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In this Letter, a rapid origin classification device and method for Baishao (Radix Paeoniae Alba) slices based on auto-focus laser-induced breakdown spectroscopy (LIBS) is proposed. The enhancement of spectral signal intensity and stability through auto-focus was investigated, as were different preprocessing methods, with area normalization (AN) achieving the best results-increasing by 7.74%-but unable to replace the improved spectral signal quality provided by auto-focus. A residual neural network (ResNet) was used as both a classifier and feature extractor, achieving higher classification accuracy than traditional machine learning methods. The effectiveness of auto-focus was elucidated by extracting LIBS features from the last pooling layer output using uniform manifold approximation and projection (UMAP). Our approach demonstrated that auto-focus could efficiently optimize the LIBS signal, providing broad prospects for rapid origin classification of traditional Chinese medicines.
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Aprendizado de Máquina , Redes Neurais de Computação , Análise Espectral , LasersRESUMO
To meet the growing demand for food quality and safety, there is a pressing need for fast and visible techniques to monitor the food crop and product production processing, and to understand the chemical changes that occur during these processes. Herein, the fundamental principles, instruments, and characteristics of three major laser-based imaging techniques (LBITs), namely, laser-induced breakdown spectroscopy, Raman spectroscopy, and laser ablation-inductively coupled plasma-mass spectrometry, are introduced. Additionally, the advances, challenges, and prospects for the application of LBITs in food crops and products are discussed. In recent years, LBITs have played a crucial role in mapping primary metabolites, secondary metabolites, nanoparticles, toxic metals, and mineral elements in food crops, as well as visualizing food adulteration, composition changes, pesticide residue, microbial contamination, and elements in food products. However, LBITs are still facing challenges in achieving accurate and sensitive quantification of compositions due to the complex sample matrix and minimal laser sampling quantity. Thus, further research is required to develop comprehensive data processing strategies and signal enhancement methods. With the continued development of imaging methods and equipment, LBITs have the potential to further explore chemical distribution mechanisms and ensure the safety and quality of food crops and products.
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Laser-induced breakdown spectroscopy (LIBS) shows promising applications in the analysis of environmental heavy metals. However, direct analysis in water by LIBS faces the problems of droplet splashing and laser energy decay. In this study, a novel liquid-solid conversion method based on agarose films is proposed to provide an easy-to-operate and sensitive detection of heavy metals. First, the water samples were converted into semi-solid hydrogels with the aid of agarose and then dried into agarose films to make the signal intensities stronger. The calibration curves of Cd, Pb and Cr were constructed. The proposed method was validated by standard heavy metal solutions and real water samples. The results showed that the values of R2 were 0.990, 0.989 and 0.975, and the values of the LOD were 0.011, 0.122 and 0.118 mg L-1 for Cd (I) 228.80, Pb (I) 405.78 and Cr (I) 427.48 nm, respectively. The RMSEs of validation were 0.068 (Cd), 0.107 (Pb) and 0.112 mg·L-1 (Cr), and the recovery values were in the range of 91.2-107.9%. The agarose film-based liquid-solid conversion method achieved the desired ease of operation and sensitivity of LIBS in heavy-metal detection, thereby, showing good application prospects in heavy metal monitoring of water.
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Tea flow rate is a key indicator in tea production and processing. Due to the small real-time flow of tea leaves on the production line, the noise caused by the transmission system is greater than or close to the real signal of tea leaves. This issue may affect the dynamic measurement accuracy of tea flow. Therefore, a variational mode decomposition combined with a wavelet threshold (VMD-WT) denoising method is proposed to improve the accuracy of tea flow measurement. The denoising method of the tea flow signal based on VMD-WT is established, and the results are compared with WT, VMD, empirical mode decomposition (EMD), and empirical mode decomposition combined with wavelet threshold (EMD-WT). In addition, the dynamic measurement of different tea flow in tea processing is carried out. The result shows that the main noise of tea flow measurement comes from mechanical vibration. The VMD-WT method can effectively remove the noise in the tea dynamic weighing signal, and the denoising performance is better than WT, VMD, EMD, and EMD-WT methods. The average cumulative measurement accuracy of the tea flow signal based on the VMD-WT algorithm is 0.88%, which is 55% higher than that before denoising. This study provides an effective method for dynamic and accurate measurement of tea flow and offers technical support for digital control of the tea processing.
