Mean Squared Error Of Cross-validation Research Articles

Quality control of naringenin-carbamazepine drug-drug cocrystal: Quantitative analytical method construction of ATR-FTIR and Raman combined with chemometrics

Naringenin, commonly found in citrus fruits, is one of the active pharmaceutical ingredient (API) in naringenin-carbamazepine drug-drug cocrystal (NR-CBZ). In the preparation of cocrystal, quantitative determination of NR-CBZ is essential for the quality control. In this paper, ATR-FTIR and Raman spectroscopies combined with partial least squares (PLS) and principal component regression (PCR) were used to quantify NR-CBZ in the mixtures. To improve the accuracy of the prediction models, median, denoising, multiple scattering correction (MSC), first and second order derivatives, Savitzky-Golay filter and SNV were used and their performance was evaluated using prediction errors in combination with different spectral ranges. Raman spectra, PLS combined with Savitzky-Golay filter over the entire spectral range were found to determine the best content prediction result for NR-CBZ. The root mean square error of cross-validation (RMSECV), root mean square error of prediction (RMSEP) and squared correlation coefficient (R2) of the model were 0.101, 0.132 and 0.870, respectively.

Machine learning-enhanced drug testing for simultaneous morphine and methadone detection in urinary biofluids

The simultaneous identification of drugs has considerable difficulties due to the intricate interplay of analytes and the interference present in biological matrices. In this study, we introduce an innovative electrochemical sensor that overcomes these hurdles, enabling the precise and simultaneous determination of morphine (MOR), methadone (MET), and uric acid (UA) in urine samples. The sensor harnesses the strategically adapted carbon nanotubes (CNT) modified with graphitic carbon nitride (g-C3N4) nanosheets to ensure exceptional precision and sensitivity for the targeted analytes. Through systematic optimization of pivotal parameters, we attained accurate and quantitative measurements of the analytes within intricate matrices employing the fast Fourier transform (FFT) voltammetry technique. The sensor’s performance was validated using 17 training and 12 test solutions, employing the widely acclaimed machine learning method, partial least squares (PLS), for predictive modeling. The root mean square error of cross-validation (RMSECV) values for morphine, methadone, and uric acid were significantly low, measuring 0.1827 µM, 0.1951 µM, and 0.1584 µM, respectively, with corresponding root mean square error of prediction (RMSEP) values of 0.1925 µM, 0.2035 µM, and 0.1659 µM. These results showcased the robust resiliency and reliability of our predictive model. Our sensor’s efficacy in real urine samples was demonstrated by the narrow range of relative standard deviation (RSD) values, ranging from 3.71 to 5.26%, and recovery percentages from 96 to 106%. This performance underscores the potential of the sensor for practical and clinical applications, offering precise measurements even in complex and variable biological matrices. The successful integration of g-C3N4-CNT nanocomposites and the robust PLS method has driven the evolution of sophisticated electrochemical sensors, initiating a transformative era in drug analysis.

Determining Moisture Content of Basil Using Handheld Near-Infrared Spectroscopy

Accurate and rapid determination of moisture content is essential in crop production and decision-making for irrigation. Near-infrared (NIR) spectroscopy has been shown to be a promising method for determining moisture content in various agricultural products, including herbs and vegetables. This study tested the hypothesis that NIR spectroscopy is effective in accurately measuring the moisture content of Genovese basil (Ocimum basilicum L.), with the objective of developing a respective calibration model. Spectral data were obtained from a total of 120 basil leaf samples over a period of six days. These included freshly harvested and detached leaves, as well as those left in ambient air for 1–6 days. Five spectra were taken from each leaf using a handheld NIR spectrophotometer, which covers the first and second overtones of the NIR spectral region: 950–1650 nm. After the spectral acquisition, the leaves were weighed for fresh mass and then put in an oven for 72 h at 80 °C to determine the dry weight and calculate the reference moisture content. The calibration model was developed using multivariate analysis in MATLAB, including preprocessing and regression modeling. The data obtained from 75% of the samples were used for model training and 25% for validation. The final model demonstrates strong performance metrics. The root mean square error of calibration (RMSEC) is 2.9908, the root mean square error of cross-validation (RMSECV) is 3.2368, and the root mean square error of prediction (RMSEP) reaches 2.4675. The coefficients of determination for calibration (R2C) and cross-validation (R2CV) are consistent, with values of 0.829 and 0.80, respectively. The model’s predictive ability is indicated by a coefficient of determination for prediction (R2P) of 0.86. The range error ratio (RER) stands at 11.045—highlighting its predictive performance. Our investigation, using handheld NIR spectrophotometry, confirms NIR’s usefulness in basil moisture determination. The rapid determination offers valuable insights for irrigation and crop management.

