Reactions of oxygen with hemerythrin, myoglobin and hemocyanin: effects of deuterium oxide on equilibration rate constants and evidence for hydrogen-bonding

1986 ◽  
Vol 25 (18) ◽  
pp. 3135-3139 ◽  
Author(s):  
Graeme D. Armstrong ◽  
A. Geoffrey Sykes
Keyword(s):  
Hydrogen Bonding ◽  
Rate Constants ◽  
Deuterium Oxide ◽  
Equilibration Rate

Aqueous Nonelectrolyte Solutions. Part IX. Enthalpies of Mixing of Water and Deuterium Oxide with Ethylene Oxide

1971 ◽  
Vol 49 (11) ◽  
pp. 1830-1840 ◽  
Author(s):  
D. N. Glew ◽  
Harry Watts
Keyword(s):  
Hydrogen Bonding ◽  
Ethylene Oxide ◽  
Composition Range ◽  
Deuterium Oxide ◽  
Enthalpy Of Mixing ◽  
Water Systems ◽  
Oxide System ◽  
Water Proton ◽  
Oxide Systems ◽  
Enthalpies Of Mixing

Calorimetric enthalpies of mixing have been measured over the whole composition range for the water – ethylene oxide system at 10.75 and 20.00 °C and for the deuterium oxide – ethylene oxide system at 13.45 and 20.00 °C. Less extensive measurements have been made for dilute ethylene oxide solutions in water at 0.6 °C and in deuterium oxide at 4.1 and 7.3 °C. The experimental S-shaped, enthalpy of mixing – composition curves are interpreted in terms of solution hydrogen bonding changes, with particular reference to the hydrogen bonding of water. At low ethylene oxide mole fractions the deuterium oxide systems are more exothermal and at high ethylene oxide mole fractions more endothermal than the corresponding water systems. A good correlation is found between the enthalpy of mixing and the water proton magnetic resonance chemical shift for solutions with greater than 0.55 mol fraction of ethylene oxide.

Singlet Oxygen Generation by 8-Methoxypsoralen in Deuterium Oxide:  Relaxation Rate Constants and Dependence of the Generation Efficacy on the Oxygen Partial Pressure

2002 ◽  
Vol 106 (22) ◽  
pp. 5776-5781 ◽  
Author(s):  
Roland Engl ◽  
Robert Kilger ◽  
Max Maier ◽  
Kathrin Scherer ◽  
Christoph Abels ◽  
...  
Keyword(s):  
Oxygen Partial Pressure ◽  
Partial Pressure ◽  
Singlet Oxygen ◽  
Relaxation Rate ◽  
Rate Constants ◽  
Deuterium Oxide ◽  
Oxygen Generation ◽  
Singlet Oxygen Generation

scholarly journals Catalysis by acetylcholinesterase in two-hydronic-reactive states. Integrity of deuterium oxide effects and hydron inventories

1992 ◽  
Vol 285 (2) ◽  
pp. 451-460 ◽  
Author(s):  
E Salih
Keyword(s):  
Kinetic Parameters ◽  
Conformational Change ◽  
Rate Constants ◽  
Literature Abstract ◽  
Deuterium Oxide ◽  
Ph Dependence ◽  
Reversible Inhibitor ◽  
Induced Fit ◽  
Rate Limiting ◽  
Hydrolysis Of