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Algoritmos , Processamento de Sinais Assistido por Computador , Ruído , Razão Sinal-Ruído , CháRESUMO
Traceability of honey is highly required by consumers and food administration with the consideration of food safety and quality. In this study, a technique named laser-induced breakdown spectroscopy (LIBS) was used to fast trace geographical origins of acacia honey and multi-floral honey. LIBS emissions from elements of Mg, Ca, Na, and K had significant differences among different geographical origins. The clusters of honey from different geographical origins were visualized with principal component analysis. In addition, support vector machine (SVM) and linear discrimination analysis (LDA) were used to quantitively classify the origins. The results indicated that SVM performed better than LDA, and the discriminant results of multi-floral honey were better than acacia honey. The accuracy and mean average precision for multi-floral honey were 99.7% and 99.7%, respectively. This study provided a fast approach for geographical origin classification, and might be helpful for food traceability.
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Mapeamento Geográfico , Mel/classificação , Análise Espectral/métodos , Mel/análise , Humanos , Lasers , Análise MultivariadaRESUMO
The rapid identification of kudzu powder of different origins is of great significance for studying the authenticity identification of Chinese medicine. The feasibility of rapidly identifying kudzu powder origin was investigated based on laser-induced breakdown spectroscopy (LIBS) technology combined with chemometrics methods. The discriminant models based on the full spectrum include extreme learning machine (ELM), soft independent modeling of class analogy (SIMCA), K-nearest neighbor (KNN) and random forest (RF), and the accuracy of models was more than 99.00%. The prediction results of KNN and RF models were best: the accuracy of calibration and prediction sets of kudzu powder from different producing areas both reached 100%. The characteristic wavelengths were selected using principal component analysis (PCA) loadings. The accuracy of calibration set and the prediction set of discrimination models, based on characteristic wavelengths, is all higher than 98.00%. Random forest and KNN have the same excellent identification results, and the accuracy of calibration and prediction sets of kudzu powder from different producing areas reached 100%. Compared with the full spectrum discriminant analysis model, the discriminant analysis model based on the characteristic wavelength had almost the same discriminant effects, and the input variables were reduced by 99.92%. The results of this research show that the characteristic wavelength can be used instead of the LIBS full spectrum to quickly identify kudzu powder from different producing areas, which had the advantages of reducing input, simplifying the model, increasing the speed and improving the model effect. Therefore, LIBS technology is an effective method for rapid identification of kudzu powder from different habitats. This study provides a basis for LIBS to be applied in the genuineness and authenticity identification of Chinese medicine.
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High-accuracy and fast detection of nutritive elements in traditional Chinese medicine Panax notoginseng (PN) is beneficial for providing useful assessment of the healthy alimentation and pharmaceutical value of PN herbs. Laser-induced breakdown spectroscopy (LIBS) was applied for high-accuracy and fast quantitative detection of six nutritive elements in PN samples from eight producing areas. More than 20,000 LIBS spectral variables were obtained to show elemental differences in PN samples. Univariate and multivariate calibrations were used to analyze the quantitative relationship between spectral variables and elements. Multivariate calibration based on full spectra and selected variables by the least absolute shrinkage and selection operator (Lasso) weights was used to compare the prediction ability of the partial least-squares regression (PLS), least-squares support vector machines (LS-SVM), and Lasso models. More than 90 emission lines for elements in PN were found and located. Univariate analysis was negatively interfered by matrix effects. For potassium, calcium, magnesium, zinc, and boron, LS-SVM models based on the selected variables obtained the best prediction performance with Rp values of 0.9546, 0.9176, 0.9412, 0.9665, and 0.9569 and root mean squared error of prediction (RMSEP) of 0.7704 mg/g, 0.0712 mg/g, 0.1000 mg/g, 0.0012 mg/g, and 0.0008 mg/g, respectively. For iron, the Lasso model based on full spectra obtained the best result with an Rp value of 0.9348 and RMSEP of 0.0726 mg/g. The results indicated that the LIBS technique coupled with proper multivariate chemometrics could be an accurate and fast method in the determination of PN nutritive elements for traditional Chinese medicine management and pharmaceutical analysis.
