Organic reactions in ionic liquids:A new method for the synthesis of alkyl aryl sulfones by alkylation of sodium arenesulfinates with unactivated alkyl chlorides

A new method is reported for the synthesis of alkyl aryl sulfones by alkylation of sodium arenesulfinates with unactivated alkyl chlorides using ionic liquid based on 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF 4) mixed with water (2:1) as reaction media. The ionic liquid can be reused and the procedure gives the sulfones in moderate yields.

Studies in clay chemistry

A study of clay chemistry has been approached with three aims: - to modify the conducting properties by intercalation of tetrathiafulvalene, - to study the electrochemistry of redox-active coordination compounds immobilised on clay coated electrodes, and - to study the role of clays as reagents in inorganic glass forming reactions using mainly solid-state magic-angle-spinning NMR. TTF was intercalated by smectites containing different interlayer and lattice cations. Evidence from ESR and 57Fe Mossbauer indicated charge-transfer from TTF to structural iron in natural montmorillonite, and to interlayer Cu2+ in Cu2+ exchanged laponite. No charge transfer was observed for laponite (Na+ form) itself. Ion exchange of TTF3(BF4)2 with laponite was found to proceed quantitatively. The intercalated species were believed to be (TTF)2+ dimers. Conductivity data showed an order of magnitude increase for the intercalated clays. The mechanism is thought to be ionic rather than CT as Na+ laponite showed a similar enhancement in conductivity. Mechanically robust colloidal clay films were prepared on platinum electrodes. After immersion in solutions containing redox active complexes [Co(bpy)3]3+ and [Cr(bpy)3]3+, the films became electroactive when a potential was applied. Cyclic voltammograms obtained for both complexes were found to be of the diffusion controlled type. For [Co(bpy)3]3+ immobilised on clay coated electrodes, a one-step oxidation and four-step reduction wave was observed corresponding to a one electron stepwise reversible reduction of Co(III), through Co(II), Co(I), Co(O) to Co(I) oxidation state. For [Cr(bpy)3]3+ the electrochemistry was complicated by the presence of additional waves corresponding to the dissociation of [Cr(bpy)3]3+ into the diaquo complex. ESR and diffuse reflectance data supported such a mechanism. 29Si, 27Al and 23Na MAS NMR spectroscopy, supported by powder XRD and FTIR, was used to probe the role of clays as reagents in glass forming reactions. 29Si MAS NMR was found to be a very sensitive technique for identifying the presence and relative abundance of crystalline and non-crystalline phases. In thermal reactions of laponite formation of new mineral phases such as forsterite, akermanite, sillimanite and diopside were detected. The relative abundance of each phase was dependent on thermal history, chemical nature and concentration of the modifier oxide present. In continuing work, the effect of selected oxides on the glass forming reactions of a model feldspar composition was investigated using solid state NMR alone. Addition of network modifying oxides generally produced less negative 29Si chemical shifts and larger linewidths corresponding to a wider distribution of Si-O-Si bond angles and lengths, and a dominant aluminosilicate phase with a less polymerised structure than the starting material. 29Si linewidths and 27Al chemical shifts were respectively correlated with cationic potential and Lewis acidity of the oxide cations. Anomalous Al(4) chemical shifts were thought to be due to precipitation of aluminate phases rather than a breakdown in Lowenstein's aluminium avoidance principle.

Control of electronic channel affiliates:an exploratory study and research propositions

Electronic channel affiliates are important online intermediaries between customers and host retailers. However, no work has studied how online retailers control online intermediaries. By conducting an exploratory content analysis of 85 online contracts between online retailers and their online intermediaries, and categorizing the governing mechanisms used, insights into the unique aspects of the control of online intermediaries are presented. Findings regarding incentives, monitoring, and enforcement are presented. Additionally, testable research propositions are presented to guide further theory development, drawing on contract theory, resource dependence theory and agency theory. Managerial implications are discussed. © 2012 Elsevier Inc.

