Search results for "Virial coefficient"

Transfer Free Energies of Test Proteins Into Crowded Protein Solutions Have Simple Dependence on Crowder Concentration

2019

The effects of macromolecular crowding on the thermodynamic properties of test proteins are determined by the latter's transfer free energies from a dilute solution to a crowded solution. The transfer free energies in turn are determined by effective protein-crowder interactions. When these interactions are modeled at the all-atom level, the transfer free energies may defy simple predictions. Here we investigated the dependence of the transfer free energy (Δμ) on crowder concentration. We represented both the test protein and the crowder proteins atomistically, and used a general interaction potential consisting of hard-core repulsion, non-polar attraction, and solvent-screened electrostati…

1988

Deviations in the determination of the unperturbed dimensions of polymers arising in ternary polymer systems (solvent (1)/solvent (2)/polymer) can be explained by the inaccurate use of an interaction parameter independent of polymer molecular weight. On this basis, a new formalism for the calculation of the second virial coefficient from intrinsic viscosity is proposed. This formalism was tested (and compared with well established formalisms) for all ternary polymer systems with simultaneous intrinsic viscosity and second virial coefficient data in the literature.

1987

The intrinsic viscosities, [η], for the ternary systems alkane (1)/2-butanone (2)/poly(dimethylsiloxane) (PDMS)(3), with the alkanes decane, dodecane and hexadecane, are determined at 20,0°C. The constants a of the Mark-Houwink equation and the constant of the unperturbed dimensions, KΘ, of the polymer are evaluated over the whole composition range of the binary solvent mixture. [η] shows a pronounced maximum at intermediate compositions as found in cosolvent mixtures. In these cosolvent mixtures, the numerical values of KΘ are higher than in the single-component solvents, because the cosolvent mixtures correspond to a mixed solvent with an excess free energy, GE ≥ 0, the increase in KΘ bei…

Size, Form and Flexibility of the Rubber Molecule

1962

Abstract Natural rubber can be brominated in dilute cyclohexane solution, whereby the molecular weight, corresponding to the bromine content, increases. For brominated rubber, increasing bromine content makes cyclohexane an increasingly poorer solvent, which is shown by a contraction of the molecule coils and a decrease in the second virial coefficient. Quantitative results were obtained through viscosity and light scattering measurements. Cyclohexane solutions of brominated rubber containing about 43% bromine have a θ point at room temperature. Here the second virial coefficient is zero and the coil has an ideal Gaussian density distribution. In this state the coil diameter is about 1.6 ti…

Über die verdünnungsentropie der lösungen von fadenmolekülen

1953

Es wird versucht, auf breiter experimenteller Basis, einen allgemeinen uberblick uber die Wechselwirkung zwischen Polymeren und Losungsmitteln (LM) in masigen Konzentrationen (bis 3%) zu gewinnen. Zu diesem Zweck wird der osmotische Druck in Abhangigkeit von der Konzentration und der Temperatur fur 2 verschiedene Polymere in einer groseren Anzahl von Losungsmitteln gemessen und daraus die Virialkoeffizienten und die thermodynamischen Funktionen Δμ1, Δh1 und Δs1 berechnet. Der 1. Virialkoeffizient (VK) A hangt, wie zu erwarten war, nur vom Molekularge which des Polymeren ab. Der 2. und der 3. VK werden in der Grose B zusammengefast, die ein Mas fur die „Gute” des LM ist. Die differentielle V…

Experimenteller nachweis des molekulardispersen charakters der mischung von zwei polymeren und bestimmung des chemischen potentials in diesen mischun…

1976

Mit Hilfe der Neutronenkleinwinkelstreuung wird der molekulardisperse Charakter einer glasklaren Mischung von zwei Polymeren bei Abwesenheit eines niedermolekularen Losungsmittels in einem Fall nachgewiesen, im anderen widerlegt. Falls eine molekulardisperse Mischung vorliegt, konnen das chemische Potential und die Knaueldimensionen bestimmt werden. Polymethylmethacrylat und Styrol-Acrylnitril-Copolymere bilden fur gewisse Zusammensetzungen des Copolymeren molekulardisperse Mischungen. Sie sind exotherm, besitzen eine negative Exzesentropie und die Molekulknauel sind gegenuber den ungestorten Knaueldimensionen expandiert. Die Theorie der Loslichkeitsparameter von Hildebrand und Scott ermogl…

Solution behavior of 4-arm poly(tert-butyl acrylate) star polymers

2010

Abstract This paper reports the synthesis of 4-arm poly( tert -butyl acrylate) stars of different molar masses up to 10 6  g/mol by the “core-first” method using ATRP. All obtained stars have a monomodal and narrow molar-mass distribution ( The dilute-solution properties of these star polymers were investigated in good solvents (tetrahydrofuran and acetone). Gel permeation chromatography and dynamic and static light scattering were used to measure the hydrodynamic properties including intrinsic viscosity [ η ], radius of gyration R g , hydrodynamic radius R h , second virial coefficient A 2 and diffusion coefficient D 0 . These data were used to establish relationships between these paramet…

Molecular characterization of α,β-poly[( N -hydroxyethyl)- dl –aspartamide] by light scattering and viscometry studies

2000

Abstract α,β-poly[(N-hydroxyethyl)- dl -aspartamide] (PHEA) is a new synthetic polymer which is of interest in biomedical applications. In this paper, the molecular characterization of PHEA by multi-angle laser light scattering and viscometry off-line and on-line to a size exclusion chromatography system is reported. These techniques furnish an exhaustive and consistent characterization of the PHEA polymer. The fractionation of the PHEA macromolecules was relatively simple. Using an aqueous mobile phase of medium ionic strength, the elution was substantially regular and the macromolecules were not aggregate. The molar mass M of four PHEA samples approximately ranges from 46 to 53 K g/mol, t…

BoltzmaNN: Predicting effective pair potentials and equations of state using neural networks

2019

Neural networks (NNs) are employed to predict equations of state from a given isotropic pair potential using the virial expansion of the pressure. The NNs are trained with data from molecular dynamics simulations of monoatomic gases and liquids, sampled in the NVT ensemble at various densities. We find that the NNs provide much more accurate results compared to the analytic low-density limit estimate of the second virial coefficient and the Carnahan-Starling equation of state for hard sphere liquids. Furthermore, we design and train NNs for computing (effective) pair potentials from radial pair distribution functions, g(r), a task that is often performed for inverse design and coarse-graini…

A generalization of the Carnahan–Starling approach with applications to four- and five-dimensional hard spheres

2018

Abstract Development of good equations of state for hard spheres is an important task in the study of real fluids. In a way consistent with other theoretical results, we generalize the famous Carnahan–Starling approach for arbitrary dimensions and apply it to four- and five-dimensional hard spheres. We obtain simple and integer representations for virial coefficients of lower orders and accurate equations of state. Since theoretically and practically validated, these results improve understanding of hard sphere fluids.