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Elementos Químicos , Lasers , Panax notoginseng/química , Análise Espectral/métodos , Máquina de Vetores de Suporte , Bases de Dados como Assunto , Análise dos Mínimos Quadrados , Análise Multivariada , Padrões de ReferênciaRESUMO
Fast detection of heavy metals is very important for ensuring the quality and safety of crops. Laser-induced breakdown spectroscopy (LIBS), coupled with uni- and multivariate analysis, was applied for quantitative analysis of copper in three kinds of rice (Jiangsu rice, regular rice, and Simiao rice). For univariate analysis, three pre-processing methods were applied to reduce fluctuations, including background normalization, the internal standard method, and the standard normal variate (SNV). Linear regression models showed a strong correlation between spectral intensity and Cu content, with an R 2 more than 0.97. The limit of detection (LOD) was around 5 ppm, lower than the tolerance limit of copper in foods. For multivariate analysis, partial least squares regression (PLSR) showed its advantage in extracting effective information for prediction, and its sensitivity reached 1.95 ppm, while support vector machine regression (SVMR) performed better in both calibration and prediction sets, where R c 2 and R p 2 reached 0.9979 and 0.9879, respectively. This study showed that LIBS could be considered as a constructive tool for the quantification of copper contamination in rice.
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Rapid detection of soil nutrient elements is beneficial to the evaluation of crop yield, and it's of great significance in agricultural production. The aim of this work was to compare the detection ability of single-pulse (SP) and collinear double-pulse (DP) laser-induced breakdown spectroscopy (LIBS) for soil nutrient elements and obtain an accurate and reliable method for rapid detection of soil nutrient elements. 63 soil samples were collected for SP and collinear DP signal acquisition, respectively. Macro-nutrients (K, Ca, Mg) and micro-nutrients (Fe, Mn, Na) were analyzed. Three main aspects of all elements were investigated, including spectral intensity, signal stability, and detection sensitivity. Signal-to-noise ratio (SNR) and relative standard deviation (RSD) of elemental spectra were applied to evaluate the stability of SP and collinear DP signals. In terms of detection sensitivity, the performance of chemometrics models (univariate and multivariate analysis models) and the limit of detection (LOD) of elements were analyzed, and the results indicated that the DP-LIBS technique coupled with PLSR could be an accurate and reliable method in the quantitative determination of soil nutrient elements.
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Fast detection of toxic metals in crops is important for monitoring pollution and ensuring food safety. In this study, laser-induced breakdown spectroscopy (LIBS) was used to detect the chromium content in rice leaves. We investigated the influence of laser wavelength (532 nm and 1064 nm excitation), along with the variations of delay time, pulse energy, and lens-to-sample distance (LTSD), on the signal (sensitivity and stability) and plasma features (temperature and electron density). With the optimized experimental parameters, univariate analysis was used for quantifying the chromium content, and several preprocessing methods (including background normalization, area normalization, multiplicative scatter correction (MSC) transformation and standardized normal variate (SNV) transformation were used to further improve the analytical performance. The results indicated that 532 nm excitation showed better sensitivity than 1064 nm excitation, with a detection limit around two times lower. However, the prediction accuracy for both excitation wavelengths was similar. The best result, with a correlation coefficient of 0.9849, root-mean-square error of 3.89 mg/kg and detection limit of 2.72 mg/kg, was obtained using the SNV transformed signal (Cr I 425.43 nm) induced by 532 nm excitation. The results indicate the inspiring capability of LIBS for toxic metals detection in plant materials.
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Oryza , Cromo , Lasers , Luz , Análise EspectralRESUMO
Rapid detection of Cd content in soil is beneficial to the prevention of soil heavy metal pollution. In this study, we aimed at exploring the rapid quantitative detection ability of laser- induced breakdown spectroscopy (LIBS) under the conditions of air and Ar for Cd in soil, and finding a fast and accurate method for quantitative detection of heavy metal elements in soil. Spectral intensity of Cd and system performance under air and Ar conditions were analyzed and compared. The univariate model and multivariate models of partial least-squares regression (PLSR) and least-squares support vector machine (LS-SVM) of Cd under the air and Ar conditions were built, and the LS-SVM model under the Ar condition obtained the best performance. In addition, the principle of influence of Ar on LIBS detection was investigated by analyzing the three-dimensional profile of the ablation crater. The overall results indicated that LIBS combined with LS-SVM under the Ar condition could be a useful tool for the accurate quantitative detection of Cd in soil and could provide reference for environmental monitoring.
