Phase transitions of nonlinear waves in quadratic waveguide arrays

We study two-color parametric nonlinear modes in waveguide arrays with a quadratic nonlinear response. We predict theoretically and observe experimentally a new type of phase transition manifested in an abrupt power-controlled change of the mode structure from unstaggered to staggered, due to the interplay of localization and synchronization in parametrically driven discrete systems.     

Pseudoisocyanine J-aggregate to optical waveguiding crystallite transition: microscopic and microspectroscopic exploration

Using fluorescent microscopy and microspectroscopy, optical properties and morphology transformations in individual pseudoisocyanine (PIC) J-aggregates in aqueous electrolyte solutions have been explored. A stringlike structure of J-aggregates with a string diameter much less than 1 microm has been observed. Photodestruction of the strings under short-wavelength excitation has been revealed. Rodlike PIC crystallites, about 1 microm in diameter, have been observed with time. The fluorescence spectrum of rodlike crystallites has been found to differ from that of stringlike J-aggregate and from PIC crystal powder spectra. The crystallites are very stable, and their photodestruction has not been observed under any excitation conditions. It has been found that rodlike crystallites in contrast to stringlike J-aggregates possess optical waveguide properties. The luminescence of crystallites can be observed only at the excitation spot and at butt ends located up to hundreds of micrometers from the excitation spot.     

Experimental and modeling studies of B atom number density distributions in hot filament activated B2H6/H2 and B2H6/CH4/H2 gas mixtures

Experimental and modeling studies of the gas-phase chemistry occurring in dilute, hot filament (HF) activated B2H6/H2 and B2H6/CH4/H2 gas mixtures are reported. Spatially resolved relative number densities of B (and H) atoms have been measured by resonance enhanced multiphoton ionization methods, as a function of process conditions (e.g. the HF material and its temperature, the B2H6/H2 mixing ratio, and the presence (or not) of added CH4). Three-dimensional modeling of the H/B chemistry prevailing in such HF activated gas mixtures using a simplified representation of the gas phase chemistry succeeds in reproducing all of the experimentally observed trends, and in illustrating the key role of the "H-shifting" reactions BHx + H <= => BHx-1 + H2 (x = 1-3) in enabling rapid interconversion between the various BHx (x = 0-3) species. CH4 addition, at partial pressures appropriate for growth of boron-doped diamond by chemical vapor deposition methods, leads to approximately 30% reduction in the measured B atom signal near the HF. The modeling suggests that this is mainly due to concomitant H atom depletion near the HF, but it also allows us a first assessment of the possible contributions from B/C coupling reactions upon CH4 addition to HF activated B2H6/H2 gas mixtures.     

Effect of agents modifying the membrane dipole potential on properties of syringomycin E channels

We evaluated the effect of agents modifying the membrane dipole potential: phloretin, 6-ketocholestanol and RH 421 on the properties of single channels formed by lipodepsipeptide syringomycin E (SRE) in planar lipid bilayers. SRE forms two conductive states in lipid bilayers: "small" and "large." Large SRE channels are clusters of several small ones, demonstrating synchronous openings and closures. The increase in the membrane dipole potential led to (i) an increase in SRE channel conductance, (ii) an increase in the channel's lifetime, and (iii) a decrease in a number of synchronously operating small channels in the clusters. Overall, the results support the model of the small SRE channel synchronization in the cluster as voltage-dependent orientation of the lipid dipoles associated with the channel pores.     

Solution of the master equation for Wigner's quasiprobability distribution in phase space for the Brownian motion of a particle in a double well potential

Quantum effects in the Brownian motion of a particle in the symmetric double well potential V(x)=ax(2)2+bx(4)4 are treated using the semiclassical master equation for the time evolution of the Wigner distribution function W(x,p,t) in phase space (x,p). The equilibrium position autocorrelation function, dynamic susceptibility, and escape rate are evaluated via matrix continued fractions in the manner customarily used for the classical Fokker-Planck equation. The escape rate so yielded has a quantum correction depending strongly on the barrier height and is compared with that given analytically by the quantum mechanical reaction rate solution of the Kramers turnover problem. The matrix continued fraction solution substantially agrees with the analytic solution. Moreover, the low-frequency part of the spectrum associated with noise assisted Kramers transitions across the potential barrier may be accurately described by a single Lorentzian with characteristic frequency given by the quantum mechanical reaction rate.     

