Homo- and heteronuclear meso,meso-(E)-Ethene-1,2-diyl-Linked Diporphyrins : preparation, X-ray crystal structure, electronic absorption and emission spectra and density functional theory calculations

Homo-and heteronuclear meso,meso-(E)-ethene-1,2-diyl-linked diporphyrins have been prepared by the Suzuki coupling of porphyrinylboronates and iodovinylporphyrins. Combinations comprising 5,10,15-triphenylporphyrin (TriPP) on both ends of the ethene-1,2-diyl bridge M 210 (M 2=H 2/Ni, Ni 2, Ni/Zn, H 4, H 2Zn, Zn 2) and 5,15-bis(3,5-di-tert-butylphenyl)porphyrinato-nickel(II) on one end and H 2, Ni, and ZnTriPP on the other (M 211), enable the first studies of this class of compounds possessing intrinsic polarity. The compounds were characterized by electronic absorption and steady state emission spectra, 1H NMR spectra, and for the Ni 2 bis(TriPP) complex Ni 210, single crystal X-ray structure determination. The crystal structure shows ruffled distortions of the porphyrin rings, typical of Ni II porphyrins, and the (E)-C 2H 2 bridge makes a dihedral angle of 50° with the mean planes of the macrocycles. The result is a stepped parallel arrangement of the porphyrin rings. The dihedral angles in the solid state reflect the interplay of steric and electronic effects of the bridge on interporphyrin communication. The emission spectra in particular, suggest energy transfer across the bridge is fast in conformations in which the bridge is nearly coplanar with the rings. Comparisons of the fluorescence behaviour of H 410 and H 2Ni10 show strong quenching of the free base fluorescence when the complex is excited at the lower energy component of the Soret band, a feature associated in the literature with more planar conformations. TDDFT calculations on the gas-phase optimized geometry of Ni 210 reproduce the features of the experimental electronic absorption spectrum within 0.1 eV. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mesoporous bioactive glass scaffolds for efficient delivery of vascular endothelial growth factor

In this article, we, for the first time, investigated mesoporous bioactive glass scaffolds for the delivery of vascular endothelial growth factor. We have found that mesoporous bioactive glass scaffolds have significantly higher loading efficiency and more sustained release of vascular endothelial growth factor than non-mesoporous bioactive glass scaffolds. In addition, vascular endothelial growth factor delivery from mesoporous bioactive glass scaffolds has improved the viability of endothelial cells. The study has suggested that mesopore structures in mesoporous bioactive glass scaffolds play an important role in improving the loading efficiency, decreasing the burst release, and maintaining the bioactivity of vascular endothelial growth factor, indicating that mesoporous bioactive glass scaffolds are an excellent carrier of vascular endothelial growth factor for potential bone tissue engineering applications.

Strontium-containing mesoporous bioactive glass scaffolds with improved osteogenic/cementogenic differentiation of periodontal ligament cells for periodontal tissue engineering

To achieve the ultimate goal of periodontal tissue engineering, it is of great importance to develop bioactive scaffolds which could stimulate the osteogenic/cementogenic differentiation of periodontal ligament cells (PDLCs) for the favorable regeneration of alveolar bone, root cementum, and periodontal ligament. Strontium (Sr) and Sr-containing biomaterials have been found to induce osteoblast activity. However, there is no systematic report about the interaction between Sr or Sr-containing biomaterials and PDLCs for periodontal tissue engineering. The aims of this study were to prepare Sr-containing mesoporous bioactive glass (Sr-MBG) scaffolds and investigate whether the addition of Sr could stimulate the osteogenic/cementogenic differentiation of PDLCs in tissue engineering scaffold system. The composition, microstructure and mesopore properties (specific surface area, nano-pore volume and nano-pore distribution) of Sr-MBG scaffolds were characterized. The proliferation, alkaline phosphatase (ALP) activity and osteogenesis/cementogenesis-related gene expression (ALP, Runx2, Col I, OPN and CEMP1) of PDLCs on different kinds of Sr-MBG scaffolds were systematically investigated. The results show that Sr plays an important role in influencing the mesoporous structure of MBG scaffolds in which high contents of Sr decreased the well-ordered mesopores as well as their surface area/pore volume. Sr2+ ions could be released from Sr-MBG scaffolds in a controlled way. The incorporation of Sr into MBG scaffolds has significantly stimulated ALP activity and osteogenesis/cementogenesis-related gene expression of PDLCs. Furthermore, Sr-MBG scaffolds in simulated body fluids environment still maintained excellent apatite-mineralization ability. The study suggests that the incorporation of Sr into MBG scaffolds is a viable way to stimulate the biological response of PDLCs. Sr-MBG scaffolds are a promising bioactive material for periodontal tissue engineering application.