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Cádmio/análise , Monitoramento Ambiental/métodos , Poluentes do Solo/análise , Solo/química , Ar , Análise de Variância , Argônio , Lasers , Análise dos Mínimos Quadrados , Modelos Teóricos , Espectrofotometria Atômica , Máquina de Vetores de SuporteRESUMO
Quick access to cadmium (Cd) contamination in lettuce is important to supervise the leafy vegetable growth environment and market. This study aims to apply laser-induced breakdown spectroscopy (LIBS) technology for fast determination of Cd content and diagnosis of the Cd contamination degree in lettuce. Emission lines Cd II 214.44 nm, Cd II 226.50 nm, and Cd I 228.80 nm were selected to establish the univariate analysis model. Multivariate analysis including partial least squares (PLS) regression, was used to establish Cd content calibration models, and PLS model based on 22 variables selected by genetic algorithm (GA) obtained the best performance with correlation coefficient in the prediction set Rp² = 0.9716, limit of detection (LOD) = 1.7 mg/kg. K-Nearest Neighbors (KNN) and random forest (RF) were used to analyze Cd contamination degree, and RF model obtained the correct classification rate of 100% in prediction set. The preliminary results indicate LIBS coupled with chemometrics could be used as a fast, efficient and low-cost method to assess Cd contamination in the vegetable industry.
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Cádmio/análise , Contaminação de Alimentos , Lactuca/química , Análise Espectral , Poluição Ambiental , Reprodutibilidade dos Testes , Análise Espectral/métodosRESUMO
Fast detection of heavy metals in plant materials is crucial for environmental remediation and ensuring food safety. However, most plant materials contain high moisture content, the influence of which cannot be simply ignored. Hence, we proposed moisture influence reducing method for fast detection of heavy metals using laser-induced breakdown spectroscopy (LIBS). First, we investigated the effect of moisture content on signal intensity, stability, and plasma parameters (temperature and electron density) and determined the main influential factors (experimental parameters F and the change of analyte concentration) on the variations of signal. For chromium content detection, the rice leaves were performed with a quick drying procedure, and two strategies were further used to reduce the effect of moisture content and shot-to-shot fluctuation. An exponential model based on the intensity of background was used to correct the actual element concentration in analyte. Also, the ratio of signal-to-background for univariable calibration and partial least squared regression (PLSR) for multivariable calibration were used to compensate the prediction deviations. The PLSR calibration model obtained the best result, with the correlation coefficient of 0.9669 and root-mean-square error of 4.75 mg/kg in the prediction set. The preliminary results indicated that the proposed method allowed for the detection of heavy metals in plant materials using LIBS, and it could be possibly used for element mapping in future work.
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Metais Pesados/análise , Oryza/química , Folhas de Planta/química , Calibragem , Lasers , Análise dos Mínimos Quadrados , Oxirredução , Análise Espectral , MolhabilidadeRESUMO
INTRODUCTION: Osmanthus fragrans flowers are used as folk medicine and additives for teas, beverages and foods. The metabolites of O. fragrans flowers from different geographical origins were inconsistent in some extent. Chromatography and mass spectrometry combined with multivariable analysis methods provides an approach for discriminating the origin of O. fragrans flowers. OBJECTIVE: To discriminate the Osmanthus fragrans var. thunbergii flowers from different origins with the identified metabolites. METHODS: GC-MS and UPLC-PDA were conducted to analyse the metabolites in O. fragrans var. thunbergii flowers (in total 150 samples). Principal component analysis (PCA), soft independent modelling of class analogy analysis (SIMCA) and random forest (RF) analysis were applied to group the GC-MS and UPLC-PDA data. RESULTS: GC-MS identified 32 compounds common to all samples while UPLC-PDA/QTOF-MS identified 16 common compounds. PCA of the UPLC-PDA data generated a better clustering than PCA of the GC-MS data. Ten metabolites (six from GC-MS and four from UPLC-PDA) were selected as effective compounds for discrimination by PCA loadings. SIMCA and RF analysis were used to build classification models, and the RF model, based on the four effective compounds (caffeic acid derivative, acteoside, ligustroside and compound 15), yielded better results with the classification rate of 100% in the calibration set and 97.8% in the prediction set. CONCLUSIONS: GC-MS and UPLC-PDA combined with multivariable analysis methods can discriminate the origin of Osmanthus fragrans var. thunbergii flowers. Copyright © 2017 John Wiley & Sons, Ltd.
