水溶液中MTsPc分子聚集态的吸收光谱研究

合成并提纯了六种第四周期过渡金属的MTsPc(M=Mn,Fe,Co,Ni,Cu,Zn)分子,并利用吸收光谱对不同浓度和pH下水溶液中MTsPc分子的聚集态进行了系统研究。实验结果表明MTsPc在水溶液中形成分子二聚体的能力顺序为NiTsPc>CuTsPc>ZnTsPc>CoTsPc。根据吸收光谱结果,可将六种MTsPc分成三类。第一类为ZnTsPc、CuTsPc和NiTsPc,这三种分子在溶液中只能形成正常面对面二聚体,而不能与氧加合。第二类为CoTsPc,其在溶液中既可以形成分子二聚体也可以与氧加合,而生成分子氧桥二聚体。第三类为MnTsPc和FeTsPc,这两种分子在溶液中多数以含氧桥二聚体形式存在,且多为原子氧桥二聚体。溶液pH值的变化可以改变溶液中MTsPc分子的存在状态。对于第一类MTsPc,酸碱性条件均促使其分子二聚体的形成,而对于第二、三类的MTsPc,酸性条件使得其形成分子氧桥二聚体,碱性中则形成原子氧桥二聚体。     

近红外光谱分析法测定菜籽油中芥酸的含量

采用多通道PDA型近红外光谱仪,应用偏最小二乘法建立了菜籽油中芥酸含量与近红外透射光谱的校正模型,讨论多项式求导及平滑的窗口宽度和相关系数法筛选有效波长对校正模型的影响,并对10个预测集样品利用预测相关系数R_p和预测均方根误差RMSEP指标进行了预测精度分析,结果发现：在使用全谱数据进行偏最小二乘回归建模时,一阶7点求导及平滑的预处理方法结果最佳,此时建模效果为：R_p=0.739,RMSEP=1.659;在此基础上通过相关系数法筛选波长后的建模效果为：R_p=0.958,RMSEP=0.963。后者R_p提高29%,RMSEP减少42%。由此可得出多项式求导及平滑法和相关系数法相结合对校正模型稳健性,预测精度都有较大提高的结论。研究证明：多通道近红外光谱仪快速测测菜籽油中芥酸含量的方法是可行的。     

人工神经网络NIR定量分析方法及其软件实现

在Visual C＋＋环境中采用面向对象技术,开发了PCA-MBP-NIR定量分析模型软件。通过40份小麦样品的原始光谱、加噪光谱（信噪比为14dB）与含水率所建立的PLS-NIR与PCA-MBP-NIR模型,对10份未知小麦样品的原始光谱、加噪光谱分别进行含水率的PLS-NIR与PCA-MBP-NIR预测分析。分析表明,对于含噪声的光谱,与PLS建模相比,使用PCA-MBP-NIR对未知样品预测结果具有更高的相关系数,更低的预测误差标准差。     

傅立叶变换近红外光谱法检测白酒总酸和总酯

该文研究白酒总酸和总酯的快速检测技术,通过解析不同白酒样品的近红外光谱图,对光谱数据进行不同的处理,结果表明：用一阶导数预处理光谱,谱区选择6102～5446 cm^-1,利用人工神经网络与傅立叶变换近红外光谱相结合,采用内部交叉验证法建立模型,效果较好。其中,总酸模型的决定系数为96.73%,内部交叉验证均方根差为0.048 g/L;总酯模型的决定系数为99.58%,内部交叉验证均方根差为0.085 g/L;进一步对总酸和总酯的模型进行验证和评价,结果表明总酸模型验证集的相关系数为99.2%,预测标准偏差为0.074 g/L;总酯模型验证集的相关为99.7%,预测标准偏差为0.134 g/L,表明建立的模型可靠,预测效果好,能满足白酒生产中总酸和总酯的快速检测要求。     

基于激光诱导击穿光谱的地下水中Fe和Mn的检测

采用激光诱导击穿光谱(LIBS)技术并结合在锌基板上液固转换的样品处理方法,对标准水溶液样品中Fe、Mn进行检测,并根据标准曲线法建立Fe、Mn的定量模型;再利用所建立的LIBS定量模型,对洞庭湖区地下水实际水样中Fe、Mn含量进行检测,并与电感耦合等离子体质谱法(ICP–MS)的检测结果进行比较。结果表明：得到Fe、Mn的LIBS定标曲线的决定系数均大于0.98,相对标准偏差均为4.3%,留一交叉验证均方根误差分别为0.024、0.007 mg/L,Fe、Mn的检出限分别为0.028、0.008 mg/L;采用LIBS对洞庭湖地下水实际水样中Fe、Mn含量检测的结果与ICP–MS的检测结果基本一致,平均相对误差小于10%。     

