Isomer-Selective Generation and Spectroscopic Characterization of Picolyl Radicals

Nitrogen-containing resonance-stabilized radicals such as the picolyl radical are important in combustion chemistry and astrochemistry. They have only been scarcely studied because an isomer-selective generation is often difficult. Herein, we present threshold photoelectron spectra of the three picolyl radical isomers, C₆H₆N, that were obtained with synchrotron radiation. The radicals were selectively generated by flash pyrolysis from aminomethylpyridine precursors through deamination. Ionization energies of 7.70, 7.59, and 8.01 eV were determined for 2-, 3-, and 4-picolyl, respectively. The observed vibrational structure was assigned to an in-plane deformation mode of the aromatic ring. The spectroscopic insight gained in this study can be used to distinguish different picolyl isomers in on-line combustion analysis, for example.     

Conformation of ATP and ADP Molecules in Aqueous Solutions Determined by High-Energy X-ray Diffraction

High-energy X-ray diffraction measurements were carried out at 26 °C for aqueous 1.0, 2.0 and 2.05 mol% disodium adenosine 5′-triphosphate (ATP) and 2.0 and 2.05 mol% disodium adenosine 5′-diphosphate (ADP) solutions in order to obtain direct experimental information on the intramolecular conformations of ATP and ADP molecules in aqueous solutions. Observed interference terms were analyzed in terms of the intramolecular geometry of the ATP and ADP molecules. Dihedral angles between adenine and the ribose group (t ₁), ribose-ring and methylene group of ribose (t ₂), and the methylene group of ribose and triphosphate (or diphosphate) group (t ₃), were determined through the least-squares fitting procedure of the observed interference term.     

Generation and Reactivity of Amidyl Radicals: Manganese-Mediated Atom-Transfer Reaction

A simple and efficient protocol to generate amidyl radicals from amine functionalities through a manganese-mediated atom-transfer reaction has been developed. This approach employs an earth-abundant and inexpensive manganese complex, Mn₂(CO)₁₀, as the catalyst and visible light as the energy input. Using this strategy, site-selective chlorination of unactivated C(sp³)−H bonds of aliphatic amines and intramolecular/intermolecular chloroaminations of unactivated alkenes were readily realized under mild reaction conditions, thus providing efficient access to a range of synthetically valuable alkyl chlorides, chlorinated pyrrolidines, and vicinal chloroamine derivatives. These practical reactions exhibit a broad substrate scope and tolerate a wide array of functional groups, and complex molecules including various marketed drug derivatives.     

Removal of Toxic Impurities from Air by Pulsed Electron Beams

The results of experimental studies on the removal of various impurities from gas mixtures excited by pulsed electron beams are presented. As found, it is the use of pulsed beams that ensures a significantly decrease in power consumption for the removal of impurities, as compared with continuous electron beams, and obtaining gaseous or solid substances as final products in some cases.     

Investigation of the Formation and Energy Density of High-Current Pulsed Electron Beams

High-current pulsed electron beams (HCPEB) irradiation is a new potential method to polish hard steels and alloys. After HCPEB machining, the performance of machined surface, such as corrosion resistance and microstructure, has been greatly improved. Because of its good performance, HCPEB irradiation is playing more and more important roles in polishing hard steels and alloys. However, it is not clear about the energy density of HCPEB under different beam conditions. In this study, experiments have been conducted to investigate the formation of HCPEB and its energy density. Then, effects of argon gas pressure and the applied voltage to solenoid coil on the formation of HCPEB are analyzed. Finally, a mathematical model is developed to describe the relationship between five dominant beam parameters with the energy density of HCPEB, which has a good accuracy in comparison to the experimental results.     

Fast Pulsed Field Minigel Electrophoresis of Large DNA Molecules.

Abstract

Pulsed field gel electrophoresis runs were performed in small Contour Clamped Homogeneous Electric Field (miniCHEF) and Transverse Alternating Electric Field (miniTAFE) chambers. Minichambers use minigels and they could be suitable for analytical and preparative purposes. In minichambers higher electric fields and equal heat evolution were achieved with the same voltage applied to conventional chambers. Nine to ten Saccharomyces cerevisiae chromosomes were resolved in minichambers applying 13–14 V/cm and 50 s of pulse time during 3.2 - 5 h. It was found a linear relationship between the migration per pulse and the electric field (at constant pulse time). An equation relating the pulse time and the electric fields was attained. It was used to obtain isopatterns at several electric fields despite the chamber dimensions. Miniapparati use simple power supplies and cooling systems and save samples, reagents, laboratory bench space and time.     

Kinetic Energy of Methane Molecules Formed from Methyl Radicals Adsorbed on Copper

The method of temperature-programmed reaction (TPR) with the spatial resolution of desorbed product molecules and the measurements of their average rates (v) are used to study the transformation of methyl radicals adsorbed on polycrystalline copper. In the products of TPR, only methane is found. The spatial distribution of its desorption flow (SDDF) is described by the equation CH₃ ^·. The results of SDDF and I/I ₀= cos¹⁶ measurements agree with each other. Under these conditions, translationally excited methane molecules are desorbed from the copper surface. The energy of these molecules is 10–15 times higher than the thermal energy.     