Four chemometric models enhanced by Latin hypercube sampling design for quantification of anti-COVID drugs: sustainability profiling through multiple greenness, carbon footprint, blueness, and whiteness metrics

Montelukast sodium (MLK) and Levocetirizine dihydrochloride (LCZ) are widely prescribed medications with promising therapeutic potential against COVID-19. However, existing analytical methods for their quantification are unsustainable, relying on toxic solvents and expensive instrumentation. Herein, we pioneer a green, cost-effective chemometrics approach for MLK and LCZ analysis using UV spectroscopy and intelligent multivariate calibration. Following a multilevel multifactor experimental design, UV spectral data was acquired for 25 synthetic mixtures and modeled via classical least squares (CLS), principal component regression (PCR), partial least squares (PLS), and genetic algorithm-PLS (GA-PLS) techniques. Latin hypercube sampling (LHS) strategically constructed an optimal validation set of 13 mixtures for unbiased predictive performance assessment. Following optimization of the models regarding latent variables (LVs) and wavelength region, the optimum root mean square error of cross-validation (RMSECV) was attained at 2 LVs for the 210–400 nm spectral range (191 data points). The GA-PLS model demonstrated superb accuracy, with recovery percentages (R%) from 98 to 102% for both analytes, and root mean square error of calibration (RMSEC) and prediction (RMSEP) of (0.0943, 0.1872) and (0.1926, 0.1779) for MLK and LCZ, respectively, as well bias-corrected mean square error of prediction (BCMSEP) of -0.0029 and 0.0176, relative root mean square error of prediction (RRMSEP) reaching 0.7516 and 0.6585, and limits of detection (LOD) reaching 0.0813 and 0.2273 for MLK and LCZ respectively. Practical pharmaceutical sample analysis was successfully confirmed via standard additions. We further conducted pioneering multidimensional sustainability evaluations using state-of-the-art greenness, blueness, and whiteness tools. The method demonstrated favorable environmental metrics across all assessment tools. The obtained Green National Environmental Method Index (NEMI), and Complementary Green Analytical Procedure Index (ComplexGAPI) quadrants affirmed green analytical principles. Additionally, the method had a high Analytical Greenness Metric (AGREE) score (0.90) and a low carbon footprint (0.021), indicating environmental friendliness. We also applied blueness and whiteness assessments using the high Blue Applicability Grade Index (BAGI) and Red–Green–Blue 12 (RGB 12) algorithms. The high BAGI (90) and RGB 12 (90.8) scores confirmed the method's strong applicability, cost-effectiveness, and sustainability. This work puts forward an optimal, economically viable green chemistry paradigm for pharmaceutical quality control aligned with sustainable development goals.

Traceability of Microplastic Fragments from Waste Plastic Express Packages Using Near-Infrared Spectroscopy Combined with Chemometrics.