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Flores/química , Oleaceae/química , Compostos Fitoquímicos/análise , Cromatografia Líquida de Alta Pressão , Cromatografia Gasosa-Espectrometria de Massas , GeografiaRESUMO
Striped stem-borer (SSB) infestation is one of the most serious sources of damage to rice growth. A rapid and non-destructive method of early SSB detection is essential for rice-growth protection. In this study, hyperspectral imaging combined with chemometrics was used to detect early SSB infestation in rice and identify the degree of infestation (DI). Visible/near-infrared hyperspectral images (in the spectral range of 380 nm to 1030 nm) were taken of the healthy rice plants and infested rice plants by SSB for 2, 4, 6, 8 and 10 days. A total of 17 characteristic wavelengths were selected from the spectral data extracted from the hyperspectral images by the successive projection algorithm (SPA). Principal component analysis (PCA) was applied to the hyperspectral images, and 16 textural features based on the gray-level co-occurrence matrix (GLCM) were extracted from the first two principal component (PC) images. A back-propagation neural network (BPNN) was used to establish infestation degree evaluation models based on full spectra, characteristic wavelengths, textural features and features fusion, respectively. BPNN models based on a fusion of characteristic wavelengths and textural features achieved the best performance, with classification accuracy of calibration and prediction sets over 95%. The accuracy of each infestation degree was satisfactory, and the accuracy of rice samples infested for 2 days was slightly low. In all, this study indicated the feasibility of hyperspectral imaging techniques to detect early SSB infestation and identify degrees of infestation.
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Análise de Alimentos/instrumentação , Análise de Alimentos/métodos , Oryza/parasitologia , Espectroscopia de Luz Próxima ao Infravermelho , Algoritmos , Redes Neurais de Computação , Análise de Componente Principal , Plântula/parasitologia , Fatores de TempoRESUMO
The research achievements and trends of spectral technology in fast detection of Camellia sinensis growth process information and tea quality information were being reviewed. Spectral technology is a kind of fast, nondestructive, efficient detection technology, which mainly contains infrared spectroscopy, fluorescence spectroscopy, Raman spectroscopy and mass spectroscopy. The rapid detection of Camellia sinensis growth process information and tea quality is helpful to realize the informatization and automation of tea production and ensure the tea quality and safety. This paper provides a review on its applications containing the detection of tea (Camellia sinensis) growing status(nitrogen, chlorophyll, diseases and insect pest), the discrimination of tea varieties, the grade discrimination of tea, the detection of tea internal quality (catechins, total polyphenols, caffeine, amino acid, pesticide residual and so on), the quality evaluation of tea beverage and tea by-product, the machinery of tea quality determination and discrimination. This paper briefly introduces the trends of the technology of the determination of tea growth process information, sensor and industrial application. In conclusion, spectral technology showed high potential to detect Camellia sinensis growth process information, to predict tea internal quality and to classify tea varieties and grades. Suitable chemometrics and preprocessing methods is helpful to improve the performance of the model and get rid of redundancy, which provides the possibility to develop the portable machinery. Future work is to develop the portable machinery and on-line detection system is recommended to improve the further application. The application and research achievement of spectral technology concerning about tea were outlined in this paper for the first time, which contained Camellia sinensis growth, tea production, the quality and safety of tea and by-produce and so on, as well as some problems to be solved and its future applicability in modern tea industrial.
