Search results for "THERMODYNAMICS"
showing 10 items of 2774 documents
Chromatographically separable rotamers of an unhindered amide
2014
Surprisingly stable formamide rotamers were encountered in the tetrahydroisoquinoline and morphinan series of alkaloids. We investigated the hindered rotation around the amide bond by dynamic high-performance liquid chromatography (DHPLC) and kinetic measurements of the interconversion of the rotamers which can readily be separated by HPLC as well as TLC. The experimental results of the different methods were compared to each other as well as to results obtained by DFT calculations.
Capillary electrophoresis–inductively coupled plasma-mass spectrometry hyphenation for the determination at the nanogram scale of metal affinities an…
2012
Abstract A screening strategy based on hyphenated capillary electrophoresis and inductively coupled plasma mass spectrometry (CE–ICP-MS) was developed to classify phosphorylated ligands according to their europium(III) binding affinity in a hydro-organic medium (sodium formate, pH 3.7, H2O/MeOH 90:10, v/v). Taking advantage of the high sensibility of ICP-MS for detecting phosphorus, this method enabled to assess the affinity of a variety of phosphorylated compounds, including phosphine oxides, thiophosphines, phosphonates, and phosphinates, in less than 1 h and using less than 5 ng of substance. By varying the total europium concentration, complexation constants could be determined accordin…
Redox potentials and acidity constants from density functional theory based molecular dynamics.
2014
CONSPECTUS: All-atom methods treat solute and solvent at the same level of electronic structure theory and statistical mechanics. All-atom computation of acidity constants (pKa) and redox potentials is still a challenge. In this Account, we review such a method combining density functional theory based molecular dynamics (DFTMD) and free energy perturbation (FEP) methods. The key computational tool is a FEP based method for reversible insertion of a proton or electron in a periodic DFTMD model system. The free energy of insertion (work function) is computed by thermodynamic integration of vertical energy gaps obtained from total energy differences. The problem of the loss of a physical refe…
Breakdown of weak-turbulence and nonlinear wave condensation
2009
Abstract The formation of a large-scale coherent structure (a condensate) as a result of the long time evolution of the initial value problem of a classical partial differential nonlinear wave equation is considered. We consider the nonintegrable and unforced defocusing NonLinear Schrodinger (NLS) equation as a representative model. In spite of the formal reversibility of the NLS equation, the nonlinear wave exhibits an irreversible evolution towards a thermodynamic equilibrium state. The equilibrium state is characterized by a homogeneous solution (condensate), with small-scale fluctuations superposed (uncondensed particles), which store the information necessary for “time reversal”. We an…
Self-consistent GW calculations of electronic transport in thiol- and amine-linked molecular junctions
2011
The electronic conductance of a benzene molecule connected to gold electrodes via thiol, thiolate, or amino anchoring groups is calculated using nonequilibrium Green functions in combination with the fully self-consistent GW approximation for exchange and correlation. The calculated conductance of benzenedithiol and benzenediamine is one-fifth that predicted by standard density functional theory (DFT), in very good agreement with experiments. In contrast, the widely studied benzenedithiolate structure is found to have a significantly higher conductance due to the unsaturated sulfur bonds. These findings suggest that more complex gold-thiolate structures where the thiolate anchors are chemic…
Three-circle method in the investigations of shapes of gas bubble clusters in two-phase flow
1991
We present an attempt of formulating a quantitative criterion for division into homogeneous and heterogeneous flow patterns basing on the probabilistic analysis of gas bubble distribution in the liquid
Scale-up and viscosity effects on gas–liquid mass transfer rates in unbaffled stirred tanks
2018
Abstract The interest in the process industry on unbaffled stirred tanks has greatly expanded in the last years because they may bring about significant advantages in a number of applications, including biochemical, food and pharmaceutical processes where the presence of baffles is undesirable for several reasons. Despite their application potential, unbaffled vessels still lack fundamental information, due to the fact that only recently their capabilities have started being dug out. The lack of information on scale up effects is possibly the main reason hindering practical applications. In this work the influence of vessel size and liquid viscosity on the mass transfer performance in unbaf…
In vivo measurement of gastric fluid volume in anesthetized dogs
2020
Abstract The drug solubility is critical for the Biopharmaceutics Classification System (BCS), yet the criteria for solubility have not been precisely defined for dogs. In particular, the gastric fluid volume (GFV) of dogs which is used to measure the solubility has not been quantified in vivo. The aim of the work is to measure the GFV using magnetic resonance imaging (MRI) from 12 Beagle dogs weighing 9–12 kg (6 male and 6 female). We found that the average GFV within this weight range was 24.0 ± 4.2 mL. The result can be used for the BCS studies of canine drugs and also serves as a reference for other species.
Reference Typing Reportfor Complement Component C3
1998
A comparison of five C3 variant samples has been performed by conventional high-voltage gel electrophoresis in three laboratories (Palermo, Berlin and Mainz). Local designation was shown within SD = ±0.75 mm migration distance in the Mainz laboratory. Methodological modifications by laboratories were not accounted for (cooling temperature, relative mobilities between runs). In parallel, all reference samples were also sequenced after exon-specific amplification. As a result, two variants with identical final designations and two variants with different mobilities were shown to conform at the molecular basis exhibiting an amino acid exchange that causes the corresponding change in relative m…
Photo-thermal effects in gold nanorods/DNA complexes
2015
An ingenious combination of plasmonic nanomaterials and one of the most relevant biological systems, deoxyribonucleic acid (DNA) is achieved by bioconjugating gold nanorods (GNRs) with DNA via electrostatic interaction between positively charged GNRs and negatively charged short DNA. The obtained system is investigated as a function of DNA concentration by means of gel electrophoresis, zeta-potential, DNA melting and morphological analysis. It turns out that the obtained bioconjugated systems present both effective electric charge and aggregate size that are particularly amenable for gene therapy and nanomedicine applications. Finally, the effect of the localized (photo-thermal heating) and…