The pollution from waste plastic express packages (WPEPs), especially microplastic (MP) fragments, caused by the blowout development of the express delivery industry has attracted widespread attention. On account of the variety of additives, strong complexity, and high diversity of plastic express packages (PEPs), the multi-class classification of WPEPs is a typical large-class-number classification (LCNC). The traceability and identification of microplastic fragments from WPEPs is very challenging. An effective chemometric method for large-class-number classification would be very beneficial for the comprehensive treatment of WPEP pollution through the recycling and reuse of waste plastic express packages, including microplastic fragments and plastic debris. Rather than using the traditional one-against-one (OAO) and one-against-all (OAA) dichotomies, an exhaustive and parallel half-against-half (EPHAH) decomposition, which overcomes the defects of the OAO's classifier learning limitations and the OAA's data proportion imbalance, is proposed for feature selection. EPHAH analysis, combined with partial least squares discriminant analysis (PLS-DA) for large-class-number classification, was performed on 750 microplastic fragments of polyethylene WPEPs from 10 major courier companies using near-infrared (NIR) spectroscopy. After the removal of abnormal samples through robust principal component analysis (RPCA), the root mean square error of cross-validation (RMSECV) value for the model was reduced to 0.01, which was 21.5% lower than that including the abnormal samples. The best models of PLS-DA were obtained using SNV combined with SG-17 smoothing and 2D (SNV+SG-17+2D); the latent variables (LVs), the error rates of Monte Carlo cross-validation (ERMCCVs), and the final classification accuracies were 6.35, 0.155, and 88.67% for OAO-PLSDA; 5.37, 0.103, and 87.33% for OAA-PLSDA; and 3.12, 0.054, and 96.00% for EPHAH-PLSDA. The results showed that the EPHAH strategy can completely learn the complex LCNC decision boundaries for 10 classes, effectively break the tie problem, and greatly improve the voting resolution, thereby demonstrating significant superiority to both the OAO and OAA strategies in terms of classification accuracy. Meanwhile, PLS-DA further maximized the covariance and data interpretation abilities between the potential variables and categories of microplastic debris, thereby establishing an ideal performance identification model with a recognition rate of 96.00%.

Predicting Silicate Glass Geochemistry Using Raman Spectroscopy and Supervised Machine Learning: Partial Least Square Applications to Amorphous Raman Spectra.

Here, Raman spectroscopy is used to develop a univariate partial least squares (PLS) calibration capable of quantifying geochemistry in synthetic and natural silicate glass samples. The calibration yields eight oxide-specific models that allow predictions of silicon dioxide (SiO2), sodium oxide (Na2O), potassium oxide (K2O), calcium oxide (CaO), titanium dioxide (TiO2), aluminum oxide (Al2O3), ferrous oxide (FeOT), and magnesium oxide (MgO) (wt%) in glasses spanning a wide range of compositions, while also providing correlation-coefficient matrices that highlight the importance of specific Raman channels in the regression of a particular oxide. The PLS suite is trained on 48 of the 69 total glasses, and tested against 21 validation samples (i.e., held out of training). Trends in root mean square error of calibration (RMSEC), root mean square error of cross-validation (RMSECV), and root mean square error of prediction (RMSEP) model accuracy metrics are investigated to uncover the efficacy of utilizing multivariate analysis for such Raman data and are contextualized against recently produced strategies. The technique yields an average root mean of calibration (∼2.4 wt%), cross-validation (∼ 2.9 wt%), prediction (∼ 2.6 wt%), and normalized variance (∼ 28%). Raman band positional shifts are also mapped against underlying chemical variations; with major influences arising primarily as a function of overall oxidation state and silica concentration: via ferric cation (Fe3+)/ferrous cation (Fe2+) ratios and SiO2 (wt%). The algorithm is further validated preliminarily against a separate external set of 11 natural basaltic glasses to unravel the limitations of the synthetic models on natural samples, and to determine the suitability of "universal" Raman-model applications in scenarios where prior chemical contextualization of the target sample is possible. This study represents the first time Raman spectra of amorphous silicates have been paired with PLS, offering a foundation for future improvements utilizing these systems.

Spider chart, greenness and whiteness assessment of experimentally designed multivariate models for simultaneous determination of three drugs used as a combinatory antibiotic regimen in critical care units: Comparative study

