Titanium dioxide as an adsorbent to enhance the detection ability of near-infrared diffuse reflectance spectroscopy

A method for quantitative determination of fish sperm deoxyribonucleic acid(fsDNA)was developed by using titanium dioxide(TiO2)as an adsorbent and near-infrared diffuse reflectance spectroscopy(NIRDRS).The selective enrichment of fsDNA was proved by comparing the adsorption efficiency of bovine serum albumin,tyrosine and tryptophan,and the low adsorption background of TiO2 was illustrated by comparing the spectra of four commonly-used inorganic adsorbents(alkaline aluminium oxide,neutral aluminium oxide,nano-hydroxyapatite and silica).The spectral feature of fsDNA can be clearly observed in the spectrum of the sample.Partial least squares(PLS)model was built for quantitative determination of fsDNA using 28 solutions,and 13 solutions with interferences were used for validation of the model.The results showed that the correlation coefficient(R)between the predicted and the reference concentration is 0.9727 and the recoveries of the validation samples are in the range of 98.2%-100.7%.

Determination of triglycerides in human serum by near-infrared diffuse reflectance spectroscopy using silver mirror as a substrate

Near infrared diffuse reflectance spectroscopy(NIRDRS) has gained wide attention due to its convenience for rapid quantitative analysis of complex samples. A method for rapid analysis of triglycerides in human serum using NIRDRS with silver mirror as the substrate is developed. Due to the even and high reflectance of the silver mirror, the spectral response is enhanced and the background interference is reduced.Furthermore, both linear and nonlinear modeling strategies were investigated adopting the partial least squares(PLS) and least squares support vector regression(LS-SVR), continuous wavelet transform(CWT)was used for spectral preprocessing, and variable selection was tried using Monte Carlo uninformative variable elimination(MC-UVE), randomization test(RT) and competitive adaptive reweighted sampling(CARS) for optimization the models. The results show that the determination coefficient(R) between the predicted and reference concentration is 0.9624 and the root mean squared error of prediction(RMSEP) is 0.21. The maximum deviation of the prediction results is as low as 0.473 mmol/L. The proposed method may provide an alternative method for routine analysis of serum triglycerides in clinical applications.

Determination of Cysteine Using Near-infrared Diffuse Reflectance Spectroscopy with Enrichment via Thiol-maleimide Click Reaction

Enrichment technique has been proved to be an efficient way to make the near-infrared diffuse reflectancespectroscopy（NIRDRS） suitable for micro analysis. However, low selectivity presented by conventional enrichmentmethods makes the quantitative analysis easy to be affected by the coexisting components. In this study, a specificenrichment method with chemical bonding via thiol-maleimide click reaction was used to achieve the reduction of theinterferences. Taking cysteine as the analyzing target, maleimide-functionalized SiO2 nanoparticles were prepared forthe enrichment of cysteine. Then determination of cysteine in aqueous solution and human serum was studied usingthe partial least squares model built from the NIRDRS spectra of the adsorbate. The results show that the concentra-tion that can be quantitatively detected is as low as 2.0 μg/mL, and the correlation coefficient（R） between thereference and predicted concentration is 0.9871 for the validation samples. The recoveries are in the range of89.5%-113.8% for human serum samples in the concentration range of 0--16.2 μg/mL.

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.

Rapid, Non-Destructive, Textile Classification Using SIMCA on Diffuse Near-Infrared Reflectance Spectra

Soft independent modeling of class analogy (SIMCA) was successful in classifying a large library of 758 commercially available, non-blended samples of acetate, cotton, polyester, rayon, silk and wool 89% - 98% of the time at the 95% confidence level (p = 0.05 significance level). In the present study, cotton and silk had a 62% and 24% chance, respectively, of being classified with their own group and also with rayon. SIMCA correctly identified a counterfeit “silk” sample as polyester. When coupled with diffuse NIR reflectance spectroscopy and a large sample library, SIMCA shows considerable promise as a quick, non-destructive, multivariate method for fiber identification. A major advantage is simplicity. No sample pretreatment of any kind was required, and no adjust-ments were made for fiber origin, manufacturing process residues, topical finishes, weave pattern, or dye content. Increasing the sample library should make the models more robust and improve identification rates over those reported in this paper.

