A Five‐year Study of Solar Ultraviolet Radiation in Southern Chile (39° S): Potential Impact on Physiology of Coastal Marine Algae?

This study reports 5 years of (1998-2003) data on continuous solar-irradiation measurements from a scanning spectroradiometer (SUV-100) in Valdivia, Chile (39 degrees S), accompanied by evaluation of the impact of ultraviolet radiation (UVR) on marine macroalgae of this site. UVR conditions showed a strong seasonal variation, which was less pronounced toward longer wavelengths. Daily maximum dose rates (clear days) averaged in winter-summer: UV-B(290-315 nm) 0.30-2.1, UV-B(290-320 nm) 0.70-3.7, UV-A(315-400 nm) 20.6-62.1, UV-A(320-400 nm) 20.2-60.5 W m(-2), and photosynthetically active radiation (PAR) 969-2423 micromol m(-2) s(-1). The corresponding daily doses (all the days) ranged: UV-B(290-315 nm) 2.6-40.7, UV-B(290-320 nm) 6.7-78.5, UV-A(315-400 nm) 228-1539, UV-A(320-400 nm) 224-1501, and PAR 2008-13308 kJ m(-2) d(-1). Taking into consideration action spectra of a biological interest, the risk of UV exposure could be up to 37 times higher in summer than in winter. The photosynthetic activity (as maximum quantum yield of chlorophyll fluorescence, F(v)/F(m)) of the brown alga Lessonia nigrescens from the infralittoral zone was markedly more sensitive to UVR than of the green alga Enteromorpha intestinalis from the upper midlittoral, and the UV-B wave band increased markedly photoinhibition. In L. nigrescens, maximal photoinhibition (40%) took place at weighted (the action spectrum for photoinhibition of photosynthesis) UVR doses of 800 kJ m(-2), irrespective of the season (corresponding midsummer daily dose in Valdivia is 480 kJ m(-2)). In winter, when this alga was at its most sensitive, the weighted UV dose causing 35-40% photoinhibition was around 200 kJ m(-2). In E. intestinalis, weighted doses of 800 kJ m(-2) resulted in low photoinhibition (<10 %) and no clear seasonal patterns could be inferred. These results confirm that midday summer levels of UV-B and their daily doses in southern Chile are high enough to produce stress to intertidal macroalgae.     

Enantiomeric separation of acidic compounds using single-isomer amino cyclodextrin derivatives in nonaqueous capillary electrophoresis

The enantiomeric separation of a series of acidic pharmaceuticals (mostly nonsteroidal anti-inflammatory drugs) has been investigated in NACE systems using single-isomer amino beta-CD derivatives. The first part of this study consisted of the selection of the basic experimental conditions to separate efficiently the enantiomers of acidic drugs. Several parameters, such as the nature of the ionic BGE components, were studied and a methanolic solution of ammonium acetate containing the cationic CD was selected as BGE. A D-optimal design with 20 experimental points was then applied and the nature and concentration of the CD were found to have a significant effect on the enantiomeric resolution for all studied compounds. Resolution (R(s)) values were always higher with 6-monodeoxy-6-mono(3-hydroxy)propylamino-beta-CD (PA-beta-CD) compared to those obtained with 6-monodeoxy-6-mono(2-hydroxy)propylamino-beta-CD (IPA-beta-CD). However, the latter led to shorter migration times. Generic NACE conditions were then selected by means of the multivariate approach in order to obtain the highest R(s) values in a minimum amount of time. Finally, dependence of separation selectivity, resolution, as well as mobility difference on chiral selector concentration was discussed and binding constants with PA-beta-CD were estimated for the two enantiomers of one of the model compounds, suprofen in these NACE systems.     

Quantum mechanical calculation of the effects of stiff and rigid constraints in the conformational equilibrium of the alanine dipeptide

If constraints are imposed on a macromolecule, two inequivalent classical models may be used: the stiff and the rigid one. This work studies the effects of such constraints on the conformational equilibrium distribution (CED) of the model dipeptide HCO-L-Ala-NH(2)without any simplifying assumption. We use ab initio quantum mechanics calculations including electron correlation at the MP2 level to describe the system, and we measure the conformational dependence of all the correcting terms to the naive CED based in the potential energy surface that appear when the constraints are considered. These terms are related to mass-metric tensors determinants and also occur in the Fixman's compensating potential. We show that some of the corrections are non-negligible if one is interested in the whole Ramachandran space. On the other hand, if only the energetically lower region, containing the principal secondary structure elements, is assumed to be relevant, then, all correcting terms may be neglected up to peptides of considerable length. This is the first time, as far as we know, that the analysis of the conformational dependence of these correcting terms is performed in a relevant biomolecule with a realistic potential energy function.     