基于可见/近红外光谱技术的毛脚茧的光谱快速鉴别方法研究

基于可见/近红外光谱技术,研究了鲜茧毛脚茧快速鉴别的方法。采用主成分分析法对毛脚茧和成熟茧进行定性分析,再对光谱数据采用最小二乘支持向量机方法建模鉴别,通过连续投影算法从400-1000 nm波段的鲜茧光谱数据中选取了12个特征波长。采用最小二乘支持向量机法基于400 nm,430 nm,487 nm,512 nm,604 nm,616 nm,732 nm,759 nm,784 nm,852 nm,985 nm,999 nm这12个特征波长建模,结果对毛脚茧的判别准确率达到100%。表明可见/近红外光谱可以用于毛脚茧的鉴别检测。     

Pedotransfer functions to assess adsorbed phosphate using iron oxide content and magnetic susceptibility in an Oxisol

Adsorbed phosphate in soils can be chemically extracted; however, this process is both time‐consuming and not cost‐effective if large numbers of samples have to be analysed. Indirect assessment of adsorbed phosphate by pedotransfer functions (PTFs) can help optimize fertilizer strategies. This study aimed to evaluate the spatial variability of adsorbed phosphate (P_ads), iron oxides and magnetic susceptibility (MS) in oxisols and to calibrate PTFs to predict P_ads. A total of 308 soil samples were collected from Hapludox and Eutrudox soils formed from sandstone in Brazil. The contents of clay (196–607 g/kg), iron oxides (40–165 g/kg), MS (1.2–29 × 10^?6 m³/kg) and P_ads (327–842 mg/kg) were in the range of typical values for these highly weathered soils. This study showed that the attributes studied were spatially dependent. Geomorphic surfaces enabled understanding of spatial variability and helped to develop a more efficient sampling scheme to calibrate PTFs. Moreover, the adsorbed phosphate in these oxisols could be predicted by a PTF using iron oxides and MS as predictors. The MS attribute enabled the most accurate prediction (concordance coefficient = 0.95, root‐mean‐square error = 46 mg/kg and relative improvement in root‐mean‐square error = ?4.12) of spatial variability through PTF compared to other predictors.     

Feasibility analysis of NIR for detecting sweet corn seeds vigor

This paper explores the feasibility of particle-based detection and grading of seed vigor based on a self-built seed single-granulation device using near infrared spectroscopy (NIRS). Sweet corn with uniform kernel size was used for this study. The seed samples were divided into three types, they were normal seeds, artificially aged seeds and heat-damaged seeds. A 2-part spectral acquisition of each seed were performed, one for the collection of seeds that fall into the detection zone within the separation pipe, another was on the static platform, whose collection was performed on 5 faces of each seed. Partial least squares discriminant analysis (PLS-DA) was used to classify the original data of the seeds. In the 2 parts, the discriminant results of the unprocessed normal seeds and the artificial accelerated aging seeds, the untreated normal seeds and the heat-damaged seeds showed that classification accuracy was higher than 98%. The research indicates that the spectral data of different positions of seeds can reflect their activity information, and it is feasible to detect and classify seeds in real time in the detection area of the separation pipeline.     

Influence of Soil Particle Size on the Measurement of Sodium by Near-Infrared Reflectance Spectroscopy

This study evaluates the effect of soil particle size (SPS) on the measurement of exchangeable sodium (Na) (EXC-Na) by near-infrared reflectance (NIR) spectroscopy. Three hundred thirty-two (n = 332) top soil samples (0–10 cm) were taken from different locations across Uruguay, analyzed by EXC-Na using emission spectrometry, and scanned in reflectance using a NIR spectrophotometer (1100–2500 nm). Partial least squares (PLS) and principal component regression (PCR) models between reference chemical data and NIR data were developed using cross validation (leaving one out). The coefficient of determination in calibration (R²) and the root mean square of the standard error of cross validation (RMSECV) for EXC-Na concentration were 0.44 (RMSECV: 0.12 mg kg^–1) for soil with small particle size (SPS-0.053) and 0.77 (RMSECV: 0.09 mg kg^–1) for soils with particle sizes greater than 0.212 mm (SPS-0.212), using the NIR region after second derivative as mathematical transformation. The R² and RMSECV for EXC-Na concentration using PCR were 0.54 (RMSECV: 0.07 mg kg^–1) and 0.80 (RMSECV: 0.03 mg kg^–1) for SPS-0.053 and SPS-0.212 samples, respectively.