Novel properties and potential applications of functional ligand-modified polyoxotitanate cages.

Functional ligand-modified polyoxotitanate (L-POT) cages of the general type [TixOy(OR)z(L)m] (OR = alkoxide, L = functional ligand) can be regarded as molecular fragments of surface-sensitized solid-state TiO2, and are of value as models for studying the interfacial charge and energy transfer between the bound functional ligands and a bulk semiconductor surface. These L-POTs have also had a marked impact in many other research fields, such as single-source precursors for TiO2 deposition, inorganic-organic hybrid material construction, photocatalysis, photoluminescence, asymmetric catalysis and gas adsorption. Their atomically well-defined structures provide the basis for the understanding of structure/property relationships and ultimately for the rational design of new cages targeting specific uses. This highlight focuses on recent advances in L-POTs research, with emphasis on their novel properties and potential applications.EPSRCThis is the final version of the article. It first appeared from Royal Society of Chemistry via https://doi.org/10.1039/C6CC03788G

The influence of halides in polyoxotitanate cages; dipole moment, splitting and expansion of d-orbitals and electron-electron repulsion

Metal-doped polyoxotitanate (M-POT) cages have been shown to be efficient single-source precursors to metal-doped titania [TiO$_2$(M)] (state-of-the-art photocatalytic materials) as well as molecular models for the behaviour of dopant metal ions in bulk titania. Here we report the influence halide ions have on the optical and electronic properties of a series of halide-only, and cobalt halide-‘doped’ POT cages. In this combined experimental and computational study we show that halide ions can have several effects on the band gaps of halide-containing POT cages, influencing the dipole moment (hole–electron separation) and the structure of the valance band edge. Overall, the band gap behaviour stems from the effects of increasing orbital energy moving from F to I down Group 17, as well as crystal-field splitting of the d-orbitals, the potential effects of the Nephelauxetic influence of the halides and electron–electron repulsion.We thank the EPSRC (Doctoral Prize for P. D. M.), A*STAR Singapore (Scholarship for N. L.), the Studienstiftung des deutschen Volkes, Fonds of the Chemical Industry (S. H.) for funding. The authors would like to acknowledge the use of the EPSRC UK National Service for Computational Chemistry Software (NSCCS) at Imperial College London and contributions from its staff in carrying out this work

Triggering of a volcanic dome collapse by rainwater infiltration

The thermodynamic processes in a one-dimensional model of a porous lava dome are considered in the presence of a rising magmatic gas flux through the void spaces and rainfall interacting with the dome surface. The steady state surface temperature of the dome depends on both magmatic gas mass flux and rainfall rate. A critical rainfall rate is determined, that cools the dome surface to 100°C. Rainfall rates above this critical value allow liquid infiltration into the void spaces of the dome, thus restricting the escape of magmatic gas. A model which restricts the gas flow through the surface predicts internal gas pressures much higher than the overburden pressure in the top few meters, approximately one hour after the onset of rainfall. For a marginally stable dome, this could cause small Vulcanian explosions, which (depending on their location) could trigger a dome collapse, on a timescale consistent with observations

Reactome - a knowledgebase of human biological pathways

Pathway curation is a powerful tool for systematically associating gene products with functions. Reactome (www.reactome.org) is a manually curated human pathway knowledgebase describing a wide range of biological processes in a computationally accessible manner. The core unit of the Reactome data model is the Reaction, whose instances form a network of biological interactions through entities that are consumed, produced, or act as catalysts. Entities are distinguished by their molecular identities and cellular locations. Set objects allow grouping of related entities. Curation is based on communication between expert authors and staff curators, facilitated by freely available data entry tools. Manually curated data are subjected to quality control and peer review by a second expert. Reactome data are released quarterly. At release time, electronic orthology inference performed on human data produces reaction predictions in 22 species ranging from mouse to bacteria. Cross-references to a large number of publicly available databases are attached, providing multiple entry points into the database. The Reactome Mart allows query submission and data retrieval from Reactome and across other databases. The SkyPainter tool provides visualization and statistical analysis of user supplied data, e.g. from microarray experiments. Reactome data are freely available in a number of data formats (e.g. BioPax, SBML)

Thermal structure of a gas-permeable lava dome and timescale separation in its response to perturbation

