Effects of Ultraviolet Radiation (UVA+UVB) and Copper on the Morphology,Ultrastructural Organization and Physiological Responses of the Red Alga Pterocladiella capillacea

The effect of ultraviolet (UV) radiation and copper (Cu) on apical segments of Pterocladiella capillacea was examined under two different conditions of radiation, PAR (control) and PAR+UVA+UVB (PAR+UVAB), and three copper concentrations, ranging from 0 (control) to 0.62, 1.25 and 2.50 μm . Algae were exposed in vitro to photosynthetically active radiation (PAR) at 70 μmol photons m^?2 s^?1, PAR + UVB at 0.35 W m^?2 and PAR +UVA at 0.70 W m^?2 during a 12‐h photocycle for 3 h each day for 7 days. The effects of radiation and copper on growth rates, content of photosynthetic pigments and photosynthetic performance were analyzed. In addition, samples were processed for light and transmission electron microscopy. The content of photosynthetic pigments decreased after exposure to radiation and Cu. Compared with PAR radiation and copper treatments modified the kinetics patterns of the photosynthesis/irradiance curve. The treatments also caused changes in the ultrastructure of cortical and subcortical cells, including increased cell wall thickness and accumulation of plastoglobuli, as well as changes in the organization of chloroplasts. The results indicate that the synergistic interaction between UV radiation and Cu in P. capillacea, led to the failure of protective mechanisms and causing more drastic changes and cellular imbalances.     

Naked five-coordinate Fe(III)(NO) porphyrin complexes: vibrational and reactivity features

Model ferric heme nitrosyl complexes, [Fe(TPP)(NO)](+) and [Fe(TPFPP)(NO)](+), where TPP is the dianion of 5,10,15,20-tetrakis-phenyl-porphyrin and TPFPP is the dianion of 5,10,15,20-tetrakis-pentafluorophenyl-porphyrin, have been obtained as isolated species by the gas phase reaction of NO with [Fe(III)(TPP)](+) and [Fe(III) (TPFPP)](+) ions delivered in the gas phase by electrospray ionization, respectively. The so-formed nitrosyl complexes have been characterized by vibrational spectroscopy also exploiting (15)N-isotope substitution in the NO ligand. The characteristic NO stretching frequency is observed at 1825 and 1859 cm(-1) for [Fe(III)(TPP)(NO)](+) and [Fe(III)(TPFPP)(NO)](+) ions, respectively, providing reference values for genuine five-coordinate Fe(III)(NO) porphyrin complexes differing only for the presence of either phenyl or pentafluorophenyl substituents on the meso positions of the porphyrin ligand. The vibrational assignment is aided by hybrid density functional theory (DFT) calculations of geometry and electronic structure and frequency analysis which clearly support a singlet spin electronic state for both [Fe(TPP)(NO)](+) and [Fe(TPFPP)(NO)](+) complexes. Both TD-DFT and CASSCF calculations suggest that the singlet ground state is best described as Fe(II)(NO(+)) and that the open-shell AFC bonding scheme contribute for a high-energy excited state. The kinetics of the NO addition reaction in the gas phase are faster for [Fe(III)(TPFPP)](+) ions by a relatively small factor, though highly reliable because of a direct comparative evaluation. The study was aimed at gaining vibrational and reactivity data on five-coordinate Fe(III)(NO) porphyrin complexes, typically transient species in solution, ultimately to provide insights into the nature of the Fe(NO) interaction in heme proteins.     

Antimicrobial graphene polymer (PVK-GO) nanocomposite films

The first report on the fabrication and application of a nanocomposite containing poly-N-vinyl carbazole (PVK) polymer and graphene oxide (GO) as an antimicrobial film was demonstrated. The antimicrobial film was 90% more effective in preventing bacterial colonization relative to the unmodified surface. More importantly, the nanocomposite thin film showed higher bacterial toxicity than pure GO-modified surface.     

