The SN3–SN2 spectrum. Rate constants and product selectivities for solvolyses of benzenesulfonyl chlorides in aqueous alcohols

Rate constants for a wide range of binary aqueous mixtures and product selectivities (S) in ethanol–water (EW) and methanol–water (MW) mixtures, are reported at 25 °C for solvolyses of benzenesulfonyl chloride and the 4‐chloro‐derivative. S is defined as follows using molar concentrations: S = ([ester product]/[acid product]) × ([water solvent]/[alcohol solvent]). Additional selectivity data are reported for solvolyses of 4‐Z‐substituted sulfonyl chlorides (Z = OMe, Me, H, Cl and NO₂) in 2,2,2‐trifluoroethanol–water. To explain these results and previously published data on kinetic solvent isotope effects (KSIEs) and on other solvolyses of 4‐nitro and 4‐methoxybenzenesulfonyl chloride, a mechanistic spectrum involving a change from third order to second order is proposed. The molecularity of these reactions is discussed, along with new term ‘S_N3–S_N2 spectrum’ and its connection with the better established term ‘S_N2–S_N1 spectrum’. Copyright © 2009 John Wiley & Sons, Ltd.     

一种改进型多组分气体的Tikhonov正则化特征光谱提取方法

针对FTIR光谱分析数据计算量大,具有相同基团的多组分混合气体交叉灵敏度过高,以及在线分析过程中基线漂移等问题,提出了一种改进的TR2-1(Tikhonov 2norm-1norm)正则化特征变量提取法。该方法借鉴TR1和TR2模型的基本思想,引入谱线距离和谱线系数绝对值最小化两个约束项来保证所提取特征量的准确度,消除基线漂移所带来的影响,并结合上述两种模型建立了不适定问题的最优化求解通式。该通式有效地克服了经验法和实验法确定正则矩阵和参数所带来的误差。实验以浓度为0.01%~20%的甲烷、乙烷、丙烷、正丁烷、异丁烷、正戊烷和异戊烷气体为例进行了特征光谱选取。结果表明,对于浓度为0.2%的甲烷气体,其预测误差平方和仅为2.6×10-4,可决系数达到0.959 2,分析准确度高,有效增强了TR正则法的实用性。     

大鼠粪样中几种糖类物质的结构确定

粪样代谢组能够反映宿主和肠道菌群相互作用的共代谢信息,然而粪样中糖类物质的归属信息迄今仍不完善. 该研究使用1D NMR技术检测到大鼠粪样中木糖、阿拉伯糖、半乳糖等单糖以及由阿拉伯糖和木糖组成的寡聚糖. 在使用固相萃取（SPE）方法进行分离富集的基础上,结合使用2D NMR实验技术（¹H-¹H COSY,¹H-¹H TOCSY,¹H-¹³C HSQC,¹H-¹³C HMBC以及DOSY）确定了这些糖类物质的结构,并对其1H NMR和¹³C NMR谱峰进行了归属.     

纳米尺度流动速度计算的新方法

采用流体力学中流量与流速的计算和分子动力学相结合的方法,模拟液态氩在纳米通道内的三维Poiseuille流动和驱动方腔流动,计算流体流速.结果表明:平板形纳米通道内,该方法求得的流速与传统分子动力学方法所求流速基本吻合,可以用该方法计算不同壁面情况下的流速;对于纳米方腔通道内的流体,在不同模型下两种方法计算出的流速分布大致相同,但是其边界速度差别很大,在边界的速度计算方面新方法的精确度更高,收敛速度比传统方法快.     

