Nondestructive discrimination of internal defects in jujube (Huizao) of Xinjiang based on visible and near-infrared spectroscopy

Abstract

During harvest and transport, defects are most likely to affect the interior of jujubes and thus shorten their storage period. This study applied visible and near-infrared transmission spectroscopy to detect such internal defects. Spectra were acquired on the equator area at 0, 90, 180, and 270 degrees of each sample, and a model was constructed to obtain three-dimensional damage and defect detection model. The first derivative, multiplicative scatter correction, standard normal variate, and median filtering were used for preprocessing. Modeling by mean spectra achieved a better effect than using unidirectional spectra. Then, naive Bayes classifier and support vector machine were employed for the model establishment at 600–950?nm and 680–950?nm bands, respectively, using mean spectra. Median filtering effectively improved the signal to noise ratio and the discrimination accuracy of the support vector machine model at 600–950?nm reached 96.77%, which was the best value among all models. This result indicates that the support vector machine model was the optimum model and 600–950?nm was a suitable data range for the detection of internal defects. This research confirms the feasibility of implementing visible and near-infrared spectroscopy for the detection of internal defects in jujubes.     

Opp‐Dibenzoporphyrins as a Light‐Harvester for Dye‐Sensitized Solar Cells

New opp‐dibenzoporphyrins were prepared in a concise method that was based on a Pd⁰‐catalyzed cascade reaction. These porphyrins, which contained carboxylic‐acid linker groups on benzene rings that were fused to the porphyrin at their β,β′‐positions, were examined as sensitizers for dye‐sensitized solar cells for the first time. Whereas all of the porphyrins showed solar‐energy‐to‐electricity conversion, an opp‐dibenzoporphyrin with conjugated carboxylic‐acid linkers displayed the highest conversion efficiency and an exceptionally high J_sc value. Cyclic voltammetry of these porphyrins suggested that the fusion of two aromatic benzene rings onto the periphery of the porphyrin lowered the HOMO–LUMO energy gap; the incorporation of a conjugated carboxylic‐acid linker group decreased the HOMO–LUMO gap even further. These CV data are consistent with DFT calculations for these porphyrins and agree well with the UV/Vis absorption‐ and fluorescence spectra of these porphyrins.     

Simultaneous determination of five commercial cationic dyes in stream waters using diatomite solid-phase extractant and multivariate calibration

A simple spectrophotometric method was developed for the simultaneous determination of five commercial cationic dyes at 2.0?8.5 μg L^?1 level after using diatomite as solid-phase extractant. The method is based on preconcentration of the five dyes on natural diatomite solid-phase extractant and on multivariate calibration using partial least squares method (PLS-1). Compared with commonly used chromatographic or electrophoretic methods the developed method is simple and sensitive. With enrichment factors between 89 and 96, diatomite outperformed zeolite and activated carbon for dyes preconcentration. Before preconcentration and using PLS-1 method, the cationic dyes were simultaneously analyzed with linear ranges of 0.18–4.5, 0.32–5.0, 0.23–4.5, 0.45–8.0 and 0.82–12.0 mg L^?1 for crystal violet, malachite green, methylene blue, safranine O, and thioflavin T, respectively. The detection limits of dyes were estimated using Lorber’s method and found to be within the range 43–245 μg L^?1. The proposed SPE/PLS-1 method was applied to spiked stream water samples with good accuracy (79–91%) and precision (RSD 1.8–7.3%) but with slightly lower enrichment factors (80–92).     

Tuning the Spectroscopic,Electrochemical, and Photovoltaic Properties of Triaryl Amine Based Sensitizers through Ring‐Fused Thiophene Bridges

The ring‐fused thiophene derivatives benzo[c]thiophene and its precursor bicyclo[2.2.2]octadiene (BCOD) have been introduced as π‐conjugated spacers for organic push–pull sensitizers with dihexyloxy‐substituted triphenylamine as donor and cyanoacrylic acid as acceptor ( OL1 , OL2 , OL3 , OL4 , OL5 , OL6 ). The effects of the fused ring on the spectroscopic and electrochemical properties of these sensitizers and their photovoltaic performance in dye‐sensitized solar cells have been evaluated. Introduction of a binary benzo[c]thiophene and ethylenedioxy thiophene as π bridge caused a significant red shift of the characteristic intramolecular charge‐transfer band to 642 nm. It is found that the sensitizer OL3 , which contains one benzo[c]thiophene unit as π linker, gives the highest overall conversion efficiency of 5.03 % among all these dyes.     

Comparative study on the process behavior and reaction kinetics in sonocatalytic degradation of organic dyes by powder and nanotubes TiO2

Sonocatalytic degradation of various organic dyes (Congo Red, Reactive Blue 4, Methyl Orange, Rhodamine B and Methylene Blue) catalyzed by powder and nanotubes TiO₂ was studied. Both catalysts were characterized using transmission electron microscope (TEM), surface analyzer, Raman spectroscope and thermal gravimetric analyzer (TGA). Sonocatalytic activity of powder and nanotubes TiO₂ was elucidated based on the degradation of various organic dyes. The former catalyst was favorable for treatment of anionic dyes, while the latter was more beneficial for cationic dyes. Sonocatalytic activity of TiO₂ nanotubes could be up to four times as compared to TiO₂ powder under an ultrasonic power of 100 W and a frequency of 42 kHz. This was associated with the higher surface area and the electrostatic attraction between dye molecules and TiO₂ nanotubes. Fourier transform-infrared spectrometer (FT-IR) was used to identify changes that occurred on the functional group in Rhodamine B molecules and TiO₂ nanotubes after the reaction. Sonocatalytic degradation of Rhodamine B by TiO₂ nanotubes apparently followed the Langmuir-Hinshelwood adsorption kinetic model with surface reaction rate of 1.75 mg/L min. TiO₂ nanotubes were proven for their high potential to be applied in sonocatalytic degradation of organic dyes.     

