A Combined Experimental and Computational Study of Halogen and Hydrogen Bonding in Molecular Salts of 5-Bromocytosine

Although natural or artificial modified pyrimidine nucleobases represent important molecules with valuable properties as constituents of DNA and RNA, no systematic analyses of the structural aspects of bromo derivatives of cytosine have appeared so far in the literature. In view of the biochemical and pharmaceutical relevance of these compounds, six different crystals containing proton-transfer derivatives of 5-bromocytosine are prepared and analyzed in the solid-state by single crystal X-ray diffraction. All six compounds are organic salts, with proton transfer occurring to the N_imino atom of the pyridine ring. Experimental results are then complemented with Hirshfeld surface analysis to quantitively evaluate the contribution of different intermolecular interactions in the crystal packing. Furthermore, theoretical calculations, based on different arrangements of molecules extracted from the crystal structure determinations, are carried out to analyze the formation mechanism of halogen bonds (XBs) in these compounds and provide insights into the nature and strength of the observed interactions. The results show that the supramolecular architectures of the six molecular salts involve extensive classical intermolecular hydrogen bonds. However, in all but one proton-transfer adducts, weak to moderate XBs are revealed by C–Br^…O short contacts between the bromine atom in the fifth position, which acts as XB donor (electron acceptor). Moreover, the lone pair electrons of the oxygen atom of adjacent pyrimidine nucleobases and/or counterions or water molecules, which acts as XB acceptor (electron donor).     

Friction and Wear of Semi-Crystalline Polytetrafluoroethylene with Spherulitic Micro-Morphology

Polytetrafluoroethylene (PTFE) is an important engineering material with a low coefficient of friction but a high rate of wear. As a semi‐crystalline polymer, its wear resistance is related to its micro‐morphology. Friction and wear properties of semi‐crystalline non‐spherulitic PTFE have been widely studied, but no investigation is reported about tribological properties of spherulitic PTFE due to difficulties in finding such properties. In this paper, friction and wear properties of PTFE with spherulitic micro‐morphology are studied for the first time. The results show that, first, under the same experimental condition, when two kinds of PTFE are rubbed against the steel disc, the number and size of debris of spherulitic PTFE are much less and smaller than that of debris of PTFE without spherulitic crystals. This means that the wear resistance of spherulitic PTFE is better than that of semi‐crystalline PTFE without spherulitic micro‐morphology. Second, the friction property of spherulitic PTFE is also different from that of PTFE without spherulitic crystals. Finally, the friction and wear mechanisms of spherulitic PTFE and non‐spherulitic PTFE are compared.     

Add a Pinch of Tetrel: The Transformation of a Centrosymmetric Metal into a Nonsymmorphic and Chiral Semiconductor

Centrosymmetric skutterudite RhP₃ was converted to a nonsymmorphic and chiral compound RhSi_0.3P_2.7 (space group P2₁2₁2₁) by means of partial replacement of Si for P. The structure, determined by a combination of X-ray crystallography and solid state ³¹P NMR, exhibits branched polyanionic P/Si chains that are unique among metal phosphides. A driving force to stabilize the locally noncentrosymmetric cis-RhSi₂P₄ and fac-RhSi₃P₃ fragments is π-electron back-donation between the Rh t_2g-type orbitals and the unoccupied antibonding Si/P orbitals, which is more effective for Si than for P. In situ studies and total energy calculations revealed the metastable nature of RhSi_0.3P_2.7. Electronic structure calculations predicted centrosymmetric cubic RhP₃ to be metallic which was confirmed by transport properties measurements. In contrast, the electronic structure for chiral orthorhombic RhSi_0.3P_2.7 contained a bandgap, and this compound was shown to be a narrow gap semiconductor.     

