In sub nanometer carbon nanotubes,water exhibits unique dynamic characteristics,and in the high-frequency region of the infrared spectrum,where the stretching vibrations of the internal oxygen-hydrogen(O-H)bonds are c...In sub nanometer carbon nanotubes,water exhibits unique dynamic characteristics,and in the high-frequency region of the infrared spectrum,where the stretching vibrations of the internal oxygen-hydrogen(O-H)bonds are closely related to the hydrogen bonds(H-bonds)network between water molecules.Therefore,it is crucial to analyze the relationship between these two aspects.In this paper,the infrared spectrum and motion characteristics of the stretching vibrations of the O-H bonds in one-dimensional confined water(1DCW)and bulk water(BW)in(6,6)single-walled carbon nanotubes(SWNT)are studied by molecular dynamics simulations.The results show that the stretching vibrations of the two O-H bonds in 1DCW exhibit different frequencies in the infrared spectrum,while the O-H bonds in BW display two identical main frequency peaks.Further analysis using the spring oscillator model reveals that the difference in the stretching amplitude of the O-H bonds is the main factor causing the change in vibration frequency,where an increase in stretching amplitude leads to a decrease in spring stiffness and,consequently,a lower vibration frequency.A more in-depth study found that the interaction of H-bonds between water molecules is the fundamental cause of the increased stretching amplitude and decreased vibration frequency of the O-H bonds.Finally,by analyzing the motion trajectory of the H atoms,the dynamic differences between 1DCW and BW are clearly revealed.These findings provide a new perspective for understanding the behavior of water molecules at the nanoscale and are of significant importance in advancing the development of infrared spectroscopy detection technology.展开更多
Although there are numerous optical spectroscopy techniques and methods that have been used to extract the fundamental bandgap of a semiconductor,most of them belong to one of these three approaches:(1)the excitonic a...Although there are numerous optical spectroscopy techniques and methods that have been used to extract the fundamental bandgap of a semiconductor,most of them belong to one of these three approaches:(1)the excitonic absorption,(2)modulation spectroscopy,and(3)the most widely used Tauc-plot.The excitonic absorption is based on a many-particle theory,which is physically the most correct approach,but requires more stringent crystalline quality and appropriate sample preparation and experimental implementation.The Tauc-plot is based on a single-particle theo⁃ry that neglects the many-electron effects.Modulation spectroscopy analyzes the spectroscopy features in the derivative spectrum,typically,of the reflectance and transmission under an external perturbation.Empirically,the bandgap ener⁃gy derived from the three approaches follow the order of E_(ex)>E_(MS)>E_(TP),where three transition energies are from exci⁃tonic absorption,modulation spectroscopy,and Tauc-plot,respectively.In principle,defining E_(g) as the single-elec⁃tron bandgap,we expect E_(g)>E_(ex),thus,E_(g)>E_(TP).In the literature,E_(TP) is often interpreted as E_(g),which is conceptual⁃ly problematic.However,in many cases,because the excitonic peaks are not readily identifiable,the inconsistency be⁃tween E_(g) and E_(TP) becomes invisible.In this brief review,real world examples are used(1)to illustrate how excitonic absorption features depend sensitively on the sample and measurement conditions;(2)to demonstrate the differences between E_(ex),E_(MS),and E_(TP) when they can be extracted simultaneously for one sample;and(3)to show how the popular⁃ly adopted Tauc-plot could lead to misleading results.Finally,it is pointed out that if the excitonic absorption is not ob⁃servable,the modulation spectroscopy can often yield a more useful and reasonable bandgap than Tauc-plot.展开更多
