Interrogation of a sonogashira cross-coupling of 8-bromoguanosine with phenylacetylene on amberlite:evidence for Pd/Cu ion binding and propagation of Pd/Cu nanoparticles

The reactivity of Amberlite (IRA-67) base "heterogeneous" resin in Sonogashira cross-coupling of 8-bromoguanosine 1 with phenylacetylene 3 to give 2 has been examined. Both 1 and 2 coordinate to Pd and Cu ions, which explains why at equivalent catalyst loadings, the homogeneous reaction employing triethylamine base is poor yielding. X-ray photo-electron spectroscopy (XPS) has been used to probe and quantify the active nitrogen base sites of the Amberlite resin, and postreaction Pd and Cu species. The Pd2Cl3(PPh)2 precatalyst and CuI cocatalyst degrade to give Amberlite-supported metal nanoparticles (average size ∼2.7 nm). The guanosine product 2 formed using the Amberlite Pd/Cu catalyst system is of higher purity than reactions using a homogeneous Pd precatalyst, a prerequisite for use in biological applications. Copyright © Taylor and Francis Group, LLC.

In-situ XPS study on the reducibility of Pd-promoted Cu/CeO2 catalysts for the oxygen-assisted water-gas-shift reaction

Cu/CeO2, Pd/CeO2, and CuPd/CeO2 catalysts were prepared and their reduction followed by in-situ XPS in order to explore promoter and support interactions in a bimetallic CuPd/CeO2 catalyst effective for the oxygen-assisted water-gas-shift (OWGS) reaction. Mutual interactions between Cu, Pd, and CeO2 components all affect the reduction process. Addition of only 1 wt% Pd to 30 wt% Cu/CeO2 greatly enhances the reducibility of both dispersed CuO and ceria support. In-vacuo reduction (inside XPS chamber) up to 400 °C results in a continuous growth of metallic copper and Ce3+ surface species, although higher temperatures results in support reoxidation. Supported copper in turn destabilizes metallic palladium metal with respect to PdO, this mutual perturbation indicating a strong intimate interaction between the Cu–Pd components. Despite its lower intrinsic reactivity towards OWGS, palladium addition at only 1 wt% loading significantly improved CO conversion in OWGS reaction over a monometallic 30 wt% Cu/CeO2 catalysts, possibly by helping to maintain Cu in a reduced state during reaction.

Reduced graphene oxide wrapped Cu2O supported on C3N4: An efficient visible light responsive semiconductor photocatalyst

Herein, Cu 2O spheres were prepared and encapsulated with reduced graphene oxide (rGO). The Cu 2O–rGO–C3N4 composite covered the whole solar spectrum with significant absorption intensity. rGO wrapped Cu 2O loading caused a red shift in the absorption with respect to considering the absorption of bare C3N4. The photoluminescence study confirms that rGO exploited as an electron transport layer at the interface of Cu 2O and C3N4 heterojunction. Utmost, ∼2 fold synergistic effect was achieved with Cu 2O–rGO–C3N4 for the photocatalytic reduction of 4-nitrophenol to 4-aminophenol in comparison with Cu 2O–rGO and C3N4. The Cu 2O–rGO–C3N4 photocatalyst was reused for four times without loss in its activity.

High performance of Cu/CeO2-Nb2O5 catalysts for preferential CO oxidation and total combustion of toluene

Copper-based catalysts supported on niobium-doped ceria have been prepared and tested in the preferential oxidation of CO in excess of H2 (PROX) and in total oxidation of toluene. Supports and catalysts have been characterized by several techniques: N2 adsorption, ICP-OES, XRF, XRD, Raman Spectroscopy, SEM, TEM, H2-TPR and XPS, and their catalytic performance has been measured in PROX, with an ideal gas mixture (CO, O2 and H2) with or without CO2 and H2O, and in total oxidation of toluene. The effects of the copper loading and the amount of niobium in the supports have been evaluated. Remarkably, the addition of niobia to the catalysts may improve the catalytic performance in total oxidation of toluene. It allows us to prepare cheaper catalysts (niobia it is far cheaper than ceria) with improved catalytic performance.

