Search results for "chemical reaction"

The Greenland shark Somniosus microcephalus—Hemoglobins and ligand-binding properties

2017

A large amount of data is currently available on the adaptive mechanisms of polar bony fish hemoglobins, but structural information on those of cartilaginous species is scarce. This study presents the first characterisation of the hemoglobin system of one of the longest-living vertebrate species (392 +/- 120 years), the Arctic shark Somniosus microcephalus. Three major hemoglobins are found in its red blood cells and are made of two copies of the same a globin combined with two copies of three very similar beta subunits. The three hemoglobins show very similar oxygenation and carbonylation properties, which are unaffected by urea, a very important compound in marine elasmobranch physiology.…

Characteristic asymptotics for fast chemical reaction

1995

Origin of Enzymatic Kinetic Isotope Effects in Human Purine Nucleoside Phosphorylase

2017

Here we report a study of the effect of heavy isotope labeling on the reaction catalyzed by human purine nucleoside phosphorylase (hPNP) to elucidate the origin of its catalytic effect and of the enzymatic kinetic isotope effect (EKIE). Using quantum mechanical and molecular mechanical (QM/MM) molecular dynamics (MD) simulations, we study the mechanism of the hPNP enzyme and the dynamic effects by means of the calculation of the recrossing transmission coefficient. A free energy surface (FES), as a function of both a chemical and an environmental coordinate, is obtained to show the role of the environment on the chemical reaction. Analysis of reactive and nonreactive trajectories allows us …

Gold/Isophorone Interaction Driven by Keto/Enol Tautomerization

2016

The binding behavior of isophorone (C9H14O) to Au adatoms and clusters deposited on MgO/Ag(001) thin films is investigated by scanning tunneling microscopy (STM) and density functional theory (DFT). The STM data reveal the formation of various metal/organic complexes, ranging from Au1/isophorone pairs to larger Au aggregates with molecules bound to their perimeter. DFT calculations find the energetically preferred keto-isophorone to be unreactive toward gold, while the enol-tautomer readily binds to Au monomers and clusters. The interaction is governed by electrostatic forces between the hydroxyl group of the enol and negative excess charges residing on the ad-gold. The activation barrier b…

Effect of Superbasic Ionic Liquids on the Synthesis of Dendritic PolyaminesviaAza-Michael Addition Reaction

2017

Catalytic effect of selected superbasic ionic liquids on the yield and selectivity of aza-Michael addition of ethylenediamine and ammonia to acrylonitrile was investigated. The reactions were performed in calorimetric reactor equipped with RT-IR probe (real-time IR), where all energy changes associated with chemical reactions and physical transformations were monitored. Catalytic activity of selected superbasic ionic liquids in aza-Michael addition ethylenediamine and ammonia to acrylonitrile were determined and obtained polynitriles were then hydrogenatated to final three- and four-directional dendritic polyamines. The products were characterized by instrumental analytical methods, includi…

Generation of oxysterols formed by free radicals and enzymes by electrochemical oxidation

2016

International audience; It is commonly accepted that cholesterol oxide derivatives, also named oxysterols, are 27 carbon-atom molecules deriving either from enzymatic and non-enzymatic oxidation of cholesterol. Most of these compounds can be synthesized by more or less difficult and time consuming chemical reactions, and some of them have been discovered before the identification of the enzymes [mainly cytochrome P450 enzymes (CYP enzymes)] involved in their biosynthesis. A wide range of biological activities depends on oxysterols. Some oxysterols are also involved in the synthesis of cholesterol metabolites which have various properties. The paper by Weber et al. in this issue of European …

Lack of a peroxiredoxin suppresses the lethality of cells devoid of electron donors by channelling electrons to oxidized ribonucleotide reductase

2017

The thioredoxin and glutaredoxin pathways are responsible of recycling several enzymes which undergo intramolecular disulfide bond formation as part of their catalytic cycles such as the peroxide scavengers peroxiredoxins or the enzyme ribonucleotide reductase (RNR). RNR, the rate-limiting enzyme of deoxyribonucleotide synthesis, is an essential enzyme relying on these electron flow cascades for recycling. RNR is tightly regulated in a cell cycle-dependent manner at different levels, but little is known about the participation of electron donors in such regulation. Here, we show that cytosolic thioredoxins Trx1 and Trx3 are the primary electron donors for RNR in fission yeast. Unexpectedly,…

Molecular Diversity Required for the Formation of Autocatalytic Sets

2019

Systems chemistry deals with the design and study of complex chemical systems. However, such systems are often difficult to investigate experimentally. We provide an example of how theoretical and simulation-based studies can provide useful insights into the properties and dynamics of complex chemical systems, in particular of autocatalytic sets. We investigate the issue of the required molecular diversity for autocatalytic sets to exist in random polymer libraries. Given a fixed probability that an arbitrary polymer catalyzes the formation of other polymers, we calculate this required molecular diversity theoretically for two particular models of chemical reaction systems, and then verify …

Analysis of metabolic pathways by the growth of cells in the presence of organic solvents

1996

A new approach to the analysis of metabolic pathways involving poorly water-soluble intermediates is proposed. It relies upon the ability of the hydrophobic intermediates formed by a sequence of intracellular reactions to cross the membrane(s) and partition between aqueous and organic phases, when cells are incubated in the presence of a nonpolar and nontoxic organic solvent. As a result of this thermodynamically driven efflux of the formed intermediates from the cell, they accumulate in the organic medium in sufficient quantities for GC-MS analysis and identification. This enables direct determination of the sequence of chemical reactions involved with no requirement for the isolation of e…

Spectrophotometric determination of ethiofencarb in waters by reaction with p-aminophenol

1993

An automatized procedure has been developed for the spectrophotometric determination of ethiofencarb in water by reaction with p-aminophenol after alkaline hydrolysis to obtain the corresponding phenol sulphone. The hydrolyzed samples are continuously introduced into different manifolds at the same time as 300 mg/l p-aminophenol, 0.004 mol/l KIO4 and 0.04 mol/l NaOH solutions. The absorbance is measured at 638 nm after a reaction time of 6 min in stop flow. This absorbance band corresponds to the indo dye obtained from the reaction between the phenol sulphone of ethiofencarb and the quinoneimine form of the p-aminophenol and it permits a matrix-free spectrophotometric determination of ethio…