Electrochemical study of the thermodynamics and kinetics of hydrophilic ion transfers across water | <Emphasis Type="Italic">n</Emphasis>-octanol interface

Thermodynamics and kinetics of hydrophilic ion transfers across water|n-octanol (W|OCT) interface have been electrochemically studied by means of novel three-phase and thin-film electrodes. Three-phase electrodes used for thermodynamics measurements comprise edge plane pyrolytic graphite, the surface of which was partly modified with an ultrathin film of OCT, containing hydrophobic lutetium bis(tetra-tert-butylphthalocyaninato) (Lu[tBu₄Pc]₂) as a redox probe. The transfers of anions and cations from W to OCT were electrochemically driven by reversible redox transformations of Lu[tBu₄Pc]₂ to chemically stable lipophilic monovalent cation and anion , respectively. Upon reduction of Lu[tBu₄Pc]₂, the transfers of alkali metal cations from W to OCT have been studied for the first time, enabling estimation of their Gibbs transfer energies. For kinetic measurements, a thin-film electrode configuration has been used, consisting of the same electrode covered completely with a thin layer of OCT that contained the redox probe and a suitable electrolyte. Combining the fast and sensitive square-wave voltammetry with thin-film electrodes, the kinetics of , , and Cl⁻ transfers have been estimated. Dedicated to Professor Dr. Yakov I. Tur’yan on the occasion of his 85th birthday.     

Modeling equilibrium concentrations of Bjerrum and molecular point defects and their complexes in ice Ih

We present a model for the determination of the thermal equilibrium concentrations of Bjerrum defects, molecular point defects, and their aggregates in ice I(h). First, using a procedure which minimizes the free energy of an ice crystal with respect to the numbers of defect species, we derive a set of equations for the equilibrium concentrations of free Bjerrum and point defects, as well their complexes. Using density-functional-theory calculations, we then evaluate the binding energies of Bjerrum-defect/vacancy and Bjerrum-defect/interstitial complexes. In contrast to the complexes which involve the molecular vacancy, the results suggest that the molecular interstitial binds preferentially to the D-type Bjerrum defect. Using both theoretical binding and formation free energies as well as the available experimental data, we find that the preferential binding and the substantial presence of the interstitial as the predominant point defect in ice I(h) may lead to conditions in which the number of free D defects becomes considerably smaller than that of free L defects. Such a scenario could possibly be involved in the experimentally observed inactivity of D-type Bjerrum defects in the electrical properties of ice I(h).     

Femtosecond time-resolved photoelectron-photoion coincidence imaging of multiphoton multichannel photodynamics in NO2

The multiphoton multichannel photodynamics of NO(2) has been studied using femtosecond time-resolved coincidence imaging. A novel photoelectron-photoion coincidence imaging machine was developed at the laboratory in Amsterdam employing velocity map imaging and "slow" charged particle extraction using additional electron and ion optics. The NO(2) photodynamics was studied using a two color pump-probe scheme with femtosecond pulses at 400 and 266 nm. The multiphoton excitation produces both NO(2) (+) parent ions and NO(+) fragment ions. Here we mainly present the time dependent photoelectron images in coincidence with NO(2) (+) or NO(+) and the (NO(+),e) photoelectron versus fragment ion kinetic energy correlations. The coincidence photoelectron spectra and the correlated energy distributions make it possible to assign the different dissociation pathways involved. Nonadiabatic dynamics between the ground state and the A (2)B(2) state after absorption of a 400 nm photon is reflected in the transient photoelectron spectrum of the NO(2) (+) parent ion. Furthermore, Rydberg states are believed to be used as "stepping" states responsible for the rather narrow and well-separated photoelectron spectra in the NO(2) (+) parent ion. Slow statistical and fast direct fragmentation of NO(2) (+) after prompt photoelectron ejection is observed leading to formation of NO(+)+O. Fragmentation from both the ground state and the electronically excited a (3)B(2) and b (3)A(2) states of NO(2) (+) is observed. At short pump probe delay times, the dominant multiphoton pathway for NO(+) formation is a 3x400 nm+1x266 nm excitation. At long delay times (>500 fs) two multiphoton pathways are observed. The dominant pathway is a 1x400 nm+2x266 nm photon excitation giving rise to very slow electrons and ions. A second pathway is a 3x400 nm photon absorption to NO(2) Rydberg states followed by dissociation toward neutral electronically and vibrationally excited NO(A (2)Sigma,v=1) fragments, ionized by one 266 nm photon absorption. As is shown in the present study, even though the pump-probe transients are rather featureless the photoelectron-photoion coincidence images show a complex time varying dynamics in NO(2). We present the potential of our novel coincidence imaging machine to unravel in unprecedented detail the various competing pathways in femtosecond time-resolved multichannel multiphoton dynamics of molecules.     

