses the advantages of noninvasive and rapidity.The external pressure brought by fiber optic probe may influence the accuracy of measurement.In this paper,a sys-tematic study is focused on the effects of probe pressure on intrinsic changes of water and scattering particles in tissue.According to the biphasic nonlinear mixture model,the pressure modulated reflectance spectrum of both in vitro and in vivo tissue is measured and processed with second-derivation.The results indicate that the variations of bulk and bonded water in tissue have a nonlinear relationship with the pressure.Diferences in tissue structure and morphology contribute to site specific probe pressure effects.Then the finite element(FEM)and Monte Carlo(MC)method is employed to simulate the deformation and reflectance spectrum variations of tissue before and after compression.The simulation results show that as the pressure of fiber optic probe applied to the detected skin increased to 80kPa,the effective photon proportion form dermis decreases significantly from 86%to 76%.Future designs might benefit from the research of change of water volume inside the tissue to mitigate the pressure applied to skin.

Geographic Classification of Chinese Grape Wines by Near-Infrared Reflectance Spectroscopy

Near-infrared reflectance spectroscopy (NIRS) was applied to classify grape wines of different geographical origins (Changli, Huailai, and Yantai, China). Near infrared (NIR) spectra were collected in transmission mode in the wavelength range of 800-2500 nm. Wines (n=90) were randomly split into two sets, calibration set (n=54) and validation set (n=36). Discriminant analysis models were developed using BP neural network and discriminant partial least-squares discriminant analysis (PLS-DA). The prediction performance of calibration models in different wavelength range was also investigated. BP neural network models and PLS-DA models correctly classified 100% of the wines in calibration set. When used to predict wines in validation set, BP neural network models correctly classified 100%, 81.8%, and 90.9% of the wines from Changli, Huailai, and Yantai respectively, and PLS-DA models correctly classified 100% of all samples. The results demonstrated that NIRS could be used to discriminate Chinese grape wines as a rapid and reliable method.

A practical and effective method for reducing differential reflectance spectroscopy noise

Differential reflectance spectroscopy(DRS)is a powerful tool to study processes during thin-film growth,especially that of transition metal dichalcogenides and organic thin films.To satisfy the requirements for in situ and real-time monitoring of film growth,including spectral resolution and sensitivity at the level of monolayers and even sub-monolayers,the most challenging technical task in DRS is to reduce noise to an extremely low level so that the best possible signal-to-noise ratio can be achieved.In this paper,we present a simplified and cost-effective DRS apparatus,with which we show that the measurement noise is mainly composed of thermal drift noise and explore the temperature-dependence of the DRS signal.Based on the results obtained,we propose an easily realized and effective scheme aiming to reduce the noise.Experimental results demonstrate that this scheme is effective in stabilizing reliable signals for a long period of several hours.Significant noise reduction is achieved,with the typical average noise of the DRS system being decreased to 0.05%over several hours.The improved DRS system is applied to study the growth of an organic semiconductor layer for an organic field-effect transistor device.The results indicate that the apparatus proposed in this paper has potential applications in fabrication of devices on the nanoscale and even the sub-nanoscale.

RAPID DETERMINATION OF PROTEIN IN MILLET BY FOURIER TRANSFORM NEAR-INFRARED(FTNIR)DIFFUSE REFLECTANCE SPECTROSCOPY

In this paper,the Fourier transform near-infrared(FTNIR)diffuse reflectance spectroscopy is applied for the rapid determination of protein in millet.The partial least-squares(PLS)regression is successfully used as an effective multivariate calibration technique.The calibration set is composed of 20 standard millet samples that the protein contents were determined by the traditional Kjeldahl method.The optimal model dimension is found to be 5 by cross-validation.22 millet samples were determined by the proposed FTNIR-PLS method.The correlation coefficient between the concentration values obtained by the FTNIR-PLS method and the traditional Kjeldahl method is 0.9805.The standard error of prediction(SEP)is 0.28% and the mean recovery is 100.2%.The proposed method has been successfully applied for the routine analysis of protein in about 10,000 grain samples.

Monitoring real time polymorphic transformation of sulfanilamide by diffuse reflectance visible spectroscopy

This study investigated the development of a novel approach to surface characterization of drug poly- morphism and the extension of the capabilities of this method to perform ＇real time＇ in situ measure- ments. This was achieved using diffuse reflectance visible （DRV） spectroscopy and dye deposition, using the pH sensitive dye, thymol blue （TB）. Two polymorphs, SFN-β and SFN-γ, of the drug substance sulfanilamide （SFN） were examined. The interaction of adsorbed dye with polymorphs showed different behavior, and thus reported different DRV spectra. Consideration of the acid/base properties of the morphological forms of the drug molecule provided a rationalization of the mechanism of differential coloration by indicator dyes. The kinetics of the polymorphic transformation of SFN polymorphs was monitored using treatment with TB dye and DRV spectroscopy. The thermally-induced transformation fitted a first-order solid-state kinetic model （R2=0.992）, giving a rate constant of 2.43 × 10^- 2 s 1.

Process Characterization of the Transesterification of Rapeseed Oil to Biodiesel Using Design of Experiments and Infrared Spectroscopy

For optimization of production processes and product quality,often knowledge of the factors influencing the process outcome is compulsory.Thus,process analytical technology(PAT)that allows deeper insight into the process and results in a mathematical description of the process behavior as a simple function based on the most important process factors can help to achieve higher production efficiency and quality.The present study aims at characterizing a well-known industrial process,the transesterification reaction of rapeseed oil with methanol to produce fatty acid methyl esters(FAME)for usage as biodiesel in a continuous micro reactor set-up.To this end,a design of experiment approach is applied,where the effects of two process factors,the molar ratio and the total flow rate of the reactants,are investigated.The optimized process target response is the FAME mass fraction in the purified nonpolar phase of the product as a measure of reaction yield.The quantification is performed using attenuated total reflection infrared spectroscopy in combination with partial least squares regression.The data retrieved during the conduction of the DoE experimental plan were used for statistical analysis.A non-linear model indicating a synergistic interaction between the studied factors describes the reactor behavior with a high coefficient of determination(R^(2))of 0.9608.Thus,we applied a PAT approach to generate further insight into this established industrial process.