Carbon-carbon bond formation methods for the preparation of shape-persistent architectures

Carbon-rich, conjugated organic scaffolding is a popular basis for functional materials, especially for electronic and photonic applications. However, synthetic methods for generating these types of materials lack diversity and, in many cases, efficiency; the insistence of investigators focusing on the properties of the end product, rather than the process in which it was created, has led to the current state of the relatively homogeneous synthetic chemistry of functional organic materials. Because of this, there is plenty of room for improvement at the most basic level. Problems endemic to the preparation of carbon-rich scaffolding can, in many cases, be solved with modern advances in synthetic methodology. We seek to apply this synthesis-focused paradigm to solve problems in the preparation of carbon-rich scaffolds. Herein, the development and utilization of three methodologies: iridium-catalyzed arene C-H borylation; zinc- mediated alkynylations; and Lewis acid promoted Mo nitride-alkyne metathesis, are presented as improvements for the preparation of carbon-rich architectures. In addition, X-ray crystallographic analysis of two classes of compounds are presented. First, an analysis of carbazole-containing arylene ethynylene macrocycles showcases the significance of alkyl chain identity on solid-state morphology. Second, a class of rigid zwitterionic metal-organic compounds display an unusual propensity to crystallize in the absence of inversion symmetry. Hirshfeld surface analysis of these crystalline materials demonstrates that subtle intermolecular interactions are responsible for the overall packing motifs in this class of compounds.

Análise mecânica e microestrutural das ligas de cobalto-cromo de uso odontológico após sucessivas refundições

The cobalt-chromium alloy is extensively used in the Odontology for the confection of metallic scaffolding in partial removable denture. During the last few years, it has been reported an increasing number of premature imperfections, with a few months of prosthesis use. The manufacture of these components is made in prosthetic laboratories and normally involves recasting, using parts of casting alloy and parts of virgin alloy. Therefore, the objective of the present study was to analyze the mechanical properties of a commercial cobalt-chromium alloy of odontological use after successive recasting, searching information to guide the dental prosthesis laboratories in the correct manipulation of the cobalt-chromium alloy in the process of casting and the possible limits of recasting in the mechanical properties of this material. Seven sample groups were confectioned, each one containing five test bodies, divided in the following way: G1: casting only with virgin alloy; G2: casting with 50% of the alloy of the G1 + 50% of virgin alloy; G3: casting with 50% of the alloy of the G2 + 50% of virgin alloy; G4: casting with 50% of the alloy of the G3 + 50% of virgin alloy; G5: 50% of alloy of the G4 + 50% of virgin alloy; G6: 50% of alloy of the G5 + 50% of virgin alloy and finally the G7, only with recasting alloy. The modifications in the mechanical behavior of the alloy were evaluated. Moreover, it was carried the micro structural characterization of the material by optic and electronic scanning microscopy, and X ray diffraction.and fluorescence looking into the correlatation of the mechanical alterations with structural modifications of the material caused by successive recasting process. Generally the results showed alterations in the fracture energy of the alloy after successive recasting, resulting mainly of the increasing presence of pores and large voids, characteristic of the casting material. Thus, the interpretation of the results showed that the material did not reveal significant differences with respect to the tensile strength or elastic limit, as a function of successive recasting. The elastic modulus increased from the third recasting cycle on, indicating that the material can be recast only twice. The fracture energy of the material decreased, as the number of recasting cycles increased. With respect to the microhardness, the statistical analyses showedno significant differences. Electronic scanning microscopy revealed the presence of imperfections and defects, resulting of the recasting process. X ray diffraction and fluorescence did not show alterations in the composition of the alloy or the formation of crystalline phases between the analyzed groups. The optical micrographs showed an increasing number of voids and porosity as the material was recast. Therefore, the general conclusion of this study is that the successive recasting of of Co-Cr alloys affects the mechanical properties of the material, consequently leading to the failure of the prosthetic work. Based on the results, the best recommendadition is that the use of the material should be limited to two recasting cycles

