Bimetallic Cooperativity in Proton Reduction with an Amido‐Bridged Cobalt Catalyst

The bimetallic catalyst [CoII2(L1)(bpy)2]ClO4 (1), in which L1 is an [NN′2O2] fused ligand, efficiently reduced H+ to H2 in CH3CN in the presence of 100 equiv of HOAc with a turnover number of 18 and a Faradaic efficiency of 94 % after 3 h of bulk electrolysis at −1.6 V (vs. Ag/AgCl). This observation allowed the proposal that this bimetallic cooperativity is associated with distance, angle, and orbital alignment of the two Co centers, as promoted by the unique Co−Namido−Co environment offered by L1. Experimental results revealed that the parent [CoIICoII] complex undergoes two successive metal‐based 1 e− reductions to generate the catalytically active species [CoICoI], and DFT calculations suggested that addition of a proton to one CoI triggers a cooperative 1 e− transfer by each of these CoI centers. This 2 e− transfer is an alternative route to generate a more reactive [CoII(CoII−H−)] hydride, thus avoiding the CoIII−H− required in monometallic species. This [CoII(CoII−H−)] species then accepts another H+ to release H2

THE H3/H4 HISTONE GENE CLUSTER OF LAND SNAILS (GASTROPODA: STYLOMMATOPHORA): TS/TV RATIO, GC3 DRIVE AND SIGNALS IN STYLOMMATOPHORAN PHYLOGENY

Histone gene primers were developed for land snails (Stylommatophora). The partial H3/H4 histone gene cluster was cloned and sequenced for 18 species. Transcription of the H3 and H4 genes was divergent (each gene is transcribed in the opposite direction) as has been found for other protostome and diploblast animals, with the exception of Mytilus. In the bivalve Mytilus transcription of both genes occurs in the same direction, i.e. land snails and bivalves seem to differ in their histone gene organization. The non-transcribed H3/H4 spacer varied in length between 279 and 691 basepairs. Nucleotide polymorphisms in this non-transcribed spacer might be of significance to study phylogenetics and systematics of closely related species and genera. As expected, the coding regions exhibited no amino acid substitution among land snail species. However, one amino acid substitution was found in comparison between land snails and Drosophila. The transition/transversion (TS/TV) ratio of H3 and H4 was predominately shaped by the third codon position and ranged in most cases from 1.0 to 2.0, indicating low nucleotide saturation. GC content was calculated for the third codon position (GC3 index at the ‘wobble' base position). The histone GC3 values were far lower in land snails than values currently available for other genomes (i.e. mammals). This indicates that H3/H4 histone wobble bases of land snails evolve without strong GC drive. Phylogenetic trees were reconstructed from the coding regions. We used Succinea putris (Elasmognatha) as outgroup. Trichia villosa (Helicoidea) showed six apomorphic nucleotide signals. Moreover, the nucleotide signals give evidence that the Cochlicopidae, Vertiginidae and Valloniidae are paraphyletic family categories. The paraphyletic status of cochlicopid, vertiginid and valloniid gastropods is also supported by our unpublished ribosomal DNA tree

Wolbachia distribution in selected beetle taxa characterized by PCR screens and MLST data

Wolbachia (Alphaproteobacteria) is an inherited endosymbiont of arthropods and filarial nematodes and was reported to be widespread across insect taxa. While Wolbachia’s effects on host biology are not understood from most of these hosts, known Wolbachia-induced phenotypes cover a spectrum from obligate beneficial mutualism to reproductive manipulations and pathogenicity. Interestingly, data on Wolbachia within the most species-rich order of arthropods, the Coleoptera (beetles), are scarce. Therefore, we screened 128 species from seven beetle families (Buprestidae, Hydraenidae, Dytiscidae, Hydrophilidae, Gyrinidae, Haliplidae, and Noteridae) for the presence of Wolbachia. Our data show that, contrary to previous estimations, Wolbachia frequencies in beetles (31% overall) are comparable to the ones in other insects. In addition, we used Wolbachia MLST data and host phylogeny to explore the evolutionary history of Wolbachia strains from Hydraenidae, an aquatic lineage of beetles. Our data suggest that Wolbachia from Hydraenidae might be largely host genus specific and that Wolbachia strain phylogeny is not independent to that of its hosts. As this contrasts with most terrestrial Wolbachia–arthropod systems, one potential conclusion is that aquatic lifestyle of hosts may result in Wolbachia distribution patterns distinct from those of terrestrial hosts. Our data thus provide both insights into Wolbachia distribution among beetles in general and a first glimpse of Wolbachia distribution patterns among aquatic host lineages

