Search results for "THERMODYNAMICS"

A Theoretical and Experimental Study of Electrochemical pH Control at Gold Interdigitated Microband Arrays

2021

In electroanalysis, solution pH is a critical parameter that often needs to be adjusted and controlled for the detection of particular analytes. This is most commonly performed by the addition of chemicals, such as strong acids or bases. Electrochemical in-situ pH control offers the possibility for the local adjustment of pH at the point of detection, without additional reagents. FEA simulations have been performed to guide experimental design for both electroanalysis and in-situ control of solution pH. No previous model exists that describes the generation of protons at an interdigitated electrode array in buffered solution with one comb acting as a protonator, and the other as the sensor.…

Three‐Component Castagnoli‐Cushman Reaction of 3‐Arylglutaconic Acid Anhydrides, Carbonyl Compounds, and Ammonium Acetate: a Quick and Flexible Way t…

2021

1984

By means of data from critical demixing and vapour pressure measurements and by inverse gas chromatography, including the results of published light scattering measurments, a consistent picture is obtained for the entire dependence of the Flory-Huggins parameter χ on the weight fraction w2 of the polymer and on the temperature T for the system tert-butyl acetate/polystyrene. Within the entire T-range (ca. 0°C – 140°C), χ increases stronger than exponentially with w2, the rise being the larger the larger χH (the enthalpy contribution to χ) becomes in the limit of infinite dilution. At sufficiently high temperatures (≳ 50°C), χH changes its sign from negative to positive as w2 is raised. This…

Linear ViscoElastic (LVE) Behaviour of Pure Bitumen via Fractional Model

2012

AbstractBy fitting experimental data from static creep/recovery carried out on pure bitumen, it is shown that the fractional model proposed enables the description of both creep and recovery behaviour with fewer parameters than those needed by other models in the literature. In particular, the model is fitted to experimental data of complex modulus |G*| and phase angle δ° obtained from Dynamic Mechanical Analysis. Lastly, it is demonstrated that when the fractional model is used, complex modulus isotherms for a range of frequencies can be created simply starting from isochronals at f = 1Hz.

Methionine in a protein hydrophobic core drives tight interactions required for assembly of spider silk

2019

Web spiders connect silk proteins, so-called spidroins, into fibers of extraordinary toughness. The spidroin N-terminal domain (NTD) plays a pivotal role in this process: it polymerizes spidroins through a complex mechanism of dimerization. Here we analyze sequences of spidroin NTDs and find an unusually high content of the amino acid methionine. We simultaneously mutate all methionines present in the hydrophobic core of a spidroin NTD from a nursery web spider’s dragline silk to leucine. The mutated NTD is strongly stabilized and folds at the theoretical speed limit. The structure of the mutant is preserved, yet its ability to dimerize is substantially impaired. We find that side chains of…

A Simple Complex on the Verge of Breakdown: Isolation of the Elusive Cyanoformate Ion

2014

Cyanide Hitches a Ride Cyanide is a by-product of the biosynthesis of ethylene in plants and it has been somewhat puzzling how the ion is safely removed before it can shut down enzymatic pathways by coordination to catalytic iron centers. A proposed mechanism has implicated the cyanoformate ion—essentially, a weak adduct of cyanide and carbon dioxide—as the initial product, although its lifetime was uncertain. Murphy et al. (p. 75 ; see the Perspective by Alabugin and Mohamed ) crystallized this previously elusive adduct and found that its solution-phase stability varies inversely with the dielectric properties of the medium. The results bolster a picture in which the adduct shuttles the cy…

B‐DNA structure and stability: the role of nucleotide composition and order

2022

Abstract We have quantum chemically analyzed the influence of nucleotide composition and sequence (that is, order) on the stability of double‐stranded B‐DNA triplets in aqueous solution. To this end, we have investigated the structure and bonding of all 32 possible DNA duplexes with Watson–Crick base pairing, using dispersion‐corrected DFT at the BLYP‐D3(BJ)/TZ2P level and COSMO for simulating aqueous solvation. We find enhanced stabilities for duplexes possessing a higher GC base pair content. Our activation strain analyses unexpectedly identify the loss of stacking interactions within individual strands as a destabilizing factor in the duplex formation, in addition to the better‐known eff…

Thermodynamics and Biophysics of Biomedical Nanosystems Applications and Practical Considerations

2019

This book highlights the recent advances of thermodynamics and biophysics in drug delivery nanosystems and in biomedical nanodevices. The up-to-date book provides an in-depth knowledge of bio-inspired nanotechnological systems for pharmaceutical applications. Biophysics and thermodynamics, supported by mathematics, are the locomotive by which the drug transportation and the targeting processes will be achieved under the light of the modern pharmacotherapy. They are considered as scientific tools that promote the understanding of physicochemical and thermotropic functionality and behavior of artificial cell membranes and structures like nanoparticulate systems. Therefore, this book focusses …

Conformational equilibrium of chorismate. A QM/MM theoretical study combining statistical simulations and geometry optimisations in gas phase and in …

2003

We report a theoretical study on the conformational equilibrium of chorismate that precedes its rearrangement to prephenate, an important enzyme-catalyzed reaction. In first place we show that the usual classification of chorismate conformers based on the relative position of the hydroxyl and ether bridge, pseudo-diaxial and pseudo-diequatorial, is not the only relevant factor from the point of view of the a posteriori rearrangement. Here we also analyse another complementary geometrical classification based on the interatomic distance between the carbon atoms to be bounded. Using the umbrella sampling approach and this distance as distinguished internal reaction coordinate, the gas phase A…

Fibre break failure processes in unidirectional composites: evaluation of critical damage states

2016

Earlier work which successfully modelled the kinetics of fibre breakage in unidirectional composites under monotonic tensile loading has been extended to quantify the kinetics of fibre failure during both monotonic and sustained tensile loading. In both cases, failure was seen to occur when a critical density of large clusters (more than 16 fibres are broken within the representative volume element) of fibre breaks developed. However, in monotonic loading failure occurred very quickly after the first development of these large clusters, whereas under sustained loading the composite could accommodate greater levels of large clusters because of the lower applied load. This article is part of …