To address the issues of peak overlap caused by complex matrices in agricultural product terahertz(THz)spectral signals and the dynamic,nonlinear interference induced by environmental and system noise,this study explo...To address the issues of peak overlap caused by complex matrices in agricultural product terahertz(THz)spectral signals and the dynamic,nonlinear interference induced by environmental and system noise,this study explores the feasibility of adaptive-signal-decomposition-based denoising methods to improve THz spectral quality.THz time-domain spectroscopy(THz-TDS)combined with an attenuated total reflection(ATR)accessory was used to collect THz absorbance spectra from 48 peanut samples.Taking the quantitative prediction model of peanut moisture content based on THz-ATR as an example,wavelet transform(WT),empirical mode decomposition(EMD),local mean decomposition(LMD),and its improved methods-segmented local mean decomposition(SLMD)and piecewise mirror extension local mean decomposition(PME-LMD)-were employed for spectral denoising.The applicability of different denoising methods was evaluated using a support vector regression(SVR)model.Experimental results show that the peanut moisture content prediction model constructed after PME-LMD denoising achieved the best performance,with a root mean square error(RMSE),coefficient of determination(R^(2)),and mean absolute percentage error(MAPE)of 0.010,0.912,and 0.040,respectively.Compared with traditional methods,PME-LMD significantly improved spectral quality and model prediction performance.The PME-LMD denoising strategy proposed in this study effectively suppresses non-uniform noise interference in THz spectral signals,providing an efficient and accurate preprocessing method for THz spectral analysis of agricultural products.This research provides theoretical support and technical guidance for the application of THz technology for detecting agricultural product quality.展开更多
3-Nitro-1,2,4-triazol-5-one(NTO)is a typical high-energy,low-sensitivity explosive,and accurate concentration monitoring is critical for crystallization process control.In this study,a high-precision quantitative anal...3-Nitro-1,2,4-triazol-5-one(NTO)is a typical high-energy,low-sensitivity explosive,and accurate concentration monitoring is critical for crystallization process control.In this study,a high-precision quantitative analytical model for NTO concentration in ethanol solutions was developed by integrating real-time ATR-FTIR spectroscopy with chemometric and machine learning techniques.Dynamic spectral data were obtained by designing multi-concentration gradient heating-cooling cycle experiments,abnormal samples were eliminated using the isolation forest algorithm,and the effects of various preprocessing methods on model performance were systematically evaluated.The results show that partial least squares regression(PLSR)exhibits superior generalization ability compared to other models.Vibrational bands corresponding to C=O and–NO_(2)were identified as key predictors for concentration estimation.This work provides an efficient and reliable solution for real-time concentration monitoring during NTO crystallization and holds significant potential for process analytical applications in energetic material manufacturing.展开更多
利用野外实时快速获取的土壤光谱进行土壤有机质(SOM)预测与制图是精确农业与土壤遥感制图的必然需要,利用ASD FieldSpec Pro FR野外型光谱仪实时快速获取的光谱数据,去除噪声较大的边缘波段后,进行倒数的对数转换(Log(1/R))为吸收光谱...利用野外实时快速获取的土壤光谱进行土壤有机质(SOM)预测与制图是精确农业与土壤遥感制图的必然需要,利用ASD FieldSpec Pro FR野外型光谱仪实时快速获取的光谱数据,去除噪声较大的边缘波段后,进行倒数的对数转换(Log(1/R))为吸收光谱。在分析吸收光谱和光谱指数与SOM关系的基础上,采用偏最小二乘回归法进行SOM的建模预测并借助地统计学方法进行SOM空间变异制图研究。结果表明,建模效果好的指标分别为特征波段(R2=0.91,RPD=3.28),归一化光谱指数(R2=0.90,RPD=3.08),特征波段与3个光谱指数组合(R2=0.87,RPD=2.67),全波段(R2=0.95,RPD=4.36)。光谱指标的克里格制图与实测SOM制图表现出相同的空间变异趋势,不同的指标均达到了较好的预测效果。展开更多
Based on three different kinds of conductive paths in microstructure of soil and theory of electrochemical impedance spectroscopy(EIS), an integrated equivalent circuit model and impedance formula for soils were propo...Based on three different kinds of conductive paths in microstructure of soil and theory of electrochemical impedance spectroscopy(EIS), an integrated equivalent circuit model and impedance formula for soils were proposed, which contain 6 meaningful resistance and reactance parameters. Considering the conductive properties of soils and dispersion effects, mathematical equations for impedance under various circuit models were deduced and studied. The mathematical expression presents two semicircles for theoretical EIS Nyquist spectrum, in which the center of one semicircle is degraded to simply the equivalent model. Based on the measured parameters of EIS Nyquist spectrum, meaningful soil parameters can easily be determined. Additionally, EIS was used to investigate the soil properties with different water contents along with the mathematical relationships and mechanism between the physical parameters and water content. Magnitude of the impedance decreases with the increase of testing frequency and water content for Bode graphs. The proposed model would help us to better understand the soil microstructure and properties and offer more reasonable explanations for EIS spectra.展开更多