Ab Initio Study of the Structures, Properties, and Heats of Formation of Fluorochloromethanes and -silanes, ( m + n = 0-4)

Equilibrium geometries and vibrational frequencies for CH,+,,,-,F,Cl, and SiH4-,,,-,F,C1, (m + n = 0-4) were computed at the HF/6-31G* levels; electron correlation contributions were calculated at the MP4/6-31G** level. Heats of formation were obtained from isodesmic reactions using the experimental AHfo for AH4, AF4, and AC14 (A = C, Si). Good agreement between theory and experiment is found for CH,+,,,-nF,Cl,. For the mixed fluorochlorosilanes, the calculations predict the following heats of formation (in kcal/mol at 298 K and 1 atm): SiH2FCl, -129.3 f 3; SiHF,Cl, -230.3 f 3; SiHFC12, -171.6 f 3; SiF3Cl, -329.5 f 3; SiF2C12, -272.9 f 3; SiFC13, -215.8. Trends in the bond lengths, AH vibrational frequencies, and stabilization energies can be explained as a balance between electrostatic effects due to the electronegative substituents and negative hyperconjugation from the halogen lone pairs to adjacent u* orbitals

Patterns of richness across forest beetle communities—A methodological comparison of observed and estimated species numbers

Abstract Species richness is a frequently used measure of biodiversity. The compilation of a complete species list is an often unattainable goal. Estimators of species richness have been developed to overcome this problem. While the use of these estimators is becoming increasingly popular, working with the observed number of species is still common practice. To assess whether patterns of beetle communities based on observed numbers may be compared among each other, we compared patterns from observed and estimated numbers of species for beetle communities in the canopy of the Leipzig floodplain forest. These patterns were species richness and the number of shared species among three tree species and two canopy strata. We tested the applicability of the asymptotic Chao1 estimator and the estimate provided by the nonasymptotic rarefaction–extrapolation method for all tree species and both upper canopy and lower canopy. In the majority of cases, the ranking patterns of species richness for host tree species and strata were the same for the observed and estimated number of species. The ranking patterns of the number of species shared among host tree species and strata, however, were significantly different between observed and estimated values. Our results indicate that the observed number of species under‐represents species richness and the number of shared species. However, ranking comparisons of published patterns based on the number of observed species may be acceptable for species richness but likely not reliable for the number of shared species. Further studies are needed to corroborate this conclusion. We encourage to use estimators and to provide open access to data to allow comparative assessments

HCO + dissociation in a strong laser field: An ab initio classical trajectory study

a b s t r a c t We have investigated the photodissociation of HCO + in a strong field with a wavelength of 10 lm using ab initio molecular dynamics. Classical trajectories were calculated at three field intensities. At 2.9 Â 10 14 W/cm 2 and phase / = 0, protons have two distinct dissociation times, mainly due to the reorientation of HCO + relative to the field direction prior to dissociation. The kinetic energy distribution at this intensity agrees with Wardlaw's wagging tail model, suggesting that dissociation occurs through barriersuppression. At 1.7 Â 10 14 and 8.8 Â 10 13 W/cm 2 , barrier suppression is incomplete and the maximum kinetic energy is less than predicted by the wagging tail model

The mitochondrial DNA of Xenoturbella bocki: genomic architecture and phylogenetic analysis

The phylogenetic position of Xenoturbella bocki has been a matter of controversy since its description in 1949. We sequenced a second complete mitochondrial genome of this species and performed phylogenetic analyses based on the amino acid sequences of all 13 mitochondrial protein-coding genes and on its gene order. Our results confirm the deuterostome relationship of Xenoturbella. However, in contrast to a recently published study (Bourlat et al. in Nature 444:85–88, 2006), our data analysis suggests a more basal branching of Xenoturbella within the deuterostomes, rather than a sister-group relationship to the Ambulacraria (Hemichordata and Echinodermata)