Visible-Light-Induced Palladium-Catalyzed Generation of Aryl Radicals from Aryl Triflates

A mild visible-light-induced Pd-catalyzed intramolecular C−H arylation of amides is reported. The method operates by cleavage of a C(sp²)−O bond, leading to hybrid aryl Pd-radical intermediates. The following 1,5-hydrogen atom translocation, intramolecular cyclization, and rearomatization steps lead to valuable oxindole and isoindoline-1-one motifs. Notably, this method provides access to products with readily enolizable functional groups that are incompatible with traditional Pd-catalyzed conditions.     

Dithienopyrrole Derivatives with Nitronyl Nitroxide Radicals and Their Oxidation to Cationic High-Spin Molecules

Three 1 N-phenyl nitronyl nitroxide (NN) 4-substituted dithieno[3,2-b:2′,3′-d]pyrrole ( DTP ) derivatives with R1=4-phenyl-, 4H-, and 4-methylthiothiophenyl- ( R¹ ₂ DTP-Ph-NN , R¹=H, Ph and MeSTh) were designed, synthesized and characterized. The electrochemical properties were studied by cyclic voltammetry (CV). All the molecules exhibited two main oxidation peaks, first for radical cation and next for dication formation. The cation and dication formation were also confirmed by UV/Vis absorption spectroscopy for Ph₂DTP-Ph-NN and MeSTh₂DTP-Ph-NN titrated with tris(4-bromophenyl)aminiumhexachloroantimonate (magic blue). In addition, the cation and dication formation were verified by EPR spectroscopy. Finally, the exchange interactions (J/k_B) of NN and radical cation were calculated by DFT studies.     

Catalytic Generation of Radicals in Supramolecular Systems with Acetylcholine

Kinetics and Catalysis - The catalytic effect of the most important neurotransmitter, acetylcholine (ACh), which, like cationic surfactants (S+), is able to form mixed microaggregates with...     

Photochemical Generation of 9H‐Fluorenyl Radicals

A series of 9‐substituted fluorenols and 9,9′‐disubstituted‐9,9′‐bifluorenyls were irradiated to give products derived from fluorenyl radicals. Product distribution was solvent dependent. A TEMPO adduct was isolated from the photoexcitation of 9‐fluorenol. An unusual unsymmetrical 3,9′‐bifluorenyl was observed from the photolysis of 9‐trifluoromethylfluorenol and 9,9′‐di(trifluoromethyl)‐9,9′‐bifluorenyl in more polar or hydrogen‐bonding solvents. The electronic nature of 9‐substituted fluorenyl radicals was probed using theoretical calculations showing the dipolar character of species with electron‐deficient groups. These constitute the first examples of “doubly destabilized” radicals.     

烷烃和胺类分子对电子激发态CH(A~2Δ和B~2Σ~-)自由基猝灭

用266nm激光光解CHBr_3分子产生CH(A,B)态自由基,通过测量CH(A,B→X)自发辐射的时间分辨信号测定室温下(CH_3)_2NH、(C_2H_5)_2NH、(C_2H_5)_3N、n-C_5H_(12)、n-C_6H_(14)和n-C_7H_(16)对CH(A,B,v'=0)的猝灭速率常数.发现猝灭速率常数与猝灭剂烷烃分子中的C-H键数近似成线性关系,但对大的烷烃分子,这种增加逐渐趋缓.用碰撞络合物模型计算胺类分子及烷烃分子与CH形成碰撞络合物时的生成截面,结果表明,在电子激发态CH自由基的猝灭过程中,碰撞对子间的多极相互吸引势和色散力作用势可能起重要作用.     

Generation of Aromatic N-Heterocyclic Radicals for Functionalization of Unactivated Alkenes

Nitrogen-centered radicals (NCRs) have been widely recognized as versatile synthetic intermediates for the construction of nitrogen containing molecules of high value. As such, there has been a long-standing interest in the field of organic synthesis to develop novel nitrogen-based radicals and explore their inherent reactivity. In this study, we present the generation of aromatic N-heterocyclic radicals and their application in a novel and diverse functionalization of unactivated alkenes. Bench-stable aromatic N-heterocyclic pyridinium salts were employed as crucial NCR precursors, which enabled the efficient conversion of various unactivated alkenes into medicinally relevant alkylated N-heterocyclic amines. This approach offers an unexplored retrosynthetic disconnection for the synthesis of related molecules that commonly possess therapeutic value. Furthermore, this platform can be extended to the synthesis of densely functionalized heterocyclic amines by utilizing disulfides and diethyl bromomalonate as radical quenchers. Mechanistic investigations indicate an energy transfer (EnT) pathway involving the formation of a transient aromatic N-heterocyclic radical, radical addition to unactivated alkenes, and subsequent generation of the amination product through either hydrogen atom transfer (HAT) or radical addition processes.     