Synthesis, characterization of palygorskite supported zero-valent iron and its application for methylene blue adsorption

In this work, natural palygorskite impregnated with zero-valent iron (ZVI) was prepared and characterised. The combination of ZVI particles on surface of fibrous palygorskite can help to overcome the disadvantage of ultra-fine powders which may have strong tendency to agglomerate into larger particles, resulting in an adverse effect on both effective surface area and catalyst performance. There is a significant increase of methylene blue (MB) decolourized efficiency on acid treated palygorskite with ZVI grafted, within 5 mins, the concentration of MB in the solution was decreased from 94 mg/L to around 20 mg/L and the equilibration was reached at about 30 to 60 mins with only around 10 mg/L MB remained in solution. Changes in the surface and structure of prepared materials were characterized using X-ray diffraction (XRD), infrared (IR) spectroscopy, surface analysing and scanning electron microscopy (SEM) with element analysis and mapping. Comparing with zero-valent iron and palygorskite, the presence of zero-valent iron reactive species on the palygorskite surface strongly increases the decolourization capacity for methylene blue, and it is significant for providing novel modified clay catalyst materials for the removal of organic contaminants from waste water.

Primary students' group metacognitive processes in a computer supported collaborative learning environment

The current understanding of students’ group metacognition is limited. The research on metacognition has focused mainly on the individual student. The aim of this study was to address the void by developing a conceptual model to inform the use of scaffolds to facilitate group metacognition during mathematical problem solving in computer supported collaborative learning (CSCL) environments. An initial conceptual framework based on the literature from metacognition, cooperative learning, cooperative group metacognition, and computer supported collaborative learning was used to inform the study. In order to achieve the study aim, a design research methodology incorporating two cycles was used. The first cycle focused on the within-group metacognition for sixteen groups of primary school students working together around the computer; the second cycle included between-group metacognition for six groups of primary school students working together on the Knowledge Forum® CSCL environment. The study found that providing groups with group metacognitive scaffolds resulted in groups planning, monitoring, and evaluating the task and team aspects of their group work. The metacognitive scaffolds allowed students to focus on how their group was completing the problem-solving task and working together as a team. From these findings, a revised conceptual model to inform the use of scaffolds to facilitate group metacognition during mathematical problem solving in computer supported collaborative learning (CSCL) environments was generated.

Elastic lateral buckling of simply supported LiteSteel beams subject to transverse loading

The buckling strength of a new cold-formed hollow flange channel section known as LiteSteel beam (LSB) is governed by lateral distortional buckling characterised by simultaneous lateral deflection, twist and web distortion for its intermediate spans. Recent research has developed a modified elastic lateral buckling moment equation to allow for lateral distortional buckling effects. However, it is limited to a uniform moment distribution condition that rarely exists in practice. Transverse loading introduces a non-uniform bending moment distribution, which is also often applied above or below the shear centre (load height). These loading conditions are known to have significant effects on the lateral buckling strength of beams. Many steel design codes have adopted equivalent uniform moment distribution and load height factors to allow for these effects. But they were derived mostly based on data for conventional hot-rolled, doubly symmetric I-beams subject to lateral torsional buckling. The moment distribution and load height effects of transverse loading for LSBs, and the suitability of the current design modification factors to accommodate these effects for LSBs is not known. This paper presents the details of a research study based on finite element analyses on the elastic lateral buckling strength of simply supported LSBs subject to transverse loading. It discusses the suitability of the current steel design code modification factors, and provides suitable recommendations for simply supported LSBs subject to transverse loading.

Lateral buckling strength of simply supported LiteSteel beams subject to moment gradient effects

The flexural capacity of of a new cold-formed hollow flange channel section known as LiteSteel beam (LSB) is limited by lateral distortional buckling for intermediate spans, which is characterised by simultaneous lateral deflection, twist and web distortion. Recent research has developed suitable design rules for the member capacity of LSBs. However, they are limited to a uniform moment distribution that rarely exists in practice. Many steel design codes have adopted equivalent uniform moment distribution factors to accommodate the effect of non-uniform moment distributions in design. But they were derived mostly based on the data for conventional hot-rolled, doubly symmetric I-beams subject to lateral torsional buckling. The effect of moment distribution for LSBs, and the suitability of the current steel design code rules to include this effect for LSBs are not yet known. This paper presents the details of a research study based on finite element analyses of the lateral buckling strength of simply supported LSBs subject to moment gradient effects. It also presents the details of a number of LSB lateral buckling experiments undertaken to validate the results of finite element analyses. Finally, it discusses the suitability of the current design methods, and provides design recommendations for simply supported LSBs subject to moment gradient effects.

