Elementary kinetics of nitrogen electroreduction on Fe surfaces

2019 ◽  
Vol 150 (4) ◽  
pp. 041708 ◽  
Author(s):  
Sharad Maheshwari ◽  
Gholamreza Rostamikia ◽  
Michael J. Janik
Keyword(s):  
Elementary Kinetics ◽  
Kinetics Of

scholarly journals Particle-based simulation reveals macromolecular crowding effects on the Michaelis-Menten mechanism

2018 ◽  
Author(s):  
Daniel R. Weilandt ◽  
Vassily Hatzimanikatis
Keyword(s):  
Computational Models ◽  
Enzyme Reaction ◽  
Phosphoglycerate Mutase ◽  
Cell Physiology ◽  
Enzymatic Reactions ◽  
Elementary Reactions ◽  
Elementary Kinetics ◽  
Kinetics Of

AbstractMany computational models for analyzing and predicting cell physiology rely onin vitrodata, collected in dilute and cleanly controlled buffer solutions. However, this can mislead models because about 40% of the intracellular volume is occupied by a dense mixture of proteins, lipids, polysaccharides, RNA, and DNA. These intracellular macromolecules interact with enzymes and their reactants and affect the kinetics of biochemical reactions, makingin vivoreactions considerably more complex than thein vitrodata indicates. In this work, we present a new type of kinetics that captures and quantifies the effect of volume exclusion and any other spatial phenomena on the kinetics of elementary reactions. We further developed a framework that allows for the efficient parameterization of this type of kinetics using particle simulations. Our formulation, entitled GEneralized Elementary Kinetics (GEEK), can be used to analyze and predict the effect of intracellular crowding on enzymatic reactions and was herein applied to investigate the influence of crowding on phosphoglycerate mutase inEscherichia coli, which exhibits prototypical reversible Michaelis-Menten kinetics. Current research indicates that many enzymes are reaction limited and not diffusion limited, and our results suggest that the influence of fractal diffusion is minimal for these reaction-limited enzymes. Instead, increased association rates and decreased dissociation rates lead to a strong decrease in the effective maximal velocitiesVmaxand the effective Michaelis-Menten constantsKMunder physiologically relevant volume occupancies. Finally, the effects of crowding in the context of a linear pathway were explored, with the finding that crowding can have a redistributing effect, relative to ideal conditions, on the effective flux responses in the case of two-fold enzyme overexpression. We suggest that the presented framework in combination with detailed kinetics models will improve our understanding of enzyme reaction networks under non-ideal conditions.

scholarly journals Adenosine diphosphate sulphurylase activity in leaf tissue

1973 ◽  
Vol 133 (3) ◽  
pp. 417-428 ◽  
Author(s):  
Jim N. Burnell ◽  
John W. Anderson
Keyword(s):  
Leaf Tissue ◽  
Thiol Group ◽  
Adenosine Diphosphate ◽  
Ph Optimum ◽  
Elementary Kinetics ◽  
Crude Extracts ◽  
Standard Assay ◽  
Spinach Leaf ◽  
Kinetics Of ◽  
Assay Conditions

1. A new method is described for the assay of ADP sulphurylase. The method involves sulphate-dependent [32P]Pi–ADP exchange; the method is simpler, more sensitive and more direct than the method involving adenosine 5′-sulphatophosphate-dependent uptake of Pi. 2. ADP sulphurylase activity was demonstrated in crude extracts of leaf tissue from a range of plants. Crude spinach extract catalysed the sulphate-dependent synthesis of [32P]ADP from [32P]Pi; spinach extracts did not catalyse sulphate-dependent AMP–Pi, ADP–PPi or ATP–Pi exchange under standard assay conditions. ADP sulphurylase activity in spinach leaf tissue was associated with chloroplasts and was liberated by sonication. 3. Some elementary kinetics of crude spinach leaf and purified yeast ADP sulphurylases in the standard assay are described; addition of Ba2+ was necessary to minimize endogenous Pi–ADP exchange of the yeast enzyme and crude extracts of winter-grown spinach. 4. Spinach leaf ADP sulphurylase was activated by Ba2+ and Ca2+; Mg2+ was ineffective. The yeast enzyme was also activated by Ba2+. The activity of both enzymes decreased with increasing ionic strength. 5. Purified yeast and spinach leaf ADP sulphurylases were sensitive to thiol-group reagents and fluoride. The pH optimum was 8. ATP inhibited sulphate-dependent Pi–ADP exchange. Neither selenate nor molybdate inhibited sulphate-dependent Pi–ADP exchange and crude spinach extracts did not catalyse selenate-dependent Pi–ADP exchange. 6. The presence of ADP sulphurylase activity jeopardizes the enzymic synthesis of adenosine 5′-sulphatophosphate from ATP and sulphate with purified ATP sulphurylase and pyrophosphatase.

