Flash Vacuum Pyrolysis: Techniques and Reactions

Flash vacuum pyrolysis (FVP) had its beginnings in the 1940s and 1950s, mainly through mass spectrometric detection of pyrolytically formed free radicals. In the 1960s many organic chemists started performing FVP experiments with the purpose of isolating new and interesting compounds and understanding pyrolysis processes. Meanwhile, many different types of apparatus and techniques have been developed, and it is the purpose of this review to present the most important methods as well as a survey of typical reactions and observations that can be achieved with the various techniques. This includes preparative FVP, chemical trapping reactions, matrix isolation, and low temperature spectroscopy of reactive intermediates and unstable molecules, the use of online mass, photoelectron, microwave, and millimeterwave spectroscopies, gas‐phase laser pyrolysis, pulsed pyrolysis with supersonic jet expansion, very low pressure pyrolysis for kinetic investigations, solution‐spray and falling‐solid FVP for involatile compounds, and pyrolysis over solid supports and reagents. Moreover, the combination of FVP with matrix isolation and photochemistry is a powerful tool for investigations of reaction mechanism.     

Direct UVC photodegradation of imipramine in aqueous solutions: a mechanistic study

1. Download : Download high-res image (93KB)
2. Download : Download full-size image

     

Synthesis by FVT and Characterization of Unhindered Silanethiones

The retro-ene reaction of allylthio- and propargylthiosilanes led, under flash vacuum thermolysis (FVT) conditions, to unhindered silanethiones, characterized by their derivatives, and also directly by coupling of the FVT with gas-phase spectrometries. Monomeric silicon oxysulfide has been generated similarly. The unsubstituted silanethione was not obtained, but dehydrogenated into silicon monosulfide during FVT.     

多级离心连续逆流手性萃取模型及模拟

基于单级手性萃取数学模型和质量守恒定律,建立了多级离心手性萃取数学模型,设计了多级离心萃取数学模型程序,并对多级离心萃取分离苯基琥珀酸（PSA）对映体进行了模拟.模拟了相比、萃取剂浓度、对映体浓度、进料位置和萃取级数等工艺参数对萃取效果（产物纯度和产率）的影响.模拟结果表明,考察的工艺参数共同影响萃取相和萃余相的产物纯度及产率;采用中间位置进料和较大的W/F相比有利于对称分离.实验发现：采用中间位置进料,10级离心萃取后萃取相中苯基琥珀酸的光学纯度ee（对映体过量）达到56%以上.模拟结果还表明,采用26级离心萃取器,中间进料,逆流分级萃取,萃取相及萃余相中的光学纯度ee都能达到98%以上.     

New Reactions of N‐tert‐Butylimines; Formation of N‐Heterocycles by Methyl Radical Elimination on Flash Vacuum Thermolysis of N‐Benzylidene‐ and N‐(2‐Pyridylmethylidene)‐tert‐butylamines

Thermal reactions of N‐benzylidene‐ and N‐(2‐pyridylmethylidene)‐tert‐butylamines ( 5 and 13 ) under FVT conditions have been investigated. Unexpectedly, at 800 °C, compound 5 yields 1,2‐dimethylindole and 3‐methylisoquinoline. In the reaction of 13 at 800 °C, 3‐methylimidazo[1,5‐a]pyridine was obtained as the major product. Mechanisms of these reactions have been proposed on the basis of DFT calculations. Furthermore, UV‐photoelectron spectroscopy combined with FVT has been applied for direct monitoring and characterization of the thermolysis products in situ.     

磷酸基团在环丙沙星光敏损伤DNA中的作用

利用紫外-可见稳态吸收光谱, 稳态荧光发射光谱和激光光解瞬态光谱实验方法研究了磷酸基团在环丙沙星(CPX)光敏损伤DNA中的作用. 紫外-可见和稳态荧光光谱实验证实了磷酸根离子影响环丙沙星的稳态吸收和发射谱, 实验结果表明磷酸根是通过弱相互作用与环丙沙星结合. 我们还利用激光闪光光解实验分别研究了鸟苷(Gua), 脱氧鸟苷(dG)以及脱氧鸟苷酸(dGMP)对环丙沙星三线态(³CPX^*)的影响, 通过对比实验证实了在环丙沙星光敏损伤dGMP中, 由于磷酸基团的存在, 导致了环丙沙星三线态吸收峰的改变, 从而改变了光敏损伤反应的途径. 通过研究发现, 光敏损伤途径的改变是由于dGMP结构上磷酸基团通过氢键与环丙沙星结合所造成的. 最后, 根据实验结果并对比Gua, dG和dGMP的结构, 提出了一个合理的磷酸基团的作用机理.     