Research training and national innovation systems in Australia, Finland and the United States : a policy and systems study supported by 30 case studies of research students in the fields of geospatial science, wireless communication, biosciences, and materials science and engineering

Reforms to the national research and research training system by the Commonwealth Government of Australia sought to effectively connect research conducted in universities to Australia's national innovation system. Research training has a key role in ensuring an adequate supply of highly skilled people for the national innovation system. During their studies, research students produce and disseminate a massive amount of new knowledge. Prior to this study, there was no research that examined the contribution of research training to Australia's national innovation system despite the existence of policy initiatives aiming to enhance this contribution. Given Australia's below average (but improving) innovation performance compared to other OECD countries, the inclusion of Finland and the United States provided further insights into the key research question. This study examined three obvious ways that research training contributes to the national innovation systems in the three countries: the international mobility and migration of research students and graduates, knowledge production and distribution by research students, and the impact of research training as advanced human capital formation on economic growth. Findings have informed the concept of a research training culture of innovation that aims to enhance the contribution of research training to Australia's national innovation system. Key features include internationally competitive research and research training environments; research training programs that equip students with economically-relevant knowledge and the capabilities required by employers operating in knowledge-based economies; attractive research careers in different sectors; a national commitment to R&D as indicated by high levels of gross and business R&D expenditure; high private and social rates of return from research training; and the horizontal coordination of key organisations that create policy for, and/or invest in research training.

Scale-dependent fracture mode in Cu-Ni laminate composites

Fracture behavior of Cu-Ni laminate composites has been investigated by tensile testing. It was found that as the individual layer thickness decreases from 100 to 20nm, the resultant fracture angle of the Cu-Ni laminate changes from 72 degrees to 50 degrees. Cross-sectional observations reveal that the fracture of the Ni layers transforms from opening to shear mode as the layer thickness decreases while that of the Cu layers keeps shear mode. Competition mechanisms were proposed to understand the variation in fracture mode of the metallic laminate composites associated with length scale.

Raman spectroscopic study of the hydroxy-arsenate mineral geminite Cu(AsO3OH)•H2O

The mineral geminite, an hydrated hydroxy-arsenate mineral of formula Cu(AsO3OH)•H2O, has been studied by Raman and infrared spectroscopy. Two minerals from different origins were investigated and the spectra proved quite similar. In the Raman spectra of geminite, four bands are observed at 813, 843, 853 and 885 cm-1. The assignment of these bands is as follows: (a) The band at 853 cm-1 is assigned to the AsO43- ν1 symmetric stretching mode (b) the band at 885 cm-1 is assigned to the AsO3OH2- ν1 symmetric stretching mode (c) the band at 843 cm-1 is assigned to the AsO43- ν3 antisymmetric stretching mode (d) the band at 813 cm-1 is ascribed to the AsO3OH2- ν3 antisymmetric stretching mode. Two Raman bands at 333 and 345 cm-1 are attributed to the ν2 AsO4 3- bending mode and a set of higher wavenumber bands are assigned to the ν4 AsO43- bending mode. A very complex set of overlapping bands is observed in both the Raman and infrared spectra. Raman bands are observed at 2288, 2438, 2814, 3152, 3314, 3448 and 3521 cm-1. Two Raman bands at 2288 and 2438 cm-1 are ascribed to very strongly hydrogen bonded water. The broader Raman bands at 3152 and 3314 cm-1 may be assigned to adsorbed water and not so strongly hydrogen bonded water in the molecular structure of geminate. Two bands at 3448 and 3521 cm-1 are assigned to the OH stretching vibrations of the (AsO3OH)2- units. Raman spectroscopy identified Raman bands attributable to AsO43- and AsO3OH2- units.