超声辅助提取–固相萃取净化–高效液相色谱法测定灰渣和污泥中11种双酚类及烷基酚类化合物

建立同时测定灰渣和污泥中11种双酚类及烷基酚类化合物(双酚F、双酚A、4-叔丁基苯酚、4-丁基苯酚、4-戊基苯酚、4-己基苯酚、4-叔辛基苯酚、4-庚基苯酚、壬基酚、4-辛基苯酚和4-壬基苯酚)的超声辅助提取–固相萃取净化–高效液相色谱法.以二氯甲烷–丙酮(体积比为1:1)为提取溶剂,提取时间为20 min,提取温度为...     

基于声源方位信息和非线性时频掩蔽的语音盲提取算法

针对欠定卷积混合的语音信号模型,提出一种基于声源方位信息和非线性时频掩蔽的语音盲提取算法。首先对低频段混合语音信号进行时频分析估计瞬时相对时延(ITD)并采用势函数聚类分析方法估计出声源个数及其ITD,接着锁定目标提取准确的目标语音方位信息,最后利用独立语音在时频域上的近似W一分离正交性,采用非线性时频掩蔽的方法提取目标语音。仿真实验表明,该方法能锁定任意感兴趣目标方位,能有效提取目标语音,文中实验条件下信噪比增益平均达9.5 dB。     

Peptide-based inhibitors of protein–protein interactions: biophysical,structural and cellular consequences of introducing a constraint

Protein–protein interactions (PPIs) are implicated in the majority of cellular processes by enabling and regulating the function of individual proteins. Thus, PPIs represent high-value, but challenging targets for therapeutic intervention. The development of constrained peptides represents an emerging strategy to generate peptide-based PPI inhibitors, typically mediated by α-helices. The approach can confer significant benefits including enhanced affinity, stability and cellular penetration and is ingrained in the premise that pre-organization simultaneously pays the entropic cost of binding, prevents a peptide from adopting a protease compliant β-strand conformation and shields the hydrophilic amides from the hydrophobic membrane. This conceptual blueprint for the empirical design of peptide-based PPI inhibitors is an exciting and potentially lucrative way to effect successful PPI inhibitor drug-discovery. However, a plethora of more subtle effects may arise from the introduction of a constraint that include changes to binding dynamics, the mode of recognition and molecular properties. In this review, we summarise the influence of inserting constraints on biophysical, conformational, structural and cellular behaviour across a range of constraining chemistries and targets, to highlight the tremendous success that has been achieved with constrained peptides alongside emerging design opportunities and challenges.

This review summarizes the influence of inserting constraints on biophysical, conformational, structural and cellular behaviour for peptides targeting α-helix mediated protein–protein interactions.     

A comparison of early hydration properties of cement–steel slag binder and cement–limestone powder binder

The early hydration properties of cement–steel slag composite binder and cement–limestone powder composite binder were compared in this study by determining the hydration heat of binder within 3 days, the pore structure of paste and the compressive strength of mortar at the age of 3 days. Results show that at the curing temperature of 25 °C, the early hydration heat of the binder containing steel slag is smaller, and the early pore structure of the paste containing steel slag is coarser, but the early compressive strength of the mortar containing steel slag is higher compared with the mix containing limestone powder. Though the early reaction degree of steel slag is low, its chemical contribution to the strength of mortar cannot be neglected. At the curing temperature of 50 °C, the early hydration heat of the binder containing steel slag is larger, and the early pore structure of the paste containing steel slag is finer, and the early compressive strength of the mortar containing steel slag is even higher compared with the mix containing limestone powder. Raising curing temperature can enhance the role played by steel slag more significantly than that played by limestone powder in the hydration and hardening of the composite binder.     

Delayed Doublet Emission in a Cerium(III) Complex

Doublet emission from open-shell molecules has demonstrated its research and application value in recent years. However, understandings of the photoluminescence mechanism of open-shell molecules are far less than that of closed-shell molecules, leading to challenges in molecular design of efficient doublet emission systems. Here we report a cerium(III) 4-(9H-carbozol-9-yl)phenyl-tris(pyrazolyl)borate complex Ce(CzPhTp)₃ with a new luminescence mechanism of delayed doublet emission, which also represents the first example with metal-centered delayed photoluminescence. The energy gap between the doublet and triplet excited states of Ce(CzPhTp)₃ is reduced by the management of the inner and outer coordination spheres, thereby promoting efficient energy transfer between the two excited states and activating the delayed emission. The photoluminescence mechanism discovered may provide a new way for the design of efficient doublet emission and bring insights into rational molecular design and energy level regulation in open-shell molecules.     