In this study, five earth-friendly spectrophotometric methods using multivariate techniques were developed to analyze levofloxacin, linezolid, and meropenem, which are utilized in critical care units as combination therapies. These techniques were used to determine the mentioned medications in laboratory-prepared mixtures, pharmaceutical products and spiked human plasma that had not been separated before handling. These methods were named classical least squares (CLS), principal component regression (PCR), partial least squares (PLS), genetic algorithm partial least squares (GA-PLS), and artificial neural network (ANN). The methods used a five-level, three-factor experimental design to make different concentrations of the antibiotics mentioned (based on how much of them are found in the plasma of critical care patients and their linearity ranges). The approaches used for levofloxacin, linezolid, and meropenem were in the ranges of 3–15, 8–20, and 5–25 µg/mL, respectively. Several analytical tools were used to test the proposed methods' performance. These included the root mean square error of prediction, the root mean square error of cross-validation, percentage recoveries, standard deviations, and correlation coefficients. The outcome was highly satisfactory. The study found that the root mean square errors of prediction for levofloxacin were 0.090, 0.079, 0.065, 0.027, and 0.001 for the CLS, PCR, PLS, GA-PLS, and ANN models, respectively. The corresponding values for linezolid were 0.127, 0.122, 0.108, 0.05, and 0.114, respectively. For meropenem, the values were 0.230, 0.222, 0.179, 0.097, and 0.099 for the same models, respectively. These results indicate that the developed models were highly accurate and precise. This study compared the efficiency of artificial neural networks and classical chemometric models in enhancing spectral data selectivity for quickly identifying three antimicrobials. The results from these five models were subjected to statistical analysis and compared with each other and with the previously published ones. Finally, the whiteness of the methods was assessed by the recently published white analytical chemistry (WAC) RGB 12, and the greenness of the proposed methods was assessed using AGREE, GAPI, NEMI, Raynie and Driver, and eco-scale, which showed that the suggested approaches had the least negative environmental impact. Furthermore, to demonstrate solvent sustainability, a greenness index using a spider chart methodology was employed.

Urban Traffic Flow Prediction Based on Bayesian Deep Learning Considering Optimal Aggregation Time Interval

Predicting short-term urban traffic flow is a fundamental and cost-effective strategy in traffic signal control systems. However, due to the interrupted, periodic, and stochastic characteristics of urban traffic flow influenced by signal control, there are still unresolved issues related to the selection of the optimal aggregation time interval and the quantifiable uncertainties in prediction. To tackle these challenges, this research introduces a method for predicting urban interrupted traffic flow, which is based on Bayesian deep learning and considers the optimal aggregation time interval. Specifically, this method utilizes the cross-validation mean square error (CVMSE) method to obtain the optimal aggregation time interval and to establish the relationship between the optimal aggregation time interval and the signal cycle. A Bayesian LSTM-CNN prediction model, which extends the LSTM-CNN model under the Bayesian framework to a probabilistic model to better capture the stochasticity and variation in the data, is proposed. Experimental results derived from real-world data demonstrate gathering traffic flow data based on the optimal aggregation time interval significantly enhances the prediction accuracy of the urban interrupted traffic flow model. The optimal aggregation time interval for urban interrupted traffic flow data corresponds to a multiple of the traffic signal control cycle. Comparative experiments indicate that the Bayesian LSTM-CNN prediction model outperforms the state-of-the-art prediction models.

Simultaneous spectrophotometric determination of Co (II) and Co (III) in acidic medium with partial least squares regression and artificial neural networks

This study aims at the application of two chemometric techniques to visible spectra of acetic acid solutions of Co (II) and Co (III) for simultaneous determination thereof. Spectral data of 145 samples in the range of 400–700 nm were used to build the models. Partial least squares regression models were developed for which latent variables were determined using internal cross-validation with a leave-one-out strategy and 3 and 2 latent variables were selected for Co(II) and Co(III) based on root mean square error of cross-validation. For these models, root mean square errors of prediction were 1.16 and 0.536 mM and coefficients of determination were 0.975 and 0.892 for Co (II) and Co (III). As an alternate method, artificial neural networks consisting of three layers, with 10 neurons in hidden layer, were trained to model spectra and concentrations of cobalt species. Levenberg-Marquardt algorithm with feed-forward back-propagation learning resulted root mean square errors of prediction of 0.316 and 0.346 mM for Co (II) and Co (III) respectively and coefficients of determination were 0.996 and 0.988.