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Camellia sinensis/crescimento & desenvolvimento , Análise Espectral , Chá/química , Cafeína/análise , Catequina/análise , Polifenóis/análiseRESUMO
Laser-induced breakdown spectroscopy (LIBS), as a kind of atomic emission spectroscopy, has been considered to be a future new tool for chemical analysis due to its unique features, such as no need of sample preparation, stand-off or remote analysis. What's more it can achieve fast and multi-element analysis. Therefore, LIBS technology is regarded as a future "SurperStar" in the field of chemical analysis and green analytical techniques. At present, rapid and accurate detection and prevention of soil contamination (mainly in pollutants of heavy metals and organic matter) is deemed to be a concerned and serious central issue in modern agriculture and agricultural sustainable development. In this paper, the reseach achievements and trends of soil elements detection based on LIBS technology were being reviewed. The structural composition and foundmental of LIBS system is first briefly introduced. And the paper offers a review of on LIBS applications and fruits including the detection and analysis of major element, nutrient element and heavy metal element. Simultaneously, some studies on soil related metials and fields are briefly stated. The research tendency and developing prospects of LIBS in soil detection are presented at last.
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An overview is presented with regard to applications of visible and near infrared (Vis/NIR) spectroscopy, multispectral imaging and hyperspectral imaging techniques for quality attributes measurement and variety discrimination of various fruit species, i.e., apple, orange, kiwifruit, peach, grape, strawberry, grape, jujube, banana, mango and others. Some commonly utilized chemometrics including pretreatment methods, variable selection methods, discriminant methods and calibration methods are briefly introduced. The comprehensive review of applications, which concentrates primarily on Vis/NIR spectroscopy, are arranged according to fruit species. Most of the applications are focused on variety discrimination or the measurement of soluble solids content (SSC), acidity and firmness, but also some measurements involving dry matter, vitamin C, polyphenols and pigments have been reported. The feasibility of different spectral modes, i.e., reflectance, interactance and transmittance, are discussed. Optimal variable selection methods and calibration methods for measuring different attributes of different fruit species are addressed. Special attention is paid to sample preparation and the influence of the environment. Areas where further investigation is needed and problems concerning model robustness and model transfer are identified.
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To facilitate rehabilitation training for patients, we proposed the implementation of an anthropomorphic exoskeleton structure that incorporates a variable instantaneous center of rotation (ICR). This design considers the variability in knee ICR among individuals, resulting from the irregular form of the human knee joint, and leverages a double-degrees-of-freedom (2DOF) five-bar mechanism to adapt to these differences. The walking gait of the human lower limb and the corresponding knee ICR were measured and calculated using an optical 3D motion capture system. The optimal dimension parameters of the five-bar mechanism were then obtained through the optimization of human movement position inputs and rod length constraints to minimize the error in knee ICR, gait angle, and ankle trajectory between the human and the exoskeleton. Finally, we established an exoskeleton prototype to conduct relevant experimental tests. The experiment results showed that the average errors of knee ICR trajectory, hip angle, knee angle, and ankle trajectory were 5.52 × 10-4 m, 0.010 rad, 0.014 rad, and 1.57 × 10-3 m, respectively. The experimental results demonstrated that the exoskeleton's movement trajectory was close to the human's, reducing the human-mechanism interaction force and improving patient comfort during rehabilitation training.
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Minerals in rice leaves is a crucial indicator of plant health, and their concentrations can be used to guide plant management. It is important to predict mineral content in contaminated rice rapidly. In this study, laser-induced breakdown spectroscopy (LIBS) was applied to quantify minerals (Ca, Cu, Fe, K, Mg, Mn, and Na) in rice leaves under chromium (Cr) stress. Two feature extraction methods, including principal component analysis (PCA) and extreme gradient boosting (XGBoost), were compared to identify important variables that related to mineral concentrations. Results showed that partial least square regression (PLSR) achieved good performance in Ca, Fe Mg, K, Mn, and Na, with correlation coefficient of 0.9782, 0.8712, 0.8933, 0.9206, 0.9856, and 0.9865, root mean square error of 219.25, 14.78, 1192.47, 385.12, 9.56, and 124.32 mg/kg, respectively. In addition, the correlation between different spectral lines were further analyzed. Cr exhibited a positive correlation with Ca, Mg, and Na, and a negative correlation with Mn, Cu, and K. The proposed method provides a high-accuracy and fast approach for minerals prediction in rice leaves under Cr stress, which is important for environmental protection and food safety.