Microwave-assisted Cu-catalyzed Ullmann ether synthesis in a continuous-flow milli-plant

The combination of milli-scale processing and microwave heating has been investigated for the Cu-catalyzed Ullmann etherification in fine-chemical synthesis, providing improved catalytic activity and selective catalyst heating. Wall-coated and fixed-bed milli-reactors were designed and applied in the Cu-catalyzed Ullmann-type CO coupling of phenol and 4-chloropyridine. In a batch reactor the results show clearly increased yields for the microwave heated process at low microwave powers, whereas high powers and catalyst loadings reduced the benefits of microwave heating. Slightly higher yields were found in the Cu/ZnO wall-coated as compared to the Cu/TiO fixed-bed flow-reactor. The benefit here is that the reaction occurs at the surface of the metal nanoparticles confined within a support film making the nano-copper equally accessible. Catalyst deactivation was mainly caused by Cu oxidation and coke formation; however, at longer process times leaching played a significant role. Catalyst activity could partially be recovered by removal of deposited by-product by means of calcination. After 6h on-stream the reactor productivities were 28.3 and 55.1kgprod/(mR3h) for the fresh Cu/ZnO wall-coated and Cu/TiO fixed-bed reactor, respectively. Comparison of single- and multimode microwaves showed a threefold yield increase for single-mode microwaves. Control of nanoparticles size and loading allows to avoid high temperatures in a single-mode microwave field and provides a novel solution to a major problem for combining metal catalysis and microwave heating. Catalyst stability appeared to be more important and provided twofold yield increase for the CuZn/TiO catalyst as compared to the Cu/TiO catalyst due to stabilized copper by preferential oxidation of the zinc. For this catalyst a threefold yield increase was observed in single-mode microwaves which, to the best of our knowledge, led to a not yet reported productivity of 172kgprod/(mR3h) for the microwave and flow Ullmann CO coupling. © 2012 Elsevier B.V.

The colonization of macroalgal rafts by the genus Idotea (sub-phylum Crustacea; Order Isopoda):An active or passive process?

The association of invertebrate communities with macroalgae rafts has received much attention over recent decades, yet significant gaps in our knowledge remain with respect to the colonization process. Using laboratory-based experiments and in situ field trials in Strangford Lough, Northern Ireland, this study investigated whether members of the known rafting genus Idotea (sub-phylum Crustacea; order Isopoda) could effectively colonize rafts after shore seaweed detachment, or if their presence merely reflected a passive marooning process. Test tank arenas were used to identify traits that may influence the rafting potential of the dominant shore species Idotea granulosa and the well known rafter Idotea baltica. When released mid-water, I. granulosa initially ascended and associated with floating seaweed whereas I. baltica tended to descend with no clear habitat association. These findings conflict with the differential distribution of these Idotea species among rafts and shore algae, thus highlighting the complex nature of the potential of organisms to raft. In the field we considered the relative ability of different Idotea species to colonize tethered rafts composed of Ascophyllum nodosum and Fucus vesiculosus, cleaned of all vagile organisms and deployed at locations adjacent to established intertidal Idotea species populations. At the end of the experiment (after 44 days) rafts were inhabited by known rafting and shoreline species, confirming that colonization can occur after algal detachment. Previously considered shoreline species on occasion outnumbered well known rafters suggesting that a wide range of Idotea species can readily avail of macroalgal rafts as a potential dispersal mechanism or alternative habitat. © 2012 Marine Biological Association of the United Kingdom.

A more direct way to make catalysts: one-pot ligand-assisted aerobic stripping and electrodeposition of copper on graphite

Electrodeposition of metals onto conductive supports such as graphite potentially provides a lower-waste method to form heterogeneous catalysts than the standard methods such as wet impregnation. Copper electrodeposition onto pressed graphite disc electrodes was investigated from aqueous CuSO4-ethylenediamine solutions by chronoamperometry with scanning electron microscopy used to ascertain the particle sizes obtained by this method. The particle size was studied as a function of pH, CuSO4-ethylenediamine concentration, and electrodeposition time. It was observed that decreasing the pH, copper-ethylenediamine concentration and time each decreased the size of the copper particles observed, with the smallest obtained being around 5-20 nm. Furthermore, electroless aerobic oxidation of copper metal in the presence of ethylenediamine was successfully coupled with the electrodeposition in the same vessel. In this way, deposition was achieved sequentially on up to twenty different graphite discs using the same ethylenediamine solution, demonstrating the recyclability of the ligand. The materials thus prepared were shown to be catalytically active for the mineralisation of phenol by hydrogen peroxide. Overall, the results provide a proof-of-principle that by making use of aerobic oxidation coupled with electrochemical deposition, elemental base metals can be used directly as starting materials to form heterogeneous catalysts without the need to use metal salts as catalyst precursors.

