Fast assay of glucosamine in pharmaceuticals and nutraceuticals by capillary zone electrophoresis with contactless conductivity detection

A novel capillary electrophoresis (CE) method with contactless conductivity detection suitable for the determination of glucosamine (GlAm) and K(+) in pharmaceuticals was devised. Under the optimum conditions (aqueous 30 mM acetate buffer of pH 5.2 as the background electrolyte; voltage 30 kV; 25 degrees C), GlAm (migrating as glucosaminium cation) was well separated from K(+) that could occur in the dosage forms as excipient. The CE analysis was performed in fused-silica capillaries (50 microm i.d., 75 cm total length, 27 cm to detector) and the separation took <3 min. The calibration graphs were linear for both GlAm (100-300 microg/mL; r(2)=0.997) and K(+) (15-75 microg/mL; r(2)=0.997) when using ethanolamine (100 microg/mL) as the internal standard. The LOD values (S/N=3) were 9.3 microg/mL for GlAm and 2.9 microg/mL for K(+). The method was applied to the assay of GlAm content in various dosage forms. Intermediate precision evaluated by determining the content of GlAm in a single formulation on 3 consecutive days was characterized by RSD 2.35% (n=15). Acceptable accuracy of the CE method was confirmed by the added/found GlAm recovery experiments (recoveries 94.6-103.3%) and by statistical comparison of the results attained by the proposed CE and a reference HPLC method.     

Theoretical study of the nucleation/growth process of carbon clusters under pressure

We used molecular dynamics and the empirical potential for carbon LCBOPII to simulate the nucleation/growth process of carbon clusters both in vacuum and under pressure. In vacuum, our results show that the growth process is homogeneous and yields mainly sp(2) structures such as fullerenes. We used an argon gas and Lennard-Jones potentials to mimic the high pressures and temperatures reached during the detonation of carbon-rich explosives. We found that these extreme thermodynamic conditions do not affect substantially the topologies of the clusters formed in the process. However, our estimation of the growth rates under pressure are in much better agreement with the values estimated experimentally than our vacuum simulations. The formation of sp(3) carbon was negligible both in vacuum and under pressure which suggests that larger simulation times and cluster sizes are needed to allow the nucleation of nanodiamonds.     

Influence of Initial Correlations on Evolution of a Subsystem in a Heat Bath and Polaron Mobility

A regular approach to accounting for initial correlations, which allows to go beyond the unrealistic random phase (initial product state) approximation in deriving the evolution equations, is suggested. An exact homogeneous (time-convolution and time-convolutionless) equations for a relevant part of the two-time equilibrium correlation function for the dynamic variables of a subsystem interacting with a boson field (heat bath) are obtained. No conventional approximation like RPA or Bogoliubov’s principle of weakening of initial correlations is used. The obtained equations take into account the initial correlations in the kernel governing their evolution. The solution to these equations is found in the second order of the kernel expansion in the electron–phonon interaction, which demonstrates that generally the initial correlations influence the correlation function’s evolution in time. It is explicitly shown that this influence vanishes on a large timescale (actually at \(t\rightarrow \infty \)) and the evolution process enters an irreversible kinetic regime. The developed approach is applied to the Fröhlich polaron and the low-temperature polaron mobility (which was under a long-time debate) is found with a correction due to initial correlations.     

Resilience in reaction-diffusion systems

Reaction-diffusion systems with zero-flux Neumann boundariesare widely used to model various kinds of interaction in, forexample, the scientific fields of ecology, biology, chemistry,medicine and industry. The physical systems within these fieldsare often known to be (conditionally or unconditionally) resilientwith respect to shocks, disturbances or catastrophies in theimmediate environment. In order to be good mathematical modelsof such situations the reaction-diffusion systems must havethe same resilient or asymptotic behaviour as that of the physicalsituation. Three fundamentally different kinds of reaction termsare usually distinguished according to the entry signs of thereaction Jacobian: mutualism, mixed (predator-prey) interactionand competition. The asymptotic stability (in the Poincarésense) of mutualistic systems has already been studied extensively,but the results cannot be generalized (globally) to the othertwo fundamental types, which are not order-preserving. A partial(local) generalization is, however given here for these twotypes, involving simple Jacobian inequalities and knowledge(often prompted by the underlying physical situation) of invariantsets in solution space. The return time of resilient systemsand the approach rate of asymptotically stable solutions arealso estimated.     

Red and near infra-red signaling: Hypothesis and perspectives

The review covers some of the proposed cellular photoreceptors responsible for the effect of red and near infra-red (NIR) light on mammalian cells, including cytochrome-c-oxidase, photoactive porphyrins, flavoproteins, and molecular oxygen. We do not discuss the clinical studies but consider animal models, especially fibroblasts. Several key hypotheses such as mitochondria signaling and free-radical conception of the effects of red light and NIR light based on the changes in redox properties of photoreceptor molecules as well as membrane conception are examined. Special attention is paid to common mechanisms of light signaling in mammalian and plant organisms.     

The photocurrent response of human cones is fast and monophasic

Background  

The precise form of the light response of human cone photoreceptors in vivo has not been established with certainty. To investigate the response shape we compare the predictions of a recent model of transduction in primate cone photoreceptors with measurements extracted from human cones using the paired-flash electroretinogram method. As a check, we also compare the predictions with previous single-cell measurements of ground squirrel cone responses.     

On the definition of a Monte Carlo model for binary crystal growth

We show that consistency of the transition probabilities in a lattice Monte Carlo (MC) model for binary crystal growth with the thermodynamic properties of a system does not guarantee the MC simulations near equilibrium to be in agreement with the thermodynamic equilibrium phase diagram for that system. The deviations remain small for systems with small bond energies, but they can increase significantly for systems with large melting entropy, typical for molecular systems. These deviations are attributed to the surface kinetics, which is responsible for a metastable zone below the liquidus line where no growth occurs, even in the absence of a 2D nucleation barrier. Here we propose an extension of the MC model that introduces a freedom of choice in the transition probabilities while staying within the thermodynamic constraints. This freedom can be used to eliminate the discrepancy between the MC simulations and the thermodynamic equilibrium phase diagram. Agreement is achieved for that choice of the transition probabilities yielding the fastest decrease of the free energy (i.e., largest growth rate) of the system at a temperature slightly below the equilibrium temperature. An analytical model is developed, which reproduces quite well the MC results, enabling a straightforward determination of the optimal set of transition probabilities. Application of both the MC and analytical model to conditions well away from equilibrium, giving rise to kinetic phase diagrams, shows that the effect of kinetics on segregation is even stronger than that predicted by previous models.