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.

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.

Application of Short-wave Near-infrared Reflectance Spectroscopy in Controlling Extract of Fructus Cnidii Using Supercritical Carbon Dioxide

Fructus cnidii （Chinese name shechuangzi） is the fruit produced by Cnidium monnieri （L.） Cusson （Umbelliferae）. It is a perennial herb that is used to treat skin-related diseases and gynecopathyell. Recent pharmacological studies have revealed crude extracts or components isolated from fructus cnidii possess antiallergic, antipruritic, antidermatophytic, antibacterial, antifungal, and antiosteoporotic activities. Osthole and imperatorin are the major compounds present in shechuangzi. They are often used as standards for the evaluation of the quality of shechuangzi products.

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.

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.

Changes in diffuse reflectance spectroscopy properties of hematite in sediments from the North Pacific Ocean and implications for eolian dust evolution history

Eolian dust preserved in deep-sea sediments of the North Pacific Ocean(NPO) is an important recorder of paleoclimatic and paleoenvironmental changes in the Asian inland. To better understand changes in the dust provenances, in this study diffuse reflectance spectroscopy(DRS) was used to extract the eolian signal recorded in sediments of ODP Hole 885 A recovered from the NPO. First, we systematically investigated sieving effects on the DRS data; then band positions of hematite(obtained from the second order derivative curves of the K-M remission function spectrum derived from the DRS) were used to distinguish different provenances of the eolian dust preserved in the pelagic sediments of this hole. Our results show that the sieving(38 μm) process can suppress effectively the experimental errors. Eolian signatures from Chinese Loess Plateau(CLP) sources and non-CLP-sources have been identified in the pelagic sediments of ODP Hole 885 A from the late Pliocene to the early Pleistocene. The provenance differences account for the discrepancies in the eolian records recovered from the pelagic sediments in the NPO and profiles in the CLP. Temporal changes in dust provenances are caused by the latitudinal movement of the westerly jet mainstream. The hematite DRS band position is a useful tool to distinguish the provenance of eolian components preserved in pelagic sediments.

Determination of the Deep Optical Properties of Healthy and Diseased Skin Using Diffuse Reflectance Spectroscopy

In this study, we focused on diffuse reflectance spectroscopy, a rapid and noninvasive spectroscopy technique that has considerable potential for medical diagnosis. In order to better understand and analyze the signals induced by this method, we performed a series of in vivo measurements on healthy and diseased skin. Measurement sites on a human hand and feet were chosen. Some preliminary results obtained on these sites show the feasibility of this technique in clinics.

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.

Synthesis and Diffuse Reflectance Spectrum of Open－framework Cobalt Phosphate DAF－2 From Alcoholic System

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DISCRIMINATION OF MENTAL WORKLOAD LEVELS IN HUMAN SUBJECTS WITH FUNCTIONAL NEAR-INFRARED SPECTROSCOPY

We have applied functional near-infrared spectroscopy(fNIRS)to the human forehead to distinguish different levels of mental workload on the basis of hemodynamic changes occurring in the prefrontal cortex.We report data on 3 subjects from a protocol involving 3 mental workload levels based on to working memory tasks.To quantify the potential of fNIRS for mental workload discrimination,we have applied a 3-nearest neighbor classification algorithm based on the amplitude of oxyhemoglobin(HbO2)and deoxyhemoglobin(HbR)concentration changes associated with the working memory tasks.We have found classification success rates in the range of 44%-72%,which are significantly higher than the corresponding chance level(for random data)of 19.1%.This work shows the potential of fNIRS for mental workload classification,especially when more parameters(rather than just the amplitude of concentration changes used here)and more sophisticated classification algorithms(rather than the simple 3-nearest neighbor algorithm used here)are considered and optimized for this application.

Development and implementation of incident response near-infrared models for analyzing contaminated medicines containing diethylene glycol solvent

Samples of preparations contaminated by diethylene glycol(DEG),diethylene glycol raw materials and laboratory prepared solutions were measured to get NIR spectra.Then the iden-tification models were developed using the collected spectra and the spectra of distilled water,propylene glyool and the preparations without diethylene glyool.Besides,the quantification model was also established for determining the concentration of diethylene glyool in the pre-parations.V alidation results show the identification and quantification models have ideal pre-diction performance.The emergency NIR models are rapid,easy to use and accurate,and can be implemented for identifying diethylene glycol raw material,screening the preparations contam-inated by diethylene glycol in the markets and analyzing the concentrations of DEG.