Parent compounds of cyclopentadienyltitanium substituted heteropolytungstates with Keggin structure,An[(CpTi)XW11O39]·xH2O(A=Me4N,K;X=P,Si,Co;Cp=η5-C5H5) were synthesized in aqueous phase.By allowing parent hete...Parent compounds of cyclopentadienyltitanium substituted heteropolytungstates with Keggin structure,An[(CpTi)XW11O39]·xH2O(A=Me4N,K;X=P,Si,Co;Cp=η5-C5H5) were synthesized in aqueous phase.By allowing parent heteropoly compounds to react with protonated 8-quinolinol,the title supermolecular compounds(C9H8NO)mAn[(CpTi)XW11O39]·xH2O(A=Me4N,H;X=P,Si,Co) were synthesized.The title compounds were characterized by means of elementary analysis,IR,UV,1H NMR,XRD and TG-DSC.The results indicate that the title compounds are new heteropoly compounds,and there is a charge transfer interaction between the organic cation and heteropoly anion.The results obtained from thermal analysis show that QCpTiPW,QCpTiSiW and QCpTiCoW begin to decompose at 212.4,194.2 and 171.2 ℃,respectively.The results obtained from antibacterial test reveal that QCpTiSiW has the best antibacterial activity,and the MIC values of QCpTiSiW against Escherichia coli and Staphylococcus aurous are 64.0 and 0.500 μg·mL-1,respectively.展开更多
Near infrared spectrometer technology under a wavelength range of 918-1045 nm was used to rapidly detect paddy rice that was stored at 5℃, 15℃ and 25℃. A total of 121 paddy rice samples were collected from artifici...Near infrared spectrometer technology under a wavelength range of 918-1045 nm was used to rapidly detect paddy rice that was stored at 5℃, 15℃ and 25℃. A total of 121 paddy rice samples were collected from artificial infection with moulds to build the calibration models to calculate the total number colony of moulds based on the principal component regression method and multiple linear regression method. The results of statistical analysis indicated that multiple linear regression method was applicable to the detection of the total number colony of moulds. The correlation of calibration data set was 0.943. The correlation of prediction data set was 0.897. Therefore, the result showed that near infrared spectroscopy could be a useful instrumental method for determining the total number colony of moulds in paddy rice. The near infrared spectroscopy methodology could be applied for monitoring mould contamination in postharvest paddy rice during storage and might become a powerful tool for monitoring the safety of the grain.展开更多
基金Supported by the Natural Science Foundation of China(51705326,52075339)。
文摘In sub nanometer carbon nanotubes,water exhibits unique dynamic characteristics,and in the high-frequency region of the infrared spectrum,where the stretching vibrations of the internal oxygen-hydrogen(O-H)bonds are closely related to the hydrogen bonds(H-bonds)network between water molecules.Therefore,it is crucial to analyze the relationship between these two aspects.In this paper,the infrared spectrum and motion characteristics of the stretching vibrations of the O-H bonds in one-dimensional confined water(1DCW)and bulk water(BW)in(6,6)single-walled carbon nanotubes(SWNT)are studied by molecular dynamics simulations.The results show that the stretching vibrations of the two O-H bonds in 1DCW exhibit different frequencies in the infrared spectrum,while the O-H bonds in BW display two identical main frequency peaks.Further analysis using the spring oscillator model reveals that the difference in the stretching amplitude of the O-H bonds is the main factor causing the change in vibration frequency,where an increase in stretching amplitude leads to a decrease in spring stiffness and,consequently,a lower vibration frequency.A more in-depth study found that the interaction of H-bonds between water molecules is the fundamental cause of the increased stretching amplitude and decreased vibration frequency of the O-H bonds.Finally,by analyzing the motion trajectory of the H atoms,the dynamic differences between 1DCW and BW are clearly revealed.These findings provide a new perspective for understanding the behavior of water molecules at the nanoscale and are of significant importance in advancing the development of infrared spectroscopy detection technology.