Biochemical studies of postsynaptic density signaling proteins with a focus on synaptic GTPase activating protein and PDZ domains

<p>Memory storage in the brain involves adjustment of the strength of existing synapses and formation of new neural networks. A key process underlying memory formation is synaptic plasticity, the ability of excitatory synapses to strengthen or weaken their connections in response to patterns of activity between their connected neurons. Synaptic plasticity is governed by the precise pattern of Ca&#178;&#8314; influx through postsynaptic N-methyl-D-aspartate-type glutamate receptors (NMDARs), which can lead to the activation of the small GTPases Ras and Rap. Differential activation of Ras and Rap acts to modulate synaptic strength by promoting the insertion or removal of 2-amino-3-(3-hydroxy-5-methyl-isoxazol-4-yl)propanoic acid receptors (AMPARs) from the synapse. Synaptic GTPase activating protein (synGAP) regulates AMPAR levels by catalyzing the inactivation of GTP-bound (active) Ras or Rap. synGAP is positioned in close proximity to the cytoplasmic tail regions of the NMDAR through its association with the PDZ domains of PSD-95. SynGAP’s activity is regulated by the prominent postsynaptic protein kinase, Ca&#178;&#8314;/calmodulin-dependent protein kinase II (CaMKII) and cyclin-dependent kinase 5 (CDK5), a known binding partner of CaMKII. Modulation of synGAP’s activity by phosphorylation may alter the ratio of active Ras to Rap in spines, thus pushing the spine towards the insertion or removal of AMPARs, subsequently strengthening or weakening the synapse. To date, all biochemical studies of the regulation of synGAP activity by protein kinases have utilized impure preparations of membrane bound synGAP. Here we have clarified the effects of phosphorylation of synGAP on its Ras and Rap GAP activities by preparing and utilizing purified, soluble recombinant synGAP, Ras, Rap, CaMKII, CDK5, PLK2, and CaM. Using mass spectrometry, we have confirmed the presence of previously identified CaMKII and CDK5 sites in synGAP, and have identified novel sites of phosphorylation by CaMKII, CDK5, and PLK2. We have shown that the net effect of phosphorylation of synGAP by CaMKII, CDK5, and PLK2 is an increase in its GAP activity toward HRas and Rap1. In contrast, there is no effect on its GAP activity toward Rap2. Additionally, by assaying the GAP activity of phosphomimetic synGAP mutants, we have been able to hypothesize the effects of CDK5 phosphorylation at specific sites in synGAP. In the course of this work, we also found, unexpectedly, that synGAP is itself a Ca&#178;&#8314;/CaM binding protein. While Ca&#178;&#8314;/CaM binding does not directly affect synGAP activity, it causes a conformational change in synGAP that increases the rate of its phosphorylation and exposes additional phosphorylation sites that are inaccessible in the absence of Ca&#178;&#8314;/CaM.</p> <p>The postsynaptic density (PSD) is an electron-dense region in excitatory postsynaptic neurons that contains a high concentration of glutamate receptors, cytoskeletal proteins, and associated signaling enzymes. Within the PSD, three major classes of scaffolding molecules function to organize signaling enzymes and glutamate receptors. PDZ domains present in the Shank and PSD-95 scaffolds families serve to physically link AMPARs and NMDARs to signaling molecules in the PSD. Because of the specificity and high affinity of PDZ domains for their ligands, I reasoned that these interacting pairs could provide the core components of an affinity chromatography system, including affinity resins, affinity tags, and elution agents. I show that affinity columns containing the PDZ domains of PSD-95 can be used to purify active PDZ domain-binding proteins to very high purity in a single step. Five heterologously expressed neuronal proteins containing endogenous PDZ domain ligands (NMDAR GluN2B subunit Tail, synGAP, neuronal nitric oxide synthase PDZ domain, cysteine rich interactor of PDZ three and cypin) were purified using PDZ domain resin, with synthetic peptides having the sequences of cognate PDZ domain ligands used as elution agents. I also show that conjugation of PDZ domain-related affinity tags to Proteins Of Interest (POIs) that do not contain endogenous PDZ domains or ligands does not alter protein activity and enables purification of the POIs on PDZ domain-related affinity resins.</p>

