Synthesis, structural analysis, and thermal decomposition studies of [(NH3)2BH2]B3H8

Boron–nitrogen containing compounds with high hydrogen contents as represented by ammonia borane (NH3BH3) have recently attracted intense interest for potential hydrogen storage applications. One such compound is [(NH3)2BH2]B3H8 with a capacity of 18.2 wt% H. Two safe and efficient synthetic routes to [(NH3)2BH2]B3H8 have been developed for the first time since it was discovered 50 years ago. The new synthetic routes avoid a dangerous starting chemical, tetraborane (B4H10), and afford a high yield. Single crystal X-ray diffraction analysis reveals N–Hδ+Hδ−–B dihydrogen interactions in the [(NH3)2BH2]B3H8·18-crown-6 adduct. Extended strong dihydrogen bonds were observed in pure [(NH3)2BH2]B3H8 through crystal structure solution based upon powder X-ray analysis. Pyrolysis of [(NH3)2BH2]B3H8 leads to the formation of hydrogen gas together with appreciable amounts of volatile boranes below 160 °C.

Experimental studies of the shear behaviour and strength of lipped channel beams with web openings

Cold-formed steel members are increasingly used as primary structural elements in the building industries around the world due to the availability of thin and high strength steels and advanced cold-forming technologies. Cold-formed lipped channel beams (LCB) are commonly used as flexural members such as floor joists and bearers. However, their shear capacities are determined based on conservative design rules. Current practice in flooring systems is to include openings in the web element of floor joists or bearers so that building services can be located within them. Shear behaviour of LCBs with web openings is more complicated while their shear strengths are considerably reduced by the presence of web openings. However, limited research has been undertaken on the shear behaviour and strength of LCBs with web openings. Hence a detailed experimental study involving 40 shear tests was undertaken to investigate the shear behaviour and strength of LCBs with web openings. Simply supported test specimens of LCBs with aspect ratios of 1.0 and 1.5 were loaded at midspan until failure. This paper presents the details of this experimental study and the results of their shear capacities and behavioural characteristics. Experimental results showed that the current design rules in cold-formed steel structures design codes are very conservative for the shear design of LCBs with web openings. Improved design equations have been proposed for the shear strength of LCBs with web openings based on the experimental results from this study.

Studies of the off-field behaviours of sportspeople : are sponsors' objectives at risk?

The research reported here addresses the problem of athlete off-field behaviours as they influence sports’ sponsors, particularly the achievement of sponsorship objectives. The question arises because of incidents of sponsorship contract cancellation following news-media reporting of athletes’ off-field behaviours. Two studies are used to investigate the research question; the first establishes the content of news-media reports, and the second tests the effects of news’ reports on athlete, team and sponsor evaluations using an experimental design. Key assumptions of the research are that sponsorship objectives are principally consumer-based and mediated. Models of sponsorship argue that sponsors aim to reach and influence consumers through sponsees. Assuming this pathway exists is central to sponsorship activities. A corollary is that other mediators, in this case the news-media, may also communicate (uncontrollable) messages such that a consumer audience may be told of negative news that may then be associated with the sponsor. When sponsors cancel contracts it is assumed that their goal is to control the links between their brand and a negative referent. Balance theory is used to discuss the potential effects of negative off-field behaviours of athletes on sponsor’s objectives. Heider’s balance theory (1958) explains that individuals prefer to evaluate linked individuals or entities consistently. In the sponsorship context this presents the possibility that a negative evaluation of the athlete’s behaviour will contribute to correspondingly negative evaluations of the athlete’s team and sponsors. A content analysis (Study 1) was used to survey the types of athlete off-field behaviours commonly reported in a newspaper. In order to provide a local context for the research, articles from the Courier Mail were sampled and teams in the National Rugby League (NRL) competition were the focus of the research. The study identified nearly 2000 articles referring to the NRL competition; 258 of those refer to off-field incidents involving athletes. The various types of behaviours reported include assault, sexual assault allegations, driving under the influence of alcohol, illicit drug use, breaches of club rules, and positive off-field activities (i.e., charitable activities). An experiment (Study 2) tested three news’ article stimuli developed from the behaviours identified in Study 1 in a between-subjects design. A measure of Identification with the Team was used as a covariate variable in the Multivariate Analysis of Covariance analysis. Social identity theory suggests that when an individual identifies with a group, their attitudes and behaviours towards both in- and out-group members are modified. Use of Identification with the Team as a covariate acknowledges that respondents will evaluate behaviours differently according to the attribution of those behaviours to an in- or out-group member. Findings of the research suggest that the news’ article stimuli have significant, large effects on evaluations of athlete off-field behaviour and athlete Likability. Consistent with pretest results, charitable fundraising is regarded as extremely positive; the athlete, correspondingly, is likable. Assault is evaluated as extremely negative, and the athlete as unlikable. DUI scores reveal that the athlete’s behaviour is very negative; however, the athlete’s likability was evaluated as neutral. Treatment group does not produce any significant effects on team or sponsor variables. This research also finds that Identification with the Team has significant, large effects on team variables (Attitude toward the Brand and Corporate Image). Identification also has a significant large effect on athlete Likability, but not on Attitude toward the Act. Identification with the Team does not produce any significant effects on sponsor variables. The results of this research suggest that sponsor’s consumer-based objectives are not threatened by newspaper reports linking athlete off-field behaviour with their brand. Evaluations of sponsor variables (Attitude toward the Sponsor’s Brand and Corporate Image) were consistently positive. Variance in that data, however, cannot be attributed to experimental stimuli or Identification with the Team. These results argue that respondents may regard sponsorships, in principle, as good. Although it is good news for sponsors that negative evaluations of athletes will not produce correspondingly negative evaluations of consumer-based sponsorship objectives, the results indicate problems for sponsorship managers. The failure of Identification with the Team to explain sponsor variable variance indicates that the sponsor has not been evaluated as a linked entity in a relationship with the sporting team and athlete in this research. This result argues that the sponsee-mediated affective communication path that sponsors aim use to communicate with desirable publics is not necessarily a path available to them.

