Mechanistic study of the reaction of methyl peroxy radical (CH3O2) with formaldehyde (CH2O)

ABSTRACT

A direct dynamic study on the reactions of CH₃O₂?+?CH₂O was carried out over the temperature range of 300–1500?K. All stationary points were calculated with the M06-2X/6-311++G(d,p) level of theory and identified for local minimum. The energetic parameters were refined at QCISD (T)/cc-pVTZ and CCSD (T)/cc-pVTZ levels of theory. Three channels were explored and a reaction of hydrogen abstraction from CH₂O by CH₃O₂ was identified as dominant channel which involves the formation of a prereactive complex in the entrance channel. The rate coefficient of the dominant channel was calculated with TST and TST/Eck and the Eckart tunnelling effect is only important over the lower temperature region. The calculated rate coefficient of the dominant channel has positive temperature dependence and agrees reasonably with the available literature data.     

Engineering Multifunctional DNA Hybrid Nanospheres through Coordination‐Driven Self‐Assembly

Developing simple and general approaches for the synthesis of nanometer‐sized DNA materials with specific morphologies and functionalities is important for various applications. Herein, a novel approach for the synthesis of a new set of DNA‐based nanoarchitectures through coordination‐driven self‐assembly of Fe^II ions and DNA molecules is reported. By fine‐tuning the assembly, Fe–DNA nanospheres of precise sizes and controlled compositions can be produced. The hybrid nanoparticles can be tailored for delivery of functional DNA to cells in vitro and in vivo with enhanced biological function. This highlights the potential of metal ion coordination as a tool for directing the assembly of DNA architectures, which conceptualizes a new pathway to expand the repertoire of DNA‐based nanomaterials. This methodology will advance both the fields of DNA nanobiotechnology and metal–ligand coordination chemistry.     

Preparation of erythromycin imprinted polymer by metal-free visible-light–induced ATRP and its application in sensor

Journal of Solid State Electrochemistry - Erythromycin (ERY) molecular imprinted polymer was prepared on the surface of Au electrode modified with Ni and Au nanoclusters (MIP/AuNCs/Ni/Au) via...     

开关型Pickering乳液体系

Pickering乳液以胶体尺寸的固体粒子代替传统表面活性剂作为稳定剂,具有超稳定,生物相容性好以及对环境友好等优点。开关型Pickering乳液可随pH值、CO₂/N₂浓度、温度、磁场强度及光强度等条件的变化而改变固体乳化剂的表面润湿性,实现在“乳化”与“破乳”之间的快速转换,在非均相催化、乳液聚合等诸多领域有广泛的应用前景。本文全面总结了近年来开关型Pickering乳液的研究进展及其在界面催化系统、液膜处理有机废水、药物的包封与释放等方面的应用。     

Injectable and self-healing hydrogels with tissue adhesiveness and antibacterial activity as wound dressings for infected wound healing

The design of wound dressings with excellent self-healing ability, adequate adhesion, good biocompatibility, and potential antibacterial ability is of great significance for the healing of infected wounds arising from human activities. Herein, a series of multi-functional hydrogel dressings, poly(ionized isocyanoethyl methacrylate-glutamine)/poly(hexamethylene guanidine) (iG_x/PHMG_y) hydrogels, were obtained through homopolymerization of fully ionized isocyanoethyl methacrylate-glutamine (iIEM-Gln) in the presence of poly(hexamethylene guanidine) (PHMG), in which strong hydrogen bonds were formed among urea groups in the P (iIEM-Gln) chain to form a stable hydrogel network. The prepared iG_x/PHMG_y hydrogels exhibited adequate self-healing ability and tissue adhesion, which could be firmly adhered to the wound surface and remained intact during application. In addition, the presence of PHMG imparted good antibacterial activity to the hydrogels for the effective promotion of the wound healing in S. aureus infected skin wound on mice. Overall, this multi-functional hydrogel provides a facile and effective strategy for the design of infected wound dressings, and may show great potential in clinical applications.     