High-precision hemoglobin detection based on hyperspectral reconstruction of RGB images

Hemoglobin concentration is an important indicator for evaluating human health. The concentration value is an important evidence for early diagnosis of anemia and other blood diseases. However, existing optical detection methods usually suffer from low precision, strong noise and tedious operation, makes it difficult to obtain an accurate hemoglobin concentration evaluation. In this work, we propose and demonstrate a method for hemoglobin detection with the hyperspectral reconstruction of RGB images. To be specific, this overall model consists of a SHR-Net (Skin Hyperspectral Reflectance Network) to reconstruct hyperspectral images from RGB images of fingers, a feature selection process to capture full-band reflectance spectra based on the maximum blood perfusion region and an SVR (Support Vector Regression) algorithm to predict the hemoglobin concentration. The experimental results show that the coefficient of determination between the predicted and true values is 0.945. The mean square error of cross-validation is 0.49 g/dL. Therefore, this method provides a new solution for the accurate and noninvasive measurement of hemoglobin.

Application of near-infrared spectroscopy and chemometrics for the rapid detection of insect protein adulteration from a simulated matrix

The popularity of insect protein as a food and feed supplement is growing. Protein quality, end use and prices vary considerably between different insect species, which may incentivise insect protein adulteration. Here, near-infrared (NIR) spectroscopy and chemometrics were used to detect the presence of cricket, black soldier fly larvae (BSFL) and mealworm proteins in a simulated complex insect protein mixture. Additionally, BSFL protein powders collected from three commercial sources were investigated to determine whether the NIR-based technology can discriminate the proteins obtained from different companies based on their composition. The proximate analysis suggests compositional protein, fat and chitin differences between insect species. A partial least square (PLS) regression model obtained Q2 values ranging from 0.991 to 0.997 for the predictions of the content of protein mixtures containing BSFL, cricket and mealworm powders mixed at various proportions. The root mean square error of cross-validation (RMSCV) values range from 1.8% to 2.9%, and residual prediction deviation (RPD) values from 10.4 to 17.1 for the adulterated insect protein powders. The accuracy of the prediction model (∼2%) for the adulterated percentages varied depending on the insect species. The NIR spectra could differentiate (Q2 = 0.999) the origin of BSFL protein powders from three different companies and two types of processing (whole meal and defatted samples). Overall, this study established a rapid and low-cost insect protein adulteration monitoring pipeline for the three common insect protein powders. We envisage that NIR can be applied to assess insect adulteration, authentication, and quality control in the emerging insect food and feed industries.

Nondestructive online measurement of pineapple maturity and soluble solids content using visible and near-infrared spectral analysis

Pineapple is a popular tropical fruit with economic value, and the measurement of its maturity and soluble solids content (SSC) is crucial for quality control and sorting purposes. This study developed a non-destructive and rapid method for internal color-based maturity and SSC in pineapples using online visible and near-infrared spectroscopy (VIS-NIRS). The spectral data for light transmitted through the pineapple sample was measured on the conveyor belt while the machine was moving at a speed of 100 mm/s. A spectrometer with a wavelength range of 200–1100 nm was used during online spectral measurements. The pre-processed spectral data were analyzed using partial least squares regression (PLSR). The internal color-based maturity model achieved a correlation coefficient of double cross-validation (Rv) of 0.97 and a root mean square error of double cross-validation (RMSEV) of 0.034. The SSC model achieved a Rv of 0.88 and a RMSEV of 1.04%. The study demonstrates the potential of online VIS-NIRS as a non-destructive and rapid method for measuring pineapple maturity and SSC. Therefore, this offers a potential for real-time quality monitoring of pineapples at a mass production scale.

Quantitative Analysis of Mixtures Based on Portable Spatial Heterodyne Raman Spectrometer

Spatial heterodyne Raman spectroscopy has been widely applied in various fields due to its non-contact, nondestructive, fast, high stability, and high spectral resolution characteristics. This article integrated spatial heterodyne Raman spectroscopy with chemometric methodologies to assess the feasibility of peak-to-peak ratio regression, partial least squares regression, support vector machine regression, and non-negative matrix factorization for the quantitative analysis of mixtures. Chemometrics methods were used to model and analyze the interference data in the interferogram domain, and variational mode decomposition was used to extract features from the interference data, further improving the interference data’s modeling and prediction accuracy. The results demonstrate that modal intensities obtained through variational mode decomposition of interference data improve the prediction accuracy of regression analysis. Support vector regression exhibited the most favorable predictive performance among the tested models. The root mean square error of cross-validation was reduced from 5.55% to 2.64%, and the prediction root mean square error was reduced from 5.08% to 1.5%. The improved model utilizing interference data showed higher fitting accuracy and more precise sample predictions compared to spectral data modeling.

