Search results for "Degree"
showing 10 items of 875 documents
Modeling of biomolecular machines in non-equilibrium steady states
2021
Numerical computations have become a pillar of all modern quantitative sciences. Any computation involves modeling--even if often this step is not made explicit--and any model has to neglect details while still being physically accurate. Equilibrium statistical mechanics guides both the development of models and numerical methods for dynamics obeying detailed balance. For systems driven away from thermal equilibrium such a universal theoretical framework is missing. For a restricted class of driven systems governed by Markov dynamics and local detailed balance, stochastic thermodynamics has evolved to fill this gap and to provide fundamental constraints and guiding principles. The next step…
Improving the QM/MM Description of Chemical Processes: A Dual Level Strategy To Explore the Potential Energy Surface in Very Large Systems.
2005
Potential energy surfaces are fundamental tools for the analysis of reaction mechanisms. The accuracy of these surfaces for reactions in very large systems is often limited by the size of the system even if hybrid quantum mechanics/molecular mechanics (QM/MM) strategies are employed. The large number of degrees of freedom of the system requires hundreds or even thousands of optimization steps to reach convergence. Reactions in condensed media (such as enzymes or solutions) are thus usually restricted to be analyzed using low level quantum mechanical methods, thus introducing a source of error in the description of the QM region. In this paper, an alternative method is proposed, coupled to t…
13C NMR study on the methoxy carbon chemical shifts in chloro-substituted anisoles and guaiacols
1983
The 13C NMR chemical shifts of methoxy carbons in chlorinated anisoles and guaiacols have been measured for acetone-d6 solutions. Multiple linear regression analysis, and also ‘simple sum rule’ calculations, have been used to estimate the effects of the chlorine atoms (the position and degree of substitution) on the chemical shifts. The most important effects have shown to be due to the chlorine atoms adjacent to the methoxy and hydroxy substituents. For chlorinated guaiacols, the greatest effect is due to the chlorine atom adjacent to the methoxy group. For chlorinated anisoles, the substituents adjacent to the methoxy group (2,6-disubstitution) cause large effects. For both groups of comp…
Modelling of thermo-chemical properties over the sub-solidus MgO–FeO binary, as a function of iron spin configuration, composition and temperature
2014
Thermo-chemical properties and T–X phase relations diagram of the (Mg,Fe)O solid solution are modelled using mixing Helmholtz energy, ΔF(T,x)mixing, calculated by quantum mechanical and semi-empirical techniques. The sub-solidus MgO–FeO binary has been explored as a function of composition, with iron either in high-spin (HS) or low-spin (LS) configuration. Only the HS model provides physically sound results at room pressure, yielding a correct trend of cell edge versus composition, whereas LS’s issues are at variance with observations. Mixing Helmholtz energy has been parametrized by the following relationship: ΔF(T,x)mixing = x × y × [U0(T) + U1(T) × (x – y) + U2(T) × (x − y)2]−T × S(x,y)c…
Studies on the mechanism of PMN activation. I. By dextran sulfates.
1982
Evidence is presented that enhanced reduction of the dye nitroblue-tetrazolium (NBT) by polymorphonuclear leukocytes (PMN) which are stimulated by dextran sulfates (DS) is not exclusively due to the phagocytosis of particles formed by NBT and DS. Not only the size of phagocytizable particles but the degree of substitution determines the acceleration of NBT-reduction. A likely cause of this acceleration is the triggering of the alternative pathway of the complement activation.
Poly(glycolide) multi-arm star polymers: Improved solubility via limited arm length.
2010
Due to the low solubility of poly(glycolic acid) (PGA), its use is generally limited to the synthesis of random copolyesters with other hydroxy acids, such as lactic acid, or to applications that permit direct processing from the polymer melt. Insolubility is generally observed for PGA when the degree of polymerization exceeds 20. Here we present a strategy that allows the preparation of PGA-based multi-arm structures which significantly exceed the molecular weight of processable oligomeric linear PGA (<1000 g/mol). This was achieved by the use of a multifunctional hyperbranched polyglycerol (PG) macroinitiator and the tin(II)-2-ethylhexanoate catalyzed ring-opening polymerization of gly…
Üuber eine abgekürzte Fraktioniermethode zur Bestimmung von Molekulargewichtsverteilungen
1950
Es wird ein Verfahren beschrieben, welches die Breite und ungefahre Gestalt der Verteilungskurve cines polymolekularen Stoffs auf Grund folgender experimenteller Daten zu bestimmen erlaubt: 1 Mittlerer Polymerisationsgrad (z. B. durch eine osmotische Bestimmung). 2 Gewichtsanteil und mittlerer Polymerisationsgrad einer obersten Fraktion. 3 Gewichtsanteil und mittlerer Polymerisationsgrad einer untersten Fraktion. Anwendungsbereich und Grenzen des neuen Verfahrens werden experimentell ermittelt. A method is described permitting to determine latitude and approximate shape of the distribution curve of a polymolecular substance by means of the following experimental data: 1 Average degree of po…
Chiral dynamics in the γ→p→pπ0 reaction
2015
Abstract We investigate the neutral pion photoproduction on the proton near threshold in covariant chiral perturbation theory with the explicit inclusion of Δ degrees of freedom. This channel is specially sensitive to chiral dynamics and the advent of very precise data from the Mainz microtron has shown the limits of the convergence of the chiral series for both the heavy baryon and the covariant approaches. We show that the inclusion of the Δ resonance substantially improves the convergence leading to a good agreement with data for a wider range of energies.
Hierarchical Self-Organization of Perylene Bisimide–Melamine Assemblies to Fluorescent Mesoscopic Superstructures
2000
A series of three perylene tetracarboxylic acid bisimide dyes 3a-c bearing phenoxy substituents at the four bay positions of the perylene core were synthesized and their complexation behavior to complementary ditopic dialkyl melamines 8a-c was investigated. Binding constants and Gibbs binding energies for the hydrogen bonds between the imide and the complementary melamine moiety have been determined in several solvents by NMR and UV/Vis titration experiments with monotopic model compounds 5 and 9. The effects of the solvent polarity and specific solvent-solute interactions on the degree of polymerization of (3 x 8)n are discussed, and a general formula to estimate the chain length of [AA-BB…
New approaches based on modified Gaussian models for the prediction of chromatographic peaks
2012
Abstract The description of skewed chromatographic peaks has been discussed extensively and many functions have been proposed. Among these, the Polynomially Modified Gaussian (PMG) models interpret the deviations from ideality as a change in the standard deviation with time. This approach has shown a high accuracy in the fitting to tailing and fronting peaks. However, it has the drawback of the uncontrolled growth of the predicted signal outside the elution region, which departs from the experimental baseline. To solve this problem, the Parabolic-Lorentzian Modified Gaussian (PLMG) model was developed. This combines a parabola that describes the variance change in the peak region, and a Lor…