Ar、NO和CHBr_3对电子激发态CH的淬灭

由于若干应用背景，人们对CH自由基及其它含氢R原子自由基有着特别的兴趣．＊H自由基是碳氢化合物火焰中的反应中间体＊，它们还存在于星际空间的星云和慧星的大气中卜和．此外，由于其简单，它是用来考察碳氢化合物中CH键的极好的模型分子问，所以研究它的动力学具有重要的基础意义．基态cHK’…自由基的动力学研究进行较为广泛，对C贝A’凸）的动力学研究较少，主要报导了它被若干分子种灭的总述申常数（包括化学反应和能量转移），少数报导了速车常数与温度关系．普遍认为，CH（助种灭这率常数与A态的转动态有关，但这种依赖关系的…     

氨基酸分子的光学活性和频效应

用带限制场Hartree-Fock (RHF/6-311++G^**)从头算的方法进行分子构型优化, 单激发态组态相互作用(CIS/6-311++G^**)计算各种需要的相关数据; 应用态求和理论, 以长度偶极矩和速度偶极矩两种形式模拟了一系列氨基酸离子的光学活性和频效应(OA-SFG)光谱. 结果表明速度偶极矩计算得到的一系列氨基酸离子的和频效应光谱强度顺序能很好地与实验相吻合, 而长度偶极矩形式计算得到的结果与实验不吻合. 引起这两种形式和频效应光谱理论计算结果差别的原因是由于长度偶极矩形式具有原点敏感性, 而速度偶极矩没有. 速度偶极矩方法更适用于分子光学活性和频效应的模拟.     

Aryl Oxalate Derivatives as Convenient Precursors for Generation of Aryloxyl Radicals

The use of aryloxy oxalyl chlorides (AOCs), aryloxy oxalyl tert-butyl peroxides (AOBs), and diaryl oxalates (DAOs) for unimolecular generation of phenoxyl-based radicals under solution and rigid matrix conditions is described. AOCs are usable for photochemical generation of phenoxyl radicals, but are only conveniently stable as precursors when 2,6-di-tert-butylated derivatives are used. AOBs may be used as thermal precursors to aryloxyl radicals, since they typically decompose within 2-3 h at 60-85 degrees C to give phenols. (1)H-NMR solution kinetic studies find that DeltaH() = 31 kcal/mol, and DeltaS() = +3.4 cal/mol-K for decomposition of phenoxyoxalyl tert-butyl peroxide, consistent with substantial concertedness in peroxide bond cleavage. AOBs and the more stable DAOs are also convenient photochemical phenoxyl radical precursors. AOBs yield phenoxyl radicals more readily by photolysis than do corresponding DAOs, but the DAOs have fewer side reactions that can quench the product phenoxyl radicals.     

Antioxidant Activity Evaluation Assay Based on Peroxide Radicals Generation and Potentiometric Measurement

A new version of potentiometric evaluation of antioxidant activity in biological liquids, food, drinks, and so forth, based on the mediator system combined with the free radicals generation has been proposed. A radical initiator, 2,2′-azobis(2-amidinopropane) dihydrochloride (AAPH), and K₃[Fe(CN)₆]/K₄[Fe(CN)₆] as a mediator system were used. Interactions of the mediator system with radicals, radicals with antioxidants, and erythrocytes have been investigated. The correlation coefficient between the data obtained in the presence and the absence of AAPH equals 0.98. In addition, the possibility to determine a free radical generation rate by using the mediator system has been demonstrated.     

基于反应力场分子模拟的乙烯燃烧自由基与氮气相互作用研究

采用反应力场分子动力学(ReaxFF-MD)方法, 模拟了富燃料条件下乙烯在空气中的燃烧以及燃烧产生的自由基与氮气的相互作用. 采用ReacNetGenerator程序提取反应网络, 结合自编后处理程序确定反应网络上的相关反应, 分析了乙烯燃烧的反应路径, 以及自由基与N₂的相关反应和NO的生成路径. 结果表明, 乙烯燃烧路径与已报道的通过乙烯燃烧反应机理模拟得到的燃烧路径一致, 说明用ReaxFF-MD方法模拟乙烯高温燃烧有效而可靠; 乙烯在富燃料条件下燃烧产生的CH, C₂H, C₂, C₂O自由基是瞬发型NO生成的重要反应物. 这些自由基与N₂的反应和NO的生成路径, 为构建乙烯和大分子碳氢燃料燃烧氮氧化物排放的反应机理提供了重要参考.     

Generation of Oxygen-Centered Radicals by Reaction of Nitrate Esters with Tri-n-Butyltin Hydride

Treatment of nitrate esters wilh tri-n-butyltin hydride and AIBN in benzene at reflux is a convenient way to generate oxygen-centered (alkoxyl) radicals.