A theoretical kinetics study on low-temperature oxidation of n-C4H9 radicals

The low-temperature oxidation mechanism of n?butyl radicals (n-C₄H₉) has been investigated by high level quantum chemical calculations coupled with the Rice–Ramsperger–Kassel–Marcus/Master Equation (RRKM/ME) theory. The potential energy surfaces (PES) were explored at the QCISD(T)/CBS//B3LYP/6-311++G(d,p) level. The temperature- and pressure-dependent rate constants were computed and fitted in modified Arrhenius parameters. The major reaction channels were discussed to more deeply understand the competing relationships between chain branching, chain propagation and termination reactions. The results show that the 1,5 H-shift reaction is more competitive than the 1,6 H-shift and 1,4 H-shift for isomerization reactions of n?butyl peroxy radicals, and the concerted HO₂ elimination channel to form butene becomes more important at high temperatures. Furthermore, based on our calculations, a revised kinetic model was developed to describe n-butane oxidation. Good consistency between model predictions and experimental data was shown. This study enhances our understanding of the combustion mechanism of n-butane and can be used as a reliable reference for mechanistic understanding of larger alkanes.     

气液界面微观结构研究的一种实验新方法

许多物理、化学和生物过程发生于气液界面,且受到局域微观结构的深远影响. 不同于液体的体相,分子取向是界面处微观结构突出的不对称特征之一. 本文综述了电子碰撞时间延迟质谱方法和近期取得的进展. 利用这个崭新的方法,不仅可以侦测得到利用小角度X射线或中子散射以及振动和频光谱方法获得的界面微观结构,同时也提供了一种研究气液界面处电子驱动化学反应的实验方案.     

挡板对数据中心热环境影响的模拟研究

针对数据机房高架地板下静压箱内送风压力不平衡导致地板格栅送风不均匀而引起机柜过热的问题,以某大型数据中心内气流组织为研究对象,采用6SigmaRoom软件进行数值模拟,求解获取地板静压箱内架设挡板时数据中心内机柜进口温度分布,温度场分布和不同高度平面的速度场分布,进而对比静压箱架设挡板末端不同高度对数据中心内机柜最大进口温度的影响,最后运用供热指数(SHI)、回热指数(RHI)、机架冷却指数(RCI)和回风温度指数(RTI)详细分析其优劣.研究结果表明:静压箱架设挡板能改善数据中心的气流组织,且架设的挡板末端越高,其节能程度越高.与未架设挡板的数据中心相比,静压箱挡板末端为0.56 m时SHI降低43.1％,静压箱中压力分布更均匀,可有效解决数据中心近空调端机柜过热的问题.     

全光汤姆孙散射

随着激光和加速器技术的发展,激光场强度和粒子能量也有所提升,在高场强和高电子能量的条件下,电子与光子的汤姆孙散射过程将达到高度非线性状态,在这种状态下会发生多光子效应,即单个电子同时与多个光子相互作用并辐射一个高能光子,此过程通常称为多光子汤姆孙散射.当场强和粒子能量变得更高时,需要引入量子电动力学理论来解决极端光场物理中的动理学过程.近期,全球多台数拍瓦激光装置逐渐投入使用,激光等离子体相互作用中的此类效应会变得极其显著.而全光汤姆孙散射成为目前研究极端光场物理最佳的实验方案,因此,系统地研究全光多光子汤姆孙散射是本领域未来十年极其重要的方向.本文对近年来全光汤姆孙散射实验从单光子、低阶多光子到高阶多光子的研究进展进行了综述,并对其未来的发展方向进行了展望.另外,伴随着散射过程产生的准直高亮X/伽马射线,有望发展成为具有重要应用价值的紧凑型超亮高能光源.     

极强激光场驱动超亮伽马辐射和正负电子对产生的研究进展

高功率超短超强激光脉冲的诞生开启了相对论非线性光学、高强场物理、新型激光聚变、实验室天体物理等前沿领域.近年来,随着数拍瓦级乃至更高峰值功率激光装置的建成,超强激光与等离子体相互作用进入到一个全新的高强场范畴.这种极强激光场与等离子体相互作用蕴含着丰富的物理过程,除了经典的波与粒子作用、相对论效应、有质动力效应等非线性物理过程外,量子电动力学(QED)效应变得格外重要,例如辐射阻尼效应、正负电子对产生、强伽马射线辐射、QED级联、真空极化等.本文主要介绍我们近年来在极端强激光场与等离子体相互作用中激发的QED效应以及伴随的超亮强伽马射线辐射和稠密正负电子对产生等方面的研究进展.     

