Interfacial electron transfer into functionalized crystalline polyoxotitanate nanoclusters

Interfacial electron transfer (IET) between a chromophore and a semiconductor nanoparticle is one of the key processes in a dye-sensitized solar cell. Theoretical simulations of the electron transfer in polyoxotitanate nanoclusters Ti(17)O(24)(OPr(i))(20) (Ti(17)) functionalized with four p-nitrophenyl acetylacetone (NPA-H) adsorbates, of which the atomic structure has been fully established by X-ray diffraction measurements, are presented. Complementary experimental information showing IET has been obtained by EPR spectroscopy. Evolution of the time-dependent photoexcited electron during the initial 5 fs after instantaneous excitation to the NPA LUMO + 1 has been evaluated. Evidence for delocalization of the excitation over multiple chromophores after excitation to the NPA LUMO + 2 state on a 15 fs time scale is also obtained. While chromophores are generally considered electronically isolated with respect to neighboring sensitizers, our calculations show that this is not necessarily the case. The present work is the most comprehensive study to date of a sensitized semiconductor nanoparticle in which the structure of the surface and the mode of molecular adsorption are precisely defined.     

Assigning kinetic 3D-signatures to glycocodes

Reconciling glycocodes and their associated bioactivities, via 3D-structure, will rationalise burgeoning high-throughput functional glycomics data and underpin a new era of opportunity in chemical biology. A major impasse to achieving this goal is a detailed understanding of pyranose sugar ring 3D-conformation (or pucker) and the affiliated microsecond-timescale exchange kinetics. Here, we perform hardware-accelerated kinetically-rigorous equilibrium simulations of fundamental monosaccharides to produce the hypothesis that pyranoses have microsecond-timescale kinetic puckering signatures in water, classified as unstable (rare in the glycome), metastable (infrequently observed) and stable (prevalent). The predicted μs-metastability of β-d-glucose explained hitherto irreconcilable experimental measurements. Twisted puckers seen in carbohydrate enzymes were present in the aqueous 3D-ensemble (suggesting preorganization) and pyranose-water interactions accounted for the relative stability of β-d-galactose. Characteristic 3D-shapes for biologically- and commercially-important carbohydrates and new rules linking chemical modifications with pyranose μs-puckering kinetics are proposed. The observations advance structural-glycomics towards dynamic 3D-templates suitable for structure-based design.     

Total synthesis of trunkamide A, a novel thiazoline-based prenylated cyclopeptide metabolite from Lissoclinum sp.

Full details of a total synthesis of the doubly prenylated cyclic peptide trunkamide A of marine origin, and also its C45 epimer, are described.     

SPH for 3D floating bodies using variable mass particle distribution

A floating body with substantial heave motion is a challenging fluid–structure interaction problem for numerical simulation. In this paper we develop SPH in three dimensions to include variable particle mass distribution using an arbitrary Lagrange–Eulerian formulation with an embedded Riemann solver. A wedge or cone in initially still water is forced to move with a displacement equal to the surface elevation of a focused wave group. A two‐dimensional wedge case is used to evaluate two forms of repulsive‐force boundary condition on the body; the force depending on the normal distance from the object surface produced closer agreement with the experiment. For a three‐dimensional heaving cone the comparison between SPH and experiment shows excellent agreement for the force and free surface for motion with low peak spectral frequencies while for a higher peak frequency the agreement is reasonable in terms of phase and magnitude, but a small discrepancy appears at the troughs in the motion. Capturing the entire three‐dimensional flow field using an initially uniform particle distribution with sufficiently fine resolution requires an extremely large number of particles and consequently large computing resource. To mitigate this issue, we employ a variable mass distribution with fine resolution around the body. Using a refined mass distribution in a preselected area avoids the need for a dynamic particle refinement scheme and leads to a computational speedup of more than 600% or much improved results for a given number of particles. SPH with variable mass distribution is then applied to a single heaving‐float wave energy converter, the ‘Manchester Bobber’, in extreme waves and compared with experiments in a wave tank. The SPH simulations are presented for two cases: a single degree‐of‐freedom system with motion restricted to the vertical direction and with general motion allowing six degrees‐of‐freedom. The motion predicted for the float with general motion is in much closer agreement with experimental data than the vertically constrained system. Using variable particle mass distribution is shown to produce close agreement with a computation time 20% of that required with a uniformly fine resolution. Copyright © 2012 John Wiley & Sons, Ltd.     

High-pressure X-ray diffraction study of the δ-phase in the uranium-neptunium binary system

Abstract

High pressure X-ray diffraction studies were performed at room temperature on a uranium-neptunium binary alloy (U_{0, 40} Np_0.60) using a diamond anvil cell in an energy dispersive facility. The sample maintained its simple cubic phase up to 62 GPa (highest pressure reached in This experiment). The bulk modulus and its pressure derivative were determined to be B₀ = 82 (2) GPa and B₀′ = 9.4 (1.3), from the experimental data in the pressure range 0–20 GPa. The present results are compared with those obtained by the same techniques used for uranium and neptunium.     

