2,2-双(4-氯-2-氟苄基)丙二酸二乙酯的晶体结构和密度泛函理论研究

标题化合物是一个重要的精细化工中间体,可用于制备嘧啶类、吡唑类等产品.本文利用红外光谱(IR)、质谱(MS)、核磁共振氢谱(1 H NMR)、核磁共振碳谱(13 C NMR)和X-射线单晶衍射对此化合物进行了表征,并在B3LYP/6-311G(d,p)模式下使用密度泛函理论(DFT)计算了此化合物的最稳定晶体结构以及最...     

Azides in the Synthesis of Various Heterocycles

In this review, we focus on some interesting and recent examples of various applications of organic azides such as their intermolecular or intramolecular, under thermal, catalyzed, or noncatalyzed reaction conditions. The aforementioned reactions in the aim to prepare basic five-, six-, organometallic heterocyclic-membered systems and/or their fused analogs. This review article also provides a report on the developed methods describing the synthesis of various heterocycles from organic azides, especially those reported in recent papers (till 2020). At the outset, this review groups the synthetic methods of organic azides into different categories. Secondly, the review deals with the functionality of the azido group in chemical reactions. This is followed by a major section on the following: (1) the synthetic tools of various heterocycles from the corresponding organic azides by one-pot domino reaction; (2) the utility of the chosen catalysts in the chemoselectivity favoring C−H and C-N bonds; (3) one-pot procedures (i.e., Ugi four-component reaction); (4) nucleophilic addition, such as Aza-Michael addition; (5) cycloaddition reactions, such as [3+2] cycloaddition; (6) mixed addition/cyclization/oxygen; and (7) insertion reaction of C-H amination. The review also includes the synthetic procedures of fused heterocycles, such as quinazoline derivatives and organometal heterocycles (i.e., phosphorus-, boron- and aluminum-containing heterocycles). Due to many references that have dealt with the reactions of azides in heterocyclic synthesis (currently more than 32,000), we selected according to generality and timeliness. This is considered a recent review that focuses on selected interesting examples of various heterocycles from the mechanistic aspects of organic azides.     

Surface Modification Strategy for Enhanced NO2 Capture in Metal–Organic Frameworks

The interaction strength of nitrogen dioxide (NO₂) with a set of 43 functionalized benzene molecules was investigated by performing density functional theory (DFT) calculations. The functional groups under study were strategically selected as potential modifications of the organic linker of existing metal–organic frameworks (MOFs) in order to enhance their uptake of NO₂ molecules. Among the functional groups considered, the highest interaction energy with NO₂ (5.4 kcal/mol) was found for phenyl hydrogen sulfate (-OSO₃H) at the RI-DSD-BLYP/def2-TZVPP level of theory—an interaction almost three times larger than the corresponding binding energy for non-functionalized benzene (2.0 kcal/mol). The groups with the strongest NO₂ interactions (-OSO₃H, -PO₃H₂, -OPO₃H₂) were selected for functionalizing the linker of IRMOF-8 and investigating the trend in their NO₂ uptake capacities with grand canonical Monte Carlo (GCMC) simulations at ambient temperature for a wide pressure range. The predicted isotherms show a profound enhancement of the NO₂ uptake with the introduction of the strongly-binding functional groups in the framework, rendering them promising modification candidates for improving the NO₂ uptake performance not only in MOFs but also in various other porous materials.     

缓冲层ZnPc对有机电致发光器件特性的影响

本文研究了酞菁锌(ZnPc)薄膜的表面形貌及ZnPc薄膜作为缓冲层对有机电致发光器件(OLEDs)光电特性的影响.对比两组样品的AFM图像,ZnPc薄膜相比于ITO薄膜,其表面的岛面积较大,薄膜表面更连续平整,基本上覆盖了ITO膜表面针孔,减少了表面的缺陷.另外,ZnPc薄膜的岛分布均匀有序.使用ZnPc作为缓冲层的器件性能明显好于未使用ZnPc修饰的器件,在7.42V的驱动电压下的最大发光亮度达到1.428kcd/m2,在4.3V电压驱动下时,最大光功率效率为1.411m/W;而未使用缓冲层的器件在8V的驱动电压下达到最大发光亮度达到1.212kcd/m2,在5.5V电压驱动下时,最大光功率效率为0.931m/W.     

Fumigant Activity of Bacterial Volatile Organic Compounds against the Nematodes Caenorhabditis elegans and Meloidogyne incognita

Plant-parasitic nematodes infect a diversity of crops, resulting in severe economic losses in agriculture. Microbial volatile organic compounds (VOCs) are potential agents to control plant-parasitic nematodes and other pests. In this study, VOCs emitted by a dozen bacterial strains were analyzed using solid-phase microextraction followed by gas chromatography–mass spectrometry. Fumigant toxicity of selected VOCs, including dimethyl disulfide (DMDS), 2-butanone, 2-pentanone, 2-nonanone, 2-undecanone, anisole, 2,5-dimethylfuran, glyoxylic acid, and S-methyl thioacetate (MTA) was then tested against Caenorhabditis elegans. DMDS and MTA exhibited much stronger fumigant toxicity than the others. Probit analysis suggested that the values of LC₅₀ were 8.57 and 1.43 μg/cm³ air for DMDS and MTA, respectively. MTA also showed stronger fumigant toxicity than DMDS against the root-knot nematode Meloidogyne incognita, suggesting the application potential of MTA.     