The thermal boundary layer at the surface of a volcanic lava dome is investigated through a continuum model of the thermodynamic advection diffusion processes resulting from magmatic gas flow through the dome matrix. The magmatic gas mass flux, porosity and permeability of the rock are identified as key parameters. New, theoretical, nonlinear steady-state thermal profiles are reported which give a realistic surface temperature of 210 degC for a region of lava dome surface through which a gas flux of 3.5 x 10-3 kg s-1 m-2 passes. This contrasts favourably with earlier purely diffusive thermal models, which cool too quickly. Results are presented for time-dependent perturbations of the steady states as a response to: changes in surface pressure, a sudden rockfall from the lava dome surface, and a change in the magmatic gas mass flux at depth. Together with a generalized analysis using the method of multiple scales, this identifies two characteristic time scales associated with the thermal evolution of a dome carapace: a short time scale of several minutes, over which the magmatic gas mass flux, density, and pressure change to a new quasi-steady-state, and a longer time scale of several days, over which the thermal profile changes to a new equilibrium distribution. Over the longer time scale the dynamic properties of the dome continue to evolve, but only in slavish response to the ongoing temperature evolution. In the light of this time scale separation, the use of surface temperature measurements to infer changes in the magmatic gas flux for use in volcanic hazard prediction is discussed

Overcoming barriers to agri-environmental management at landscape scale: Balancing farmer coordination and collaboration with the aid of facilitators and pioneers

Policy instruments that integrate the actions of multiple farmers are of growing interest for improving landscape scale environmental sustainability of agriculture. We conducted in-depth, semi-structured interviews with farmers in south-east England and applied thematic analysis to the responses to perform a qualitative investigation into the combined role of economic, social, and cultural barriers to cooperative environmental management, and identify possible solutions for these barriers. Interviewees recognised environmental benefits of cooperative management, but this was a low priority compared to other management activities, being seen as complex and time-consuming, with uncertainty over direct benefits to participants. External coordination could address this by overseeing information sharing on cooperation benefits and minimising the logistical burden for participants, but given farmer mistrust of outside intervention, these projects will be more successful when collaborating farmers feel they are in control. The efforts of both pioneering farmers able to initiate projects with their peers, and respected facilitators who embody local knowledge and experience, will be vital for balancing coordination and collaboration. Finding the optimal balance between these different elements will vary with local circumstances: policy should have the flexibility to accommodate this. Farmers were wary of connecting with others possessing different farming ideals and thus having to compromise on their management approach. Some respondents sought to bridge these gaps by focusing on aspects of farming identities they shared with their peers, raising the possibility that support targeting these individuals will help develop relationships that foster lasting cultural change for farmer cooperative environmental management

'I would rather die': reasons given by 16-year-olds for not continuing their study of mathematics

Improving participation rates in specialist mathematics after the subject ceases to be compulsory at age 16 is part of government policy in England. This article provides independent and recent support for earlier findings concerning reasons for non- participation, based on free response and closed items in a questionnaire with a sample of over 1500 students in 17 schools, close to the moment of choice. The analysis supports findings that perceived difficulty and lack of confidence are important reasons for students not continuing with mathematics, and that perceived dislike and boredom, and lack of relevance, are also factors. There is a close relationship between reasons for non-participation and predicted grade, and a weaker relation to gender. An analysis of the effects of schools, demonstrates that enjoyment is the main factor differentiating schools with high and low participation indices. Building on discussion of these findings, ways of improving participation are briefly suggested

Photonic Quantum Logic with Narrowband Light from Single Atoms

Increasing control of single photons enables new applications of photonic quantum-enhanced technology and further experimental exploration of fundamental quantum phenomena. Here, we demonstrate quantum logic using narrow linewidth photons that are produced under nearly perfect quantum control from a single ^87Rb atom strongly coupled to a high-finesse cavity. We use a controlled- NOT gate integrated into a photonic chip to entangle these photons, and we observe non-classical correlations between events separated by periods exceeding the travel time across the chip by three orders of magnitude. This enables quantum technology that will use the properties of both narrowband single photon sources and integrated quantum photonics, such as networked quantum computing, narrow linewidth quantum enhanced sensing and atomic memories.Comment: 5 pates, 3 figure

Selective lability of ruthenium(II) arene amino acid complexes.

A series of organometallic complexes of the form [(PhH)Ru(amino acid)](+) have been synthesized using amino acids able to act as tridentate ligands. The straightforward syntheses gave enantiomerically pure complexes with two stereogenic centers due to the enantiopurity of the chelating ligands. Complexes were characterized in the solid-state and/or solution-state where the stability of the complex allowed. The propensity toward labilization of the coordinatively saturated complexes was investigated. The links between complex stability and structural features are very subtle. Nonetheless, H/D exchange rates of coordinated amino groups reveal more significant differences in reactivity linked to metallocycle ring size resulting in decreasing stability of the metallocycle as the amino acid side-chain length increases. The behavior of these systems in acid is unusual, apparently labilizing the carboxylate residue of the amino acid. This acid-catalyzed hemilability in an organometallic is relevant to the use of Ru(II) arenes in medicinal contexts due to the relatively low pH of cancerous cells.TGS and MO thank the EPSRC for Studentships EP/P505445/1 and EP/K503/009/1, respectively.This is the final version of the article. It was first published by ACS at http://pubs.acs.org/doi/abs/10.1021/ic502051