基金Supported by Bissell Distinguished Professor Endowment Fund at UNC-Charlotte。
文摘Although there are numerous optical spectroscopy techniques and methods that have been used to extract the fundamental bandgap of a semiconductor,most of them belong to one of these three approaches:(1)the excitonic absorption,(2)modulation spectroscopy,and(3)the most widely used Tauc-plot.The excitonic absorption is based on a many-particle theory,which is physically the most correct approach,but requires more stringent crystalline quality and appropriate sample preparation and experimental implementation.The Tauc-plot is based on a single-particle theo⁃ry that neglects the many-electron effects.Modulation spectroscopy analyzes the spectroscopy features in the derivative spectrum,typically,of the reflectance and transmission under an external perturbation.Empirically,the bandgap ener⁃gy derived from the three approaches follow the order of E_(ex)>E_(MS)>E_(TP),where three transition energies are from exci⁃tonic absorption,modulation spectroscopy,and Tauc-plot,respectively.In principle,defining E_(g) as the single-elec⁃tron bandgap,we expect E_(g)>E_(ex),thus,E_(g)>E_(TP).In the literature,E_(TP) is often interpreted as E_(g),which is conceptual⁃ly problematic.However,in many cases,because the excitonic peaks are not readily identifiable,the inconsistency be⁃tween E_(g) and E_(TP) becomes invisible.In this brief review,real world examples are used(1)to illustrate how excitonic absorption features depend sensitively on the sample and measurement conditions;(2)to demonstrate the differences between E_(ex),E_(MS),and E_(TP) when they can be extracted simultaneously for one sample;and(3)to show how the popular⁃ly adopted Tauc-plot could lead to misleading results.Finally,it is pointed out that if the excitonic absorption is not ob⁃servable,the modulation spectroscopy can often yield a more useful and reasonable bandgap than Tauc-plot.
基金Supported by the National Key R&D Program of China(2023YFD2101001)National Natural Science Foundation of China(32202144,61807001)。
文摘To address the issues of peak overlap caused by complex matrices in agricultural product terahertz(THz)spectral signals and the dynamic,nonlinear interference induced by environmental and system noise,this study explores the feasibility of adaptive-signal-decomposition-based denoising methods to improve THz spectral quality.THz time-domain spectroscopy(THz-TDS)combined with an attenuated total reflection(ATR)accessory was used to collect THz absorbance spectra from 48 peanut samples.Taking the quantitative prediction model of peanut moisture content based on THz-ATR as an example,wavelet transform(WT),empirical mode decomposition(EMD),local mean decomposition(LMD),and its improved methods-segmented local mean decomposition(SLMD)and piecewise mirror extension local mean decomposition(PME-LMD)-were employed for spectral denoising.The applicability of different denoising methods was evaluated using a support vector regression(SVR)model.Experimental results show that the peanut moisture content prediction model constructed after PME-LMD denoising achieved the best performance,with a root mean square error(RMSE),coefficient of determination(R^(2)),and mean absolute percentage error(MAPE)of 0.010,0.912,and 0.040,respectively.Compared with traditional methods,PME-LMD significantly improved spectral quality and model prediction performance.The PME-LMD denoising strategy proposed in this study effectively suppresses non-uniform noise interference in THz spectral signals,providing an efficient and accurate preprocessing method for THz spectral analysis of agricultural products.This research provides theoretical support and technical guidance for the application of THz technology for detecting agricultural product quality.
基金supported by the Aeronautical Science Foundation of China(Grant No.20230018072011)。
文摘3-Nitro-1,2,4-triazol-5-one(NTO)is a typical high-energy,low-sensitivity explosive,and accurate concentration monitoring is critical for crystallization process control.In this study,a high-precision quantitative analytical model for NTO concentration in ethanol solutions was developed by integrating real-time ATR-FTIR spectroscopy with chemometric and machine learning techniques.Dynamic spectral data were obtained by designing multi-concentration gradient heating-cooling cycle experiments,abnormal samples were eliminated using the isolation forest algorithm,and the effects of various preprocessing methods on model performance were systematically evaluated.The results show that partial least squares regression(PLSR)exhibits superior generalization ability compared to other models.Vibrational bands corresponding to C=O and–NO_(2)were identified as key predictors for concentration estimation.This work provides an efficient and reliable solution for real-time concentration monitoring during NTO crystallization and holds significant potential for process analytical applications in energetic material manufacturing.