An azine-linked 2D porphyrinic covalent organic framework for red light photocatalytic oxidative coupling of amines

The construction of two-dimensional covalent organic frameworks (2D COFs) with robust stability for photocatalysis has gained intensive attention recently. Herein, we report the design and synthesis of a highly crystalline azine-linked porphyrinic 2D COF (Por-HZ-COF). Our results clearly show that Por-HZ-COF adopts an eclipsed AA stacking structure with a high Brunauer-Emmett-Teller (BET) specific surface area of 1586 m²/g. In addition, Por-HZ-COF is chemically stable under various conditions, even in 12 M sodium hydroxide aqueous solution or 9 M hydrochloric acid. Moreover, Por-HZ-COF can be used for the photocatalytic aerobic oxidative coupling of benzylamines under red light irradiation with high activity and good reusability. This study demonstrates a novel robust 2D COF with azine linkage that has promising applications in photocatalysis.     

Design,synthesis and biological evaluation of isoxazole-containing biphenyl derivatives as small-molecule inhibitors targeting the programmed cell death-1/ programmed cell death-ligand 1 immune checkpoint

Molecular Diversity - Monoclonal antibodies targeting the programmed cell death-1/ programmed cell death-ligand 1 (PD-1/PD-L1) immune checkpoint have achieved enormous success in cancer...     

A Theoretical Investigation Into the 1,3‐Dipolar Cycloaddition of Azidotrimethylsilane Onto Nanographene

The mechanism of the 1,3‐dipolar cycloaddition reaction of azidotrimethylsilane (ATS) onto nanographene (NG) is thoroughly investigated at the B3LYP/6‐31G(d,p) level. Calculations reveal that the reaction occurs through a two‐step reaction mechanism. The first step is the chemical adsorption and the second one is the decomposition of the thereby formed nitride upon thermal activation, giving rise to an N‐bridged product ultimately. The latter is the rate‐determining step. Two possible pathways are compared to show that the [3+2] channel is favored over the [3+4] channel. The former is a symmetric synchronous process, whereas the latter follows an asymmetric concerted way, which can be rationalized by means of the frontier molecular orbital (FMO) theory. The reactivity of NG is discussed in detail, revealing that it is the electron density at the functionalization site which dominates the reactivity rather than the energetic effect. As a result, the edge area is calculated to be much more reactive than the centre.     

Suppression of Bragg reflection glitches of a single‐crystal diamond anvil cell by a polycapillary half‐lens in high‐pressure XAFS spectroscopy

In combination with a single‐crystal diamond anvil cell (DAC), a polycapillary half‐lens (PHL) re‐focusing optics has been used to perform high‐pressure extended X‐ray absorption fine‐structure measurements. It is found that a large divergent X‐ray beam induced by the PHL leads the Bragg glitches from single‐crystal diamond to be broadened significantly and the intensity of the glitches to be reduced strongly so that most of the DAC glitches are efficiently suppressed. The remaining glitches can be easily removed by rotating the DAC by a few degrees with respect to the X‐ray beam. Accurate X‐ray absorption fine‐structure (XAFS) spectra of polycrystalline Ge powder with a glitch‐free energy range from ?200 to 800 eV relative to the Ge absorption edge are obtained using this method at high pressures up to 23.7 GPa, demonstrating the capability of PHL optics in eliminating the DAC glitches for high‐pressure XAFS experiments. This approach brings new possibilities to perform XAFS measurements using a DAC up to ultrahigh pressures.     

向列相液晶中光致非线性效应的研究

分析了向列相液晶中的光致非线性效应.在此基础上,基于液晶显示器工作原理设计了光控光器件.提出简化模型并利用琼斯矩阵给出光在该模型中的传输理论;引入斜入射的控制光束代替外加电压来调控液晶盒中分子的排列,实现对出射信号光的位相和光强的光-光调控;利用5CB液晶的温度特性分析环境温度对光-光调控的影响.理论分析表明:出射光位...