Bilirubin oxidase from myrothecium verrucaria physically absorbed on graphite electrodes. Insights into the alternative resting from and the sources of activity loss

The oxygen reduction reaction is one of the most important chemical processes in energy converting systems and living organisms. Mediator-less, direct electro-catalytic reduction of oxygen to water was achieved on spectrographite electrodes modified by physical adsorption of bilirubin oxidases from Myrothecium verrucaria. The existence of an alternative resting form of the enzyme is validated. The effect on the catalytic cycle of temperature, pH and the presence of halogens in the buffer was investigated. Previous results on the electrochemistry of bilirubin oxidase and on the impact of the presence of halogens are reviewed and reinterpreted

Analysis of products from the pyrolysis of plastics recovered from the commercial scale recycling of waste electrical and electronic equipment

Three plastic fractions from a commercial waste electrical and electronic equipment (WEEE) processing plant were collected and investigated for the possibility of recycling them by batch pyrolysis. The first plastic was from equipment containing cathode ray tubes (CRTs), the second plastic was from refrigeration equipment, and the third plastic was from mixed WEEE. Initially, the decomposition of each of the plastics was investigated using a TGA linked to a FT-ir spectrometer which showed that the CRT plastic decomposed to form aliphatic and aromatic compounds, the refrigerator plastic decomposed to form aldehydes, CO2, aromatic, and aliphatic compounds, and the mixed WEEE plastic decomposed to form aromatic and aliphatic compounds, CO2, and CO. Each plastic mixture was also pyrolysed in a batch reactor to determine the halogen and metal content of the pyrolysis products, additionally, characterisation of the pyrolysis oils was carried out by GC-MS and the pyrolysis gases by GC-FID and GC-TCD. It was found that the halogen content of the oils was relatively low but the halogen and metal content of the chars was high. The pyrolysis oils were found to contain valuable chemical products and the pyrolysis gases were mainly halogen free, making them suitable as a fuel

The first mononuclear PtIII complex. Molecular structures of (NBu4)[PtIII(C6Cl5)4] and of its parent compound {NBu4}2[PtII(C6Cl5)4]·2CH2Cl2

(NBu4)[PtIII(C6Cl5)4], fully characterized by crystallographic, spectral, and magnetic measurements has been isolated by oxidation with halogens or TICl3 of the parent compound (NBu4)2[PtII(C6CL5)4], which has also been analysed by X-ray crystallography

Gas emission strength and evolution of the molar ratio of BrO/SO2 in the plume of Nyiragongo in comparison to Etna

Airborne and ground-based differential optical absorption spectroscopy observations have been carried out at the volcano Nyiragongo (Democratic Republic of Congo) to measure SO2 and bromine monoxide (BrO) in the plume in March 2004 and June 2007, respectively. Additionally filter pack and multicomponent gas analyzer system (Multi-GAS) measurements were carried out in June 2007. Our measurements provide valuable information on the chemical composition of the volcanic plume emitted from the lava lake of Nyiragongo. The main interest of this study has been to investigate for the first time the bromine emission flux of Nyiragongo (a rift volcano) and the BrO formation in its volcanic plume. Measurement data and results from a numerical model of the evolution of BrO in Nyiragongo volcanic plume are compared with earlier studies of the volcanic plume of Etna (Italy). Even though the bromine flux from Nyiragongo (2.6t/d) is slightly greater than that from Etna (1.9t/d), the BrO/SO2 ratio (maximum 7x10(-5)) is smaller than in the plume of Etna (maximum 2.1x10(-4)). A one-dimensional photochemical model to investigate halogen chemistry in the volcanic plumes of Etna and Nyiragongo was initialized using data from Multi-GAS and filter pack measurements. Model runs showed that the differences in the composition of volcanic volatiles led to a smaller fraction of total bromine being present as BrO in the Nyiragongo plume and to a smaller BrO/SO2 ratio

Halogen Bonding in Nucleic Acid Complexes

Halogen bonding (X-bonding) has attracted notable attention among noncovalent interactions. This highly directional attraction between a halogen atom and an electron donor has been exploited in knowledge-based drug design. A great deal of information has been gathered about X-bonds in protein-ligand complexes, as opposed to nucleic acid complexes. Here we provide a thorough analysis of nucleic acid complexes containing either halogenated building blocks or halogenated ligands. We analyzed close contacts between halogens and electron-rich moieties. The phosphate backbone oxygen is clearly the most common halogen acceptor. We identified 21 X-bonds within known structures of nucleic acid complexes. A vast majority of the X-bonds is formed by halogenated nucleobases, such as bromouridine, and feature excellent geometries. Noncovalent ligands have been found to form only interactions with suboptimal interaction geometries. Hence, the first X-bonded nucleic acid binder remains to be discovered.Comment: 19 pages, 12, figures, publishe

Ions at the air-water interface: An end to one hundred year old mystery?

Availability of highly reactive halogen ions at the surface of aerosols has tremendous implications for the atmospheric chemistry. Yet neither simulations, experiments, nor existing theories are able to provide a fully consistent description of the electrolyte-air interface. In this paper a new theory is proposed which allows us to explicitly calculate the ionic density profiles, the surface tension, and the electrostatic potential difference across the solution-air interface. Predictions of the theory are compared to experiments and are found to be in excellent agreement. The theory also sheds new light on one of the oldest puzzles of physical chemistry -- the Hofmeister effect

ELECTRONIC-STRUCTURE OF SELF-TRAPPED EXCITON IN SODIUM-CHLORIDE

The electronic structure of the relaxed exciton is investigated using a Hartree-Fock method. The model concentrates on a cluster of two sodium and two chlorine ions surrounded by an array of point charges. The excited states of the exciton and the associated transitions are discussed. The results are compared with experiment and with the phenomenological models proposed earlier workers. A number of features are confirmed, giving a general picture close to that of Kabler and his co-workers. One problem emerges, since it proves possible to understand the sigma luminescence or the pi luminescence, but not both at present. Possible reasons are discussed. In other respects, there is good agreement with experiment, especially for the optical transitions starting from the lowest triplet state of the exciton

Rethinking reactive halogen budgets in the midlatitude lower stratosphere

Current stratospheric models have difficulties in fully explaining the observed midlatitude ozone depletion in the lowermost stratosphere, particularly near the tropopause. Such models assume that only long-lived source gases provide significant contributions to the stratospheric halogen budget, while all the short-lived compounds are removed in the troposphere, the products being rained out. Here we show this assumption to be flawed. Using bromine species as an example, we show that in the lowermost stratosphere, where the observed midlatitude ozone trend maximizes, bromoform (CHBr3) alone likely contributes more inorganic bromine than all the conventional long-lived sources (halons and methyl bromide) combined. Copyright 1999 by the American Geophysical Union

Transferring Axial Molecular Chirality Through a Sequence of On-Surface Reactions

Fine management of chiral processes on solid surfaces has progressed over the years, yet still faces the need for the controlled and selective production of advanced chiral materials. Here, we report on the use of enantiomerically enriched molecular building blocks to demonstrate the transmission of their intrinsic chirality along a sequence of on-surface reactions. Triggered by thermal annealing, the on-surface reac-tions induced in this experiment involve firstly the coupling of the chiral reactants into chiral polymers and subsequently their transformation into planar prochiral graphene nanoribbons. Our study reveals that the axial chirality of the reactant is not only transferred to the polymers, but also to the planar chirality of the graphene nanoribbon end products. Such chirality transfer consequently allows, starting from ad-equate enantioenriched reactants, for the controlled production of chiral and prochiral organic nanoarchi-tectures with pre-defined handedness