ULTRAVIOLET SOLAR RADIATION IN THE HIGH LATITUDES OF SOUTH AMERICA

Abstract Measurements of the UV solar irradiance are available from Ushuaia, Tierra del Fuego during the spring and summer seasons of 4 consecutive years beginning in 1989. In addition, column ozone amounts derived from satellite-based measurements exist for this location over the entire period from 1980 through 1991. Monthly mean column ozone over Ushuaia shows a general decline over the observing period, and a large day-to-day variability exists within a given month. Ozone amounts for the years 1980 through 1986 combined with a model of radiative transfer provide a climatological baseline against which to interpret the more recent ground-based irradiance data. We focus on monthly mean noontime irradiances integrated over 5 nm wide spectral bands near 305 nm and 340 nm, respectively. Measurements in the 340 nm band show that cloudiness has a large influence on both the absolute monthly mean irradiances and their interannual variability. For example, during December the 340 nm band irradiance varied from approximately 50% of the clear-sky value in 1992 to 65% in 1991. When the influence of cloudiness is removed, most of the months show irradiances in the 305 nm band that are larger than predicted from the climatological ozone amounts. The largest percentage enhancement occurred in October 1991 when the irradiance exceeded the baseline by 56%. The largest absolute irradiances occur in December, where the measurements range from 5.8% below the baseline in 1991 to 31% above in 1990.     

N–N2 state to state vibrational-relaxation and dissociation rates based on quasiclassical calculations

Interpolation formulas are presented to reproduce the rate coefficients for vibrational–translational energy exchange and dissociation for the N + N₂ collision process. The original data have been obtained by quasiclassical method in a detailed way, including the effect of molecular rotation. The fitting procedure results are compared with original data and the related error is evaluated. Comparison with global experimental dissociation results is also presented.     

On the derivation of the incompressible Mavier-Stokes equation for Hamiltonian particle systems

We consider a Hamiltonian paticle system interacting by means of a pair potetial. We look at the behavior of the system on a space scale of order ^-1, times of order ^-2 and mean velocities of order , with a scale parameter. Assuming that the phase space density of the particles is give by a series in (the analog of the Chapman-Enskog expansion), the behavior of the system under this rescaling is described, to the lowest order in , by the incompressible Navier-Stokes equations. The viscosity is given in terms of microscopic correlations, and its expression agrees with the Green-Kubo formula.     

Molecular mechanics and dynamics of biomolecules using a solvent continuum model

An easy implementation of molecular mechanics and molecular dynamics simulation using a continuum solvent model is presented that is particularly suitable for biomolecular simulations. The computation of solvation forces is made using the linear Poisson-Boltzmann equation (polar contribution) and the solvent-accessible surface area approach (nonpolar contribution). The feasibility of the methodology is demonstrated on a small protein and a small DNA hairpin. Although the parameters employed in this model must be refined to gain reliability, the performance of the method, with a standard choice of parameters, is comparable with results obtained by explicit water simulations. Copyright 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1830-1842, 2001     

Kinetic limits of the HPP cellular automaton

We study the Boltzmann-Grad limit in various versions of the two-dimensional HPP cellular automaton. In the completely deterministic case we prove convergence to an evolution that is not of kinetic type, a well-known phenomenon after Uchyiama's paper on the Broadwell gas, whereas the limiting equation becomes of kinetic type in the model with random collisions. The main part of the paper concerns the case where the collisions are deterministic and the randomness comes from inserting, between any two successive HPP updatings, ^- stirring updatings, <1 being any fixed positive number and a parameter which tends to 0. The initial measure is a product measure with average occupation numbers of the order of (low-density limit) and varying on distances of the order of ^–1. The limit as 0 of the system evolved for times of the order of ^-1- corresponds to the Boltzmann-Grad limit. We prove propagation of chaos and that the renormalized average occupation numbers (i.e., divided by) converge to the solution of the Broadwell equation. Convergence is proven at all times for which the solution of the Broadwell equation is bounded.     

Sol-Gel Synthesis of Humidity-Sensitive P2O5-SiO2 Amorphous Films

The sol-gel synthesis of silicophosphate gels using phosphoryl chloride and tetraethoxysilane as molecular precursors is reported and discussed. Gel-derived glasses and films having the molar compositions 10P₂O₅ · 90SiO₂ and 30P₂O₅ · 70SiO₂ have been obtained. The structure of the dried gels as well as the structural modifications that occurs during the transformations in gel-derived glasses are analyzed by Fourier transform infrared spectroscopy (FTIR). It has been found that the evidence of the P—O—Si linkages begins to appear only on the FTIR spectra of the bulk gels heat treated up to 400°C while they are well resolved on the FTIR spectra of the bulk gel samples heated up to 1000°C indicating that at this temperature the transformation in the corresponding gel-derived glasses occurs. The humidity sensitive properties of the gel-films have been evaluated by electrochemical impedance spectroscopy (EIS). The phosphorous content as well as the temperature of the heat treatments strongly affect the sensitivity to RH of the gel-derived films.     

Synthesis of Piperidine Nucleosides as Conformationally Restricted Immucillin Mimics

The de novo synthesis of piperidine nucleosides from our homologating agent 5,6-dihydro-1,4-dithiin is herein reported. The structure and conformation of nucleosides were conceived to faithfully resemble the well-known nucleoside drugs Immucillins H and A in their bioactive conformation. NMR analysis of the synthesized compounds confirmed that they adopt an iminosugar conformation bearing the nucleobases and the hydroxyl groups in the appropriate orientation.