Spontaneous dehydrocoupling in peri-substituted phosphine-borane adducts

This work was financially supported by the EPSRC and COST action CM1302 SIPs.Bis(borane) adducts Acenap(PiPr2·BH3)(PRH·BH3) (Acenap = acenaphthene-5,6-diyl; 4a, R = Ph; 4b, R = ferrocenyl, Fc; 4c, R = H) were synthesised by the reaction of excess H3B·SMe2 with either phosphino-phosphonium salts [Acenap(PiPr2)(PR)]+Cl− (1a, R = Ph; 1b, R = Fc), or bis(phosphine) Acenap(PiPr2)(PH2) (3). Bis(borane) adducts 4a–c were found to undergo dihydrogen elimination at room temperature, this spontaneous catalyst-free phosphine-borane dehydrocoupling yields BH2 bridged species Acenap(PiPr2)(µ-BH2)(PR·BH3) (5a, R = Ph; 5b, R = Fc; 5c, R = H). Thermolysis of 5c results in loss of the terminal borane moiety to afford Acenap(PiPr2)(µ-BH2)(PH) (14). Single crystal X-ray structures of 3, 4b and 5a–c are reported.Publisher PDFPeer reviewe

A MITE-based genotyping method to reveal hundreds of DNA polymorphisms in an animal genome after a few generations of artificial selection

<p>Abstract</p> <p>Background</p> <p>For most organisms, developing hundreds of genetic markers spanning the whole genome still requires excessive if not unrealistic efforts. In this context, there is an obvious need for methodologies allowing the low-cost, fast and high-throughput genotyping of virtually any species, such as the Diversity Arrays Technology (DArT). One of the crucial steps of the DArT technique is the genome complexity reduction, which allows obtaining a genomic representation characteristic of the studied DNA sample and necessary for subsequent genotyping. In this article, using the mosquito <it>Aedes aegypti </it>as a study model, we describe a new genome complexity reduction method taking advantage of the abundance of miniature inverted repeat transposable elements (MITEs) in the genome of this species.</p> <p>Results</p> <p><it>Ae. aegypti </it>genomic representations were produced following a two-step procedure: (1) restriction digestion of the genomic DNA and simultaneous ligation of a specific adaptor to compatible ends, and (2) amplification of restriction fragments containing a particular MITE element called <it>Pony </it>using two primers, one annealing to the adaptor sequence and one annealing to a conserved sequence motif of the <it>Pony </it>element. Using this protocol, we constructed a library comprising more than 6,000 DArT clones, of which at least 5.70% were highly reliable polymorphic markers for two closely related mosquito strains separated by only a few generations of artificial selection. Within this dataset, linkage disequilibrium was low, and marker redundancy was evaluated at 2.86% only. Most of the detected genetic variability was observed between the two studied mosquito strains, but individuals of the same strain could still be clearly distinguished.</p> <p>Conclusion</p> <p>The new complexity reduction method was particularly efficient to reveal genetic polymorphisms in <it>Ae. egypti</it>. Overall, our results testify of the flexibility of the DArT genotyping technique and open new prospects as regards its application to a wider range of species, including animals which have been refractory to it so far. DArT has also a role to play in the current burst of whole-genome scans carried out in various organisms, which track signatures of selection in order to unravel the basis of genetic adaptation.</p

(Decacarbonyl)(1-isopropyl-2-phenyl-1,2,5,6-tetrahydroacenaphtho [5,6-cd][1,2]diphosphole)ditungsten(0) : Molbank

A binuclear tungsten(0) complex with an asymmetric bridging 1,2-diphosphole ligand was prepared by the photolysis of tungsten hexacarbonyl in the presence of 1-isopropyl-2-phenyl-1,2,5,6-tetrahydroacenaphtho [5,6-cd][1,2]diphosphole. The tungsten complex 1 was characterized by high resolution mass spectrometry, multinuclear NMR spectroscopy (1H, 13C, 31P), and elemental microanalysis. The structure of the trans isomer was resolved by single crystal X-ray diffraction, showing a slight elongation of the P−P bond upon coordination to the W(CO)5 groups.Publisher PDFPeer reviewe

Synthesis and structural studies of peri-substituted acenaphthenes with tertiary phosphine and stibine groups