3D-printing of highly uniform CaSiO3 ceramic scaffolds : preparation, characterization and in vivo osteogenesis

Calcium silicate (CaSiO3, CS) ceramics have received significant attention for application in bone regeneration due to their excellent in vitro apatite-mineralization ability; however, how to prepare porous CS scaffolds with a controllable pore structure for bone tissue engineering still remains a challenge. Conventional methods could not efficiently control the pore structure and mechanical strength of CS scaffolds, resulting in unstable in vivo osteogenesis. The aim of this study is to set out to solve these problems by applying a modified 3D-printing method to prepare highly uniform CS scaffolds with controllable pore structure and improved mechanical strength. The in vivo osteogenesis of the prepared 3D-printed CS scaffolds was further investigated by implanting them in the femur defects of rats. The results show that the CS scaffolds prepared by the modified 3D-printing method have uniform scaffold morphology. The pore size and pore structure of CS scaffolds can be efficiently adjusted. The compressive strength of 3D-printed CS scaffolds is around 120 times that of conventional polyurethane templated CS scaffolds. 3D-Printed CS scaffolds possess excellent apatite-mineralization ability in simulated body fluids. Micro-CT analysis has shown that 3D-printed CS scaffolds play an important role in assisting the regeneration of bone defects in vivo. The healing level of bone defects implanted by 3D-printed CS scaffolds is obviously higher than that of 3D-printed b-tricalcium phosphate (b-TCP) scaffolds at both 4 and 8 weeks. Hematoxylin and eosin (H&E) staining shows that 3D-printed CS scaffolds induce higher quality of the newly formed bone than 3D-printed b-TCP scaffolds. Immunohistochemical analyses have further shown that stronger expression of human type I collagen (COL1) and alkaline phosphate (ALP) in the bone matrix occurs in the 3D-printed CS scaffolds than in the 3D-printed b-TCP scaffolds. Considering these important advantages, such as controllable structure architecture, significant improvement in mechanical strength, excellent in vivo osteogenesis and since there is no need for second-time sintering, it is indicated that the prepared 3D-printed CS scaffolds are a promising material for application in bone regeneration.

Preparation, characterization and in vitro angiogenic capacity of cobalt substituted β-tricalcium phosphate ceramics

Divalent cobalt ions (Co2+) have been shown to possess the capacity to induce angiogenesis by activating hypoxia inducible factor-1α (HIF-1α) and subsequently inducing the production of vascular endothelial growth factor (VEGF). However, there are few reports about Co-containing biomaterials for inducing in vitro angiogenesis. The aim of the present work was to prepare Co-containing β-tricalcium phosphate (Co-TCP) ceramics with different contents of calcium substituted by cobalt (0, 2, 5 mol%) and to investigate the effect of Co substitution on their physicochemical and biological properties. Co-TCP powders were synthesized by a chemistry precipitation method and Co-TCP ceramics were prepared by sintering the powder compacts. The effect of Co substitution on phase transition and the sintering property of the β-TCP ceramics was investigated. The proliferation and VEGF expression of human bone marrow mesenchymal stem cells (HBMSCs) cultured with both powder extracts and ceramic discs of Co-TCP was further evaluated. The in vitro angiogenesis was evaluated by the tube-like structure formation of human umbilical vein endothelial cells (HUVECs) cultured on ECMatrix™ in the presence of powder extracts. The results showed that Co substitution suppressed the phase transition from β- to α-TCP. Both the powder extracts and ceramic discs of Co-TCP had generally good cytocompatibility to support HBMSC growth. Importantly, the incorporation of Co into β-TCP greatly stimulated VEGF expression of HBMSCs and Co-TCP showed a significant enhancement of network structure formation of HUVECs compared with pure TCP. Our results suggested that the incorporation of Co into bioceramics is a potential viable way to enhance angiogenic properties of biomaterials. Co-TCP bioceramics may be used for bone tissue regeneration with improved angiogenic capacity.

Becoming Partners: Partnerships reshaping preservice teachers’ preparation to teach in rural Queensland schools

Preparing preservice teachers for successful rural and remote teaching is an ongoing and significant issue that impacts on equity issues for Australian students (Sharplin, 2002) and the sustainability of rural communities (Green & Reid, 2004). Improving the preparation of preservice teachers for teaching in rural schools is a key recommendation from the Human Rights and Equal Opportunity Commission (2000). This presentation analyses how an innovative partnership between a teacher employer and a teacher education institution as a response to a mandated reform within the Improving Teacher Quality National Partnership Agreement has been established to address the important need to prepare and recruit preservice teachers to teach in rural and remote areas of Queensland.