Carbon dioxide hydrogenation to formic acid by using a heterogeneous gold catalyst

AUROlite, consisting of gold supported on titania (picture shows extrudates in a steel net cage), is a robust catalyst for the production of catalyst-free HCOOH/NEt(3) adducts from H(2), CO(2), and neat NEt(3). Pure HCOOH is freed from the adducts by amine exchange.     

The Slow Erosion Limit in a Model of Granular Flow

We study a 2 × 2 system of balance laws that describes the evolution of a granular material (avalanche) flowing downhill. The original model was proposed by Hadeler and Kuttler (Granul Matter 2:9–18, 1999). The Cauchy problem for this system has been studied by the authors in recent papers (Amadori and Shen in Commun Partial Differ Equ 34:1003–1040, 2009; Shen in J Math Anal Appl 339:828–838, 2008). In this paper, we first consider an initial-boundary value problem. The boundary condition is given by the flow of the incoming material. For this problem we prove the global existence of BV solutions for a suitable class of data, with bounded but possibly large total variations. We then study the “slow erosion (or deposition) limit”. We show that, if the thickness of the moving layer remains small, then the profile of the standing layer depends only on the total mass of the avalanche flowing downhill, not on the time-law describing the rate at which the material slides down. More precisely, in the limit as the thickness of the moving layer tends to zero, the slope of the mountain is provided by an entropy solution to a scalar integro-differential conservation law.     

High order methods for weakly singular integral equations with nonsmooth input functions

To solve one-dimensional linear weakly singular integral equations on bounded intervals, with input functions which may be smooth or not, we propose to introduce first a simple smoothing change of variable, and then to apply classical numerical methods such as product-integration and collocation based on global polynomial approximations. The advantage of this approach is that the order of the methods can be arbitrarily high and that the associated linear systems one has to solve are very well-conditioned.

     

Efficient Verification Tools for Reduced Derivatives Computed by a First-Optimize-Then-Discretize Approach for Optimal Control Problems

We give an overview about several verification tools to study consistency between discrete optimization problem and discrete derivatives when using independent discretization schemes for state and adjoint systems within the context of optimal control problems. We present strategies that detect impreciseness within a considered quantity without any additional effort. They are therefore a suitable tool to control the grid refinement within a multilevel setting. More detailed tools are useful to verify the problem implementation and to analyze the quantities discretization error order. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Global existence of BV solutions and relaxation limit for a model of multiphase reactive flow

We consider a strictly hyperbolic system of balance laws in one space variable, that represents a simple model for a fluid flow in the presence of phase transitions. The state variables are specific volume, velocity and mass-density fraction λ of the vapor in the fluid. A reactive source term drives the dynamics of the phase mixtures; such a term depends on a relaxation parameter and involves an equilibrium pressure, allowing for metastable states.First we prove the global existence of weak solutions to the Cauchy problem, where the initial datum for λ is close either to 0 or 1 (the pure phases) and has small total variation, while the initial variations of pressure and velocity are not necessarily small. Then we consider the relaxation limit and prove that the weak solutions of the full system converge to those of the reduced system.     

High-performance liquid chromatography coupled to ultraviolet diode array detection and electrospray ionization mass spectrometry for the analysis of intermediates produced in the initial steps of the photocatalytic degradation of sulfonated azo dyes

High-performance liquid chromatography coupled to ultraviolet diode array detection and electrospray ionization mass spectrometry was applied to monitor the photocatalytic degradation mediated by TiO2 of three sulfonated monoazo dyes (Orange I, Orange II, and Ethylorange) present in aqueous solution. Photobleaching, organic carbon, nitrogen and sulfur evolution were also followed during the process. Delayed carbon mineralization was observed with respect to both dyes disappearance and photobleaching, due to the formation of transient intermediate compounds which were in turn completely degraded. Among the intermediates produced during the initial degradation steps the formation of several hydroxylated derivatives, mostly coloured, was evidenced. The MS(2) spectra allowed one to formulate hypothesis about the OH attack positions; a peculiar reactivity of the azo moiety was shown by Orange I and Orange II.