Search results for "Computation"

Computer Simulation Studies of Chain Dynamics in Polymer Brushes

2012

Center-of-mass and single monomer motion in grafted chains comprising a strongly stretched polymer brush in thermal equilibrium are studied by large scale molecular dynamics and Monte Carlo simulations of a coarse-grained model. Good solvent conditions are assumed. Our findings seriously question earlier theoretical predictions about the relaxation described by Rouse dynamics of brush coatings. Thus, the correlation functions of parallel and perpendicular components of the mean distance of the center-of-mass from the grafting site, the squared gyration radius and end-to-end distance, are found to deviate strongly from a simple exponential decay. While the relaxation times extracted from the…

Numerical study of the accuracy of temperature measurement by thermocouples in small-scale reactors

2018

Proper temperature measurement is imperative in any laboratory study if reliable data are to be obtained, particularly in the field of chemical kinetics. In this paper we analyze in silico some typical thermowell configurations used in small-scale reactors by coupling computational fluid dynamics (CFD) with conjugated heat transfer phenomena. This allows us to identify deviations in measurements arising from thermal radiation and self-conductivity in mid and high temperature ranges, in addition to radial temperature gradients. A novel design is proposed and optimized by additional simulation, showing potential for faster and more accurate temperature measurements.

Relations frequency hypermatrices in mutual, conditional and joint entropy-based information indices.

2012

Graph-theoretic matrix representations constitute the most popular and significant source of topological molecular descriptors (MDs). Recently, we have introduced a novel matrix representation, named the duplex relations frequency matrix, F, derived from the generalization of an incidence matrix whose row entries are connected subgraphs of a given molecular graph G. Using this matrix, a series of information indices (IFIs) were proposed. In this report, an extension of F is presented, introducing for the first time the concept of a hypermatrix in graph-theoretic chemistry. The hypermatrix representation explores the n-tuple participation frequencies of vertices in a set of connected subgrap…

Taspase1: a 'misunderstood' protease with translational cancer relevance

2015

Proteolysis is not only a critical requirement for life, but the executing enzymes also play important roles in numerous pathological conditions, including cancer. Therefore, targeting proteases is clearly relevant for improving cancer patient care. However, to effectively control proteases, a profound knowledge of their mechanistic function as well as their regulation and downstream signalling in health and disease is required. The highly conserved protease Threonine Aspartase1 (Taspase1) is overexpressed in numerous liquid and solid malignancies and was characterized as a 'non-oncogene addiction' protease. Although Taspase1 was shown to cleave various regulatory proteins in humans as well…

Through-space spin-spin coupling in acetylenic systems. Ab initio and DFT calculations

2003

Abstract: We have investigated, by means of ab initio and DFT calculations, the magnitude of through-space spin-spin couplings ( J CH and J HH ) in CH/π bonded van der Waals dimers involving acetylene, and in a structurally related covalent compound (4-ethynylphenanthrene). Within regions where the interaction is stabilizing J HH couplings are very small (< 0.1 Hz) for all complexes. In the acetylene-methane complex J CH is also very small, whereas in the acetylene-benzene complex and the acetylene dimer it shows a relatively large dependence on the tilt angle from the T-shaped arrangement, for which the smallest values are calculated, to a parallel slipped arrangement where J CH is ca. 0.5…

Molecular orbital studies on brominated diphenyl ethers. Part II—reactivity and quantitative structure–activity (property) relationships

2005

Polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants and are increasingly turning up in the environment. Their structural similarities to polychlorinated biphenyls and thyroid hormones suggest they may be a risk to human health. The present study examines the reactivity of brominated diphenyl ethers (BDEs) on the basis of the electronic structures as calculated by semiempirical AM1 self-consistent field molecular orbital (SCF-MO) method. Frontier orbital energies were used to elucidate the reactivity of BDEs in electrophilic, nucleophilic and photolytic reactions. From an examination of the frontier electron densities, the regioselectivity, or orientation, of metabolic…

Deconvolution of Multiple Spectral Lines Shapes by Means of Tikhonov’s Regularization Method

2013

We present deconvolution of multiple narrow Zeeman split Hg lines, emitted from Hg/Xe micro-size capillary and measured by the Fourier Transform spectrometer. The ill-posed inverse problem was solved using the Tikhonov& rsquo;s regularization method.

Inter-Model Consistency and Complementarity: Learning from ex-vivo Imaging and Electrophysiological Data towards an Integrated Understanding of Cardi…

2011

International audience; Computational models of the heart at various scales and levels of complexity have been independently developed, parameterised and validated using a wide range of experimental data for over four decades. However, despite remarkable progress, the lack of coordinated efforts to compare and combine these computational models has limited their impact on the numerous open questions in cardiac physiology. To address this issue, a comprehensive dataset has previously been made available to the community that contains the cardiac anatomy and fibre orientations from magnetic resonance imaging as well as epicardial transmembrane potentials from optical mapping measured on a per…

Equilibrium coverage fluctuations: a new approach to quantify reversible adsorption of proteins.

2005

First-principles simulations of hydrogen peroxide formation catalyzed by small neutral gold clusters.

2009

Energetics and dynamical pathways for hydrogen peroxide formation from H(2) and O(2) bound to neutral gold dimers and tetramers have been investigated by applying several strategies: T = 0 K geometry optimizations, constrained Car-Parrinello molecular dynamics simulations at T = 300 K and metadynamics at T = 300 K. The competing reaction channels for water and hydrogen peroxide formation have been found and characterized. In each case, the reaction barriers for Au cluster catalyzed proton transfer are less than 1 eV. Water formation is a competitive reaction channel, and the relative weight of H(2)O and H(2)O(2) products may depend on the chosen Au cluster size. Dynamic simulations demonstr…