A general route to synthesize supported isolated oxide and mixed-oxide nanoclusters at sizes below 5 nm

A simple and efficient route to prepare supported nanocrystalline oxides is presented. The synthesis procedure, i.e. in situ autocombustion of a glycine complex, allows the production of nanocrystals in a porous matrix presenting larger pore size. An example of successful formation of 2-5 nm nanocrystals is given for a single oxide (Fe2O3), a mixed-oxide structure (LaCoO3 perovskite-type) and a nickel-doped oxide. © 2011 The Royal Society of Chemistry.

A sensing mechanism for the detection of carbon nanotubes using selective photoluminescent probes based on ionic complexes with organic dyes

The multifunctional properties of carbon nanotubes (CNTs) make them a powerful platform for unprecedented innovations in a variety of practical applications. As a result of the surging growth of nanotechnology, nanotubes present a potential problem as an environmental pollutant, and as such, an efficient method for their rapid detection must be established. Here, we propose a novel type of ionic sensor complex for detecting CNTs – an organic dye that responds sensitively and selectively to CNTs with a photoluminescent signal. The complexes are formed through Coulomb attractions between dye molecules with uncompensated charges and CNTs covered with an ionic surfactant in water. We demonstrate that the photoluminescent excitation of the dye can be transferred to the nanotubes, resulting in selective and strong amplification (up to a factor of 6) of the light emission from the excitonic levels of CNTs in the near-infrared spectral range, as experimentally observed via excitation-emission photoluminescence (PL) mapping. The chirality of the nanotubes and the type of ionic surfactant used to disperse the nanotubes both strongly affect the amplification; thus, the complexation provides sensing selectivity towards specific CNTs. Additionally, neither similar uncharged dyes nor CNTs covered with neutral surfactant form such complexes. As model organic molecules, we use a family of polymethine dyes with an easily tailorable molecular structure and, consequently, tunable absorbance and PL characteristics. This provides us with a versatile tool for the controllable photonic and electronic engineering of an efficient probe for CNT detection.

Perceptions and experiences of the implementation, management, use and optimisation of electronic prescribing systems in hospital settings:protocol for a systematic review of qualitative studies

Introduction: There is increasing evidence that electronic prescribing (ePrescribing) or computerised provider/physician order entry (CPOE) systems can improve the quality and safety of healthcare services. However, it has also become clear that their implementation is not straightforward and may create unintended or undesired consequences once in use. In this context, qualitative approaches have been particularly useful and their interpretative synthesis could make an important and timely contribution to the field. This review will aim to identify, appraise and synthesise qualitative studies on ePrescribing/CPOE in hospital settings, with or without clinical decision support. Methods and analysis: Data sources will include the following bibliographic databases: MEDLINE, MEDLINE In Process, EMBASE, PsycINFO, Social Policy and Practice via Ovid, CINAHL via EBSCO, The Cochrane Library (CDSR, DARE and CENTRAL databases), Nursing and Allied Health Sources, Applied Social Sciences Index and Abstracts via ProQuest and SCOPUS. In addition, other sources will be searched for ongoing studies (ClinicalTrials.gov) and grey literature: Healthcare Management Information Consortium, Conference Proceedings Citation Index (Web of Science) and Sociological abstracts. Studies will be independently screened for eligibility by 2 reviewers. Qualitative studies, either standalone or in the context of mixed-methods designs, reporting the perspectives of any actors involved in the implementation, management and use of ePrescribing/CPOE systems in hospital-based care settings will be included. Data extraction will be conducted by 2 reviewers using a piloted form. Quality appraisal will be based on criteria from the Critical Appraisal Skills Programme checklist and Standards for Reporting Qualitative Research. Studies will not be excluded based on quality assessment. A postsynthesis sensitivity analysis will be undertaken. Data analysis will follow the thematic synthesis method. Ethics and dissemination: The study does not require ethical approval as primary data will not be collected. The results of the study will be published in a peer-reviewed journal and presented at relevant conferences.