Building a local design and entrepreneurship ecosystem

Design and creativity are becoming greatly sought out skills in leading industries around the world, big businesses are developing the &ldquo;Chief Design Officer&rdquo; to engage with strategic and company shaping discussions. Design as an economic driver is now abundantly clear with companies such as Nike and Apple leading this way of thinking, but how do we as Australian industry capture this and how do we instil &ldquo;creativity&rdquo; into our secondary school and university level education to drive the next level of innovation and development. The local region where Deakin University is situated has undergone significant changes in the last 10 years, what was once an economy dominated by oil, automotive and metal production industries has been wound down to a local economy dominated by health, services and education. However, manufacturing and design being the front end of manufacturing is still a key economic driver this study is looking at the embryonic initiatives undertaken to build an ecosystem of design and entrepreneurship in a regional area. Several aspects will be looked at, high school and university student engagement in the process, established SME's and start-up culture. With the establishment of an ecosystem it is believed that success will breed success. With student engagement showing that being creative and playing can yield tangible results, it also gets students comfortable with the element of risk. The efforts of Deakin University is about providing the framework and scaffolding for students to pursue a start-up idea and test it validity. The final part of the ecosystem is for SME's and recent start-ups to share their success stories and acting as mentors as future start-ups emerge. By creating an ecosystem that is driven by design, manufacturing and entrepreneurship key economic outcomes will be generated; a regional area will be more resilient to economic uncertainty and ultimately a cohort of innovative thinkers that will generate value for their community.

Transforming roles to support student development of academic literacies: a reflection on one team’s experience

Abstract: Social work is a discipline that attracts students from diverse academic backgrounds. Many are first in family to attend university, and come to university through alternative pathways such as vocational education. As a result, there are higher levels of attrition compared to other disciplines, especially in the first year. To address this, and in keeping with a commitment to provide accessible education, one school of social work undertook a project to embed academic literacies into the curriculum. This paper used Gibb&rsquo;s reflective process to explore how this was experienced by team members. Data were collected via staff focus groups at two different points in time across the project and compared. The reflection unpacked a number of tensions experienced by team members, including concerns about potential loss of resources as a result of academics adopting new roles, and concerns about implementing what was seen as Westernised academic skills which may not fit with students&rsquo; ways of thinking and creating knowledge. Overfull curricula and constant change also appeared to be of concern. The reflection highlighted that to achieve effective and sustainable change, action was required at multiple levels.

Boron nitride nanotube films: preparation, properties, and implications for biology applications

The difference in the chemical and physical properties of boron nitride nanotube (BNNT) films and carbon nanotube (CNT) films can benefit tissue scaffolding and engineering. However, the production of dense films of pure BNNTs is more challenging than that of CNT films. In addition, BNNT films are usually extremely nonwettable to water, so surface modification is required before they can be used in bioapplications. In this chapter, the synthesis routes of high-density BNNT films are introduced, followed by their wettability properties and surface modification by plasma treatments. The cell proliferation on both pristine and wettability-modified BNNT films is discussed.

Investigating the effects of cognitive apprenticeship-based instructional coaching on science teaching efficacy beliefs