Influence of inorganic mobile phase additives on the retention, efficiency and peak symmetry of protonated basic compounds in reversed-phase liquid chromatography

Inorganic eluent additives affect the retention of protonated basic analytes in reversed-phase HPLC. This influence is attributed to the disruption of the analyte solvation-desolvation equilibria in the mobile phase, also known as "chaotropic effect". With an increase of counteranion concentration analyte retention increases with concomitant decrease in the tailing factor. Different inorganic counteranions at equimolar concentrations affect protonated basic analyte retention and peak symmetry to varying degrees. The effect of the concentrations of four different inorganic mobile phase additives (KPF6, NaClO4, NaBF4, NaH2PO4) on the analyte retention, peak symmetry, and efficiency on a C8-bonded silica column has been studied. The analytes used in this study included phenols, toluene, benzyl amines, beta-blockers and ophthalmic drugs. The following trend in increase of basic analyte retention factor and decrease of tailing factor was found: PF6- > ClO4- approximately BF4- > H2PO4-. With the increase of the counteranion concentration greater analyte loading could be achieved and consequently an increase in the apparent efficiency was observed until the maximum plate number for the column was achieved. At the highest concentration of counteranions, the peak efficiency for most of the basic compounds studied was similar to that of the neutral markers. In contrast, the neutral markers, such as phenols, showed no significant changes in retention, efficiency or loading capacity as counteranion concentration was increased.     

Full-dimensional analytical ab initio potential energy surface of the ground state of HOI

Extensive ab initio calculations using a complete active space second-order perturbation theory wavefunction, including scalar and spin-orbit relativistic effects with a quadruple-zeta quality basis set were used to construct an analytical potential energy surface (PES) of the ground state of the [H, O, I] system. A total of 5344 points were fit to a three-dimensional function of the internuclear distances, with a global root-mean-square error of 1.26 kcal mol(-1). The resulting PES describes accurately the main features of this system: the HOI and HIO isomers, the transition state between them, and all dissociation asymptotes. After a small adjustment, using a scaling factor on the internal coordinates of HOI, the frequencies calculated in this work agree with the experimental data available within 10 cm(-1).     

Application of organoclays for the adsorption of recalcitrant organic molecules from aqueous media

Water purification is imperative for the welfare of a healthy population. Water is widely contaminated by recalcitrant organic chemicals such a pesticides, herbicides and hormones. One inexpensive method for purifying water from these types of molecules is through adsorption. One suite of materials for this adsorption is based upon organoclays. This paper reviews the adsorption of organics on organoclays.     

The dielectric response of interfacial water—from the ordered structures to the single hydrated shell

Water is the universal solvent in nature. Does this imply, however, that its interaction with its environment is also a universal feature? While this question maybe too fundamental to be answered by one method only, we present evidence that the broadening of the dielectric spectra of water presents universal features of dipolar interactions with different types of matrixes. If in aqueous solutions the starting point of water’s state can be considered as bulk, with only partial interactions with the solute, then the state of water adsorbed in heterogeneous materials is determined by various hydration centers of the inhomogeneous material (the matrix) and it is significantly different from the bulk. In both cases, the dielectric spectrum of water is symmetrical and can be described by the Cole–Cole (CC) function. The phenomenological model that describes a physical mechanism of the dipole–matrix interaction in complex systems underlying the CC behavior has been applied to water adsorbed in porous glasses. It was then extended to analyses of the dynamic and structural behavior of water in nonionic and ionic aqueous solutions. The same model is then used to analyze the CC relaxation processes observed in clays, aqueous solutions of nucleotides, and amino acids.