First principle studies of zigzag AlN nanoribbon

Ab initio density functional calculations were performed to study the geometry and electronic structure of a prototypical zigzag AlN nanoribbon. We find that H-terminated zigzag 10-AlN nanoribbons have a non-direct band gap and are nonmagnetic. When a transverse electric field is applied, the band gap decreases monotonically with the strength of field E. Zigzag AlN nanoribbons with the N edge unpassivated display strong spin-polarization close to the Fermi level, which will result in spin-anisotropic transport. These results suggest potential applications for the development of AlN nanoribbon-based nanoelectronics applications.

First-principle studies of electronic structure and C-doping effect in boron nitride nanoribbon

Structural and electronic properties have been studied for Boron Nitride nanoribbons (BNNR) with both zigzag and armchair shaped edge (Z-BNNR and A-BNNR) by first-principle spin-polarized total energy calculations. We found that the energy band gap of Z-BNNR is indirect and decreases monotonically with the increasing ribbon width, whereas direct energy band gap oscillation was observed for A-BNNRs. Additionally, C-substitution at either single boron or nitrogen atom site in BNNRs could induce spontaneous magnetization. Our results could be potentially useful to design magnetic nano-devices based on BNNRs.

First-principle studies of the formation and diffusion of hydrogen vacancies in magnesium hydride

Ab initio density functional theory (DFT) calculations are performed to study the formation and diffusion of hydrogen vacancies on MgH2(110) surface and in bulk. We find that the formation energies for a single H-vacancy increase slightly from the surface to deep layers. The energies for creating adjacent surface divancacies at two inplane sites and at an inplane and a bridge site are even smaller than that for the formation of a single H-vacancy, a fact that is attributed to the strong vacancy−vacancy interactions. The diffusion of an H-vacancy from an in-plane site to a bridge site on the surface has the smallest activation barrier calculated at 0.15 eV and should be fast at room temperature. The activation barriers computed for H-vacancy diffusion from the surface into sublayers are all less than 0.70 eV, which is much smaller than the activation energy for desorption of hydrogen on the MgH2(110) surface (1.78−2.80 eV/H2). This suggests that surface desorption is more likely than vacancy diffusion to be rate determining, such that finding effective catalyst on the MgH2 surface to facilitate desorption will be very important for improving overall dehydrogenation performance.

Ab initio studies of hydrogen desorption from low index magnesium hydride surface

The low index Magnesium hydride surfaces, MgH2(0 0 1) and MgH2(1 1 0), have been studied by ab intio Density Functional Theory (DFT) calculations. It was found that the MgH2(1 1 0) surface is more stable than MgH2(0 0 1) surface, which is in good agreement with the experimental observation. The H2 desorption barriers vary depending on the crystalline surfaces that are exposed and also the specific H atom sites involved – they are found to be generally high, due to the thermodynamic stability of the MgH2 system, and are larger for the MgH2(0 0 1) surface. The pathway for recombinative desorption of one in-plane and one bridging H atom from the MgH2(1 1 0) surface was found to be the lowest energy barrier amongst those computed (172 KJ/mol) and is in good agreement with the experimental estimates.