Detection of trace phosphorus in water by plasma amplification laser-induced breakdown spectroscopy.

For monitoring the extent of eutrophication in water, phosphorus (P) was detected by laser-induced breakdown spectroscopy (LIBS). A plasma amplification method was proposed and the filtered aerosol was guided to interact with the collinear laser in conjunction with a nebulizer, cyclonic spray chamber, and quartz tube. With this method, the length of the plasma was amplified from 5.27∼8.73 to 17.58 mm. Moreover, the limit of detection (LoD) values of P in water improved from 6.13∼17.75 to 3.60 ppm. Furthermore, the average relative error (REAV) values reduced from 10.23∼23.84 to 6.17%. The root mean square error of cross-validation (RMSECV) values decreased from 16.68∼64.29 to 3.24 ppm. This demonstrated that plasma amplification LIBS could improve the quantitative analysis performance of LIBS detection of trace phosphorus in water.

Rapid assessment of residual solvent content in the TEGDN dual-base propellants by near-infrared reflectance spectroscopy

Excessive residual solvent (RS) levels in triethyleneglycol dinitrate (TEGDN) dual-base propellants can significantly impair combustion performance. This work aimed to develop a rapid and accurate model for detecting the RS content in the TEGDN dual-base propellants using near-infrared (NIR) spectroscopy in the reflectance mode. The optimal wavelength range for modelling, spanning from 1124.9−1230.2 nm and 1335.5–1527.5 nm, was identified based on absorption peaks characteristic of TEGDN dual-base propellant samples and RS. To enhance the quality of the data, we determined optimal window sizes for pre-processing methods: derivative pre-processing and Savitzky-Golay (S-G) smoothing pre-processing. After evaluating the performance of different pre-treatment methods, we found that the model employing multiple scattering corrections (MSC) in conjunction with first-order derivative (FD) pre-processing demonstrated superior results. The partial least squares (PLS) method was used to build the RS model with an optimal number of factors of 6. For the developed RS model, the root mean square error of calibration (RMSEC) and the root mean square error of cross-validation (RMSECV) were 0.019 and 0.024, respectively. The determination coefficient of calibration (Rc2) and the determination coefficient of cross-validation (Rcv2) were 0.968 and 0.952, respectively. In assessing the validation set using the developed model, we observed a root mean square error of prediction (RMSEP) of 0.025 and a determination coefficient of prediction (Rp2) of 0.958. Importantly, the relative error between the predicted values obtained through the NIR method and the measured values from the reference method consistently remained below 2 % under all circumstances. Consequently, the NIR-based RS model developed in this study offers a rapid and efficient means of detecting RS content in TEGDN dual-base propellants, facilitating judgment regarding the qualification of RS content.

Multivariate statistical analysis on Japanese traditional papers, washi, for evaluation of DNA presence and quality

Traditional papermaking was a significant innovation that intrigued the information-sharing society in a wide range of the globe. The importance of finding the historical background hidden behind the historical traditional paper is critical to understanding societies in history. Advanced molecular biological research is applied to many forensic studies to identify the origin and criminal events. Yet, biological research refrained from the heritage science of traditional papers due to its damage to the samples. The current study explores the Pearson correlation between DNA in traditional paper and non-destructive measurement of characteristics of traditional paper. DNA concentration and purity were found to have a proportional relationship based on the CIEL*a*b* color system. The color of the traditional paper was assessed assessment shows green and yellow rather than red and blue. The DNA concentration demonstrated a positive linear correlation with the peaks of 992 cm−1, 1599 cm−1, and 1628 to 1638 cm−1 region, which were lignin-specific functional groups. The presence of lignin in traditional paper defines the colors green and yellow, which is related to the presence of a cell wall. The quantity of cell walls present is linked to DNA survival during the traditional papermaking process. Furthermore, the partial least square (PLS) regression model is established. The prediction model based on DNA, paper properties, and smoothing + the second derivative preprocessed attenuated total reflection-Fourier-transform infrared (ATR-FTIR) spectral data demonstrated valid purity predictions. The evaluation parameter of the cross-validated prediction model contains a low Root Mean Square Error of Cross-Validation (RMSECV) of 0.091 for DNA purity. The determination coefficient was close to 1. However, the further establishment of a validated DNA extraction methodology is required for the consistency of the prediction model for DNA concentration. The hierarchical clustering analysis demonstrated the agglomerative dendrogram on traditional paper samples. For the dendrogram, the Nasu paper mulberry (originating in northern Japan) was distinguished from another paper mulberry (originating in southwestern Japan) by clustering. By multivariate statistical analysis, the DNA presence and quality were predictable from the Japanese traditional papers. In addition, the clustering analysis provided the possible origin of paper mulberry materials for traditional papers. Based on the preliminary information, the need for DNA analysis on historical traditional paper can be determined.