Non-linear coupling in the dark sector as a running vacuum model

In this work we study a phenomenological non-gravitational interaction between dark matter and dark energy. The scenario studied in this work extends the usual interaction model proportional to the derivative of the dark component density adding to the coupling a non-linear term of the form \(Q = \rho '/3(\alpha + \beta \rho _{Dark})\) This dark sector interaction model could be interpreted as a particular case of a running vacuum model of the type \(\Lambda (H) = n_0 + n_1 H^2 + n_2 H^4\) in which the vacuum decays into dark matter. For a flat FRW Universe filled with dark energy, dark matter and decoupled baryonic matter and radiation we calculate the energy density evolution equations of the dark sector and solve them. The different sign combinations of the two parameters of the model show clear qualitative different cosmological scenarios, from basic cosmological insights we discard some of them. The linear scalar perturbation equations of the dark matter were calculated. Using the CAMB code we calculate the CMB and matter power spectra for some values of the parameters \(\alpha \) and \(\beta \) and compare it with \(\Lambda \)CDM. The model modify mainly the lower multipoles of the CMB power spectrum remaining almost the same the high ones. The matter power spectrum for low wave numbers is not modified by the interaction but after the maximum it is clearly different. Using observational data from Planck, and various galaxy surveys we obtain the constraints of the parameters, the best fit values obtained are the combinations \(\alpha = (3.7 \pm 7 )\times 10^{-4} \), \(-\,(1.5\times 10^{-5}\, \mathrm{eV}^{-1})^{4} \ll \beta < (0.07\,\mathrm{eV}^{-1})^4\).     

Microrheology and electrical conductivity of a dilute PNIPAM suspension

We study on a suspension of poly(N-isopropylacrylamide) at a low concentration using particle-tracking microrheology in two modalities: at constant temperatures and during a heating ramp. The dilute suspensions do not present a glass state at low temperatures, and at high temperatures, the polymer particles collapse, giving rise to entropic forces that induce aggregation of the tracking colloids. The viscoelastic moduli of the system, which drastically change with temperature, allow us to follow this dynamics. Furthermore, the viscosity of the system remains approximately constant with temperature but suddenly increases as it passes the lower critical solution temperature (LCST). Such effect is probably associated to hydration before the collapse of the polymer, as verified by electrical conductivity measurements.     

Easily manufactured TiO2 hollow fibers for quantum dot sensitized solar cells

TiO(2) hollow fibers with high surface area were manufactured by a simple synthesis method, using natural cellulose fibers as template. The effective light scattering properties of the hollow fibers, originating from their micron size, were observed by diffuse reflectance spectroscopy. In spite of the micrometric length of the TiO(2) hollow fibers, the walls were highly porous and high surface area (78.2 m(2) g(-1)) was obtained by the BET method. TiO(2) hollow fibers alone and mixed with other TiO(2) pastes were sensitized with CdSe quantum dots (QDs) by Successive Ionic Layer Adsorption and Reaction (SILAR) and integrated as a photoanode in quantum dot sensitized solar cells (QDSCs). High power conversion efficiency was obtained, 3.24% (V(oc) = 503 mV, J(sc) = 11.92 mA cm(-2), FF = 0.54), and a clear correspondence of the cell performance with the photoanode structure was observed. The unique properties of these fibers: high surface area, effective light scattering, hollow structure to facile electrolyte diffusion and the rather high efficiencies obtained here suggest that hollow fibers can be introduced as promising nanostructures to make highly efficient quantum dot sensitized solar cells.     

The role of orbiting resonances in the vibrational relaxation of I(2)(B,v' = 21) by collisions with He at very low energies: a theoretical and experimental study

The low-energy collisions of I(2)(B,v' = 21) with He involving collision-induced vibrational relaxation of I(2) are investigated both experimentally and by means of wave packet simulations. The theoretical cross sections exhibit a structure of peaks originated by orbiting resonances of the I(2)(B,v' = 21) - He van der Waals complex formed in the I(2) + He collisions. Such a structure has similar characteristics as the structure of peaks found in the experimental cross sections. In fact, four of the five peaks of the measured cross sections appear at positions nearly coincident with those of four of the peaks found in the theoretical cross sections. Thus this result confirms the experimental finding that enhancement of I(2) vibrational relaxation is caused by the population of I(2)(B,v' = 21) - He orbiting resonances populated upon the low-energy collisions. The possibility of using this mechanism in the vibrational cooling of diatomic molecules is discussed.     

High-valent oxo-molybdenum and oxo-rhenium complexes as efficient catalysts for X-H (X = Si, B, P and H) bond activation and for organic reductions

High-valent oxo-complexes have recently emerged as powerful catalysts for the activation of X-H (X = Si, B, P and H) bonds and for the reduction of several functional groups. This new reactivity represents a complete reversal from the traditional role of these complexes as oxidation catalysts and opened a new research area for high-valent oxo-complexes. This tutorial review highlights the work developed using high-valent oxo-molybdenum and oxo-rhenium complexes as excellent catalysts for X-H (X = Si, B, P and H) bond activation and for organic reductions.     

Reverse buoyancy in a vibrated granular bed: Computer simulations

We have performed molecular dynamics simulations of an intruder in a vibrated granular bed including interstitial fluid effects to account for the phenomenon of reverse buoyancy. We show that our model is able to reproduce the overall behaviour observed by previous experimental works and is the first finite-elements simulation to show the sinking of intruders lighter than the granular bed. To further advance our comprehension of this phenomenon, we studied the motion of the intruders in a single vibration cycle with respect to the bottom of the granular column, finding a substantial qualitative difference for heavy and light intruders and we compare these results with experiments using fine-sized glass beads. We show that, though heavy intruders seem unaffected by the force due to the fluid, the effect on light intruders is remarkable.