Tea tree oil (5%) body wash versus standard care (Johnson's Baby Softwash) to prevent colonization with methicillin-resistant Staphylococcus aureus in critically ill adults::a randomized controlled trial

OBJECTIVES: To determine whether the daily use of 5% tea tree oil (TTO) body wash (Novabac 5% Skin Wash) compared with standard care [Johnson's Baby Softwash (JBS)] had a lower incidence of methicillin-resistant Staphylococcus aureus (MRSA) colonization.

PATIENTS: The study setting was two intensive care units (ICUs; mixed medical, surgical and trauma) in Northern Ireland between October 2007 and July 2009. The study population comprised 391 patients who were randomized to JBS or TTO body wash.

METHODS: This was a Phase 2/3, prospective, open-label, randomized, controlled trial. Trial registration: ISRCTN65190967. The primary outcome was new MRSA colonization during ICU stay. Secondary outcomes included the incidence of MRSA bacteraemia and maximum increase in sequential organ failure assessment score.

RESULTS: A total of 445 patients were randomized to the study. After randomization, 54 patients were withdrawn; 30 because of a positive MRSA screen at study entry, 11 due to lack of consent, 11 were inappropriately randomized and 2 had adverse reactions. Thirty-nine (10%) patients developed new MRSA colonization (JBS n?=?22, 11.2%; TTO body wash n?=?17, 8.7%). The difference in percentage colonized (2.5%, 95% CI -?8.95 to 3.94; P?=?0.50) was not significant. The mean maximum increase in sequential organ failure assessment score was not significant (JBS 1.44, SD 1.92; TTO body wash 1.28, SD 1.79; P?=?0.85) and no study patients developed MRSA bacteraemia.

CONCLUSIONS: Compared with JBS, TTO body wash cannot be recommended as an effective means of reducing MRSA colonization.

Web-assisted first-year undergraduate teaching in engineering

A software system, recently developed by the authors for the efficient capturing, editing, and delivery of audio-visual web lectures, was used to create a series of lectures for a first-year undergraduate course in Dynamics. These web lectures were developed to serve as an extra study resource for students attending lectures and not as a replacement. A questionnaire was produced to obtain feedback from students. The overall response was very favorable and numerous requests were made for other lecturers to adopt this technology. Despite the students' approval of this added resource, there was no significant improvement in overall examination performance

Differences in Mucosal Gene Expression in the Colon of Two Inbred Mouse Strains after Colonization with Commensal Gut Bacteria

The host genotype has been proposed to contribute to individually composed bacterial communities in the gut. To provide deeper insight into interactions between gut bacteria and host, we associated germ-free C3H and C57BL/10 mice with intestinal bacteria from a C57BL/10 donor mouse. Analysis of microbiota similarity between the animals with denaturing gradient gel electrophoresis revealed the development of a mouse strain-specific microbiota. Microarray-based gene expression analysis in the colonic mucosa identified 202 genes whose expression differed significantly by a factor of more than 2. Application of bioinformatics tools demonstrated that functional terms including signaling/secretion, lipid degradation/catabolism, guanine nucleotide/guanylate binding and immune response were significantly enriched in differentially expressed genes. We had a closer look at the 56 genes with expression differences of more than 4 and observed a higher expression in C57BL/10 mice of the genes coding for Tlr1 and Ang4 which are involved in the recognition and response to gut bacteria. A higher expression of Pla2g2a was detected in C3H mice. In addition, a number of interferon-inducible genes were higher expressed in C3H than in C57BL/10 mice including Gbp1, Mal, Oasl2, Ifi202b, Rtp4, Ly6g6c, Ifi27l2a, Usp18, Ifit1, Ifi44, and Ly6g indicating that interferons may play an essential role in microbiota regulation. However, genes coding for interferons, their receptors, factors involved in interferon expression regulation or signaling pathways were not differentially expressed between the two mouse strains. Taken together, our study confirms that the host genotype is involved in the establishment of host-specific bacterial communities in the gut. Based on expression differences after colonization with the same bacterial inoculum, we propose that Pla2g2a and interferon-dependent genes may contribute to this phenomenon.