The architecture of children’s use of language and tools when problem solving collaboratively with robotics

This paper demonstrates, following Vygotsky, that language and tool use has a critical role in the collaborative problem-solving behaviour of school-age children. It reports original ethnographic classroom research examining the convergence of speech and practical activity in children’s collaborative problem solving with robotics programming tasks. The researchers analysed children’s interactions during a series of problem solving experiments in which Lego Mindstorms toolsets were used by teachers to create robotics design challenges among 24 students in a Year 4 Australian classroom (students aged 8.5–9.5 years). The design challenges were incrementally difficult, beginning with basic programming of straight line movement, and progressing to more complex challenges involving programming of the robots to raise Lego figures from conduit pipes using robots as pulleys with string and recycled materials. Data collection involved micro-genetic analysis of students’ speech interactions with tools, peers, and other experts, teacher interviews, and student focus group data. Coding the repeated patterns in the transcripts, the authors outline the structure of the children’s social speech in joint problem solving, demonstrating the patterns of speech and interaction that play an important role in the socialisation of the school-age child’s practical intellect.

In situ Raman studies of the selective oxidation of methanol to formaldehyde and ethene to ethylene oxide on a polycrystalline silver catalyst

The combined techniques of in situ Raman microscopy and scanning electron microscopy (SEM) have been used to study the selective oxidation of methanol to formaldehyde and the ethene epoxidation reaction over polycrystalline silver catalysts. The nature of the oxygen species formed on silver was found to depend critically upon the exact morphology of the catalyst studied. Bands at 640, 780 and 960 cm-1 were identified only on silver catalysts containing a significant proportion of defects. These peaks were assigned to subsurface oxygen species situated in the vicinity of surface dislocations, AgIII=O sites formed on silver atoms modified by the presence of subsurface oxygen and O2 - species stabilized on subsurface oxygen-modified silver sites, respectively. The selective oxidation of methanol to formaldehyde was determined to occur at defect sites, where reaction of methanol with subsurface oxygen initially produced subsurface OH species (451 cm-1) and adsorbed methoxy species. Two distinct forms of adsorbed ethene were identified on oxidised silver sites. One of these was created on silver sites modified by the interaction of subsurface oxygen species, and the other on silver crystal planes containing a surface coverage of atomic oxygen species. The selective oxidation of ethene to ethylene oxide was achieved by the reaction between ethene adsorbed on modified silver sites and electrophilic AgIII=O species, whereas the combustion reaction was perceived to take place by the reaction of adsorbed ethene with nucleophilic surface atomic oxygen species. Defects were determined to play a critical role in the epoxidation reaction, as these sites allowed the rapid diffusion of oxygen into subsurface positions, and consequently facilitated the formation of the catalytically active AgIII=O sites.

Spectroscopic studies of the adsorption and reactions of chlorofluorocarbons (CFC-11 and CFC-12) and hydrochlorofluorocarbon (HCFC-22) on oxide surfaces

Raman and Fourier transform infrared (FT-IR) spectroscopy have been applied to a systematic investigation of the adsorption and decomposition of dichlorodifluoromethane (CCl2F2, CFC-12), fluorotrichloromethane (CCl3F, CFC-11), chlorodifluoromethane (CHClF2, HCFC-22) and molecular chlorine on oxide surfaces. Additionally, the effects of heating and ultraviolet photolysis of the CFC and HCFCs adsorbed on the oxide surfaces have been investigated. Spectral features for these species indicated a small wavenumber shift (1-6 cm-1) associated with the adsorbed phase. Some evidence, specifically the appearance of the Raman band at 507 cm-1, is presented to show that chlorine decomposition species are associated with these oxide surfaces. It was concluded that the new spectral feature (at ca. 507 cm-1) related with the decomposition of the CFC and HCFC molecules was an important indicator of the extent to which the reaction between the adsorbed CFC and HCFC and oxide surface has taken place. The extent of CFC-surface interaction has been quantified in terms of a maximum (Raman) frequency shift parameter (AM). Wavenumber shifts suggest both cation-adsorbate and non-specific adsorption interactions are occurring in the internal channels of the zeolites. Slow decomposition of the adsorbed CFCs under ultraviolet-visible photolysis (at ? > 300 nm) and/or thermal treatment was observed spectroscopically. Using FT-IR spectroscopy, the formation of gas-phase products (CO, CO2, HCl) both onyn photolysis and heating was evident. Results of these measurements are compared with the observed atmospheric reactivity of these compounds.

