Qsar Models for Predicting the Acute Toxicity of Selected Organic Chemicals with Diverse Structures to Aquatic Non-Vertebrates and Humans

Abstract

The linear and non-linear relationships of acute toxicity (as determined on five aquatic non-vertebrates and humans) to molecular structure have been investigated on 38 structurally-diverse chemicals. The compounds selected are the organic chemicals from the 50 priority chemicals prescribed by the Multicentre Evaluation of In Vitro Cytotoxicity (MEIC) programme. The models used for the evaluations are the best combination of physico-chemical properties that could be obtained so far for each organism, using the partial least squares projection to latent structures (PLS) regression method and backpropagated neural networks (BPN). Non-linear models, whether derived from PLS regression or backpropagated neural networks, appear to be better than linear models for describing the relationship between acute toxicity and molecular structure. BPN models, in turn, outperform non-linear models obtained from PLS regression. The predictive power of BPN models for the crustacean test species are better than the model for humans (based on human lethal concentration). The physico-chemical properties found to be important to predict both human acute toxicity and the toxicity to aquatic non-vertebrates are the n?octanol water partition coefficient (Pow) and heat of formation (HF). Aside from the two former properties, the contribution of parameters that reflect size and electronic properties of the molecule to the model is also high, but the type of physico-chemical properties differs from one model to another. In all of the best BPN models, some of the principal component analysis (PCA) scores of the ¹³C-NMR spectrum, with electron withdrawing/accepting capacity (LUMO, HOMO and IP) are molecular size/volume (VDW or MS1) parameters are relevant. The chemical deviating from the QSAR models include non-pesticides as well as some of the pesticides tested. The latter type of chemical fits in a number of the QSAR models. Outliers for one species may be different from those of other test organisms.     

基于学科素养论证分析2020年高考全国卷Ⅰ物理压轴题

2020年高考物理试题依托高考评价体系,结合物理学科特点,考试内容以学科素养考查为导向,即以物理观念、科学思维、科学探究、科学态度与责任的物理学科素养为导向,注重对核心物理概念和规律的考查,引导学生夯实学习发展的基础,促进中学重视培养学生的基础知识、基本技能以及提升学生的基本素养.基于物理学科素养,论证分析2020年高考全国理综卷Ⅰ物理压轴计算题,助力培养学生科学思维.     

圆形阵列光电探测系统双目标识别方法

针对双弹丸同时着靶情况下的立靶坐标测量问题,提出一种圆形阵列光电探测系统的双目标识别方法。采用光电探测器件组成1个圆形的探测阵列,并将3个发光角度均为60°的扇形一字线激光器均匀设置于圆形探测阵列上组成探测光幕。当2发弹丸同时穿过探测光幕时,会在圆形探测阵列上产生6个弹丸投影,通过信号处理电路识别6个弹丸投影的中心位置,最后通过系统弹丸着靶坐标测量公式计算得到2发弹丸的着靶坐标。在对系统测量原理进行论述的基础上,建立了系统的弹丸着靶坐标测量模型,并对坐标测量误差进行了分析和仿真。仿真结果显示,系统在测量靶面为1 m×1 m时的X坐标测量误差标准差最大为2.7 mm,Y坐标测量误差标准差最大为0.6 mm。实验结果表明,系统在测量靶面为1 m×1 m时的X坐标测量误差标准差为2.22 mm,Y坐标测量误差标准差为1.98 mm。因此,该文所提出的系统可以有效测量弹径4.5 mm及其以上的双弹丸着靶坐标。     

显式模拟类橡胶材料Mullins效应滞回圈

通过显式、直接的方法提出一个多轴可压缩应变能函数,用来模拟类橡胶材料在加载——卸载作用下,由于Mullins效应而产生的应力——应变滞回圈. 本文的创新点在于将表征能量耗散的变量引入到应变能函数.新的弹性势具有以下两个特点:第一,在加载情况下,新引入的变量不会对弹性势产生任何影响,因此,只要给出合适的形函数显式表达,3个基准实验,包括单轴拉伸和压缩,等双轴拉伸和压缩,以及平面应变,都可精确模拟;第二,新引入的变量在卸载情况下将被激活.在不同的卸载应力下,变量将发生改变,从而影响弹性势,使其最终产生不同的应力——应变关系卸载曲线,与对应的加载曲线共同构成应力——应变滞回圈.通过对Mullins效应实验数据进行分析和研究,得出了卸载形函数在不同卸载应力下变化的规律,并预测不同卸载应力下的应力——应变关系.最后,我们将得到精确匹配实验数据的数值模拟结果,从而证明本文方法不仅可以精确匹配至少3个基准实验,还可以模拟和预测类橡胶材料在加载——卸载作用下由于Mullins效应而产生的滞回圈.      

