Search results for "Gibbs"
showing 10 items of 164 documents
Calculation of organic solvent–water partition coefficients of iron–sulfur protein models
2002
Abstract A method is presented that permits semiquantitative estimation of the partitioning of many solutes between many pairs of media. As an example, the organic solvent–water partition coefficients P are calculated. The only needed parameters are the dielectric constant and molecular volume of the organic solvent. Fe 4 S 4 Cys n models of high-potential FeS proteins are studied. The Gibbs free energies of solvation and partition coefficients for Fe 4 S 4 Cys n are calculated. The organic solvent–water partition coefficients for 1-octanol P o , cyclohexane P ch and chloroform P cf decrease 4.41, 6.22 and 4.60 log units per cysteine (Cys) ligand, respectively. P o results are compared with…
Universal model for the calculation of all organic solvent–water partition coefficients
1998
Abstract We present the basis for building a universal organic solvation model to calculate solubility in any organic solvent and in water, as well as the organic solvent–water partition coefficient ( P ). Log P values are of the same order of magnitude as reference calculations but for a few cases which are discussed. Normalized log P contributions are sensitive to the rest of the atoms. When comparing porphin with phthalocyanine, the latter results in an amphipathic molecule. For C 70 , the contribution of a–e carbons to log P correlates with the distances from the nearest pentagon. The method has been also applied to benzobisthiazole oligomers and phenyl alcohols.
Nickel(II), copper(II) and zinc(II) metallo-intercalators: structural details of the DNA-binding by a combined experimental and computational investi…
2014
We present a thorough characterization of the interaction of novel nickel(II) (1), copper(II) (2) and zinc(II) (3) Schiff base complexes with native calf thymus DNA (ct-DNA), in buffered aqueous solution at pH 7.5. UV-vis absorption, circular dichroism (CD) and viscometry titrations provided clear evidence of the intercalative mechanism of the three square-planar metal complexes, allowing us to determine the intrinsic DNA-binding constants (K(b)), equal to 1.3 × 10(7), 2.9 × 10(6), and 6.2 × 10(5) M(-1) for 1, 2 and 3, respectively. Preferential affinity, of one order of magnitude, toward AT compared to GC base pair sequences was detected by UV-vis absorption titrations of 1 with [poly(dG-d…
Complex miscibility behaviour for polymer blends in flow
1995
Abstract Experimental observations of the effect of shear flow on the miscibility of binary polymer blends are compared to calculations based on a generalized Gibbs energy of mixing Gγ˙. This mixing free energy characterizes the steady state established at shear rateγ˙, as the sum of G z , the equilibrium Gibbs energy and E s , the energy the system stores while flowing.
Phase diagrams of the system tetrahydrofuran/γ-butyrolactone/poly(ether imide) and determination of interaction parameters
1998
Abstract The thermodynamic interactions in the ternary mixture tetrahydrofuran/γ-butyrolactone/poly(ether imide) (THF/γ-BL/PEI) are investigated from 30 to 50°C. This is a membrane-forming system with a high He-selectivity. Cloud point measurements show that the two binary polymer solutions THF/PEI and γ-BL/PEI exhibit miscibility gaps which close towards the centre of the ternary phase diagram where the mixtures become homogeneous (cosolvency). Vapour pressures were determined for the subsystem THF/γ-BL. For the theoretical calculations the Gibbs energy of mixing is formulated according to the Flory-Huggins theory and the interaction parameter χ THF γ-BL calculated from the vapour pressure…
Shear influence on the phase separation of oligomer blends
1994
Shear influences on the phase separation behaviour of four different blends of ethylene glycol/propylene glycol oligomers, exhibiting upper critical solution temperatures, were investigated. Cloud point curves at rest (turbidity measurements) are reported for all systems, spinodal conditions (light scattering) and tie-lines (analysis of the coexisting phases) are given for some examples. Phase diagrams under shear were obtained from rheological data. They demonstrate that the demixing temperatures of systems where both glycols bear OH end-groups are lowered up to ca. 1°C by shear rates of 1000s−1; the critical composition, generalized to the non-equilibrium conditions of flow, is markedly s…
Fake Nodes approximation for Magnetic Particle Imaging
2020
Accurately reconstructing functions with discontinuities is the key tool in many bio-imaging applications as, for instance, in Magnetic Particle Imaging (MPI). In this paper, we apply a method for scattered data interpolation, named mapped bases or Fake Nodes approach, which incorporates discontinuities via a suitable mapping function. This technique naturally mitigates the Gibbs phenomenon, as numerical evidence for reconstructing MPI images confirms.
Recycling Gibbs sampling
2017
Gibbs sampling is a well-known Markov chain Monte Carlo (MCMC) algorithm, extensively used in signal processing, machine learning and statistics. The key point for the successful application of the Gibbs sampler is the ability to draw samples from the full-conditional probability density functions efficiently. In the general case this is not possible, so in order to speed up the convergence of the chain, it is required to generate auxiliary samples. However, such intermediate information is finally disregarded. In this work, we show that these auxiliary samples can be recycled within the Gibbs estimators, improving their efficiency with no extra cost. Theoretical and exhaustive numerical co…
Efficient anomaly detection on sampled data streams with contaminated phase I data
2020
International audience; Control chart algorithms aim to monitor a process over time. This process consists of two phases. Phase I, also called the learning phase, estimates the normal process parameters, then in Phase II, anomalies are detected. However, the learning phase itself can contain contaminated data such as outliers. If left undetected, they can jeopardize the accuracy of the whole chart by affecting the computed parameters, which leads to faulty classifications and defective data analysis results. This problem becomes more severe when the analysis is done on a sample of the data rather than the whole data. To avoid such a situation, Phase I quality must be guaranteed. The purpose…
Structure and Thermodynamics of Binary Mixtures (Solutions)
2014
The concepts of chapter 2 are generalized to binary liquid mixtures (solutions). With the help of the concept of number and concentration fluctuations contact to the thermodynamics of solutions and physical chemistry of solutions is made. The perturbative RPA is shown to be equivalent to Flory’s theory of regular solutions. The phase diagrams of regular solutions and metal-salt solutions are discussed and explained in terms of the theories.