Tailoring Pore Structure and Morphologies in Covalent Organic Frameworks for Xe/Kr Capture and Separation

As a rising star among porous solid materials, covalent organic frameworks(COFs) with excellent properties including but not limit to facilely controllable structure, high porosity, and multi-chemical functionality represent significant potential for efficient ¹²⁷Xe/⁸⁵Kr capture and separation. In this study, through tuning the length of the organic ligands, two-dimensional(2D) COF mate-rials with identical connection group but different pore properties, denoted as ATFG-COF and TpPa-COF with AA-stacking model and TpBD-COF with AB-stacking model were synthesized and tested for Kr and Xe adsorption for the first time. Adsorption measurements indicate that the narrower pore apertures and higher porosity are conducive for COF materials to capture Xe and Kr. Furthermore, the Henry's constant, isosteric heat of adsorption(Q_st), and ideal adsorbed solution theory(IAST) selectivity of ATFG-COF, the pore size of which is closest to the kinetic diameter of the Xe atom(0.41 nm) among 2D COF materials, were carried out based on the single component sorption isotherms. The results illustrate that the high isosteric heat values of Xe/Kr adsorption on ATFG-COF are 25 and 16 kJ/mol at room temperature, respectively. Henry's law predicts that the selectivity factor of Xe to Kr is 6.07, consistent with the adsorption selectivity(ca. 6) calculated based on the IAST.     

人体静电放电对有机发光二极管的影响

研究了静电放电（ESD）人体模式（HBM）下的脉冲应力对有机发光二极管（OLED）的性能及寿命的影响,并讨论了相应的物理机制。对比分析了4组OLED在施加ESD放电为0,200,800,1 600 V前后的电学和光学特性,并进行了相应的寿命测试分析。研究发现,OLED器件的光谱对ESD不敏感,随着冲击电压的增大,由于静电打击对载流子的短期抑制效应,OLED的亮度出现轻微下降。在静电冲击电压为200 V和800 V时,伏安特性没有发生变化;当静电冲击电压增至1 600 V时,反向漏电有明显增加。后续的加速寿命实验表明,静电打击对器件的工作寿命没有明显的规律性影响,但是会一定程度提高非本质老化失效的概率。     

Discriminant Analysis of the Nutritional Components between Organic Eggs and Conventional Eggs: A 1H NMR-Based Metabolomics Study

The difference of nutrient composition between organic eggs and conventional eggs has always been a concern of people. In this study, ¹H nuclear magnetic resonance (NMR) technique combined with multivariate statistical analyses was conducted to identify the metabolite different in egg yolk and egg white in order to reveal the nutritional components information between organic and conventional eggs. The results showed that the nutrient content and composition characteristics were different between organic and conventional eggs, among which the content of glucose, putrescine, amino acids and their derivatives were found higher in the organic eggs yolk, while phospholipids were demonstrated higher in conventional eggs yolk. Organic acid, alcohol, amine, choline and amino acids were higher in conventional eggs white, but glucose and lactate in organic egg were higher. Our study demonstrated that there are more nutritive components and higher nutritional value in organic eggs than conventional eggs, especially for the growth and development of infants and young children, and conventional eggs have more advantages in promoting lipid metabolism, preventing fatty liver, and reducing serum cholesterol. Eggs have important nutritional value to human body, and these two kinds of eggs can be selected according to the actual nutrient needs.     

Preparation and Photocatalytic Performance of TiO2 Nanowire-Based Self-Supported Hybrid Membranes

Nowadays, the use of hybrid structures and multi-component materials is gaining ground in the fields of environmental protection, water treatment and removal of organic pollutants. This study describes promising, cheap and photoactive self-supported hybrid membranes as a possible solution for wastewater treatment applications. In the course of this research work, the photocatalytic performance of titania nanowire (TiO₂ NW)-based hybrid membranes in the adsorption and degradation of methylene blue (MB) under UV irradiation was investigated. Characterization techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), X-ray powder diffractometry (XRD) were used to study the morphology and surface of the as-prepared hybrid membranes. We tested the photocatalytic efficiency of the as-prepared membranes in decomposing methylene blue (MB) under UV light irradiation. The hybrid membranes achieved the removal of MB with a degradation efficiency of 90% in 60 min. The high efficiency can be attributed to the presence of binary components in the membrane that enhanced both the adsorption capability and the photocatalytic ability of the membranes. The results obtained suggest that multicomponent hybrid membranes could be promising candidates for future photocatalysis-based water treatment technologies that also take into account the principles of circular economy.     

Effects of Organic Acids on the Release of Fruity Esters in Water: An Insight at the Molecular Level

It is well known that organic acids (OAs) could affect the flavour of fruit juices and beverages. However, the molecular mechanism of aroma release is still unclear. In this study, the effects of citric acid (CA), L-(-)-malic acid (MA) and L-lactic acid (LA) on the release of six selected esters and their sensory perception were investigated by means of HS-GC-MS analyses and odour detection threshold determination, respectively. Meanwhile, the density functional theory (DFT) calculation was employed to explore the interaction modes between esters and OAs. HS-GC-MS analyses showed that the concentration and the type of OAs regulated the release of esters. The results were basically consistent with the detection threshold change of those esters. The DFT calculation suggested that the main intermolecular interaction was hydrogen bonds, and several esters could form a ternary ring structure with OAs through hydrogen bonds. The interactions can induce the different release behaviours of esters in OAs water solution. The number of carboxyl functional groups in OAs and the spatial conformation of esters appeared to influence the magnitude of the interaction. The above results demonstrated the mechanism of OAs affecting the release of esters and indicated a possible flavour control way by using different OAs and OA concentrations.