Low 2H2O effects (1.0-1.5) for the parameter k(cat.)/Km in the hydrolysis of various substrates by acetylcholinesterase (AcChE) is due to normal 2H2O effects (1.8-2.8) for the parameter k(cat.) and 2H2O effects of 1.0-2.5 for the parameter Km. The analyses and interpretations of 2H2O effects in the literature utilizing the parameter k(cat.)/Km, which led to the proposal of ‘isotope insensitivity’ of the catalytic steps and the hypothesis of a rate-limiting substrate-induced-fit conformational change, are incorrect. Since k(cat.) is the only parameter that can represent the hydron-transfer step solely, the 2H2O effect can most appropriately be evaluated by using this parameter. Calculations and comparison of acylation (k+2) and deacylation (k+3) rate constants show that acylation is rate-determining for most substrates and the improved binding -0.84 to -2.09 kJ/mol (-0.2 to -0.5 kcal/mol) in 2H2O obscures the normal 2H2O effect on k(cat.) when the ratio k(cat.)/Km is utilized. Consistent with this, measurements of the inhibition constant (KI(com.)) for a reversible inhibitor, phenyltrimethylammonium, lead to KI(com.)H2O = 39 +/- 3 microM and KI(com.)2H2O = 24.5 +/- 3.5 microM, an 2H2O effect of 1.59 +/- 0.26. pH-dependence of k(cat.) in 2H2O is subject to variability of the pK(app.) values, as evaluated in terms of the two-hydronic-reactive states (EH and EH2) of AcChE, and is due to an uneven decrease in 2H2O of the kinetic parameters k'cat. for the EH2 state relative to k(cat.) for the EH state, thus leading to variable shifts in pK(app.) values of between 0.5 and 1.2 pH units for this parameter. The observed pH-independent limiting rate constants for k(cat.)/Km(app.) are made to vary between 0.5 and 1.0 in 2H2O by effects on kinetic parameters for the EH2 state, k'cat./K'm varying between 0.2 and 0.7 relative to the EH state, with k(cat.)/Km varying between 0.4 and 1.0. The effects observed on k(cat.)/Km(app.) are ultimately the result of variable effects of 2H2O on k'cat. and K'm for the EH2 state relative to k(cat.) and Km for the EH state of AcChE. These effects are responsible for the variable shifts and more than 0.5 pH unit of the pK(app.) values in 2H2O for pH-k(cat.)/Km profiles. The upward-bowing hydron inventories for k(cat.)/Km are the result of linear hydron inventories for k(cat.) and downward-bowing on Km and are not due to the rate-limiting substrate-induced fit process as claimed in the literature.(ABSTRACT TRUNCATED AT 400 WORDS)

The antioxidant activities of phenolic antioxidants in free radical peroxidation of phospholipid membranes

1990 ◽  
Vol 68 (12) ◽  
pp. 2258-2269 ◽  
Author(s):  
Lawrence Ross Coates Barclay ◽  
Kimberly Ann Baskin ◽  
Kelly Andrea Dakin ◽  
Steven Jefffrey Locke ◽  
Melinda Ruth Vinqvist
Keyword(s):  
Hydrogen Bonding ◽  
Free Radical ◽  
Rate Constants ◽  
Antioxidant Activities ◽  
Hydrogen Abstraction ◽  
Peroxyl Radicals ◽  
Phenolic Antioxidants ◽  
Inhibition Rate ◽  
Radical Chain ◽  
Tert Butyl