Pharmacokinetic studies of a Chinese triple herbal drug formula

Yin Chen Hao Tang preparation (YCHTP) is a classic traditional Chinese medicine formula, which is commonly used for clinical treatment of hepatological diseases. In this study, a rapid and validated high-performance liquid chromatography (HPLC) method was developed to simultaneously identify 6,7-dimethylesculetin and geniposide in rat plasma. This assay was performed on a Dikma Diamonsil RP(18) column (200 mmx4.6 mm, 5 mum) with acetonitrile-methanol-water (0.1% formic acid) as the mobile phase, showing acceptable linearity, intra- and inter-day precision and accuracy (R.S.D.=5%), and absolute recovery for two analytes (74%); the limits of quantitation were 0.4 and 1.12 mug/ml, and the limits of detection were 0.06 and 0.09 mug/ml for two analytes. The developed method was successfully applied to study the effect of formula compatibility on the pharmacokinetics of 6,7-dimethylesculetin and geniposide in YCHTP when orally administrating an effective human daily dose of YCHTP to rats. We surmise that formula compatibility can significantly influence the pharmacokinetics of YCHTP, and we have elucidated and validated the compatible administration of YCHTP.

Simultaneous determination of 6,7-dimethylesculetin and geniposide in rat plasma and its application to pharmacokinetic studies of Yin Chen Hao Tang preparation

A method for the rapid and simultaneous determination of 6,7-dimethylesculetin (CAS 120-08-1) and geniposide (CAS 24512-63-8) in rat plasma has been developed, using validated high performance liquid chromatography (HPLC) with solid phase extraction (SPE). The HPLC analysis was performed on a commercially available column (200 mm x 4.6 mm, 5 microm) with acetonitrile-methanol-0.1% aqueous formic acid as mobile phase and the UV detection at 343 nm and 238 nm for 6,7-dimethylesculetin and geniposide, respectively. The calibration curves for 6,7-dimethylesculetin and geniposide were linear over the range 0.4-25.6 microg/mL and 1.12-71.68 microg/mL, respectively. The lower limits of quantitation were 0.40 microg/ mL and 1.12 microg/mL, and the lower limits of detection were 0.06 microg/mL and 0.09 microg/ mL, respectively. The intra-day and inter-day precision for 6,7-dimethylesculetin and geniposide were < 5%, whereas the absolute recovery percentages were > 74%. A successful application of the developed HPLC analysis was demonstrated for the pharmacokinetic study of a Traditional Chinese Medicine formula of Yin Chen Hao Tang preparation.

Migraine association and linkage studies of an endothelial nitric oxide synthase (NOS3) gene polymorphism

Migraine shows strong familial aggregation. However, the number of genes involved in the disorder is unknown and not identified. Nitric oxide is involved in the central processing of pain stimuli and plays an important role in the regulation of basal or stimulated vasodilation. Nitric oxide synthase, which controls the synthesis of nitric oxide, could possibly be a cause, or candidate gene, in migraine etiology. In this study, we detected a polymorphism for endothelial nitric oxide synthase by polymerase chain reaction and tested this for association and linkage to migraine. Results from the study did not show an association of the nitric oxide synthase microsatellite when tested in 91 affected and 85 unaffected individuals. Using the FASTLINK program for parametric linkage analysis, the polymorphism did not show significant linkage to migraine when tested in four migraine pedigrees composed of 116 individuals, 52 affected. Total LOD scores excluded linkage up to 8.5 cM between the nitric oxide synthase polymorphism and migraine. Results using the nonparametric affected pedigree member form of analysis also did not support a role for this gene in migraine etiology.

Lateral impact response and parametric studies of axially loaded square concrete filled steel tube columns

This paper presents a numerical study on the response of axially loaded slender square concrete filled steel tube (CFST) columns under low velocity lateral impact loading. A finite element analysis (FEA) model was developed using the explicit dynamic nonlinear finite element code LS -DYNA in which the strain rate effects of both steel and concrete, contact between steel tube and concrete and confinement effect provided by the steel tube for the concrete were considered. The model also benefited from a relatively recent feature of LS-DYNA for applying a pre-loading in the explicit solver. The developed numerical model was verified for its accuracy and adequacy by comparing the results with experimental results available in the literature. The verified model was then employed to conduct a parametric study to investigate the influence of axial load level, impact location, support conditions, and slenderness ratio on the response of the CFST columns. A good agreement between the numerical and experimental results was achieved. The model could reasonably predict the impact load-deflection history and deformed shape of the column at the end of the impact event. The results of the parametric study showed that whilst impact location, axial load level and slenderness ratio can have a significant effect on the peak impact force, residual lateral deflection and maximum lateral deflection, the influence of support fixity is minimal. With an increase of axial load to up to a certain level, the peak force increases; however, a further increase in the axial load causes a decrease in the peak force. Both residual lateral deflection and maximum lateral deflection increase as axial load level increases. Shifting the impact location towards the supports increases the peak force and reduces both residual and maximum lateral deflections. A rise in slenderness ratio decreases the peak force and increases the residual and maximum lateral deflections.