Preparation, characterization, and in vitro bioactivity of nagelschmidtite bioceramics

The aim of this study is to prepare Ca, P and Si-containing ternary oxide nagelschmidtite (NAGEL, Ca7Si2P2O16) bioceramics and explore their in vitro bioactivity for potential bone tissue regeneration. We prepared dense NAGEL ceramics through high-temperature sintering of NAGEL ceramic powders. The apatite-mineralization ability, dissolution rate, and human osteoblast response (including cytotoxicity analysis, attachment, morphology, proliferation, and bone-related gene expression) to NAGEL ceramics have been systematically studied by comparing with conventional β-tricalcium phosphate (β-TCP) ceramics. The results showed that NAGEL ceramics possessed more obvious apatite mineralization and dissolution (degradation) and stimulated bone-related gene expression (OCN and OPN) of osteoblasts than β-TCP ceramics. NAGEL ceramics also showed no significant cytotoxicity. NAGEL ceramics supported osteoblast attachment, proliferation, and osteogenic gene expression, with a comparable cell proliferation activity with β-TCP ceramics. These results indicate that novel NAGEL bioceramics with the specific composition of Ca7Si2P2O16, are a promising biomaterial for bone tissue regeneration application.

Copper-containing mesoporous bioactive glass scaffolds with multifunctional properties of angiogenesis capacity, osteostimulation and antibacterial activity

It is of great importance to develop multifunctional bioactive scaffolds, which combine angiogenesis capacity, osteostimulation, and antibacterial properties for regenerating lost bone tissues. In order to achieve this aim, we prepared copper (Cu)-containing mesoporous bioactive glass (Cu-MBG) scaffolds with interconnective large pores (several hundred micrometer) and well-ordered mesopore channels (around 5 nm). Both Cu-MBG scaffolds and their ionic extracts could stimulate hypoxia-inducible factor (HIF)-1a and vascular endothelial growth factor(VEGF) expression in human bone marrow stromal cells(hBMSCs). In addition, both Cu-MBG scaffolds and their ionic extracts significantly promoted the osteogenic differentiation of hBMSCs by improving their bone-related gene expression (alkaline phosphatase (ALP), osteopontin(OPN) and osteocalcin (OCN)). Furthermore, Cu-MBG scaffolds could maintain a sustained release of ibuprofen and significantly inhibited the viability of bacteria. This study indicates that the incorporation of Cu2þ ions into MBG scaffolds significantly enhances hypoxia-like tissue reaction leading to the coupling of angiogenesis and osteogenesis. Cu2þ ions play an important role to offer the multifunctional properties of MBG scaffold system. This study has demonstrated that it is possible to develop multifunctional scaffolds by combining enhanced angiogenesis potential, osteostimulation, and antibacterial properties for the treatment of large bone defects.

Hamlet through the looking glass : Rosencrantz and Guildenstern are dead

The film adaptation of "Rosencrantz and Guildenstern Are Dead"'s constant reallocation of actor and audience roles (or subject and object positions) means that the film’s viewers are as deeply implicated in considering issues of identity, agency and determination as Rosencrantz and Guildenstern are. Tellingly, one of The Player’s outbursts reveals the philosophical connections between observing and being observed in ways that are true of the theatre, but which also transcend it: ‘You don’t understand the humiliation of it. To be tricked out of the single assumption that makes our existence bearable; that somebody is watching.’ In this statement is one of the film’s main concerns; that is, the relationship between knowing the self, knowing others, and being known by others.

Exploration and reflection in interactive art : glass pond

Glass Pond is an interactive artwork designed to engender exploration and reflection through an intuitive, tangible interface and a simulation agent. It is being developed using iterative methods. A study has been conducted with the aim of illuminating user experience, interface, design, and performance issues.The paper describes the study methodology and process of data analysis including coding schemes for cognitive states and movements. Analysis reveals that exploration and reflection occurred as well as composing behaviours (unexpected). Results also show that participants interacted to varying degrees. Design discussion includes the artwork's (novel) interface and configuration.

