Absolute rate constants for the reaction of peroxyl radicals with cardanol derivatives

2001 ◽  
pp. 2142-2146 ◽  
Author(s):  
Riccardo Amorati ◽  
Gian Franco Pedulli ◽  
Luca Valgimigli ◽  
Orazio A. Attanasi ◽  
Paolino Filippone ◽  
...  
Keyword(s):  
Rate Constants ◽  
Peroxyl Radicals ◽  
Absolute Rate

Quantitative studies of the autoxidation of linoleate monomers sequestered in phosphatidylcholine bilayers. Absolute rate constants in bilayers

1985 ◽  
Vol 63 (10) ◽  
pp. 2633-2638 ◽  
Author(s):  
Lawrence Ross Coates Barclay ◽  
Steven Jeffrey Locke ◽  
Joseph Mark MacNeil ◽  
Joann Vankessel
Keyword(s):  
Linoleic Acid ◽  
Methyl Linoleate ◽  
Rate Constant ◽  
Rate Constants ◽  
Homogeneous Solution ◽  
Propagation Rate ◽  
Water Soluble ◽  
Peroxyl Radicals ◽  
Absolute Rate ◽  
Hydrophobic Region

The kinetics of autoxidation of linoleic acid in dimyristoylphosphatidylcholine (DMPC) bilayers were studied at 30 °C and pH 7 under 760 Torr O2. Reactions were initiated using either the lipid-soluble di-tert-butylhyponitrite (DBHN) or water-soluble azobis(2-amidinopropane)•HCl (ABAP). Rates of chain initiation, Ri, were measured with a lipid-soluble antioxidant, a-tocopherol, or a water-soluble one, 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylate (Trolox). The slightly higher oxidizability obtained [Formula: see text] compared to methyl linoleate in chlorobenzene [Formula: see text] is attributed to a moderate polar solvent effect on ionized linoleate near the bilayer surface. A low initiator efficiency, e = 0.0895 for DBHN in DMPC, is attributed to the cage effect in the bilayer of high microviscosity. Similar autoxidation experiments on methyl linoleate in DMPC bilayers gave a lower oxidizability [Formula: see text], indicating that the ester is sequestered deeper in the hydrophobic region of DMPC than is ionized linoleate. Some absolute rate constants are determined using the rotating sector technique for linoleic acid in 0.50 M SDS micelles, and egg lecithin and dilinoleoylphosphatidylcholine (DLPC) bilayers. A hundredfold decrease in the termination rate constant, 2kt for DLPC bilayer compared to homogeneous solution is attributed to chain termination in a bilayer region of high polarity. A concomitant reduction (up to tenfold) in the propagation rate constant, kp, is attributed to diffusion of polar peroxyl radicals away from the oxidizable region of the bilayer.

ChemInform Abstract: ABSOLUTE RATE CONSTANTS FOR REACTIONS OF PHENYL RADICALS

1978 ◽  
Vol 9 (20) ◽  
Author(s):  
V. MADHAVAN ◽  
R. H. SCHULER ◽  
R. W. FESSENDEN
Keyword(s):  
Rate Constants ◽  
Absolute Rate ◽  
Phenyl Radicals

Reactions of the hydroxyl radical. Part 2.—Determination of absolute rate constants

1965 ◽  
Vol 61 (0) ◽  
pp. 1417-1424 ◽  
Author(s):  
G. E. Adams ◽  
J. W. Boag ◽  
B. D. Michael
Keyword(s):  
Hydroxyl Radical ◽  
Rate Constants ◽  
Absolute Rate

Absolute Rate Constants for the Reactions of O(3P) Atoms with C2H4 and C2D4

1972 ◽  
Vol 57 (12) ◽  
pp. 5403-5408 ◽  
Author(s):  
F. Stuhl ◽  
H. Niki
Keyword(s):  
Rate Constants ◽  
Absolute Rate

Absolute Rate Constants for Hydrocarbon Autoxidation. Part XX. Oxidation of Some Organic Sulfides

1971 ◽  
Vol 49 (12) ◽  
pp. 2178-2182 ◽  
Author(s):  
J. A. Howard ◽  
S. Korcek
Keyword(s):  
Liquid Phase ◽  
Hydrogen Atom ◽  
Rate Constants ◽  
Hydrogen Atom Abstraction ◽  
Absolute Rate ◽  
Organic Sulfides

Absolute rate constants for the liquid phase autoxidation of some organic sulfides at 30 °C have been measured. The reactivities of organic sulfides towards t-butylperoxy radicals are equal to or somewhat less than the reactivities of structurally analogous ethers. The α-alkylthiylalkylperoxy radicals appear to be about 3–5 times more reactive in hydrogen atom abstraction than the α-alkoxyalkylperoxy radicals.

An electron spin resonance study of the reactions of hydrogen atoms with halocarbons

1986 ◽  
Vol 64 (11) ◽  
pp. 2192-2195 ◽  
Author(s):  
William E. Jones ◽  
Joseph L. Ma
Keyword(s):  
Rate Constants ◽  
Gas Flow ◽  
Esr Spectroscopy ◽  
Flow System ◽  
Electron Spin Resonance Study ◽  
Absolute Rate ◽  
Hydrogen Atoms ◽  
Vinyl Halides ◽  
Spin Resonance ◽  
Spin Resonance Study

The absolute rate constants for the reaction of H atoms with methyl- and vinyl-halides have been determined using esr spectroscopy and a conventional gas flow system. The rate constants determined at 298 ± 2 K at a pressure of 0.55 Torr are methane, (1.7 ± 0.3) × 10−17; ethane, (2.3 ± 0.5) × 10−17; methylfluoride, (4 ± 3) × 10−15; methylchloride, (8 ± 2) × 10−16; methylbromide, (2.1 ± 0.6) × 10−14; vinylfluoride, (1.47 ± 0.02) × 10−13; vinylchloride, (1.66 ± 0.08) × 10−13; and vinylbromide (4.07 ± 0.73) × 10−13 in units of cm3 molecule−1 s−1.

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