Functional in situ evaluation of photosynthesis-protecting carotenoids in mutants of the cyanobacterium Synechocystis PCC6803

Cyanobacteria possess different carotenoids as scavengers of reactive oxygen species. In Synechocystis PCC6803, zeaxanthin, echinenone, beta-carotene and myxoxanthophyll are synthesized. By disruption of the ketolase and hydroxylase genes, it was possible to obtain mutants devoid of either zeaxanthin, echinenone, or a combination of both carotenoids. With these mutants, their function in protecting photosynthetic electron transport under high light stress as well as chlorophyll and carotenoid degradation after initiation of singlet oxygen or radical formation was analyzed. Wild type Synechocystis is very well protected against high light-mediated photooxidation. Absence of echinenone affects photosynthetic electron transport to only a small extent. However, complete depletion of zeaxanthin together with a modification of myxoxanthophyll resulted in strong photoinhibition of overall photosynthetic electron transport as well as the photosystem II reaction. In the double mutant lacking both carotenoids the effects were additive. The light saturation curves of photosynthetic electron transport of the high light-treated mutants exhibited not only a lower saturation value but also smaller slopes. Using methylviologen or methylene blue as a radical or singlet oxygen generators, respectively, massive degradation of chlorophyll and carotenoids, indicative of photooxidative destruction of the photosynthetic apparatus, was observed, especially in the mutants devoid of zeaxanthin.     

On the accelerated expansion of the cosmos

We present a short (and necessarily incomplete) review of the evidence for the accelerated expansion of the Universe. The most direct probe of acceleration relies on the detailed study of supernovae (SN) of type Ia. Assuming that these are standardizable candles and that they fairly sample a homogeneous and isotropic Universe, the evidence for acceleration can be tested in a model-independent and calibration-independent way. Various light-curve fitting procedures have been proposed and tested. While several fitters give consistent results for the so-called Constitution set, they lead to inconsistent results for the recently released SDSS SN. Adopting the SALT fitter and relying on the Union set, cosmic acceleration is detected by a purely kinematic test at 7σ when spatial flatness is assumed and at 4σ without any assumption on the spatial geometry. A weak point of the described method is the local set of SN (at z<0.2), as these SN are essential to anchor the Hubble diagram. These SN are drawn from a volume much smaller than the Hubble volume and could be affected by local structure. Without the assumption of homogeneity, there is no evidence for acceleration, as the effects of acceleration are degenerate with the effects of inhomogeneities. Unless we sit in the centre of the Universe, such inhomogeneities can be constrained by SN observations by means of tests of the isotropy of the Hubble flow.     

Novel synthesis of stable polypyrrole nanospheres using ozone

In this study, a novel and exceedingly simple method for the aqueous synthesis of stable, unagglomerated polypyrrole nanospheres was investigated. The method is template- and surfactant-free and uses only pyrrole monomer, water, and ozone. When the monomer concentration, exposure time to ozone, and temperature were varied, it was determined that the temperature was the critical factor controlling the particle size through particle size measurements via dynamic light scattering and transmission electron microscopy (TEM). From the particle size measurements, a particle size distribution with a number-weighted mean diameter of 73 nm and a standard deviation of 18 nm was achieved. The particles were also investigated using ζ-potential measurements, ultraviolet-visible (UV-vis) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric analysis in an effort to determine the identity of the nanoparticles as well as the mechanism by which the nanoparticles are formed and stabilized.     

Antioxidative Activities of Algal Keto Carotenoids Acting as Antioxidative Protectants in the Chloroplast

Very diverse carotenoid structures exist in the photosynthesis apparatus of different algae. Among them, the keto derivatives are regarded the most antioxidative. Therefore, four different keto carotenoids, peridinin, fucoxanthin, siphonaxanthin and astaxanthin fatty acid monoesters, were isolated and purified from Amphidinium carterae, Phaeodactylum tricornutum, Caulerpa taxifolia and Haematococcus pluvialis, respectively. The carotenoids were assayed as inhibitors of photosensitizer initiated reactions or scavengers of radicals in the early events generating reactive oxygen species as starters for peroxidation and as protectants against the whole reaction chain finally leading to lipid peroxidation. These in vitro studies demonstrated the substantial antioxidative properties as indicated by the IC₅₀ values of all four keto carotenoids with superior protection by astaxanthin fatty acid monoesters which were as effective as free astaxanthin and of peridinin against radicals. As an example, the in vivo relevance of fucoxanthin for protection of photosynthesis from excess light and from peroxidative agents was evaluated with intact cells. Cultures of P. tricornutum with decreased fucoxanthin content generated by inhibitor treatment were exposed to strong light or cumene hydroperoxyde. In each case, oxidation of chlorophyll as marker for damaging of the photosynthesis apparatus was less severe when the fucoxanthin was at maximum level.