Autoxidation of dilinoleoylphosphatidylcholine (DLPC) bilayers photoinitiated by benzophenone takes place by a free radical chain mechanism according to product studies of the cis, trans and trans, trans-9- and -13-linoleate hydroperoxides formed and kinetic studies of the reaction order as a function of light intensity. The absolute rate constant for hydrogen abstraction from DLPC bilayers by peroxyl radicals is found to be 36.1 M−1 s−1 at 37 °C. Preliminary measurements of activities of phenolic antioxidants, α-tocopherol (α-T), 2,2,5,7,8-pentamethyl-6-hydroxychroman (PMHC), 2,5,7,8-tetramethyl-6-hydroxychroman-2-carboxylate (Trolox), and 2,6-di-tert-butyl-4-methylphenol (BHT) by oxygen uptake studies during inhibition periods using photoinitiation gave uncorrected inhibition rate constants, Kinh, for α-T, PMHC, and Trolox several orders of magnitude lower than observed earlier in chlorobenzene. Three series of phenolic antioxidants, (a) polyalkyl-6-hydroxychromans, (b) polyalkyl-4-methoxyphenols, and (c) trialkylphenols, were examined for their antioxidant activities in DLPC membranes during thermally initiated autoxidation by azobis-2,4-dimethylvaleronitrile (DMVN). The corrected inhibition rate constants, kinh, observed in (a), α-T (5.8 × 103), PMHC (17.8 × 103), Trolox (5.8 × 103), 2,2-dimethyl-5,7-diisopropyl-6-hydroxychroman, 4a (55 × 103), and 2,2,5-trimethyl-7-tert-butyl-6-hydroxychroman, 5a (61 × 103) M−1 s−1, are dramatically lower, by several orders of magnitude, than those measured earlier in chlorobenzene and significantly lower (about 1/40–1/10) than those measured in solution in tert-butyl alcohol and less than kinh measurements (1/2–1/5) in aqueous SDS micelles. The kinh values for series (b) were 2,3,5,6-tetramethyl-4-methoxyphenol (TTMMP) (2.1 × 103), 2,3,6-trimethyl-4-methoxyphenol (TMMP) (10.4 × 103), and 2,6-di-tert-butyl-4-methoxyphenol (DBHA) (27.5 × 103) M−1 s−1 and for (c) were 2,6-di-tert-butyl-4-methylphenol (BHT) (3.7 × 103) and 2,4,6-trimethylphenol (TMP) (0.56 × 103) M−1 s−1. The results show an overall leveling and depression of antioxidant activities in DLPC membranes in the series (a), (b), (c) compared to those reported in solution in chlorobenzene, where large differences were attributed to steroelectronic effects of the para ether oxygen stabilizing the derived phenoxyl radicals in (a) and (b) types. The results in aqueous micellar and membrane systems are interpreted in terms of polar solvation effects. Hydrogen bonding by water at both the ether and phenolic groups decreases the activity of the (a) series. Hydrogen bonding at the phenolic hydroxyl appears to be the more significant factor since steric hindrance to H-bonding at hydroxyl allows 4a and 5a to be the most active antioxidants of the α-tocopherol series (a) and DBHA to be the most active antioxidant of the (b) series. Keywords: antioxidant activities, phenols, membranes, peroxidation, kinetics.

Do epoch lengths of hypnotic depth indicators affect estimated of blood-brain equilibration rate constants of propofol?

2021 ◽  
Author(s):  
Kyung Mi Kim ◽  
Sookyung Park ◽  
Bong Jin Kang ◽  
Byung-Moon Choi ◽  
Gyu-Jeong Noh ◽  
...  
Keyword(s):  
Rate Constants ◽  
Blood Brain ◽  
Equilibration Rate

Infrared Investigation of H2S Adsorption and Decomposition on Alumina and on Alumina Supported Molybdenum Sulfide

1972 ◽  
Vol 50 (21) ◽  
pp. 3416-3423 ◽  
Author(s):  
T. L. Slager ◽  
C. H. Amberg
Keyword(s):  
Hydrogen Bonding ◽  
Rate Constants ◽  
Kinetic Data ◽  
Surface Reaction ◽  
Molybdenum Sulfide ◽  
Subsequent Reaction ◽  
Alumina Support ◽  
First Order ◽  
H2s Adsorption ◽  
Surface Bond

Adsorption and subsequent reaction of H2S on alumina gave major i.r. bands at 1341, 1568, 1625, and 3400 cm−1. Relative band intensities were used to follow the first order decomposition of adsorbed H2S and formation of H2O. Rate constants of the surface reaction at 23, 55, and 80 °C were 0.70, 1.48, and 3.42 × 10−3 s−1, respectively. A mechanism consistent with the observed spectral and kinetic data involved adsorption to an exposed Al ion forming an Al—S surface bond, and hydrogen bonding to neighboring O and OH species. It was assumed that the sulfur remained on the surface as a sulfide. The 1568 cm−1 band was discussed in terms of an Al—O species.With adsorption on MoS2–Al2O3, bands appeared at 1330 and 1575 cm−1. Behavior in all respects was similar to that observed on the alumina support alone.

Enhancement of hydrogen bonding in vicinal water; heat capacity of water and deuterium oxide in silica pores

Langmuir ◽  
1988 ◽  
Vol 4 (4) ◽  
pp. 878-883 ◽  
Author(s):  
Frank M. Etzler
Keyword(s):  
Heat Capacity ◽  
Hydrogen Bonding ◽  
Deuterium Oxide
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