NEAR-INFRARED,BROAD-BAND SPECTRAL IMAGING OF THE HUMAN BREAST FOR QUANTITATIVE OXIMETRY:APPLICATIONS TO HEALTHY AND CANCEROUS BREASTS

We have examined ten human subjects with a previously developed instrument for near-infrared diffuse spectral imaging of the female breast.The instrument is based on a tandem,planar scan of two collinear optical fibers(one for illumination and one for collection)to image a gently compressed breast in a transmission geometry.The optical data collection features a spatial sampling of 25 points/cm2 over the whole breast,and a spectral sampling of 2 points/nm in the 650-900nm wavelength range.Of the ten human subjects examined,eight are healthy subjects and two are cancer patients with unilateral invasive ductal carcinoma and ductal carcinoma in situ,respectively.For each subject,we generate second-derivative images that identify a network of highly absorbing structures in the breast that we assign to blood vessels.A previously developed paired-wavelength spectral method assigns oxygenation values to the absorbing structures displayed in the second-derivative images.The resulting oxygenation images feature average values over the whole breast that are significantly lower in cancerous breasts(69±14%,n=2)than in healthy breasts(85±7%,n=18)(p<0.01).Furthermore,in the two patients with breast cancer,the average oxygenation values in the cancerous regions are also significantly lower than in the remainder of the breast(invasive ductal carcinoma:49±11%vs 61±16%,p<0.01;ductal carcinoma in situ:58±8%vs 77±11%,p<0.001).

Transformational change in the field of diffuse optics:From going bananas to going nuts

The concept of region of sensitivity is central to the field of diffuse optics and is closely related to the Jacobian matrix used to solve the inverse problem in imaging.It is well known that,in diffuse reflectance,the region of sensitivity associated with a given source-detector pair is shaped as a banana,and features maximal sensitivity to the portions of the sample that are closest to the source and the detector.We have recently introduced a dual-slope(DS)method based on a special arrangement of two sources and two detectors,which results in deeper and more localized regions of sensitivity,resembling the shapes of different kinds of nuts.Here,we report the regions of sensitivity associated with a variety of source-detector arrangements for DS measurements of intensity and phase with frequency-domain spectroscopy(modulation frequency:140 MHz)in a medium with absorption and reduced scattering coefficients of 0.1 and 12 cm^(-1),respectively.The main result is that the depth of maximum sensitivity,considering only cases that use source-detector separations of 25 and 35 mm,progressively increases as we consider single-distance intensity(2.0mm),DS intensity(4.6mm),single-distance phase(7.5mm),and DS phase(10.9 mm).These results indicate the importance of DS measurements,and even more so of phase measurements,when it is desirable to selectively probe deeper portions of a sample with diffuse optics.This is certainly the case in non-invasive optical studies of brain,muscle,and breast tissue,which are located underneath the superficial tissue at variable depths.

Reflectance spectra analysis for mucous assessment

This review report represents an overview of research and development on medical hyperspectral imaging technology and its applications.Spectral imaging technology is attracting attention as a new imaging modality for medical applications,especially in disease diagnosis and image-guided surgery.Considering the recent advances in imaging,this technology provides an opportunity for twodimensional mapping of oxygen saturation(SatO2)of blood with high accuracy,spatial spectral imaging,and its analysis and provides detection and diagnostic information about the tissue physiology and morphology.Multispectral imaging also provides information about tissue oxygenation,perfusion,and potential function during surgery.Analytical algorithm has been examined,and indication of accurate map of relative hemoglobin concentration and SatO2 can be indicated with preferable resolution and frame rate.This technology is expected to provide promising biomedical information in practical use.Several studies suggested that blood flow and SatO2 are associated with gastrointestinal disorders,particularly malignant tumor conditions.The use and analysis of spectroscopic images are expected to potentially play a role in the detection and diagnosis of these diseases.