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Showing 1 to 20 of 25 for “"Radical Cations"”.
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The Chemistry of Cyclopropylarene Radical Cations
… are frequently utilized as "probes" for radical cation intermediates in a number of important chemical and biochemical oxidation. The implicit assumption in such studies is that if a radical cation is produced, it will undergo ring opening. Through a detailed examination of follow-up …
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Applications of fluorous chalcogenides and of radical cations in organic synthesis.
Applications of fluorous chalcogenides and of radical cations in organic synthesis.
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Synthesis and electron spin resonance spectroscopy of organo-sulfur radical cations
<p>A series of new radical cations in 1,4-dithiin, 1,4-benzodithiin, 2,3-dihydro-1,4-dithiin, 1,4-dithiepin, 1,2-dithietane, 1,2-dithiolane, 1,2-dithiane series were prepared. The SOMO of 1,4-dithiin, 1,4-benzodithiin, 2,3-dihydro-1,4-dithiin radical cations were found to be symmetrical while the …
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Selective Catalytic Oxidation of Organic Sulfides by Iron (III) Porphryin Catalysts and Generation of Iron (IV)-OXO Prophyrin Radical Cations
… catalytic sulfoxidations, iron(IV)-oxo porphyrin radical cations model of Compound I were chemically produced from the corresponding iron(III) tetramesitylporphyrin precursors with excess amounts of PhI(OAc)<sub>2</sub> (20-50 equivalents) in CH<sub>3</sub>CN solvent. All …
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A Radical Approach to Syntheses and Mechanisms
The critically important nature of radical and radical ion mechanisms in biology and chemistry continues to be recognized as our understanding of these unique transient species grows. The work presented herein demonstrates the versatility of kinetic studies for understanding the elementary chemical …
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Consequences of Oxidative DNA Damage: Base-Pair Dissociation, Singlet Oxygenation and DNA-Protein Crosslinking
… reactions of 1O2 with 2′-deoxyguanosine radical cations, my research thesis expanded to the investigation of reaction dynamics of 9-methyl-8-oxoguanine (9MOG) radical cations. The experiments of following projects were realized using tandem mass spectrometry coupled with electrospray …
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Sorption mechanisms of dibenzo-p-dioxin/furan from water by smectite clays and theoretical studies on formation pathways of chlorodibenzo-p-dioxins from precursor chlorophenols on smectite clays
… water. Adsorption was promoted by exchangeable cations with low hydration energies, and negative charge in the smectite arising from the tetrahedral siloxane sheets. X-ray diffraction measurements revealed that as dibenzo-p-dioxin (DD) loading increased to ≥ 8,000 mg/kg the clay basal spacing …
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Gas-phase Ion Chemistry of Hydroxy and Amino-substituted Interstellar Polycyclic Aromatic Hydrocarbons and Protonated Polycyclic Aromatic Hydrocarbons
… trends found include: hydroxy-substituted PAH radical cations lose carbon monoxide spontaneously and amino-substituted PAH radical cations lose HCN. Mechanisms for both processes are proposed, and it appears from the present results that this process should extrapolate to larger PAHs. Another …
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GROWTH MECHANISMS OF COMPLEX ORGANICS IN THE GAS PHASE AND ON METAL NANOPARTICLES GENERATED BY A LASER VAPORIZATION PROCESS
… of acetylene neutrals with different aromatic cations, in order to infer the possible mechanisms of formation of PAHs and PANHs in different environments such as interstellar media under different ionizing conditions. Furthermore, this technique is used to probe structures, address the …
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Redox properties of Bis-Triarylamines and ligand properties of Thianthrenophane
… neutral compounds and their corresponding mono radical cations. The small solvent dependence of the experimental UV/Vis spectra in CH2Cl2 and MeCN reflects a minor charge transfer character of the electronic transitions. The UV/Vis/NIR spectra of the series of TAAs and their corresponding …
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Dissociative charge transfer of organic molecules induced by collisions with the He+ cation. A joint experimental and theoretical study of relevance for the interstellar medium evolution
… which means that the nascent DME and MF radical cations are formed in a dissociative state. Insights on both the charge transfer processes have been obtained by investigating the nature of the non-adiabatic transitions between the reactant and product potential energy surfaces (PES). The …
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Development of New N-Cyclopropyl Based Electron Transfer Probes for Cytochrome P-450 and Monoamine Oxidase Catalyzed Reactions
… pathways can pose several experimental complications due to their complexity, therefore the small molecule probe approach can be utilized in an attempt understand the more complex enzyme mechanisms. The work described in this dissertation focuses on the use of N-cyclopropyl amines that have …
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The Chemistry of Aroyl Azides in Piperidine- and Steroid-Separated Bichromophoric System: Photoinduced Long-Distance Intramolecular Electron Transfer Reactions
… intermediate states. The aryl amine radical cations were detected by pulsed laser spectroscopy and the highly reactive aroyl azide radical anions were identified by the results of steady-state photolysis. In acetonitrile and in methyl alcohol solution, the photoexcited aryl amine …
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Investigation of the Role of Groove Hydration and Charged Nucleosides in DNA Charge Transfer
… charge transfer by their reaction with guanosine radical cation to form 7,8-dihydro-8-oxo-guanine (8-oxoG), which when treated with a base leads to DNA strand cleavage. We probed the reaction of guanosine radical cation with water with series of alkyl substituted cytidines and thymidines by …
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The Exploration of a Strategy for Regioselective Arene Amination Utilising Non-Covalent Interactions
… methods which utilise reactive N-centred radicals for the synthesis of anilines from arenes have recently been developed. However, regiochemical control is a major challenge associated with these methods, with mixtures of regioisomers commonly obtained in most protocols. Non-covalent …
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Fundamental Investigations of Mechanistic Pathways of Selected Organic Reactive Intermediates
… gas-phase reaction between the ethylene oxide radical cation and neutral ethylene oxide, when performed in the high-pressure source of a tandem mass spectrometer, forms a C4Hg02 radical cation adduct. The collisionally activated dissociation (CAD) mass spectrum of the C4H802 adduct is nearly …
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Investigation of Structure and Properties of Low Temperature Deposited Diamond-Like Carbon Films
… but electrochemical cyclization of acetylene radical cations and hydrogen abstraction at the termination steps. Sodium acetylide, however, dissociates to an acetylenic ion, C2H-, in liquid ammonia. The electrochemistry heterogeneity also leads to island and two-dimensional (2D) nucleation …
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Studies of Molecular and Colloidal Semiconductors and Their Mass Transport Properties by Voltammetry, Stochastic Electrochemistry, and Electrogenerated Chemiluminescence
… was shown to be a function of generated radical cations and radical anions stability and their molecular structure. A high ECL efficiency (ΦECL > 0.6) of some of these compounds suggest their promising applications as light emitters in ECL devices.
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The Gas-Phase Oxidation of Cationic Bioanalytes via Ion/Ion Reactions
… Persulfate anion and its derivatives, sulfate radical anion and peroxymonosulfate anion are capable of generating a variety of oxidation products, including the [M+H+O]+, [M-H]+, and M+• species.
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