The effects of stepped sites and ruthenium adatom decoration on methanol dehydrogenation over platinum-based catalyst surfaces

A density functional theory study of methanol dehydrogenation over stepped Pt(2 1 1) surfaces without and with Ru modification was carried out to understand fuel catalytic reactions on Pt-based catalysts. Two main pathways of the CH3OH dehydrogenation were examined: the O–H pathway which was initiated by O–H bond scission to form the methoxy (CH3O) intermediate followed by sequential cleavage of C–H bonds to CO, and the C–H pathway which was initiated by C–H bond scission to form the hydroxymethyl (CH2OH) followed by two C–H bond cleavages to COH and then CO. Possible crossover reactions between the O–H and C–H pathways were also computed. Compared to flat Pt(1 1 1), stepped Pt(2 1 1) increases the adsorption energies of intermediates, making no significant contribution to decreasing the reaction barriers of most elementary steps involved, except in the first hydrogen scission. However, on the Ru-modified surface, a significant reduction was found in reaction barriers for the first step of the C–H bond scission and a number of further dehydrogenation steps crossing over to the O–H pathway, with the most facile paths identified. Our data reveals the complexity of methanol catalytic reaction processes at the atomic level and contributes to a fundamental understanding of fuel reactions on Pt-based catalysts.

A NOVEL LIFE-HISTORY IN AGLAOTHAMNION-DIAPHANUM-SP NOV (CERAMIACEAE, RHODOPHYTA) FROM BRITTANY AND THE BRITISH-ISLES

A diminutive species of Aglaothamnion (Ceramiaceae, Rhodophyta), A. diaphanum sp. nov., is described from Brittany (Atlantic France), the Isles of Scilly (off S.W. England) and western Ireland. Aglaothamnion diaphanum is confined to the sublittoral zone, where it grows almost exclusively on algae and sessile animals attached to hard substrata. Thalli are delicate, and branched distichously in one plane. The main axes are ecorticate but may form loose non-corticating rhizoidal filaments. The lateral branches bear a characteristic, regularly alternate distichous series of branchlets, the first of which is always adaxial. All vegetative cells are uninucleate. The majority of field-collected plants bear only bisporangia, but a few bisporangial plants also form spermatangia; some male plants and a single female specimen have been collected. The spermatangial branchlets consist of 3-5 spermatangial mother cells each bearing 2-4 spermatangia, which are constricted around a central nucleus. None of the U-shaped carpogonial branches showed any sign of fertilization, and the gametangia appear to be non-functional. The bisporangia are ovoid and contain two uninucleate spores separated by an oblique curved wall. The occurrence of bisporangia and the lack of adherent cortication distinguish A. diaphanum from two similar species, Aglaothamnion bipinnatum (P. Crouan et H. Crouan) Feldmann-Mazoyer and Aglaothamnion decompositum (J. Agardh) Halos. The life history in culture of French and Irish isolates of A. diaphanum consists of a series of bisporangial generations, a single plant of which also formed spermatangia. Apical cells of bisporophytes are haploid (n = c. 32), but the first division of meiosis, with chromosome pairing and crossing over, occurs in dividing bisporocytes. The germinating bispores are haploid. Endodiploidization may occur in the early stages of sporangium development, as in some phycomycete fungi, or in vegetative cells that subsequently give rise to bisporocytes. This is the first demonstration in the red algae of meiotic bisporangia on plants of which the apical cells, at least, are haploid.

Chromosome synapsis and recombination in simple and complex chromosomal heterozygotes of tuco-tuco (Ctenomys talarum: Rodentia: Ctenomyidae):Rodentia: Ctenomyidae)

The chromosomal speciation hypothesis suggests that irregularities in synapsis, recombination, and segregation in heterozygotes for chromosome rearrangements may restrict gene flow between karyotypically distinct populations and promote speciation. Ctenomys talarum is a South American subterranean rodent inhabiting the coastal regions of Argentina, whose populations polymorphic for Robertsonian and tandem translocations seem to have a very restricted gene flow. To test if chromosomal differences are involved in isolation among its populations, we examined chromosome pairing, recombination, and meiotic silencing of unsynapsed chromatin in male meiosis of simple and complex translocation heterozygotes using immunolocalization of the MLH1 marking mature recombination nodules and phosphorylated histone γH2A.X marking unrepaired double-strand breaks. We observed small asynaptic areas labeled by γH2A.X in pericentromeric regions of the chromosomes involved in the trivalents and quadrivalents. We also observed a decrease of recombination frequency and a distalization of the crossover distribution in the heterozygotes and metacentric homozygotes compared to acrocentric homozygotes. We suggest that the asynapsis of the pericentromeric regions are unlikely to induce germ cell death and decrease fertility of the heterozygotes; however, suppressed recombination in pericentromeric areas of the multivalents may reduce gene flow between chromosomally different populations of the Talas tuco-tuco.