Synthesis of novel fluorinated 4H-benzo[h]chromen-4-one and 4H-pyrano[3,2-h]quinolin-4-one derivatives

New fluorinated 4H-benzo[h]chromen-4-one and 4H-pyrano[3,2-h]quinolin-4-one derivatives are obtained in moderate to good yields, through a one-pot aldolization-intramolecular S_NAr process, from the tetrakis(dimethylamino)ethylene (TDAE) mediated reductive cleavage of two N,N-dimethylamino-bis-chlorodifluoroacetyl substrates in the presence of heteroaryl aldehydes.     

Using the Relaxation Oscillations Principle for Simple Phonation Modeling

Well-known multimass models of vocal folds are useful to describe main behavior observed in human voicing but their principle of functioning, based on harmonic oscillation, may appear complex. This work is designed to show that a simple one-mass model ruled by laws of relaxation oscillation can also depict main behavior of glottis dynamic. Theory of relaxation oscillation is detailed. A relaxation oscillation model is assessed through a numerical simulation using conventional values for tissue characteristics and subglottal pressure. As expected, raising the mass decreases the fundamental frequency and increases the amplitude of vocal fold vibration: for a mass ranging from 0.01 to 0.4 g, F0 decreased from 297.5 to 42.5 Hz and vibrational amplitude increased from 1.26 to 3.25 mm (for stiffness k=10Nm(-1), damping r=0.015 N s m(-1), and subglottal pressure=1 kPa). Stiffness value has the opposite effect. The subglottal pressure controls the fundamental frequency with a rate ranging from 20 to 50 Hz/kPa. The vibrational amplitude is also controlled linearly by subglottal pressure from 0.22 to 0.26 mm/kPa. The range of phonation threshold pressure (PTP) is close to the values currently proposed, that is, 0.1 to 1 kPa and varies with the fundamental frequency. The relaxation oscillator is a simple and useful tool for modeling vocal fold vibration.     

Uniformly valid approximations for non-linear oscillations with small damping

A uniformly valid zeroth-order approximation is obtained for the general equation y + εH(y)y + M(y)y = 0, where ε is a small parameter. The notion of multiple scaling is utilized to set up a systematic approximation scheme. Examples are given for simple polynomials for H(y) and M(y), which lead to results involving elliptic integrals. Further restrictions allow progress to be made in terms of gamma functions.     

Application of Electrical Capacitance Tomography to Flow Modelling within a Circulating Fluidized Bed

The results of the measurements of the solids concentration region in a circulating fluidized bed are described. An electrical capacitance tomography system has been used to measure both instantaneous and average solid distributions as a function of a superficial air velocity and a solid mass flux. The fractional wall coverage by clusters and the solids concentration within the annulus layer was measured. The data is compared with the results available from the literature.     

Improvement of the Detection Limit in Capillary Gas Chromatographic Trace Analysis of C2–C4 Hydrocarbons by Post Column Cryogenic Trapping

A method for the improvement of signal-to-noise ratios and hence detection limits in capillary gas chromatographic trace analysis of C₂–C₄ hydrocarbons was developed. It is based on the post column cryogenic trapping of the separated hydrocarbons using liquid nitrogen as coolant and its fast reinjection into the detector by rapid heating of the capillary tubing used for trapping. The improved signal-to-noise ratios were applied to decrease the sample volume and/or to lower the detection limit 10 to 27 times. The concentrations of these hydrocarbons in an urban air sample determined without and with post column cryogenic trapping were in good agreement but the precision was better when applying the cryogenic trapping mode.     

The Crystal Structure of Ba2Cu2AlF11: a New Structure Type in Copper Fluoride Crystal Chemistry

Ba₂Cu₂AlF₁₁ is trigonal: a = 7.301(1) Å, c = 14.145(2) Å, γ = 120°, Z = 3. The crystal structure was solved in the space group P3₂ (n° 145), from X-ray single crystal data using 2675 unique reflections (2476 with F/σ(F) > 4). It consists in a complex tridimensional arrangement of copper-fluorine and aluminium-fluorine octahedra, with an original kind of linkage which involves simultaneously edges and vertices.