一种基于STM32的NAND flash的块分配框架设计

STM32对大容量数据文件存储与管理问题可通过NAND flash来解决。而NAND flash的高效管理需要文件系统参与。NAND flash有特殊的块读写及擦除机制,一般的嵌入式文件系统组织结构并不完全兼容NAND flash。针对NAND flash的特点兼顾STM32的资源承受力要提出新的NAND flash块分配框架,框架通过块分配槽这种数据结构,在不使用块分配表与垃圾表的情况下,实现了NAND flash均衡负载与垃圾块的回收;同时通过节点分配栈与文件节点表的配合来提高STM32对文件的读写速度,空间利用率和系统性能。仿真实验和计算结果表明该块分配框架可有效提高NAND flash块的均衡负载与节省RAM空间。     

Water-Assisted Concerted Proton-Electron Transfer at Co(II)-Aquo Sites in Polyoxotungstates With Photogenerated RuIII(bpy)33+ Oxidant

The cobalt substituted polyoxotungstate [Co₆(H₂O)₂(α-B-PW₉O₃₄)₂(PW₆O₂₆)]¹⁷⁻ ( Co6 ) displays fast electron transfer (ET) kinetics to photogenerated Ru^III(bpy)₃³⁺, 4 to 5 orders of magnitude faster than the corresponding ET observed for cobalt oxide nanoparticles. Mechanistic evidence has been acquired indicating that: (i) the one-electron oxidation of Co6 involves Co(II) aquo or Co(II) hydroxo groups (abbreviated as Co6(II) −OH ₂ and Co6(II) −OH, respectively, whose speciation in aqueous solution is associated to a pK_a of 7.6), and generates a Co(III)−OH moiety ( Co6(III) −OH), as proven by transient absorption spectroscopy; (ii) at pH>pK_a, the Co6(II) −OH→Ru^III(bpy)₃³⁺ ET occurs via bimolecular kinetics, with a rate constant k close to the diffusion limit and dependent on the ionic strength of the medium, consistent with reaction between charged species; (iii) at pH <pK_a, the process involves Co6(II) − OH₂ → Co6(III)−OH transformation and proceeds via a multiple-site, concerted proton electron transfer (CPET) where water assists the transfer of the proton, as proven by the absence of effect of buffer base concentrations on the rate of the ET and by a H/D kinetic isotope in a range of 1.2–1.4. The reactivity of water is ascribed to its organization on the surface of the polyanionic scaffold through hydrogen bond networking involving the Co(II)−OH₂ group.     

Independent Generation and Time-Resolved Detection of 2′-Deoxyguanosin-N2-yl Radicals

Guanine radicals are important reactive intermediates in DNA damage. Hydroxyl radical (HO^.) has long been believed to react with 2′-deoxyguanosine (dG) generating 2′-deoxyguanosin-N1-yl radical (dG(N1-H)^.) via addition to the nucleobase π-system and subsequent dehydration. This basic tenet was challenged by an alternative mechanism, in which the major reaction of HO^. with dG was proposed to involve hydrogen atom abstraction from the N2-amine. The 2′-deoxyguanosin-N2-yl radical (dG(N2-H)^.) formed was proposed to rapidly tautomerize to dG(N1-H)^.. We report the first independent generation of dG(N2-H)^. in high yield via photolysis of 1 . dG(N2-H)^. is directly observed upon nanosecond laser flash photolysis (LFP) of 1 . The absorption spectrum of dG(N2-H)^. is corroborated by DFT studies, and anti- and syn-dG(N2-H)^. are resolved for the first time. The LFP experiments showed no evidence for tautomerization of dG(N2-H)^. to dG(N1-H)^. within hundreds of microseconds. This observation suggests that the generation of dG(N1-H)^. via dG(N2-H)^. following hydrogen atom abstraction from dG is unlikely to be a major pathway when HO^. reacts with dG.     

Ultrafast,Low‐Cost,and Mass Production of High‐Quality Graphene

Fast, mass, and low‐cost production of high‐quality graphene, which is alluring, remains a great challenge, even though some approaches have shown potential for mass synthesis of graphene. Very recently a great breakthrough was made by Tour and co‐workers (Nature 2020, 577, 647–651): in just a second, easily exfoliated and highly crystalline graphene was produced from abundant carbon‐containing species by cost‐effective flash Joule heating with a low energy input of 7.2 kJ per gram graphene. Such an ultrafast, economic, and scalable process for high‐quality graphene production can be considered as a milestone in the graphene field and is highlighted in this article.