The impact of sperm DNA damage in assisted conception and beyond: recent advances in diagnosis and treatment

Abstract Sperm DNA damage is a useful biomarker for male infertility diagnosis and prediction of assisted reproduction outcomes.
It is associated with reduced fertilization rates, embryo quality and pregnancy rates, and higher rates of spontaneous miscarriage
and childhood diseases. This review provides a synopsis of the most recent studies from each of the authors, all of whom have major
track records in the field of sperm DNA damage in the clinical setting. It explores current laboratory tests and the accumulating body
of knowledge concerning the relationship between sperm DNA damage and clinical outcomes. The paper proceeds to discuss the
strengths, weaknesses and clinical applicability of current sperm DNA tests. Next, the biological significance of DNA damage in
the male germ line is considered. Finally, as sperm DNA damage is often the result of oxidative stress in the male reproductive tract,
the potential contribution of antioxidant therapy in the clinical management of this condition is discussed. DNA damage in human spermatozoa is an important attribute of semen quality. It should be part of the clinical work up and properly controlled trials
addressing the effectiveness of antioxidant therapy should be undertaken as a matter of urgency.

Qubit-assisted thermometry of a quantum harmonic oscillator

We use the theory of quantum estimation in two different qubit-boson coupling models to demonstrate that the temperature of a quantum harmonic oscillator can be estimated with high precision by quantum-limited measurements on the qubit. The two models that we address embody situations of current physical interest due to their connection with ongoing experimental efforts on the control of mesoscopic dynamics. We show that population measurements performed over the qubit probe are near optimal for a broad range of temperatures of the harmonic oscillator.

Peer assisted learning in health education.

There are many forms of Peer Assisted Learning (PAL). There are well-established theoretical models as to why PAL is proven to be effective across educational sectors. To maximise gains from PAL careful consideration needs to be given to the roles of peers. Evidence suggests that PAL projects with clearly defined roles for interaction result in strongest outcomes. Effect Sizes (ES) from meta-analyses of peer assisted learning indicate ES of between 0.25-0.50. Outcomes can be social and emotional as well as academic. PAL generally requires adaptation of existing resources and can be cost-effective to implement compared to other educational developments.

Ionothermal, microwave-assisted synthesis of indium(III) selenide

Microcrystalline indium(III) selenide was prepared from a diphenyl diselenide precursor and a range of chloroindate(III) ionic liquids via a microwave-assisted ionothermal route; this is the first report on the use of either microwave irradiation or ionic liquids to prepare this material. The influence of the reaction temperature, dilution with a spectator ionic liquid and variation of the cation and the anion of the ionic liquid on the product morphology and composition were investigated. This resulted in a time-efficient and facile one-pot reaction to produce microcrystalline indium(III) selenide. The product formation in the ionic liquids has been monitored using Raman spectroscopy. The products have been characterised using PXRD, SEM and EDX. Advantages of this new route, such as the ease of solubilisation of all reactants into one phase at high concentration, the negligible vapour pressure irrespective of the reaction temperature, very fast reaction times, ease of potential scale-up and reproducibility are discussed.

Mask assisted fabrication of nanoislands of BiFeO3 by ion beam milling

We report on a low-damage method for direct and rapid fabrication of arrays of epitaxial BiFeO3(BFO) nanoislands. An array of aluminium dots is evaporated through a stencil mask on top of an epitaxial BiFeO3 thin film. Low energy focused ion beam milling of an area several microns wide containing the array-covered film leads to removal of the bismuth ferrite in between the aluminium-masked dots. By chemical etching of the remaining aluminium, nanoscale epitaxial bismuth ferrite islands with diameter ∼250 nm were obtained. Piezoresponse force microscopy showed that as-fabricated structures exhibited good piezoelectric and ferroelectric properties, with polarization state retention of several days.