Two mixed peri-substituted phosphine-chlorostibines, Acenap(PiPr2)(SbPhCl) and Acenap(PiPr2)(SbCl2) (Acenap = acenaphthene-5,6-diyl) reacted cleanly with Grignard reagents or nBuLi to give the corresponding tertiary phosphine-stibines Acenap(PiPr2)(SbRR’) (R, R’ = Me, iPr, nBu, Ph). In addition, the Pt(II) complex of the tertiary phosphine-stibine Acenap(PiPr2)(SbPh2) as well as the Mo(0) complex of Acenap(PiPr2)(SbMePh) were synthesised and characterised. Two of the phosphine-stibines and the two metal complexes were characterised by single-crystal X-ray diffraction. The peri-substituted species act as bidentate ligands through both P and Sb atoms, forming rather short Sb-metal bonds. The tertiary phosphine-stibines display through-space J(CP) couplings between the phosphorus atom and carbon atoms bonded directly to the Sb atom of up to 40 Hz. The sequestration of the P and Sb lone pairs results in much smaller corresponding J(CP) being observed in the metal complexes. QTAIM (Quantum Theory of Atoms in Molecules) and EDA-NOCV (Energy Decomposition Analysis employing Naturalised Orbitals for Chemical Valence) computational techniques were used to provide additional insight into a weak n(P)→σ*(Sb-C) intramolecular bonding interaction (pnictogen bond) in the phosphine-stibines.Peer reviewe

Optimised synthesis and characterisation of 1-adamantyltrimethylphosphonium iodide

This work was financially supported by the EPSRC (grant numbers EP/L505079/1 and EP/M506631/1) and COST action SM1302 SIPs. The authors thank the University of St Andrews NMR Service and the EPSRC UK National Mass Spectrometry Facility at Swansea University (NMSF).A synthetic route to multigram quantities of 1-adamantyltrimethylphosphonium iodide is reported. The synthesis starts from the commercially available precursor 1-adamantyl bromide and was optimised with respect to yield and ease of purification. The title compound is of interest to zeolite chemists as a potent organic structure-directing agent. Full spectroscopic characterisation data of all isolated intermediates and single crystal X-ray diffraction data of AdP(O)Cl2, [AdPMe2H]I and [AdPMe3]I (Ad = 1-adamantyl) are reported.PostprintPeer reviewe

What are the social outcomes of climate policies? A systematic map and review of the ex-post literature

It is critical to ensure climate and energy policies are just, equitable and beneficial for communities, both to sustain public support for decarbonisation and address multifaceted societal challenges. Our objective in this article is to examine the diverse social outcomes that have resulted from climate policies, in varying contexts worldwide, over the past few decades. We review 203 ex-post climate policy assessments that analyse social outcomes in the literature. We systematically and comprehensively map out this work, identifying articles on carbon, energy and transport taxes, feed-in-tariffs, subsidies, direct procurement policies, large renewable deployment projects, and other regulatory and market-based interventions. We code each article in terms of their studied social outcomes and effects, with a focus on electricity access, energy affordability, community cohesion, employment, distributional and equity issues, livelihoods and poverty, procedural justice, subjective well-being and drudgery. Our analysis finds that climate and energy policies often fall short of delivering positive social outcomes. Nonetheless, across country contexts and policy types there are manifold examples of climate policymaking that does deliver on both social and climate goals. This requires attending to distributive and procedural justice in policy design, and making use of appropriate mechanisms to ensure that policy costs and benefits are fairly shared. We emphasize the need to further advance ex-post policy assessments and learn about what policies work for a just transition

An efficient, scalable synthesis of ferrocenylphosphine and dichloroferrocenylphosphine

This work was financially supported by the Engineering and Physical Sciences Research Council (EPSRC) and by COST action (grant CM1302, SIPs).A new synthetic route to FcPH2 and FcPCl2 (Fc = Ferrocenyl) is presented. This method avoids the challenging monolithiation of ferrocene, as well as any tedious purification steps. All reactions are high yielding and easily conducted on a relatively large scale, using economical and commercially available synthetic precursors.PostprintPostprintPeer reviewe

What are the social outcomes of climate policies? A systematic map and review of the ex-post literature

