Search results for "THERMODYNAMICS"

The lineshape of the electronic spectrum of the green fluorescent protein chromophore, part I: gas phase.

2014

The vibronic spectra of the green fluorescent protein chromophore analogues p-hydroxybenzylidene-2,3-dimethylimidazolinone (HBDI) and 3,5-tert-butyl-HBDI (35Bu) are similar in the vacuum, but very different in water or ethanol. To understand this difference, we have computed the vibrationally resolved solution spectra of these chromophores, using the polarizable continuum model (PCM) to account for solvent effects on the (harmonic) potential energy surfaces (PES). In agreement with experiment, we found that the vibrational progression increases with the polarity of the solvent, but we could neither reproduce the broadening, nor the large difference between the absorption spectra of HBDI and…

Comparative Study of Different Methods for the Prediction of Drug–Polymer Solubility

2015

In this study, a comparison of different methods to predict drug-polymer solubility was carried out on binary systems consisting of five model drugs (paracetamol, chloramphenicol, celecoxib, indomethacin, and felodipine) and polyvinylpyrrolidone/vinyl acetate copolymers (PVP/VA) of different monomer weight ratios. The drug-polymer solubility at 25 °C was predicted using the Flory-Huggins model, from data obtained at elevated temperature using thermal analysis methods based on the recrystallization of a supersaturated amorphous solid dispersion and two variations of the melting point depression method. These predictions were compared with the solubility in the low molecular weight liquid ana…

1993

In a new theoretical approach the separation of a pair of chain molecules (measured thermodynamically by the second osmotic virial coefficient A2) is treated as a two-step process: In the first step the molecules are detached from each other by the addition of solvent—keeping their dimensions constant—and in the second step the now isolated coils are allowed to relax into their equilibrium dimensions. For the description of the second step, in which only segments belonging to one molecule take part, an intra-molecular interaction parameter is introduced on the basis of the intrinsic viscosity. The present two-parameter approach yields A2 = A + σ M−(1−a) for the dependence of A2 on the molec…

Interdependence of enthalpic and entropic contributions to the second osmotic virial coefficient

1972

The interdependence of the enthalpic contribution A2, H and the entropic contribution A2, s to the second osmotic virial coefficient for a given polymer-solvent system has been investigated from the experimental and the theoretical point of view. Experimentally, the following common facts were observed for various systems at temperatures and pressures below the critical values for the solvent. Both the isobaric and isothermal dependences can be approximated over relatively wide ranges of A2, H by linear relations with a slope deviating only slightly, but in a characteristic manner from a value of −1. When the temperature is increased at constant pressure one moves along an isobar towards hi…

Testing of a constitutive equation with free volume dependent relaxation spectrum

1979

A model of non-linear viscoelasticity with relaxation times dependent upon free volume is here proposed. The free volume is related to the isotropic part of the stress tensor by means of a simple differential equation. The model predictions are compared with a large amount of experimental results taken on polymeric melts or concentrated solutions and reported in the literature. The single parameter of the model is determined, within each set of data, by fitting of the viscosity curve. A satisfactory agreement is obtained with data taken under both elongation and shear for which also the relaxation behavior after single and double strain steps is considered.

DSC Studies and Stability of Frozen Foods

1991

This paper discusses the role played by the “WLF decrease in viscosity” above the temperature of the glass transition (Tg) in the temperature dependence of the stability of frozen foods. In the first part, the complex features observed before the melting endotherm on DSC/DTA thermograms of sugar-water solutions are examined; they are suggested to be representative of a glass transition associated with enthalpy relaxation. In the second part, the values of Tg for some complex foods are discussed. It is shown that ice melting adds an important contribution to the WLF effect on the decrease of the viscosity of the freeze-concentrated phase. The temperature dependence of the deterioration proce…

Die viskosität von polymerlösungen in der nähe von oberen und unteren entmischungstemperaturen

1977

Die Viskositat flussiger Mischungen zeigt in der Nahe des kritischen Entmischungspunktes eine charakteristische Temperaturabhangigkeit. fur Polymerlosungen ist diese Erscheinung bei der oberen kritischen Entmischungstemperatur gut untersucht, wahrend in der Umgebung der unteren kritischen Entmischungstemperatur keine derartigen Messungen vorliegen. ES wurden Viskositatsmessungen im System Cyclohexan/Polystyrol (obere kritische Entmischungstemperatur) und im System Orthotrimethylformiat/Diathylather/Polystyrol (untere kritische Entmischungstemperatur) durchgefuhrt. Beim ersten System ergab sich qualitative Ubereinstimmung mit den Ergebnissen von Debye und Mitarbeitern. Die Untersuchungen in …

Viscosity of n-alcohol binary mixtures

1988

In this paper liquid mixture viscosities at 25 °C for 18 binary systems formed by primary n-alcohols have been measured. These values were fitted to Topological Treatment of Mixtures (T.T.M.) The pure compound topological description is obtained following the DARC system rules. A weighting function was introduced to obtain the topological description of a mixture. The results obtained with this model agree with experimental data (average deviation less than 2% in all cases). Dans cette etude, nous avons mesure des viscosites de melanges liquides a 25°C pour dix-huit systemes binaires formes par des n-alcools primaires. Ces valeurs ont ete calees par le traitement topologique des melanges (T…

Human Reaction Times: Linking Individual and Collective Behaviour Through Physics Modeling

2021

An individual’s reaction time data to visual stimuli have usually been represented in Experimental Psychology by means of an ex-Gaussian function. In most previous works, researchers have mainly aimed at finding a meaning for the parameters of the ex-Gaussian function which are known to correlate with cognitive disorders. Based on the recent evidence of correlations between the reaction time series to visual stimuli produced by different individuals within a group, we go beyond and propose a Physics-inspired model to represent the reaction time data of a coetaneous group of individuals. In doing so, a Maxwell–Boltzmann-like distribution appeared, the same distribution as for the velocities …

Protein dynamics: conformational disorder, vibrational coupling and anharmonicity in deoxy-hemoglobin and myoglobin.

1993

In this work we study the temperature dependence of the Soret band lineshape of deoxymyoglobin and deoxyhemoglobin, in the range 300-20 K. To fit the measured spectra we use an approach originally proposed by Champion and coworkers (Srajer et al. 1986; Srajer and Champion 1991). The band profile is modelled as a Voigt function that accounts for the coupling with low frequency vibrational modes, whereas the coupling with high frequency modes is responsible for the vibronic structure of the spectra. Moreover, owing to the position of the iron atom out of the mean heme plane, inhomogeneous broadening brings about a non-Gaussian distribution of 0-0 electronic transition frequencies. The reporte…