FT-MIR-ATR Associated with Chemometrics Methods: A Preliminary Analysis of Deterioration State of Brazil Nut Oil.

Brazil nut oil is highly valued in the food, cosmetic, chemical, and pharmaceutical industries, as well as other sectors of the economy. This work aims to use the Fourier transform infrared (FTIR) technique associated with partial least squares regression (PLSR) and principal component analysis (PCA) to demonstrate that these methods can be used in a prior and rapid analysis in quality control. Natural oils were extracted and stored for chemical analysis. PCA presented two groups regarding the state of degradation, subdivided into super-degraded and partially degraded groups in 99.88% of the explained variance. The applied PLS reported an acidity index (AI) prediction model with root mean square error of calibration (RMSEC) = 1.8564, root mean square error of cross-validation (REMSECV) = 4.2641, root mean square error of prediction (RMSEP) = 2.1491, R2cal (calibration correlation coefficient) equal to 0.9679, R2val (validation correlation coefficient) equal to 0.8474, and R2pred (prediction correlation coefficient) equal to 0, 8468. The peroxide index (PI) prediction model showed RMSEC = 0.0005, REMSECV = 0.0016, RMSEP = 0.00079, calibration R2 equal to 0.9670, cross-validation R2 equal to 0.7149, and R2 of prediction equal to 0.9099. The physical-chemical analyses identified that five samples fit in the food sector and the others fit in other sectors of the economy. In this way, the preliminary monitoring of the state of degradation was reported, and the prediction models of the peroxide and acidity indexes in Brazil nut oil for quality control were determined.

Application Research of Visible Near-Infrared Spectroscopy Technology for Detecting Intracerebral Hematoma

To explore the visible near-infrared spectroscopic (VNIRS) characteristics of intracerebral hematoma, and provide experimental basis for hematoma localization and residual detection in hypertensive intracerebral hemorrhage (HICH) surgery. Using VNIRS, spectral data of cerebral hematoma and cortex were collected during HICH craniotomy, and characteristic spectra were matched with paired-sample T-test. A partial least squares (PLS) quantitative model for cerebral hematoma spectra was established. The reflectance of cerebral hematoma spectra in the 500-800nm band was lower than that of the cortex, and there were statistically significant differences in the 510, 565, and 630nm bands (P < 0.05). The calibration correlation coefficient of the PLS quantitative model for cerebral hematoma spectra was R2= 0.988, the cross-validation correlation coefficient was R2cv=0.982, the root mean square error of calibration was RMSEC=0.101, the root mean square error of cross-validation was RMSEV=0.122, the external validation correlation coefficient was CORRELATION=0.902, and the root mean square error of prediction was RMSEP=0.426, indicating that the model had high fitting degree and good predictive ability. VNIRS as a noninvasive, real-time and portable analysis technology, can be used for real-time detection of hematoma during HICH surgery, and provide reliable basis for hematoma localization and residual detection.