The overall purpose of this collected papers dissertation was to examine the utility of a cognitive apprenticeship-based instructional coaching (CAIC) model for improving the science teaching efficacy beliefs (STEB) of preservice and inservice elementary teachers. Many of these teachers perceive science as a difficult subject and feel inadequately prepared to teach it. However, teacher efficacy beliefs have been noted as the strongest indicator of teacher quality, the variable most highly correlated with student achievement outcomes. The literature is scarce on strong, evidence-based theoretical models for improving STEB.^ This dissertation is comprised of two studies. STUDY #1 was a sequential explanatory mixed-methods study investigating the impact of a reformed CAIC elementary science methods course on the STEB of 26 preservice teachers. Data were collected using the Science Teaching Efficacy Belief Instrument (STEBI-B) and from six post-course interviews. A statistically significant increase in STEB was observed in the quantitative strand. The qualitative data suggested that the preservice teachers perceived all of the CAIC methods as influential, but the significance of each method depended on their unique needs and abilities. ^ STUDY #2 was a participatory action research case study exploring the utility of a CAIC professional development program for improving the STEB of five Bahamian inservice teachers and their competency in implementing an inquiry-based curriculum. Data were collected from pre- and post-interviews and two focus group interviews. Overall, the inservice teachers perceived the intervention as highly effective. The scaffolding and coaching were the CAIC methods portrayed as most influential in developing their STEB, highlighting the importance of interpersonal relationship aspects in successful instructional coaching programs. The teachers also described the CAIC approach as integral in supporting their learning to implement the new inquiry-based curriculum. ^ The overall findings hold important implications for science education reform, including its potential to influence how preservice teacher training and inservice teacher professional development in science are perceived and implemented. Additionally, given the noteworthy results obtained over the relatively short durations, CAIC interventions may also provide an effective means of achieving improvements in preservice and inservice teachers’ STEB more expeditiously than traditional approaches.^

Samhällskunskapens dimensioner : Tio lärare ramar in sitt ämne

Denna samhällskunskapsdidaktiska studies syfte är att undersöka vad samhällskunskapslärare själva upplever som de viktigaste påverkansfaktorerna för transformeringen av samhällskunskap som skolämne till samhällskunskap som undervisning utifrån didaktiska frågor som Vad?, Hur? och Varför?, samt hur detta upplevs förändrats över en tidsperiod om cirka tjugo år eller mer. Studien bygger på hermeneutisk-fenomenologisk livsvärldsansats där fenomenologisk beskrivning och hermeneutisk tolkning är centralt. Empirin utgörs av intervjuer med tio samhällskunskapslärare med lång yrkeserfarenhet från högstadium, gymnasium eller vuxenutbildning. Resultatet tematiseras utifrån inspiration från ramfaktorteoretiska utgångspunkteri fyra dimensioner av påverkansfaktorer, vilka är Den personliga dimensionen, Den didaktiska dimensionen, Den styrande dimensionen och Den samhälleliga dimensionen. Var och en av dessa dimensioner delas upp i ett antal variationer. Dimensionerna är konstruerade utifrån principen om det personligt nära till det samhälleligt distanserade. Utöver dessa dimensioner har en aspekt på dessa lagts till. Det är Den elevnära aspekten vars innehåll utgörs av eleverna som påverkansfaktor för hur undervisningen blir. Lärarna i studien pratar aldrig om eleverna som påverkansfaktor utan att koppla detta till någon av de fyra dimensionerna. Slutsatser som dras i studien är att de tio lärarna alla har mycket olika berättelserom vad de uppfattar som viktigaste påverkansfaktorer. Några lägger mest fokus på sin personliga bakgrund eller personliga intressen. Andra fokuserar mer på didaktiska idéer, på styrdokument eller på organisatoriska ramar. Studien visar också att lärarna alla har en eller ett par dominerande dimensioner som dels syns mest i berättelsen, dels också påverkar hur de pratar om de andra dimensionerna. Lärarnas berättelser visar även att de upplever att undervisningen och vad som påverkar denna påtagligt förändras över tid. Studiens viktigaste bidrag är kanske att den exemplifierar teoretiska perspektiv. Inte minst genom att belysa att vad som påverkar undervisningen i ett ämne är så komplext att den ramfaktorteoretiska byggnadsställningen måste anpassas efter den specifika undersökningen med dess frågeställningar och undersökningsmaterial.