Simultaneous determination of boscalid and fludioxonil in grape and soil under field conditions by gas chromatography/tandem triple quadrupole mass spectrometry

A gas chromatography–tandem mass spectrometry method was developed and validated to simultaneously determine boscalid and fludioxonil in grape and soil samples. These samples were extracted with 10 mL of acetonitrile and purified using a mixed primary secondary amine/octadecylsilane sorbent. The method showed good linearity (R² > 0.99) in the calibration range 0.005–2 μg/mL for both pesticides. The limits of detection and quantification for the two analytes in grape and soil were 0.006 and 0.02 mg/kg, respectively. Fungicide recoveries in grape and soil were 81.18–92.11% for boscalid and 82.73–97.67% for fludioxonil with relative standard deviations of 1.31–10.31%. The established method was successfully applied to the residual analysis of boscalid and fludioxonil in real grape and soil samples. The terminal residue concentrations of boscalid and fludioxonil in grape samples collected from Anhui and Guizhou were <5 mg/kg (the maximum residue limit set by China) 7 days after the last application and 1 mg/kg (the maximum residue limit set by USA) 14 days after the last application. These results could provide guidance for the proper and safe use of boscalid and fludioxonil in grape and help the Chinese government to establish an MRL for fludioxonil in grape.     

每课一题教学环节的研究与实践

利用“每课一题”这个教学环节从已有知识中提取基本原理，并应用于新知识的学习；提取学生的问题编制习题，让学生暴露产生问题的根源并从根本上解决。探讨了每课一题的必要性及其基本类型。     

Weber Correspondence Analysis: The One-Dimensional Case

When designing programs or software for the implementation of Monte Carlo (MC) hypothesis tests, we can save computation time by using sequential stopping boundaries. Such boundaries imply stopping resampling after relatively few replications if the early replications indicate a very large or a very small p value. We study a truncated sequential probability ratio test (SPRT) boundary and provide a tractable algorithm to implement it. We review two properties desired of any MC p value, the validity of the p value and a small resampling risk, where resampling risk is the probability that the accept/reject decision will be different than the decision from complete enumeration. We show how the algorithm can be used to calculate a valid p value and confidence intervals for any truncated SPRT boundary. We show that a class of SPRT boundaries is minimax with respect to resampling risk and recommend a truncated version of boundaries in that class by comparing their resampling risk (RR) to the RR of fixed boundaries with the same maximum resample size. We study the lack of validity of some simple estimators of p values and offer a new, simple valid p value for the recommended truncated SPRT boundary. We explore the use of these methods in a practical example and provide the MChtest R package to perform the methods.     

Amperometric biosensor based on reductive H2O2 detection using pentacyanoferrate-bound polymer for creatinine determination

Pentacyanoferrate-bound poly(1-vinylimidazole) (PVI[Fe(CN)₅]) was selected as a mediator for amperometric creatinine determination based on the reductive H₂O₂ detection. Creatinine amidohydrolase (CNH), creatine amidohydrolase (CRH), sarcosine oxidase (SOD), peroxidase (POD), and PVI[Fe(CN)₅] were crosslinked with poly(ethylene glycol) diglycidyl ether (PEGDGE) on a glassy carbon (GC) electrode for a creatinine biosensor fabrication. Reduction current was monitored at −0.1 V in the presence of creatinine and O₂. It is revealed that PVI[Fe(CN)₅] is suitable as a mediator for a bioelectrocatalytic reaction of POD, since PVI[Fe(CN)₅] neither reacts with reactants nor works as an electron acceptor of SOD. The amounts of PVI[Fe(CN)₅], PEGDGE, and enzymes were optimized toward creatinine detection. Nafion as a protecting film successfully prevented the enzyme layer from interferences. The detection limit and linear range in creatinine determination were 12 μM and 12–500 μM (R² = 0.993), respectively, and the sensitivity was 11 mA cm⁻² M⁻¹, which is applicable for urine creatinine tests. The results of the creatinine determination for four urine samples measured with this proposed method were compared with Jaffe method, and a good correlation was obtained between the results.     

A novel turn-on fluorescent probe for Hg2+ detection based on rhodamine B spirolactam derivative

ABSTRACT

In this work, a new turn-on fluorescent probe 1 for Hg²⁺ ions detection based on rhodamine B spirolactam was reported. Among tested metal ions, probe 1 shows high selectivity towards Hg²⁺ in the the mixture solution of methanol and 0.02 M HEPES buffer (V/V = 9:1, pH = 7.2). No absorption and emission band of probe 1 was observed in the range from 450 to 700 nm. While only addition of Hg²⁺ to probe 1 could lead to appearance of a new absorption band centered at 553 nm and a fluorescence emission band around 577 nm upon excitation at 520 nm. Moreover, it exhibits excellent linear relationship (R² = 0.9993) between fluorescence intensity at 577 nm and the concentration of Hg²⁺ from 1.6 to 32 μM. The sensing mechanism was proven to be spirolactam ring open induced by Hg²⁺ through ¹H NMR, MS, absorption and fluorescence spectra. In addition, probe 1 could detect Hg²⁺ in real water samples and on filter paper, which demonstrates its application in environment science.