Search results for "Radical"
showing 10 items of 1401 documents
Ab initio study on the mechanism of the atmospheric reaction OH + O3--HO2 + O2.
2003
The atmospheric reaction (1) OH + O 3 → + O 2 was investigated theoretically by using MP2, QCISD, QCISD(T), and CCSD(T) methods with various basis sets. At the highest level of theory, namely, QCISD, the reaction is direct, with only one transition state between reactants and products. However, at the MP2 level, the reaction proceeds through a two-step mechanism and shows two transition states, TS1 and TS2, separated by an intermediate, Int. The different methodologies employed in this paper consistently predict the barrier height of reaction (1) to be within the range 2.16 - 5.11 kcal mol -1 , somewhat higher than the experimental value of 2.0 kcal mol -1 .
Reversible Dimerization and Polymerization of a Janus Diradical To Produce Labile C−C Bonds and Large Chromic Effects
2016
Conducting polymers can be synthesized by irreversible diradical monomer polymerization. A reversible version of this reaction consisting of the formation/dissociation of σ‐dimers and σ‐polymers from a stable quinonoidal diradical precursor is described. The reaction reversibility is made by a quinonoidal molecule which changes its structure to an aromatic species by forming weak and long intermolecular C−C single bonds. The reaction provokes a giant chromic effect of about 2.5 eV. The two opposite but complementary quinonoidal and aromatic tautomers provide the Janus faces of the reactants and products which produces the observed chromic effect. A reaction mechanism is proposed to explain …
Initial reaction steps in the condensed-phase decomposition of propellants
2002
Understanding the reaction mechanisms for the decomposition of NO2-containing energetic materialsin the condensed phase is critical to our development of detailed kinetic models of these energetic materials in propellant combustion. To date, the reaction mechanisms in the condensed phase have been represented by global reactions. The detailed elementary reactions subsequent to the initial NO2 bond scissioning are not known. Using quantum chemical calculations, we have investigated the possible early steps in the decomposition of energetic materials that can occur in the condensed phase. We have used methylnitrate, methylnitramine, and nitroethane as prototypes for O−NO2, N−NO2 and C−NO2 nit…
An ab initio study on the mechanism of the F+O3→FO+O2 reaction: comparative reactivity study along the isoelectronic NH2, OH and F radicals series
2004
Abstract The title reaction has been theoretically studied by using MP2, QCISD, QCISD(T), CCSD(T), CASSCF, and CASPT2 methods with various basis sets. At single-reference MP2 and QCISD levels of theory, the potential energy hypersurface (HPES) shows a two-step reaction mechanism through two transition states (TS1 and TS2) and an intermediate (Int). However, the multiconfigurational CASSCF HPES shows a one-step reaction mechanism, as was previously found for the NH2 + O3 and OH + O3 reactions. The results show that the reactivity of the isoelectronic series of NH2, OH, and F radicals increases from the amino radical to the fluorine atom.
The Reaction Mechanism of Spirocylization and Stereoselectivity Studies for the Calyculin C16 -C25 Fragment
2005
The mechanism of the double intramolecular hetero-Michael addition, a key reaction in the planned synthesis of the natural product calyculin C, has been studied by NMR. The cyclization follows Baldwin’s rules and proceeds first through a six-membered ring closure (6-endo-dig), followed by a five-membered ring cyclization (5-exo-trig). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Metal- and Reagent-Free Electrochemical Synthesis of Alkyl Arylsulfonates in a Multi-Component Reaction.
2020
Abstract This work presents the first electrochemical preparation of alkyl arylsulfonates by direct anodic oxidation of electron‐rich arenes. The reaction mechanism features a multi‐component reaction consisting of electron‐rich arenes, an alcohol of choice and excess SO2 in an acetonitrile‐HFIP reaction mixture. In‐situ formed monoalkyl sulfites are considered as key intermediates with bifunctional purpose. Firstly, this species functions as nucleophile and secondly, excellent conductivity is provided. Several primary and secondary alcohols and electron‐rich arenes are implemented in this reaction to form the alkyl arylsulfonates in yields up to 73 % with exquisite selectivity. Boron‐doped…
Radikalpolymerisation von methylmethacrylat im gesamten umsatzbereich. Stationäre und instationäre experimente zur bestimmung von wachstums- und abbr…
1989
Free-radical polymerization of methyl methacrylate in bulk at 0°C over the full range of conversion is reported. Details for stationary and non-stationary experiments are described allowing to measure both kinetically relevant ratios fk/ka and kw/ka, f representing radical efficiency, kw rate constants of propagation and ka rate constant of termination. From these ratios the absolute rate constants kw and ka are available. The photochemical decay of the initiator 1,1′-azodicyclohexanenitrile in connection with the rotating-sector technique and observation of the post-effect after stopping the initiator decay were used. The rate of polymerization and the number- and weight-average molar mass…
The use of triamcinolone combined with surgery in major ear keloid treatment: a personal two stages approach
2015
Background: Keloid is a fibroproliferative disorder characterized by an abnormal deposition of collagen within a wound. Despite an increased understanding of wound healing and collagen metabolism, the exact cause, the clinical behavior, and gold standard of treatment for keloids remain an enigma. There is no one right way of treatment, the results are variable, and the management of ear keloids can be difficult and frustrating both for patients and physicians. Traditional techniques include intralesional steroids, topical applications of silicone, vitamins, and segmental excision by lasers or surgery. The purposes of this article are to review the literature concerning the current therapies…
Radical Rings with Soluble Adjoint Groups
2002
Abstract An associative ring R , not necessarily with an identity, is called radical if it coincides with its Jacobson radical, which means that the set of all elements of R forms a group denoted by R ∘ under the circle operation r ∘ s = r + s + rs on R . It is proved that every radical ring R whose adjoint group R ∘ is soluble must be Lie-soluble. Moreover, if the commutator factor group of R ∘ has finite torsion-free rank, then R is locally nilpotent.
Efficient DNA Cleavage Induced by Copper(II) Complexes of Hydrolysis Derivatives of 2,4,6‐Tri(2‐pyridyl)‐1,3,5‐triazine in the Presence of Reducing A…
2007
The reaction of 2,4,6-tri(pyridyl)-1,3,5-triazine (ptz) and copper(II) salts in dmf/water (1:1) results in the hydrolysis of ptz and formation of the anions bis(2-pyridylcarbonyl)amide (ptO2–) and bis(2-pyridylamine)amide (ptN2–), which are found in the complexes [Cu(ptN2)(OAc)]·3H2O (1), [Cu(ptO2)(OAc)(H2O)]·H2O (2), [Cu(ptN2)(for)]·3H2O (3) (for = formate), [Cu(ptO2)(for)(H2O)] (4), [Cu(ptO2)(benz)]·H2O (5) (benz = benzoate), and [Cu(ptO2)F(H2O)]2·3H2O (6). This report includes the chemical and spectroscopic characterization of all these complexes along with the crystal structures of 4–6. The coordination spheres of CuII in 4 and 5 are best described as distorted tetragonal square pyramid…