Metal-Organic Framework (MOF) Morphology Control by Design

Exerting morphological control over metal-organic frameworks (MOFs) is critical for determining their catalytic performance and to optimize their packing behavior in areas from separations to fuel gas storage. A mechanism-based approach to tailor the morphology of MOFs is introduced and experimentally demonstrated for five cubic Zn₄O-based MOFs. This methodology provides three key features: 1) computational screening for selection of appropriate additives to change crystal morphology based on knowledge of the crystal structure alone; 2) use of additive to metal cluster geometric relationships to achieve morphologies expressing desired crystallographic facets; 3) potential for suppression of interpenetration for certain phases.     

"元素化学实验"中的热致变色现象(一)——部分Co(Ⅱ)化合物的热致变色现象及其变色机理探讨

2021年沃尔夫化学奖颁给了Leslie Leiserowitz和Meir Lahav两位教授,以此来表彰他们在证明三维分子结构与有机晶体结构之间相互影响中的贡献。他们的研究成果,极大地补充了科学界对于有机大分子自组装的相关机理的理解,为有机晶体化学领域的发展做出了杰出的贡献。本文以此为契机简要介绍了两位2021年沃尔夫化学奖获得者及沃尔夫奖的历史与地位。     

"大组讨论、小组实验"化工专业实验的新思路——以甲醇制汽油实验为例

甲醇制汽油工艺参数比较多、实验时固定床反应器中催化剂的装载和反应后的冷却过程时间比较长,在化工综合实验有限的学时内,一组学生不可能将所有的实验参数摸索清楚。针对这种情况,设计了学生“大组集体讨论+小组实验+结果汇总”的实验模式。在保证学生掌握实验基本操作的基础上,得到整个工艺的完整数据,通过对数据的处理和分析,得到一个综合性较强的实验报告。通过实践,该实验模式激发了学生的实验兴趣,提升了实验效率,取得了良好的教学效果。     

基于PDCA循环理论的完全线上教学模式探索与实践*——以化工原理课程为例

为保障新冠疫情期间“停课不停学”的高质量开展,以化工原理课程教学为例,探讨了PDCA循环理论在“3+1+4+3”完全线上教学模式中的应用,实践教学表明2者的融合能有效保证教学顺利有序开展,对于提高学生学习动力效果显著。     

Enhancing Hydrogen Evolution by Optimizing the Hydrogen Adsorption on Titanium Monoxide Nanodot-Decorated Cobalt Sulfide Nanosheets

Modulating the local electronic state of metal compounds through interfacial interaction has become a key method for manufacturing high-performance hydrogen evolution reaction (HER) electrocatalysts. The electron-rich active sites can promote the adsorption of hydrogen, which accelerates the Volmer step and thereby enhances the electrocatalytic performance of HER. Here, we found that the strong interfacial interaction between TiO nanodots (TiO/Co−S) and Co−S nanosheets could advantageously improve the performance toward HER of electrocatalyst. Meanwhile, XPS results showed that modulating the local electronic structure of the TiO nanodots produces electron-rich regions on Co. As a result, the overpotential of the TiO/Co−S nanocomposite at 10 mA cm⁻² was 107 mV, and the Tafel slope was 83.3 mV dec⁻¹. This study focused on the effect of the solid-solid interface on the local electronic structure of the catalytic metal active sites and successfully improved the catalytic activity of transition metal materials in HER catalysis.     

Transport engineering in microbial cell factories producing plant-specialized metabolites

Transport engineering strategies use altered expression of transporter proteins to change metabolite distribution within an organism. The production of plant specialized metabolites in microbial cell factories encounters a set of challenges that could benefit from the implementation of transport engineering technology. The range of challenges includes premature pathway termination due to secretion of intermediates, feedback inhibition due to inefficient export of final products, low yields in bioconversion processes due to inefficient import of precursors, and poor connectivity between subcellular compartments expressing different parts of complex biosynthetic pathways. We highlight the latest examples of transport engineering in microbial cell factories producing plant specialized metabolites, identify the current knowledge gap, and propose future research for advancing the field.