Elementary kinetics of nitrogen electroreduction to ammonia on late transition metals

2019 ◽  
Vol 9 (1) ◽  
pp. 174-181 ◽  
Author(s):  
Gholamreza Rostamikia ◽  
Sharad Maheshwari ◽  
Michael J. Janik
Keyword(s):  
Density Functional Theory ◽  
Transition Metals ◽  
Density Functional ◽  
Reduction Reaction ◽  
Functional Theory ◽  
Elementary Kinetics ◽  
Late Transition Metals ◽  
Reaction Barriers ◽  
Late Transition ◽  
Kinetics Of

Nitrogen reduction reaction barriers calculated by density functional theory quantify NRR activity and selectivity challenges.

Modelling of elementary kinetics of H2 and CO oxidation on ceria pattern cells

2015 ◽  
Vol 182 ◽  
pp. 202-211 ◽  
Author(s):  
HC Patel ◽  
AN Tabish ◽  
PV Aravind
Keyword(s):  
Co Oxidation ◽  
Elementary Kinetics ◽  
Kinetics Of

Direct observations of radiation-enhanced transformations in glass

1983 ◽  
Vol 41 ◽  
pp. 354-355
Author(s):  
J. F. DeNatale ◽  
D. G. Howitt
Keyword(s):  
Glass Matrix ◽  
Diffusion Mechanism ◽  
Bubble Formation ◽  
Silicate Glasses ◽  
Phase Decomposition ◽  
Direct Observations ◽  
Thin Foils ◽  
Oxygen Bubble ◽  
Electron Energy Loss ◽  
Kinetics Of

The electron irradiation of silicate glasses containing metal cations produces various types of phase separation and decomposition which includes oxygen bubble formation at intermediate temperatures figure I. The kinetics of bubble formation are too rapid to be accounted for by oxygen diffusion but the behavior is consistent with a cation diffusion mechanism if the amount of oxygen in the bubble is not significantly different from that in the same volume of silicate glass. The formation of oxygen bubbles is often accompanied by precipitation of crystalline phases and/or amorphous phase decomposition in the regions between the bubbles and the detection of differences in oxygen concentration between the bubble and matrix by electron energy loss spectroscopy cannot be discerned (figure 2) even when the bubble occupies the majority of the foil depth.The oxygen bubbles are stable, even in the thin foils, months after irradiation and if van der Waals behavior of the interior gas is assumed an oxygen pressure of about 4000 atmospheres must be sustained for a 100 bubble if the surface tension with the glass matrix is to balance against it at intermediate temperatures.

Irradiation behavior of pyrolytic silicon carbide

1983 ◽  
Vol 41 ◽  
pp. 72-73
Author(s):  
R. J. Lauf
Keyword(s):  
Silicon Carbide ◽  
Fission Products ◽  
Thermodynamics And Kinetics ◽  
Neutron Fluences ◽  
Fuel Particles ◽  
Sic Coatings ◽  
Irradiation Behavior ◽  
Kinetics Of ◽  
Htgr Fuel

Fuel particles for the High-Temperature Gas-Cooled Reactor (HTGR) contain a layer of pyrolytic silicon carbide to act as a miniature pressure vessel and primary fission product barrier. Optimization of the SiC with respect to fuel performance involves four areas of study: (a) characterization of as-deposited SiC coatings; (b) thermodynamics and kinetics of chemical reactions between SiC and fission products; (c) irradiation behavior of SiC in the absence of fission products; and (d) combined effects of irradiation and fission products. This paper reports the behavior of SiC deposited on inert microspheres and irradiated to fast neutron fluences typical of HTGR fuel at end-of-life.

The Ordered Phase Formation in Ti-Al-Ga Alloys

1970 ◽  
Vol 28 ◽  
pp. 440-441
Author(s):  
Shiro Fujishiro ◽  
Harold L. Gegel
Keyword(s):  
Thermal Stability ◽  
High Temperature ◽  
Titanium Alloys ◽  
Growth Kinetics ◽  
Stoichiometric Composition ◽  
Good Potential ◽  
Alpha Titanium ◽  
Cold Rolled ◽  
Kinetics Of ◽  
Thermal Stability Of

Ordered-alpha titanium alloys having a DO19 type structure have good potential for high temperature (600°C) applications, due to the thermal stability of the ordered phase and the inherent resistance to recrystallization of these alloys. Five different Ti-Al-Ga alloys consisting of equal atomic percents of aluminum and gallium solute additions up to the stoichiometric composition, Ti3(Al, Ga), were used to study the growth kinetics of the ordered phase and the nature of its interface.The alloys were homogenized in the beta region in a vacuum of about 5×10-7 torr, furnace cooled; reheated in air to 50°C below the alpha transus for hot working. The alloys were subsequently acid cleaned, annealed in vacuo, and cold rolled to about. 050 inch prior to additional homogenization

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