Rational Design of Two-Dimensional Magnetic Chromium Borides Based on First-Principles Calculation

Two-dimensional(2D) magnetic materials have been experimentally recognized recently,however,the Curie temperatures(TC) of known 2D systems are quite low.Generally,magnetic systems can be seen as constituent magnetic elements providing spins and the non-magnetic elements providing frameworks to host the magnetic elements.Short bond lengths between the magnetic and non-magnetic elements would be beneficial for strong magnetic interactions and thus high TC.Based on this,we propose to combine the magnetic element Cr and the non-magnetic element boron to design novel 2D magnetic systems.Using our self-developed software package IM2 ODE,we design a series of chromium-boride based 2D magnetic materials.Nine stable magnetic systems are identified.Among them,we find that CrB4-Ⅰ,CrB4-Ⅱ and CrBs-Ⅰ with common structural units [CrB8] are ferromagnetic metals with estimated TC of 270 K,120 K and 110 K,respectively.On the other hand,five CrB3 phases with structural units [Cr2B12] are antiferromagnetic metals.Additionally,we also find one antiferromagnetic semiconductor CrB2-Ⅰ.Our work may open new directions for identifying 2D magnetic systems with high TC.     

High-efficient surface tailoring via reverse atom transfer radical polymerization and reversible addition-fragmentation chain-transfer polymerization in an aqueous system initiated by a monocenter redox pair

The commonly used multi-center initiation methods always lead to the formation of quantities of homopolymer in the surface tailoring based on reverse atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization. In this study, a monocenter redox pair constructed of silica bearing tert-butyl hydroperoxide groups and ascorbic acid (SiO₂-TBHP/AsAc) was applied to substitute the commonly used initiation method of R-supported RAFT grafting polymerization. All the propagating radicals were restricted on the surface of solid particles during the whole procedure theoretically, resulting in a higher grafting efficiency of 95.1% combined with the “controllable” feature at 10 h. This redox pair was also used to initiate the reverse ATRP in miniemulsion successfully with a grafting efficiency of 86.3% at 10 h. The grafting efficiency obtained under this monocenter initiation method was significantly higher than that of the frequently reported surface modification by reverse ATRP and RAFT polymerization. In addition, the high-efficient surface tailoring was traced and confirmed by nuclear magnetic resonance, Fourier transform infrared, X-ray photoelectron spectroscopy, thermogravimetric analysis, transmission electron microscopy, and other analysis tests. The advantage of this monocenter redox pair will open a new avenue for the potential “high-efficient” surface tailoring of various materials.     

Monitoring the Thiol/Thiophenol Molecule-Modulated Plasmon-Mediated Silver Oxidation with Dark-Field Optical Microscopy

Surface plasmon can trigger or accelerate many photochemical reactions, especially useful in energy and environmental industries. Recently, molecular adsorption has proven effective in modulating plasmon-mediated photochemistry, however the realized chemical reactions are limited and the underlying mechanism is still unclear. Herein, by using in situ dark-field optical microscopy, the plasmon-mediated oxidative etching of silver nanoparticles (Ag NPs), a typical hot-hole-driven reaction, is monitored continuously and quantitatively. The presence of thiol or thiophenol molecules is found essential in the silver oxidation. In addition, the rate of silver oxidation is modulated by the choice of different thiol or thiophenol molecules. Compared with the molecules having electron donating groups, the ones having electron accepting groups accelerate the silver oxidation dramatically. The thiol/thiophenol modulation is attributed to the modulation of the charge separation between the Ag NPs and the adsorbed thiol or thiophenol molecules. This work demonstrates the great potential of molecular adsorption in modulating the plasmon-mediated photochemistry, which will pave a new way for developing highly efficient plasmonic photocatalysts.     

