Reconstructing Free Energy Profiles from Nonequilibrium Relaxation Trajectories

Reconstructing free energy profiles is an important problem in bimolecular reactions, protein folding or allosteric conformational changes. Nonequilibrium trajectories are readily measured experimentally, but their statistical significance and relation to equilibrium system properties still call for rigorous methods of assessment and interpretation. Here we introduce methods to compute the equilibrium free energy profile of a given variable from a set of short nonequilibrium trajectories, obtained by externally driving a system out of equilibrium and subsequently observing its relaxation. This protocol is not suitable for the Jarzynski equality since the irreversible work on the system is instantaneous. Assuming that the variable of interest satisfies an overdamped Langevin equation, which is frequently used for modeling biomolecular processes, we show that the trajectories sample a nonequilibrium stationary distribution that can be calculated in closed form. This allows for the estimation of the free energy via an inversion procedure that is analogous to that used in equilibrium and bypasses more complicated path integral methods, which we derive for comparison. We generalize the inversion procedure to systems with a diffusion constant that depends on the reaction coordinate, as is the case in protein folding, as well as to protocols in which the trajectories are initiated at random points. Using only a statistical pool of tens of synthetic trajectories, we demonstrate the versatility of these methods by reconstructing double and multi-well potentials, as well as a proposed profile for the hydrophobic collapse of a protein.     

Switching time in optically bistable injection-locked semiconductor lasers

Switching between states in a dispersive bistable injection-locked slave laser has been theoretically investigated. We show that the switching can be achieved by relatively small and short (≈10-50?ps) variation of the master laser injection power or frequency, which, besides the variation of the slave laser optical power, leads to significant variation of its photon phase (≈5π/6). By using an analytical model, we calculate the switching time dependence on the magnitude of the injection power and the frequency detuning variation.     

A new approach to the analysis of nicarbazin and ionophores in eggs by HPLC/MS/MS

An HPLC/MS/MS method has been developed and validated for the quantification and confirmation of nicarbazin and ionophores (lasalocid, monensin, salinomycin, and narasin) in eggs. Nicarbazin is determined in the negative electrospray mode with a basic mobile phase that supports creation of negative ions. Consequently, our ability to maintain instrument sensitivity over time has significantly improved. The analysis of the ionophores is done in the positive electrospray mode using ammonium buffer for HPLC separation. Monitoring ammonium adduct parent ions resulted in enhanced sensitivity and better reproducibility of the ionophore analysis. The validation of this improved HPLC/MS/MS method for the detection of nicarbazin and the ionophores demonstrated excellent precision of below 10% RSD and lower LOD values (microg/kg) for nicarbazin (0.018), lasalocid (0.015), monensin (0.015), salinomycin (0.033), and narasin (0.039).     

A correlation of the limiting viscosity number, molecular mass and composition of statistical linear styrene-methyl methacrylate copolymers

Statistical copolymers of styrene and methyl methacrylate of different compositions were synthesized by the radical solution copolymerization in a batch isothermal reactor. Copolymers were characterized by the size exclusion chromatography (SEC), elemental analysis and dilute solution viscometry. Experimental limiting viscosity numbers were described by the Mark-Houwink-Kuhn-Sakurada correlation as the function of the molar mass and by the Mendelson correlation as the function of both the molar mass and copolymer composition. A new correlation of the intrinsic viscosity number, molar mass and composition was developed, based on semiempirical considerations. The correlation takes into consideration all the effects which affect the dimensions of random linear copolymer coils in solvents. The new equation was found to be superior to the Mendelson’s one in correlating the experimentally obtained intrinsic viscosities.     

Theory of irreversible electrode reactions coupled to ion transfer across the liquid/liquid interface

Kinetically controlled electro-oxidation of a redox probe dissolved in the organic solvent, which is interposed between an electrode surface and an aqueous solution as a thin layer, is analyzed theoretically. It is demonstrated that the electrode reaction rate constant can be measured by the variation of scan rate in linear scan voltammetry both in the absence and in the superfluity of the supporting electrolyte dissolved in the film.Dedicated to Professor Dr. Alan M. Bond on the occasion of his 60th birthday     

Influence of anion-induced adsorption on D.C. polarography of metal ions

Some adsorption isotherms for anion-induced adsorption of metal ions are proposed. The influences of adsorption on d.c polarograms are examined theoretically. The consequences for the determination of stability constants from polarographic data are discussed.     

Effect of mixing on the crystal size distribution of borax decahydrate in a batch cooling crystallizer

The effect of the impeller speed upon the metastable zone width, supersaturation level, crystal growth and the crystal size distribution of borax decahydrate have been investigated to find operating conditions of a batch cooling crystallizer. The importance of impeller speed was studied in baffled stirred crystallizer with a volume of about 2 dm³, equipped with four straight blade turbine (4-SBT) cooling at a constant cooling rate. The metastable zone width was determined by visual method, while concentration changes during the process were monitored in line using ion-selective electrode. The crystal size distribution was determined by optical microscope and sieve analysis respectively. The power consumption measurements were performed for all impeller speeds examined as well. On the basis of the experimental results and observations it is evident that in an agitated batch crystallizer the above mentioned parameters are significantly influenced by hydrodynamic regime in the system determined by impeller used and its revolution speed.