Rational Design of Polymers for Selective CO2 Reduction Catalysis.

A series of copolymers comprising a terpyridine ligand and various functional groups were synthesized toward integrating a Co-based molecular CO2 reduction catalyst. Using porous metal oxide electrodes designed to host macromolecules, the Co-coordinated polymers were readily immobilized via phosphonate anchoring groups. Within the polymeric matrix, the outer coordination sphere of the Co terpyridine catalyst was engineered using hydrophobic functional moieties to improve CO2 reduction selectivity in the presence of water. Electrochemical and photoelectrochemical CO2 reduction were demonstrated with the polymer-immobilized hybrid cathodes, with a CO:H2 product ratio of up to 6:1 compared to 2:1 for a corresponding "monomeric" Co terpyridine catalyst. This versatile platform of polymer design demonstrates promise in controlling the outer-sphere environment of synthetic molecular catalysts, analogous to CO2 reductases.the Woolf Fisher Trust in New Zealand, the Winston Churchill Foundation of the United States, the Christian Doppler Research Association (Austrian Federal Ministry for Digital and Economic Affairs and the National Foundation for Research, Technology and Development), the OMV Grou

Integration of a Hydrogenase in a Lead Halide Perovskite Photoelectrode for Tandem Solar Water Splitting.

Lead halide perovskite solar cells are notoriously moisture-sensitive, but recent encapsulation strategies have demonstrated their potential application as photoelectrodes in aqueous solution. However, perovskite photoelectrodes rely on precious metal co-catalysts, and their combination with biological materials remains elusive in integrated devices. Here, we interface [NiFeSe] hydrogenase from Desulfovibrio vulgaris Hildenborough, a highly active enzyme for H2 generation, with a triple cation mixed halide perovskite. The perovskite-hydrogenase photoelectrode produces a photocurrent of -5 mA cm-2 at 0 V vs RHE during AM1.5G irradiation, is stable for 12 h and the hydrogenase exhibits a turnover number of 1.9 × 106. The positive onset potential of +0.8 V vs RHE allows its combination with a BiVO4 water oxidation photoanode to give a self-sustaining, bias-free photoelectrochemical tandem system for overall water splitting (solar-to-hydrogen efficiency of 1.1%). This work demonstrates the compatibility of immersed perovskite elements with biological catalysts to produce hybrid photoelectrodes with benchmark performance, which establishes their utility in semiartificial photosynthesis

Geographic information retrieval in a mobile environment: evaluating the needs of mobile individuals

This paper describes research that aims to define the information needs of mobile individuals, to implement a mobile information system that can satisfy those needs, and finally to evaluate the performance of that system with end-users. First a review of the emerging discipline of geographic information retrieval (GIR) is presented as background to the more specific issue of mobile information retrieval. Following this, a user needs study is described evaluating the requirements of potential users of a mobile information system; the study finds that there is a strong geographic component to users' information needs. Next, four geographic post-query filters are described which attempt to represent the region of space associated with an individual's query made at some specific spatial location. These filters are spatial proximity (distance in space), temporal proximity (travel time), speed-heading prediction surfaces (likelihood of visiting locations) and visibility (locations that can be seen). Two of these filters — spatial proximity and speed-heading prediction surfaces — are implemented in a mobile information system and subsequently evaluated with users in an outdoor setting. The results of evaluation suggest that retrieved information to which post-query geographic filters have been applied is considered more relevant than unfiltered information, and that users find information sorted by spatial proximity to be more relevant than that sorted by a prediction surface of likely future locations. The paper closes with a discussion of the wider implications of these results for developers of mobile information systems and location-based services

Duloxetine compared with fluoxetine and venlafaxine: use of meta-regression analysis for indirect comparisons

BACKGROUND: Data comparing duloxetine with existing antidepressant treatments is limited. A comparison of duloxetine with fluoxetine has been performed but no comparison with venlafaxine, the other antidepressant in the same therapeutic class with a significant market share, has been undertaken. In the absence of relevant data to assess the place that duloxetine should occupy in the therapeutic arsenal, indirect comparisons are the most rigorous way to go. We conducted a systematic review of the efficacy of duloxetine, fluoxetine and venlafaxine versus placebo in the treatment of Major Depressive Disorder (MDD), and performed indirect comparisons through meta-regressions. METHODS: The bibliography of the Agency for Health Care Policy and Research and the CENTRAL, Medline, and Embase databases were interrogated using advanced search strategies based on a combination of text and index terms. The search focused on randomized placebo-controlled clinical trials involving adult patients treated for acute phase Major Depressive Disorder. All outcomes were derived to take account for varying placebo responses throughout studies. Primary outcome was treatment efficacy as measured by Hedge's g effect size. Secondary outcomes were response and dropout rates as measured by log odds ratios. Meta-regressions were run to indirectly compare the drugs. Sensitivity analysis, assessing the influence of individual studies over the results, and the influence of patients' characteristics were run. RESULTS: 22 studies involving fluoxetine, 9 involving duloxetine and 8 involving venlafaxine were selected. Using indirect comparison methodology, estimated effect sizes for efficacy compared with duloxetine were 0.11 [-0.14;0.36] for fluoxetine and 0.22 [0.06;0.38] for venlafaxine. Response log odds ratios were -0.21 [-0.44;0.03], 0.70 [0.26;1.14]. Dropout log odds ratios were -0.02 [-0.33;0.29], 0.21 [-0.13;0.55]. Sensitivity analyses showed that results were consistent. CONCLUSION: Fluoxetine was not statistically different in either tolerability or efficacy when compared with duloxetine. Venlafaxine was significantly superior to duloxetine in all analyses except dropout rate. In the absence of relevant data from head-to-head comparison trials, results suggest that venlafaxine is superior compared with duloxetine and that duloxetine does not differentiate from fluoxetine

Geographical perspectives on location for location based services

In this position paper the question of how location is employed in location based services (LBS) is considered. The importance of the notion of location is highlighted as a means of blurring the boundary between forms of experiences that are direct, and sensed in the environment, and those that are indirect, and learned from information. It is suggested that current methods for modeling location are limited by their lack of strong theoretical underpinning. To help bridge this gap the notions of Space, Place, and Region, from geographical theory, are proposed and implications of these for considering location in LBS outlined

Analysing and aggregating visitor tracks in a protected area

The advent of location-based technologies deployed in protected areas provides both visitors and managers of such areas with new opportunities. In this paper we investigate the potential for mining individual tracks of visitors’ geospatial lifelines to both extract information describing aggregated patterns of group behaviour and characterise individual actions. Methods to spatio-temporally cluster individual behaviour and identify potential locations for specific actions (e.g. do visitors stop here to look at wildlife), whilst handling uncertainty in location, are described and applied to test the hypotheses that firstly, visitor behaviour is altered by the provision of information, and secondly whether the mode of information provision (e.g. in the form of a paper map or though an location-based service) influences visitor behaviour. The results of experiments with 140 visitors to a nature trail on the island of Texel in the Netherlands show statistically significant differences in time spent at locations where information was “pushed” to the visitors

hierarchical

Techniques for on the-fly generalisation of thematic point data usin