Transfer reactions involving boron. XVII. On the kinetics of the .alpha.-transfer reaction

1968 ◽  
Vol 90 (22) ◽  
pp. 6259-6260 ◽  
Author(s):  
Daniel J. Pasto ◽  
James. Hickman ◽  
Tai-Chun. Cheng
Keyword(s):  
Transfer Reaction ◽  
Transfer Reactions ◽  
Kinetics Of

scholarly journals Nonenzymatic NADH-Dependent Reduction of Keggin-Type 12-Tungstocobaltate(III) in Aqueous Medium

2011 ◽  
Vol 8 (3) ◽  
pp. 1152-1157
Author(s):  
Prabla Kumari ◽  
Alaka Das ◽  
Dillip Kumar Baral ◽  
A. K. Pattanaik ◽  
P. Mohanty
Keyword(s):  
Electron Transfer ◽  
Transition State ◽  
Aqueous Medium ◽  
Transfer Reaction ◽  
Activation Parameters ◽  
Electron Transfer Reaction ◽  
Transfer Reactions ◽  
Electron Transfer Reactions ◽  
First Order ◽  
Kinetics Of

The kinetics of the electron transfer reaction of NADH with 12-tungstocobaltate(III) has been studied over the range 5.07 ≤ 104[NADH] ≤ 15.22 mol dm-3, 7.0 ≤ pH ≤ 8.0 and 20 ≤ t ≤ 35oC in aqueous medium. The electron transfer reaction showed first-order dependence each in [NADH]Tand [12-tungstocobaltate(III)]T. The products of the reaction were found to be NAD+and 12-tungstocobaltate(II). The activation parameters ΔH#(kJ mol-1) and ΔS#(JK-1mol-1) of the electron transfer reactions were found to be 64.4±1.8 and -48.86±6.0. Negative value of ΔS#is an indicative of an ordered transition state for the electron transfer reaction.

scholarly journals Non enzymatic NADH-dependent reduction of Cis-[Co(en)2(H2O)2]3+ in aqueous medium

2018 ◽  
Vol 6 (2) ◽  
pp. 163
Author(s):  
Bharati Behera ◽  
Jashoda Behera
Keyword(s):  
Electron Transfer ◽  
Aqueous Medium ◽  
Transfer Reaction ◽  
Activation Parameters ◽  
Electron Transfer Reaction ◽  
Transfer Reactions ◽  
Electron Transfer Reactions ◽  
First Order ◽  
Order Dependence ◽  
Kinetics Of

The kinetics of the electron transfer reaction of NADH with Cis-[Co(en)2(H2O)2]3+ has been studied over the range 1.0 ≤ 102 [NADH] ≤ 3.0 mol dm-3, 7.0 ≤ pH ≤ 8.0 and 200C ≤ t ≤ 350C in aqueous medium. The rate of electron transfer reaction was found to be first-order dependence each in [NADH]T and Cis-[Co(en)2(H2O)2]3+T. The products of the reaction were found to be NAD+ and Co(II). The corresponding activation parameters of the electron transfer reactions were found to be as ΔH#=27.55 kJ mol-1 and  ΔS#= -189.35 JK-1mol-1. 

Thermal Decomposition Kinetics of Functionalized Polynorbornene

2002 ◽  
Vol 17 (3) ◽  
pp. 632-640 ◽  
Author(s):  
Michael D. Wedlake ◽  
Paul A. Kohl
Keyword(s):  
Thermal Decomposition ◽  
Mass Spectra ◽  
Hydrogen Transfer ◽  
Transfer Reaction ◽  
Transfer Reactions ◽  
Thermogravimetric Analyses ◽  
First Order ◽  
Degradation Reaction ◽  
Intermolecular Hydrogen Transfer ◽  
Kinetics Of

The mechanism and kinetic parameters for the thermal decomposition of four functionalized addition-polymerized polynorbornenes were studied by dynamic and isothermal thermogravimetric analyses and by mass spectrometry. The dynamic and isothermal thermogravimetric analyses showed a first-order degradation reaction mechanism with an activation energy of 229.6 ± 12.5 kJ/mol. Based on the polymer structure, reference mass spectra for related molecules, and a cross-comparison of the mass spectra, the backbone, free-radical scission mechanism was found to occur by cleavage of the linkages between bicyclic rings and the production of volatile monomer and oligomers. The degradation of polynorbornene occurred via a depropagation and transfer reaction process. Initially, the depropagation pathway was preferred, but with increasing conversion, intra- and intermolecular hydrogen transfer reactions dominated.