基于2,5-二溴对苯二甲酸配体的锌/钴配合物合成、晶体结构及性质

将有机物2,5-二溴对苯二甲酸(H₂L₁)和2,2′-联吡啶(L₂)作为双配体,使用溶剂热法和七水合硫酸锌(ZnSO₄·7H₂O)、六水合硝酸钴(Co(NO₃)₂·6H₂O)分别反应,得到配合物[Zn(L₁)(L₂)(H₂O)]_n(1)和配合物[Co(L₁)(L₂)(H₂O)]_n(2)。采用单晶X射线衍射、元素分析、红外光谱、紫外光谱、荧光光谱、热重分析等测试方法对这两种物质进行分析研究。单晶测试结果表明配合物1是单斜晶系,以Zn²⁺配位连接L^2-₁与L₂形成一维链状结构,各条链在分子间氢键和π…π共轭作用下有规律地堆叠形成三维网络结构。配合物2是三斜晶系,Co1离子和Co1ⁱ离子由H₂L₁上的羧酸氧原子O4和O4ⁱ连接,形成双齿螯合的配位结构单元,以Co²⁺配位连接 L^2-₁和L₂形成二维网格结构,各层在O—H…O分子间氢键和范德瓦耳斯力作用下有规律的堆叠形成三维网络结构。配合物1和2均含有芳香杂环、羧基杂环和氮杂环,具有良好的荧光性质和热稳定性,最大发射波长分别为345 nm和333 nm。     

磷酸酯类前药的合成方法与应用

磷酸酯类前药与原药相比,不仅能够提高药物靶向性、稳定性和生物利用度,减少药物毒副作用,还能掩蔽药物不适气味、提高水溶性从而改善给药途径。含羟基药物的磷酸酯化是该类药物前药设计的重要方法之一。本文根据中心磷原子的价态和化合物结构进行分类,综述了各种P(Ⅴ)四配位分子、P(Ⅲ)三配位分子和H-亚磷酸酯类化合物作为磷酸酯化试剂在磷酸酯类前药合成方法中的研究进展,并阐述了这些磷酸酯类药物的应用,最后总结了各类磷酸酯化试剂的优势与局限,并结合连续流反应技术应用案例展望了其发展趋势。     

MWCNTs/hydroxypropyl cellulose/polyethylene glycol-based shape-stabilized phase change materials

Journal of Thermal Analysis and Calorimetry - Polyethylene glycol (PEG) is widely used as phase change materials (PCMs). However, the leakage and low thermal conductivity issues restrict its...     

Systematic Modulation of Thiol Functionalities in Inexpensive Porous Polymers for Effective Mercury Removal

Through accumulation, mercury contamination in aquatic systems still poses serious health risks despite the strict regulations on drinking water and industrial discharge. One effective strategy against this is adsorptive removal, in which a suitably functionalized porous material is added to water treatment protocols. Thiol (SH) group-grafted structures perform commendably; however, insufficient attention is paid to the cost, scalability, and reusability or how the arrangement of sulfur atoms could affect the Hg^II binding strength. We used an inexpensive and scalable porous covalent organic polymer (COP-130) to systematically introduce thiol functional groups with precise chain lengths and sulfur content. Thiol-functionalized COP-130 demonstrates enhanced wettability and excellent Hg^II uptake of up to 936 mg g⁻¹, with fast kinetics and exceptionally high selectivity. These Hg adsorbents are easily regenerated with HCl and can be used at least six times without loss of capacity even after treatment with strong acid, a rare performance in the domain of Hg-removal research.     

Theoretical study of (e,2e) triple differential cross sections of pyrimidine and tetrahydrofurfuryl alcohol molecules using multi-center distorted-wave method

We report theoretical studies of electron impact triple differential cross sections of two bio-molecules,pyrimidine and tetrahydrofurfuryl alcohol,in the coplanar asymmetric kinematic conditions with the impact energy of 250 eV and ejected electron energy of 20 eV at three scattering angles of-5°,-10°,and-15°.Present multi-center distorted-wave method well describes the experimental data,which was obtained by performing(e,2e)experiment.The calculations show that the secondary electron produced by the primary impact electron is strongly influenced by the molecular ionic multi-center potential,which must be considered when the low energy electron interacts with DNA analogues.     

Design and exploration of 5-nitro-3-trinitromethyl-1H-1,2,4-triazole and its derivatives as energetic materials

Molecular Diversity - According to the fact that 5-nitro-3-trinitromethyl-1H-1,2,4 triazole (NTNMT) is a successful, good explosive, energetic groups such as –CH3, –NH2, –NHNO2,...     

Optimal Control of Nonlinear Fractional-Order Systems with Multiple Time-Varying Delays

Journal of Optimization Theory and Applications - This paper considers an optimal control problem governed by nonlinear fractional-order systems with multiple time-varying delays and subject to...