应用局部神经网络和可见/近红外光谱法估测土壤有效氮磷钾

要实现农田合理施肥,需要对土壤养分状况进行实时、准确地诊断,因而建立快速、稳定可靠的土壤养分定量分析方法是关键。光谱分析是一种有很大潜力的快速分析方法,从可见/近红外光谱建模的几个重要环节,即特征波段、预处理方法及回归模型方法的选择,研究了土壤有效氮、磷、钾含量快速估测的光谱建模方法。采用了多元散射校正加一阶导数进行光谱预处理,通过逐波段相关分析在可见-近红外区优选特征波段,并应用了局部非线性回归方法(BP神经网络局部回归法)建模,所建模型对土壤有效氮、磷、钾含量估测的相关系数r分别为0.90,0.82和0.94,BP神经网络局部建模比全局建模具有更好的精度和稳定性,估测精度提高幅度分别为40.63%,28.64%,22.90%。因此,采用局部BP神经网络回归建模法建立土壤有效氮、磷、钾的光谱定量分析模型,可实现对土壤养分状况的快速诊断。该研究的创新点是通过采用局部非线性回归方法提高了土壤光谱营养诊断模型的稳定性和可靠性,为作物生长过程中不同生长时期的土壤养分的动态监测和过程控制提供了技术支持。     

水相合成近红外CdTe量子点用于体液中硫醇的检测

通过降低反应物中L-半胱氨酸(L-Cys)的比例,在水相快速合成了近红外CdTe量子点,使之对巯基化合物产生荧光响应. 并以此构建了一种基于表面配体缺失的CdTe近红外荧光量子点的巯基探针,为生物样品中的硫醇检测提供简便经济、高灵敏度和高选择性的新方法. 在其它多种氨基酸和生物液体中主要离子、分子共存的情况下,我们所制备的近红外量子点对L-Cys、同型半胱氨酸(Hcy)和谷胱甘肽(GSH)的荧光检测中显示了良好的选择性和灵敏度. 在血清和细胞提取液中,加标5.0 μmol·L^-1硫醇的回收率均在90%～109%范围内. 该方法对L-Cys,Hcy和GSH的检出限(3s)分别为43,46和63 nmol·L^-1.     

黄腐酸对菁染料超分子组装及手性调控研究

利用菁染料超分子作为分子探针对黄腐酸进行标记,检测黄腐酸和药效机制,对于生命科学和药物化学领域的发展具有重要意义。采用紫外-可见吸收光谱和圆二色谱研究黄腐酸作为模板对不同结构菁染料超分子的组装及手性调控。结果表明：黄腐酸能诱导三种菁染料J-聚集体解聚为单体并伴有体系表观颜色的变化,并与菁染料单体之间具有很高亲和力。黄腐酸作为模板不仅可以诱导MTC形成具有一定手性的H-聚集体,而且能使MTC的H-聚集体的手性出现两次反转;还可以诱导ETC的J-聚集体发生分子间的重排,最终形成具有左手螺旋性的J-聚集体。除此之外,黄腐酸还对PTC的J-聚集体圆二色谱信号有显著的影响。同时,菁染料中位取代基影响到相互作用的能力：中位取代基越小,菁染料聚集体与黄腐酸的作用越强。菁染料与黄腐酸的结合能力大小为MTC>ETC>PTC。菁染料超分子可作为一类优良的分子探针对黄腐酸进行特异性识别并可达到可视化的检测效果。     

活性炭纤维耦合柠檬酸铁在中性pH条件下活化双氧水降解染料

在环境催化领域,开发pH适应范围广的类芬顿催化剂一直是活跃而极具挑战性的研究课题. 采用活性炭纤维耦合柠檬酸铁制得耐pH的类芬顿催化纤维(Cit-Fe@ACFs),在pH值2～10的范围内Cit-Fe@ACFs均表现出优异的催化性能,有效拓宽了传统芬顿反应的pH适应范围;Cit-Fe@ACFs在中性条件下能快速活化H₂O₂催化降解活性染料、酸性染料、碱性染料等多种染料,并具有良好的重复使用性. 采用探针化合物正丁醇、苯醌,结合电子顺磁共振波谱(EPR)证明了Cit-Fe@ACFs/H₂O₂催化体系中的氧化活性种主要为羟基自由基(·OH)和超氧自由基(HO₂·),推测了其催化反应机理.     

基于二维相关近红外谱参数化及BP神经网络的掺杂牛奶鉴别

将二维相关近红外谱参数化方法与BP神经网络结合,建立掺杂牛奶与纯牛奶的判别模型。分别配制含有尿素牛奶(1～20 g·L-1)和三聚氰胺牛奶(0.01～3 g·L-1)样品各40个。研究了纯牛奶、掺杂牛奶的二维相关近红外谱特性,在此基础上,分别提取了各样品二维相关同步谱的5个特征参数。将这5个特征参数作为BP神经网络的输入,分别建立掺杂尿素、掺杂三聚氰胺、两种掺杂牛奶与纯牛奶的判别模型,采用这些模型对未知样品进行预测,其预测正确率分别为95%,100%和96.7%。研究结果表明：该方法有效地提取了牛奶中掺杂目标物的特征光谱信息,同时又减少了BP神经网络输入变量的维数,实现了掺杂牛奶与纯牛奶的鉴别。