Nonclassical oxygen atom transfer reactions of an eight-coordinate dioxomolybdenum(vi) complex

2021 ◽  
Author(s):  
Leila G. Ranis ◽  
Jacqueline Gianino ◽  
Justin M. Hoffman ◽  
Seth N. Brown
Keyword(s):  
Oxygen Atom ◽  
Transfer Reaction ◽  
Transfer Reactions ◽  
Atom Transfer ◽  
Oxygen Atom Transfer ◽  
Oxygen Atom Transfer Reactions ◽  
Atom Transfer Reactions ◽  
Oxygen Atoms

Eight-coordinate MoO2(DOPOQ)2 can donate two oxygen atoms to substrates such as phosphines in a four-electron nonclassical oxygen atom transfer reaction.

scholarly journals Electron transfer studies of a conventional redox probe in human sweat and saliva bio-mimicking conditions

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
P. Krishnaveni ◽  
V. Ganesh
Keyword(s):  
Electron Transfer ◽  
Crystalline Phase ◽  
Liquid Crystalline ◽  
Transfer Reaction ◽  
Electron Transfer Reaction ◽  
Redox Couple ◽  
Liquid Crystalline Phase ◽  
Transfer Reactions ◽  
Redox Probe ◽  
Human Sweat

AbstractModern day hospital treatments aim at developing electrochemical biosensors for early diagnosis of diseases using unconventional human bio-fluids like sweat and saliva by monitoring the electron transfer reactions of target analytes. Such kinds of health care diagnostics primarily avoid the usage of human blood and urine samples. In this context, here we have investigated the electron transfer reaction of a well-known and commonly used redox probe namely, potassium ferro/ferri cyanide by employing artificially simulated bio-mimics of human sweat and saliva as unconventional electrolytes. Typically, electron transfer characteristics of the redox couple, [Fe(CN)6]3−/4− are investigated using electrochemical techniques like cyclic voltammetry and electrochemical impedance spectroscopy. Many different kinetic parameters are determined and compared with the conventional system. In addition, such electron transfer reactions have also been studied using a lyotropic liquid crystalline phase comprising of Triton X-100 and water in which the aqueous phase is replaced with either human sweat or saliva bio-mimics. From these studies, we find out the electron transfer reaction of [Fe(CN)6]3−/4− redox couple is completely diffusion controlled on both Au and Pt disc shaped electrodes in presence of sweat and saliva bio-mimic solutions. Moreover, the reaction is partially blocked by the presence of lyotropic liquid crystalline phase consisting of sweat and saliva bio-mimics indicating the predominant charge transfer controlled process for the redox probe. However, the rate constant values associated with the electron transfer reaction are drastically reduced in presence of liquid crystalline phase. These studies are essentially carried out to assess the effect of sweat and saliva on the electrochemistry of Fe2+/3+ redox couple.

Correlation of the solid-state reactivities of racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate and its 4,4′-bipyridine cocrystal with their crystal structures

2014 ◽  
Vol 70 (11) ◽  
pp. 1040-1045 ◽  
Author(s):  
Majid I. Tamboli ◽  
Vir Bahadur ◽  
Rajesh G. Gonnade ◽  
Mysore S. Shashidhar
Keyword(s):  
Solid State ◽  
Self Assembly ◽  
Transfer Reaction ◽  
Acyl Transfer ◽  
Transfer Reactions ◽  
Group Transfer ◽  
Hydrogen Bonding Interactions ◽  
Benzoyl Group ◽  
The Stability ◽  
Group Migration

Racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate, C21H18O8,(1), shows a very efficient intermolecular benzoyl-group migration reaction in its crystals. However, the presence of 4,4′-bipyridine molecules in its cocrystal, C21H18O8·C10H8N2,(1)·BP, inhibits the intermolecular benzoyl-group transfer reaction. In(1), molecules are assembled around the crystallographic twofold screw axis (baxis) to form a helical self-assembly through conventional O—H...O hydrogen-bonding interactions. This helical association places the reactive C6-O-benzoyl group (electrophile, El) and the C4-hydroxy group (nucleophile, Nu) in proximity, with a preorganized El...Nu geometry favourable for the acyl transfer reaction. In the cocrystal(1)·BP, the dibenzoate and bipyridine molecules are arranged alternately through O—H...N interactions. The presence of the bipyridine molecules perturbs the regular helical assembly of the dibenzoate molecules and thus restricts the solid-state reactivity. Hence, unlike the parent dibenzoate crystals, the cocrystals do not exhibit benzoyl-transfer reactions. This approach is useful for increasing the stability of small molecules in the crystalline state and could find application in the design of functional solids.

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