Convergent evolution of PICIs-mediated phage interference

Staphylococcal pathogenicity islands (SaPIs), the prototype members of the family of phage inducible chromosomal islands (PICIs), are extremely mobile phage satellites, which are transferred between bacterial hosts after their induction by a helper phage. The intimate relationship between SaPIs and their helper phages is one of the most studied examples of virus satellite interactions in prokaryotic cells. SaPIs encode and disseminate virulence and fitness factors, representing a driving force for bacterial adaptation and pathogenesis. Many SaPIs encode a conserved morphogenetic operon, including a core set of genes whose function allows them to parasitize and exploit the phage life cycle. One of the central mechanisms of this molecular piracy is the specific packaging of the SaPI genomes into reduced sized capsid structures derived from phage proteins. Pac phages were classically thought to be the only phages involved in the mobilisation of phage-mediated virulence genes, including the transfer of SaPIs within related and non-related bacteria. This study presents the involvement of S. aureus cos phages in the intra- and intergeneric transfer of cos SaPIs for the first time. A novel example of molecular parasitism is shown, by which this newly characterised group of cos SaPIs uses two distinct and complementary mechanisms to take over the helper phage packaging machinery for their own reproduction. SaPIbov5, the prototype of the cos SaPIs, does not encode the characteristic morphogenetic operon found in pac SaPIs. However, cos SaPIs features both pac and cos phage cleavage sequences in their genome, ensuring SaPI packaging in small- and full-sized phage particles, depending on the helper phage. Moreover, cos-site packaging in S. aureus was shown to require the activity of a phage HNH nuclease. The HNH protein functions together with the large terminase subunit, triggering cleavage and melting of the cos-site sequence. In addition, a novel piracy strategy, severely interfering with the helper phage reproduction, was identified in cos SaPIs and characterised. This mechanism of piracy depends on the cos SaPI-encoded ccm gene, which encodes a capsid protein involved in the formation of small phage particles, modifying the assembling process via a scaffolding mechanism. This strategy resembles the ones described for pac SaPIs and represents a remarkable example of convergent evolution. A further convergent mechanism of capsid size-reduction was identified and characterised for the Enterococcus faecalis EfCIV583 pathogenicity island, another member of the PICI family. In this case, the self-encoded CpmE conducts this molecular piracy through a putative scaffolding function. Similar to cos SaPIs, EfCIV583 carries the helper phage cleavage sequence in its genome enabling its mobilisation by the phage terminase complex. The results presented in this thesis show how two examples of non-related members of the PICI family follow the same evolutionary convergent strategy to interfere with their helper phage. These findings could indicate that the described strategies might be widespread among PICIs and implicate a significant impact of PICIs mediated-virulence gene transfer in bacterial evolution and the emergence of pathogenic bacteria.

Follicular dendritic cell disruption as a novel mechanism of virus-induced immunosuppression

Arboviruses (Arthropod-borne viruses) cause acute diseases that are increasingly affecting both human and animal health. Currently, there is a critical lack of understanding about the nature of arbovirus-host interactions in the lymph nodes (LNs), the place where the adaptive immune response is initiated and shaped. In this study, we used bluetongue virus (BTV) and its natural sheep host, to characterise the early events of an arbovirus infection with particular focus on the LNs. Our findings reveal a previously uncharacterized mechanism used by an arbovirus to manipulate host immunity. This study shows that BTV, similarly to other antigens delivered through the skin, is transported rapidly via the lymph to the peripheral lymph nodes. Here, BTV infects and disrupts the stromal network of marginal reticular cells and follicular dendritic cells composing the scaffolding of the follicular area. These cells contribute to antigen presentation and affinity maturation of B-cells for the production of antibodies. Consequently, we observed a loss of germinal centre structure, which hinders B-cell proliferation. This process results in a delayed production of high affinity and virus neutralizing antibodies that is directly related to the virulence of the BTV strain used and the severity of disease. Moreover the humoral immune response to a different antigen is also hampered in BTV-infected animals. Our data show that an arbovirus can evade the host antiviral responses by inducing an acute immunosuppression. Although transient, this immunosuppression occurs at the critical early stages of infection when a delayed host humoral immune response likely affects virus systemic dissemination and the clinical outcome of disease.