文摘利用野外实时快速获取的土壤光谱进行土壤有机质(SOM)预测与制图是精确农业与土壤遥感制图的必然需要,利用ASD FieldSpec Pro FR野外型光谱仪实时快速获取的光谱数据,去除噪声较大的边缘波段后,进行倒数的对数转换(Log(1/R))为吸收光谱。在分析吸收光谱和光谱指数与SOM关系的基础上,采用偏最小二乘回归法进行SOM的建模预测并借助地统计学方法进行SOM空间变异制图研究。结果表明,建模效果好的指标分别为特征波段(R2=0.91,RPD=3.28),归一化光谱指数(R2=0.90,RPD=3.08),特征波段与3个光谱指数组合(R2=0.87,RPD=2.67),全波段(R2=0.95,RPD=4.36)。光谱指标的克里格制图与实测SOM制图表现出相同的空间变异趋势,不同的指标均达到了较好的预测效果。
基金Projects(5120833351078253)supported by the National Natural Science Foundation of China+4 种基金Projects(2014011036-12014131019TYUT2014YQ017OIT2015)supported by the Natural Science Foundation of Shanxi ProvinceChina
文摘Based on three different kinds of conductive paths in microstructure of soil and theory of electrochemical impedance spectroscopy(EIS), an integrated equivalent circuit model and impedance formula for soils were proposed, which contain 6 meaningful resistance and reactance parameters. Considering the conductive properties of soils and dispersion effects, mathematical equations for impedance under various circuit models were deduced and studied. The mathematical expression presents two semicircles for theoretical EIS Nyquist spectrum, in which the center of one semicircle is degraded to simply the equivalent model. Based on the measured parameters of EIS Nyquist spectrum, meaningful soil parameters can easily be determined. Additionally, EIS was used to investigate the soil properties with different water contents along with the mathematical relationships and mechanism between the physical parameters and water content. Magnitude of the impedance decreases with the increase of testing frequency and water content for Bode graphs. The proposed model would help us to better understand the soil microstructure and properties and offer more reasonable explanations for EIS spectra.
基金supported by the chemical materials institute China academy of engineering physics,the doctoral innovation research assistance program of science and technology review
文摘Parent compounds of cyclopentadienyltitanium substituted heteropolytungstates with Keggin structure,An[(CpTi)XW11O39]·xH2O(A=Me4N,K;X=P,Si,Co;Cp=η5-C5H5) were synthesized in aqueous phase.By allowing parent heteropoly compounds to react with protonated 8-quinolinol,the title supermolecular compounds(C9H8NO)mAn[(CpTi)XW11O39]·xH2O(A=Me4N,H;X=P,Si,Co) were synthesized.The title compounds were characterized by means of elementary analysis,IR,UV,1H NMR,XRD and TG-DSC.The results indicate that the title compounds are new heteropoly compounds,and there is a charge transfer interaction between the organic cation and heteropoly anion.The results obtained from thermal analysis show that QCpTiPW,QCpTiSiW and QCpTiCoW begin to decompose at 212.4,194.2 and 171.2 ℃,respectively.The results obtained from antibacterial test reveal that QCpTiSiW has the best antibacterial activity,and the MIC values of QCpTiSiW against Escherichia coli and Staphylococcus aurous are 64.0 and 0.500 μg·mL-1,respectively.
基金Supported by the National 12th Five-year Plan for Science&Technology Support Fund(2012BAK08B04-02)the Heilongjiang Science and Technology Plan(GC12B404)
文摘Near infrared spectrometer technology under a wavelength range of 918-1045 nm was used to rapidly detect paddy rice that was stored at 5℃, 15℃ and 25℃. A total of 121 paddy rice samples were collected from artificial infection with moulds to build the calibration models to calculate the total number colony of moulds based on the principal component regression method and multiple linear regression method. The results of statistical analysis indicated that multiple linear regression method was applicable to the detection of the total number colony of moulds. The correlation of calibration data set was 0.943. The correlation of prediction data set was 0.897. Therefore, the result showed that near infrared spectroscopy could be a useful instrumental method for determining the total number colony of moulds in paddy rice. The near infrared spectroscopy methodology could be applied for monitoring mould contamination in postharvest paddy rice during storage and might become a powerful tool for monitoring the safety of the grain.