Subliquidus glass-glass immiscibility along the albite-diopside join

A calorimetric study has shown that glasses along the albite-diopside join in the system albiteanorthite-diopside have positive enthalpies of mixing. Thermodynamic calculations based on these data describe a nearly symmetric, metastable, subliquidus irascibility gap along the join with a critical temperature at 910 K. The existence of the miscibility gap was tested experimentally by annealing an Ab50Di50 glass at 748 K and 823 K. Annealed glasses were examined by optical microscopy and by scanning and transmission electron microscopy. The glasses showed morphological and chemical features consistent with unmixing of two glass phases. The apparent mechanism of phase separation involves initial spinodal decomposition followed by coarsening to produce 0.1 μm–0.3 μm spherical glass phases.

Reforming the preparation of future STEM teachers

This paper begins by identifying the key attributes for future STEM teachers. Then based on a review of the literature, a framework for informing reforms to pre-service teacher education programs to facilitate the development of these attributes in future STEM teachers is presented and discussed. This framework consists of a set of three principles together with eight strategies for the operationalization of these principles. During the discussion, the implications for the structure and implementation of future pre-service STEM teacher education programs are explored.

Preservice teachers’ perceptions of their middle schooling teacher preparation : a sample of the Australian context

Reviews into teacher education and reform measures, such as implementing professional standards for teachers, are designed to raise the quality of education. Such reviews and reforms also target preservice teachers; hence universities examine their teacher education programs to address these issues, including developing programs that are current with the literature. Over the past fifteen years, concerns have arisen about Australian early adolescents and their disengagement from the schooling system, their “at risk” behaviour and their need for social, emotional and academic support. These concerns have prompted a middle schooling movement in Australia with the literature recognising a need for specialised middle school teachers. As a result, various universities have responded by developing courses specifically designed to graduate teachers who possess the theoretical and pedagogical knowledge for engaging early adolescent learners. This mixed-method study analysed the responses of preservice teachers from three universities across two states in Australia near the completion of their middle years teacher preparation program. The three aims of the study were to: (1) investigate final-year preservice teachers’ perceptions of their confidence to teach in the middle years of schooling; (2) analyse the experiences included in their teacher preparation course that made them feel confident; and (3) describe strategies for enhancing middle schooling teacher education preparation. Data were gathered from final-year preservice teachers (n=142) using a survey that was developed in response to middle schooling literature and the Professional Standards for Queensland Teachers (Queensland College of Teachers, 2006). A questionnaire collected extended information about the participants’ (n=142) experiences that made them feel confident. It also gathered information about strategies for enhancing middle years teacher preparation. One-to-one, 45-minute interviews (n=10) were conducted to elicit in-depth responses aligned with the research aims. Quantitative results indicated that the majority of preservice teachers (n=142) claimed confidence associated with survey items relating to creating a positive classroom environment (range: 70-97%), developing positive relationships for teaching (71-98%), pedagogical knowledge for teaching (72-95%), and implementation of teaching (70-91%). Qualitative findings suggested that the experiences that assisted them to be confident for teaching were practicum and associated field studies coursework, a positive mentor teacher, specifically designed middle years subjects, the pedagogical approaches of university staff, and other real-world experiences such as volunteering in schools and participating in professional development alongside their mentors. This study demonstrated that universities presenting middle years teacher preparation need to consider: the quality of the practicum experience; the suitability of mentor teachers; the significance and practicalities of middle years subjects; university lecturers’ modelling of pedagogical practices; and the inclusion of real-world learning experiences. Although the findings of this study provided evidence as to how preservice teacher confidence for teaching has been influenced by their middle schooling teacher preparation, further research is required to investigate how confidence translates into practice within their first years of teaching.

Thermal performance of composite panels under fire conditions using numerical studies : plasterboards, rockwool, glass fibre and cellulose insulations

In recent times, light gauge steel frame (LSF) wall systems are increasingly used in the building industry. They are usually made of cold-formed and thin-walled steel studs that are fire-protected by two layers of plasterboard on both sides. A composite LSF wall panel system was developed recently, where an insulation layer was used externally between the two plasterboards to improve the fire performance of LSF wall panels. In this research, finite element thermal models of the new composite panels were developed using a finite element program, SAFIR, to simulate their thermal performance under both standard and Eurocode design fire curves. Suitable apparent thermal properties of both the gypsum plasterboard and insulation materials were proposed and used in the numerical models. The developed models were then validated by comparing their results with available standard fire test results of composite panels. This paper presents the details of the finite element models of composite panels, the thermal analysis results in the form of time-temperature profiles under standard and Eurocode design fire curves and their comparisons with fire test results. Effects of using rockwool, glass fibre and cellulose fibre insulations with varying thickness and density were also investigated, and the results are presented in this paper. The results show that the use of composite panels in LSF wall systems will improve their fire rating, and that Eurocode design fires are likely to cause severe damage to LSF walls than standard fires.