改进三帧差分算法在移动物体检测中的应用

移动物体监控系统利用检测算法识别监控区域的移动物体,并进行实时异常信息存储,检测算法中的传统三帧差分法中的阈值是固定的,因此重叠部分无法准确检测出来,存在空洞现象,可能发生误判。针对这些问题,对已有的三帧差分法进行改进,结合图像边缘提取和自适应的迭代阈值计算方法来提高移动物体检测的准确性,并对异常信息进行选择性存储,由实验结果可知,应用平台采用改进后的移动物体检测算法,较好的提高了移动物体检测的灵敏度,增强了检测系统的实时性和准确性,若仅存储异常信息,可节省视频存储空间,并在定位异常动态信息时节省查找时间。     

中药提取过程在线紫外动态趋势回归分析及终点判定

随着中药生产行业的转变,中药生产过程现代化成为了必然趋势。而目前由于缺乏有效的在线检测手段,中药生产检测滞后性大,产品质量参差不齐。针对中药提取过程在线监控及终点判定的问题,基于朗伯比尔定律及中药提取动力学方程建立提取液紫外吸光度随时间变化模型,并提出动态分析及终点判断方法, 该方法包括紫外吸光度序列拟合、稳健性分析以及终点计算。以千年健提取过程为例,使用本实验室自主研发的中药提取液在线采样系统进行光谱收集,并对离线样本求取其有效固体物质含量作为参考。分析过程中,首先对实时检测的光谱进行插值及滤波处理,计算230.2～400 nm紫外谱区的吸光度均值并结合前期数据组成吸光度均值序列;随后,进行了该吸光度序列与提取液固体含量之间的相关分析,得到线性相关系数r2=0.9828,证明二者存在较强的线性关系;最终对吸光度均值序列进行动态模型稳健回归及提取终点判定。结果表明：回归过程通过稳健性分析能够充分识别出测量异常点,提高了拟合曲线与原始吸光度的复相关系数,使其达到0.99,并通过终点判定将千年健提取时间由最初人工设定的180 min缩短至122 min。实验证明,紫外在线监控方法实现了提取过程的在线监控及终点判定,对稳定产品质量、提高经济效益具有重要意义。     

燃煤锅炉粉煤灰中痕量元素赋存形态研究

本文运用改进的Tessier法对某燃煤电厂静电除尘器收集的三个电场的粉煤灰进行分级提取(SEE)实验研究.SEE实验将粉煤灰中的重金属分为五个存在形态进行分级提取:水溶态(pH=7),酸溶态(pH=5),氧化物结合态,难还原态及残渣态.试验结果表明,残渣态在ESP除尘器所收集的飞灰中含量占据绝大部分;在容易迁移的离子可交换态和酸溶态中,所研究的痕量重金属元素均呈现出FA1相似文献   

Phase transition at 204–250 K in the crystals of β-alanine: kinetically irreproduceable,or an artefact?

The crystals and the powder samples of β-alanine were studied in the wide temperature range by adiabatic calorimetry, differential scanning calorimetry, IR- and Raman spectroscopy and X-ray diffraction. No phase transitions could be observed. A small anomaly observed at about 256 K in the Cp(T) dependences measured for the samples re-crystallized from water was shown to be due to the presence of a small (about 0.14% of the total sample mass) amount of solvent inclusions. This anomaly was not observed in the solvent-free samples, either powders or single crystals.     

Substitution and Solvent Effect of Some Substituted Hydroxy Schiff Bases

Abstract

The uv-vis spectra of eight ortho-hydroxy- andpara-hydroxy schiff bases were recorded in different solvents. Inductive and resonance effect of the substituents affect the electronic spectra of those molecules, while, intra-molecular hydrogen bond formation or breakage have little effect on the uv-visible spectra.     

A new method to accelerate depth extraction for aperture-coded camera

Depth extraction, or the retrieval of three-dimensional information of the captured scene from camera, is an important problem in computer vision and image processing. The aperture-coded camera has certain advantages in depth extraction. However, such calculation will cost huge time as it contains weighted iterative deconvolution. In order to solve the problem, this paper proposes an improved algorithm in which the image is firstly segmented and then the small image regions are sampled for deconvolution and depth judgment. Experimental results prove that the proposed method can greatly reduce time consumption and save computer memory. On this basis, by using the characteristics of aperture-coded camera obtaining image and depth, we propose a framework to handle the application of stitching the images of occluded scene, and then carry out experiments.