Site-selective Csp3-H aryloxylation of natural product Tanshinone IIA and its analogues

A novel catalyst-free Csp³-H aryloxylation approach allowing for rapid installation of a wide range of aryloxyl groups regioselectively at the C-4 position of Tanshinone IIA under simple and mild conditions was developed. This unique protocol exhibited atom-/step-economy, low cost, high efficiency and robust functional-group tolerance, which will greatly facilitate to diversify the A-ring of the bioactive natural product.     

Facile synthesis of Fmoc-protected phosphonate pSer mimetic and its application in assembling a substrate peptide of 14-3-3 ζ

Phosphatase-inert peptidomimetics containing phosphonate pSer analogue have been developed as valuable biological tools for probing and regulating pSer-dependent protein-protein interactions (PPIs) in cellular context. Herein, we report a facile and efficient synthesis route of Fmoc-protected phosphonate pSer mimetic and also present the application of this building block in the solid-phase synthesis of a phosphatase-resistant substrate peptide of 14-3-3 ζ, retaining 14-3-3 ζ binding efficacy similar to the parent pSer-containing peptide.     

Template-directed syntheses of two 3D metal oxalates: in situ N-methylation and crystal structures

Two isomorphic organically templated zinc/cobalt oxalates, (dmdabco)[Zn₂(C₂O₄)₃]·4H₂O (1), and (dmdabco)[Co₂(C₂O₄)₃]·4H₂O (2) (C₂O₄^2? = oxalate; dmdabco = N,N′-dimethyl-1,4-diazabicyclo[2,2,2]octane), have been prepared under solvothermal conditions and characterized by X-ray structural analyses. The dmdabco²⁺ templating agent was derived from simple in situ N-alkylation between methanol and 1,4-diazabicyclo[2,2,2]octane (dabco). Distinct from conventional Eschweiler-Clarke methylation containing excess formic acid and formaldehyde, such one-step methylation from methanol molecules is convenient. Both 1 and 2 exhibit a uninodal 3-connected 3-D interrupted open-framework, in which oxalate ligands have in-plane and out-of-plane connection modes.     

Synthesis of SrFe12O19 magnetic nanoparticles by EDTA complex method

A modified polyacrylamide gel route was used to prepare SrFe₁₂O₁₉ magnetic nanoparticles; ethylenediaminetetraacetic acid (EDTA) was used as a carboxyl chelating agent. The phase purity, morphology and magnetic properties of as-prepared samples were analyzed via X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and vibrating sample magnetometery (VSM). XRD analysis indicates that high-purity SrFe₁₂O₁₉ magnetic nanoparticles can be synthesized at 700°C in air. The characteristic peaks of as-prepared sample at 210, 283, 321, 340, 381, 411, 432, 475, 532, 618, 686, and 726 cm^–1 were observed in Raman spectra. SEM and TEM show that the synthesized SrFe₁₂O₁₉ magnetic nanoparticles are uniform with the mean particle size of ~60 nm. VSM measurement shows that the maximum magnetic energy product (BH)_max of sample prepared using EDTA as a chelating agent is higher than that of sample prepared using citric acid as a chelating agent.

     

New biphenantherene and nervogenic acid derivatives from Liparis regnieri Finet and their inhibitory activities against NF-κB activation

A phytochemical investigation of the whole plant of Liparis regnieri Finet led to the isolation of one new biphenantherene (1) and ten new nervogenic acid derivatives (2–11), together with nine known compounds. Their structures were elucidated mainly by extensive analyses of 1D and 2D NMR spectroscopic data and chemical reactions. Additionally, for the first time a previously unreported biphenantherene was discovered to effectively suppress TNF-α induced expression of NF-κB-Luc in Hela cells with the IC₅₀ value of 1.80 μM and the structure-activity relationshipwas also discussed.