Usefulness of mid-infrared spectroscopy as a tool to estimate body condition score change from milk samples in intensively fed dairy cows

Directly measuring individual cow energy balance is not trivial. Other traits, like body condition score (BCS) and BCS change (ΔBCS) can, however, be used as an indicator of cow energy status. Body condition score is a metric used world-wide to estimate cow body reserves and the estimation of ΔBCS was, until now, conditional on the availability of multiple BCS assessments. The aim of the present study was to estimate ΔBCS from milk mid-infrared (MIR) spectra and days in milk (DIM) in intensively-fed dairy cows using statistical prediction methods. Daily BCS was interpolated from cubic splines fitted through the BCS records and daily ΔBCS was calculated from these splines. Body condition score change records were merged with milk MIR spectra recorded on the same week. The data set comprised 37,077 ΔBCS phenotypes across 9,403 lactations from 6,988 cows in 151 herds based in Quebec (Canada). Partial least squares regression (PLSR) and a neural network (NN) were then used to estimate ΔBCS from 1) MIR spectra only, 2) DIM only, or 3) MIR spectra and DIM together. ΔBCS data in both the first 120 DIM and 305 DIM of lactation were used to develop the estimates. Daily ΔBCS had a standard deviation of 4.40*10-3 BCS units in the 120-d data set and of 3.63*10-3 BCS units in the 305-d data set. 4-fold cross-validation was used to calibrate and test the prediction equations. External validation was also conducted using more recent years of data. Irrespective of whether based on the first 120 or 305 DIM, or when MIR spectra only, DIM only or MIR spectra and DIM were jointly used as prediction variables, NN produced the lowest root mean square error (RMSE) of cross-validation (1.81*10-3 BCS units and 1.51*10-3 BCS units, respectively, using the 120-d and 305-d data set). Relative to predictions for the entire 305 DIM, the RMSE of cross-validation was 15.4% and 1.5% lower in the first 120 DIM when using PLSR and NN, respectively. Predictions from DIM only were more accurate than those using just MIR spectra data but, irrespective of the data set and of the prediction model used, the combining DIM information with MIR spectral data as prediction variables reduced the RMSE compared with inclusion of DIM alone, albeit the benefit was small (the RMSE from cross-validation was reduced up to 5.5% when DIM and spectral data were jointly used as model features instead of DIM only). However, when predicting extreme ΔBCS records, the MIR spectral data was more informative than DIM. Model performance when predicting ΔBCS records in future years was similar to that from cross-validation demonstrating the ability of MIR spectra of milk and DIM combined to estimate ΔBCS, particularly in early lactation. This can be used to routinely generate estimates of ΔBCS to aid in day-to-day individual cow management.

Near-infrared spectroscopy as a process analytical technology tool for monitoring performance of membrane filtration in a whey protein fractionation process.

A successful transition from a laboratory proof-of-principle to a functioning industrial Process Analytical Technology (PAT) application of spectroscopy and chemometrics is still an active area of research and development. A comprehensive understanding on how the design and implementation of the optical instrumentation affect the data quality, and how this will affect the performance of the prediction models is vital for the successful implementation of in-line monitoring. In a previous study, we have demonstrated that near-infrared spectroscopy (NIRS), combined with chemometric techniques, can be used to quantify α-lactalbumin and β-lactoglobulin in aqueous whey solutions. This work demonstrates the potential, both at-line and in-line, of monitoring a protein fractionation process in a full-scale production. An in-line near infrared spectrometer (NIRS) was used to monitor the individual protein concentrations in a protein fractionation process over 20 days. In addition, samples were extracted from the process and analysed with at-line NIRS and an in-house HPLC reference method. The developed models could predict β-lactoglobulin and α-lactalbumin concentrations with satisfactory precision and accuracy, yielding a root mean square error of cross-validation of 0.08 and 0.18 w/w% proteins, respectively. For the first time, the whey proteins concentrations were measured continuously in a production facility to demonstrate the potential of NIRS for at-line and in-line rapid monitoring of protein composition in industrial whey streams. A PAT tool was developed from NIRS data where Partial Least Squares regression modelling and an Exponentially Weighted Moving Average filtering were used to extract and visualize valuable information on the process dynamics and performance. The study demonstrates that continuous monitoring by in-line NIRS allowed elucidation of some process behaviours not readily detectable with the current sampling frequency and that it offers novel process optimisation opportunities by providing increased process understanding and decision support information concerning preventive maintenance and real-time process validation.