The characteristic of sound propagation in deep water and underwater source localization in the direct zone

The multiple-path sound propagation in deep water is conducive to source localization of an underwater target.The transmission losses(TLs) and broadband pulse multiple-path propagation characteristics from a deep receiver is analyzed by using the experimental data from deep water area in the South China Sea(SCS).The results indicate that the width of the direct zone near the bottom of 4300 m water depth is about 30 km.The TLs in the direct zone near the bottom are much less than those in the shadow zone.It is meaningful for underwater sound source detection.Moreover,the time delay between the direct path and the bottomsurface-reflected path for a receiver near the bottom decreases monotonically with the source range.According to the linear relationship between the time delay of multipath and source range,a source localization method is presented to estimate the range of underwater target.The experimental results show that the estimated ranges are consistent with the global position system(GPS) measurements,and the mean square error of the estimation results is less than 0.28 km.     

ANALYSIS OF MECHANICAL CHARACTERISTICS OF FROZEN CLAY AND MODIFIED S-M CREEP MODEL1)

为合理描述人工冻结法施工的矿井土层力学特性,对某矿井土样的重塑土进行单轴抗压强度实验和单轴压缩蠕变实验,得到重塑冻结黏土在不同温度及载荷加载等级下的应力-应变曲线和蠕变曲线。实验结果表明：冻结温度越低,土样的单轴强度越大;相同冻结温度下,土样的蠕变变形随着应力水平的升高而增大。单轴压缩蠕变的等时应力-应变曲线随时间发展向应变轴靠拢;土样经历初始蠕变和等速蠕变两个阶段,在较高应力水平下有进入加速蠕变的趋势;对S-M模型中各参数的意义进行修正并考虑温度的影响,得到人工冻结黏土改进S-M蠕变显式模型,然后采用粒子群算法对人工冻结黏土S-M蠕变模型参数进行优化。改进S-M蠕变显式模型理论计算值与实验值吻合良好,表明改进S-M蠕变显式模型能较好模拟人工冻结黏土的蠕变特性。改进S-M蠕变显式模型为人工冻土蠕变计算提供一种新方法。     

锁核酸分子信标在分子识别与生物分析中的应用

分子信标是一种荧光探针,闭合时呈发夹结构。其5'末端修饰荧光基团,3'末端修饰猝灭基团。当目标存在时,环部与目标结合,发夹打开,发出荧光。锁核酸是一类双环状寡核苷酸衍生物,能够遵循碱基互补配对原则与核酸结合。锁核酸分子信标技术,结合了分子信标无需分离未结合探针而直接检测的优势和锁核酸亲合力强、热稳定性好、抗酶切以及体内无毒等特点,在核酸检测方面具有灵敏度高、特异性好的独特优势,近年来得到广泛关注。本文介绍了锁核酸修饰分子信标的结构、功能、设计要点,及其研究现状和一些重要进展,并讨论了目前锁核酸分子信标在分子识别及生物分析中的应用及存在的问题和发展前景。     

Advances and prospective in thermally stable nonfullerene polymer solar cells

Science China Chemistry - Polymer solar cells (PSCs) featuring nonfullerene acceptors have attracted a great deal of attention in the research community. Exposure of these active layers to sunlight...     

Synthesis of methylene butyrolactone polymers from itaconic acid

Herein, we report the transformation of β‐monomethyl itaconate, an inexpensive and biorenewable alternative to petroleum feedstocks, to the high‐value monomer α‐methylene‐γ,γ‐dimethyl‐γ‐butyrolactone (Me₂MBL) through a selective addition strategy. This strategy is also applied to the synthesis of α‐methylene‐γ‐butyrolactone (MBL, tulipalin A), a monomer that can be polymerized to give materials with desirable properties (high decomposition temperature, glass transition temperature, and refractive index). Subsequent polymerization of both Me₂MBL and MBL through reversible addition‐fragmentation chain‐transfer polymerization generates well‐defined poly(Me₂MBL) and poly(MBL) (PMBL). Physical characterization of poly(Me₂MBL) shows good physical properties comparable with known PMBL materials. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2730–2737