It is critical to ensure climate and energy policies are just, equitable and beneficial for communities, both to sustain public support for decarbonisation and address multifaceted societal challenges. Our objective in this article is to examine the diverse social outcomes that have resulted from climate policies, in varying contexts worldwide, over the past few decades. We review 203 ex-post climate policy assessments that analyse social outcomes in the literature. We systematically and comprehensively map out this work, identifying articles on carbon, energy and transport taxes, feed-in-tariffs, subsidies, direct procurement policies, large renewable deployment projects, and other regulatory and market-based interventions. We code each article in terms of their studied social outcomes and effects, with a focus on electricity access, energy affordability, community cohesion, employment, distributional and equity issues, livelihoods and poverty, procedural justice, subjective well-being and drudgery. Our analysis finds that climate and energy policies often fall short of delivering positive social outcomes. Nonetheless, across country contexts and policy types there are manifold examples of climate policymaking that does deliver on both social and climate goals. This requires attending to distributive and procedural justice in policy design, and making use of appropriate mechanisms to ensure that policy costs and benefits are fairly shared. We emphasize the need to further advance ex-post policy assessments and learn about what policies work for a just transition

Svjetlosna mikroskopija kristaličnih uklopina cucumovirusa mozaika bagrema

In cells infected with robinia mosaic cucumovirus (RoMV) we established two basic types of crystalline virus inclusions: hollow crystals, of polyhedral and spherical to oval appearance, and ordinary polyhedral crystals. The former seem regularly present in the vacuole, and the latter in the cytoplasm. The optimal temperatures for development of RoMV crystalline inclusions were betwenn 15—20°C at the period of longer days. All forms of the crystals were more freuquent in relatively younger cells in which more intense filling of the hollow crystals took place.U stanicama zaraženim cucumovirusom mozaika bagrema (RoMV) ustanovili smo dva osnovna tipa kristaličnih virusnih uklopina: prazne kristale poliedričnog i sferičnog oblika, i obične poliedralne kristale. Prazni se kristali, kako se čini, redovito nalaze u vakuoli, a obični poliedralni kristali u dtoplazmi. Najpovoljnije temperature za razvitak kristaličnih uklopina RoMV bile su između 15—20°C u periodu dužeg dana. Svi oblici kristala bili su češći u razmjerno mlađim stanicama u kojima se također odvijalo intenzivnije ispunjavanje praznih kristala

The future of botanical monography : report from an international workshop, 12–16 March 2012, Smolenice, Slovak Republic

Monographs are fundamental for progress in systematic botany. They are the vehicles for circumscribing and naming taxa, determining distributions and ecology, assessing relationships for formal classification, and interpreting long-term and short-term dimensions of the evolutionary process. Despite their importance, fewer monographs are now being prepared by the newer generation of systematic botanists, who are understandably involved principally with DNA data and analysis, especially for answering phylogenetic, biogeographic, and population genetic questions. As monographs provide hypotheses regarding species boundaries and plant relationships, new insights in many plant groups are urgently needed. Increasing pressures on biodiversity, especially in tropical and developing regions of the world, emphasize this point. The results from a workshop (with 21 participants) reaffirm the central role that monographs play in systematic botany. But, rather than advocating abbreviated models for monographic products, we recommend a full presentation of relevant information. Electronic publication offers numerous means of illustration of taxa, habitats, characters, and statistical and phylogenetic analyses, which previously would have been prohibitively costly. Open Access and semantically enhanced linked electronic publications provide instant access to content from anywhere in the world, and at the same time link this content to all underlying data and digital resources used in the work. Resources in support of monography, especially databases and widely and easily accessible digital literature and specimens, are now more powerful than ever before, but interfacing and interoperability of databases are much needed. Priorities for new resources to be developed include an index of type collections and an online global chromosome database. Funding for sabbaticals for monographers to work uninterrupted on major projects is strongly encouraged. We recommend that doctoral students be assigned smaller genera, or natural portions of larger ones (subgenera, sections, etc.), to gain the necessary expertise for producing a monograph, including training in a broad array of data collection (e.g., morphology, anatomy, palynology, cytogenetics, DNA techniques, ecology, biogeography), data analysis (e.g., statistics, phylogenetics, models), and nomenclature. Training programs, supported by institutes, associations, and agencies, provide means for passing on procedures and perspectives of challenging botanical monography to the next generation of young systematists.Appreciation is expressed to: the Andrew W. Mellon Foundation for financial support that allowed the workshop to be convened; the International Association for Plant Taxonomy (IAPT) for additional financial support for the workshop.http://www.botanik.univie.ac.at/iapt/s_taxon.phpam201