Numerical prediction of load-displacement behaviors of adhesively bonded joints at different extension rates and temperatures

The present work focuses on simulation of nonlinear mechanical behaviors of adhesively bonded DLS (double lap shear) joints for variable extension rates and temperatures using the implicit ABAQUS solver. Load-displacement curves of DLS joints at nine combinations of extension rates and environmental temperatures are initially obtained by conducting tensile tests in a UTM. The joint specimens are made from dual phase (DP) steel coupons bonded with a rubber-toughened adhesive. It is shown that the shell-solid model of a DLS joint, in which substrates are modeled with shell elements and adhesive with solid elements, can effectively predict the mechanical behavior of the joint. Exponent Drucker-Prager or Von Mises yield criterion together with nonlinear isotropic hardening is used for the simulation of DLS joint tests. It has been found that at a low temperature (-20 degrees C), both Von Mises and exponent Drucker-Prager criteria give close prediction of experimental load-extension curves. However. at a high temperature (82 degrees C), Von Mises condition tends to yield a perceptibly softer joint behavior, while the corresponding response obtained using exponent Drucker-Prager criterion is much closer to the experimental load-displacement curve.

‘The door creaked shut’: The new breach of bail offence for youth in Queensland

As part of the 2014 amendments to the Youth Justice Act 1992 (Qld) the previous Queensland government introduced a new breach of bail offence and a reverse onus provision in relation to the new offence. Also included in the raft of amendments was a provision removing the internationally accepted principle that, in relation to young offenders, detention should be used as ‘a last resort’. This article argues that these changes are likely to increase the entrenchment of young people within the criminal justice system.

Affective sensing + wearable imaging: Vision impairment and implications for spatial enquiry

Recent interest in affect and the body have mobilized a contemporary review of aesthetics and phenomenology within architecture to unpack how environments affect spatial experience. Emerging spatial studies within the neuro-sciences, and their implications for architectural research as raised by architectural theorists Juhani Pallasmaa (2014) and Harry Mallgrave (2013) has been well supported by a raft of scientists and institutions including the prestigious Salk Institute. Although there has been some headway in spatial studies of the vision impaired (Cattaneo et al, 2011) to understand the role of their non-visual systems in assisting navigation and location, little is discussed in terms of their other abilities in sensing particular qualities of space which impinge upon emotion. This paper reviews a collection of studies exploring face vision and echo-location, amongst others, which provide insight into what might be termed affective perception of the vision impaired, and how further interplay between this research and the architectural field can contribute new knowledge regarding space and affect. By engaging with themes from the Aesthetics, Phenomenology and indeed Neuro-science fields, the paper provides background of current and potential cross disciplinary research, and highlights the role wearable technologies can play in enhancing knowledge of affective spatial experience.

A taxonomic approach to understanding managerial ethical decision making approaches of clinically and non-clinically trained healthcare managers in Australia

Objective To understand differences in the managerial ethical decision-making styles of Australian healthcare managers through the exploratory use of the Managerial Ethical Profiles (MEP) Scale. Background Healthcare managers (doctors, nurses, allied health practitioners and non-clinically trained professionals) are faced with a raft of variables when making decisions within the workplace. In the absence of clear protocols and policies healthcare managers rely on a range of personal experiences, personal ethical philosophies, personal factors and organizational factors to arrive at a decision. Understanding the dominant approaches to managerial ethical decision-making, particularly for clinically trained healthcare managers, is a fundamental step in both increasing awareness of the importance of how managers make decisions, but also as a basis for ongoing development of healthcare managers. Design Cross-sectional. Methods The study adopts a taxonomic approach that simultaneously considers multiple ethical factors that potentially influence managerial ethical decision-making. These factors are used as inputs into cluster analysis to identify distinct patterns of influence on managerial ethical decision-making. Results Data analysis from the participants (n=441) showed a similar spread of the five managerial ethical profiles (Knights, Guardian Angels, Duty Followers, Defenders and Chameleons) across clinically trained and non-clinically trained healthcare managers. There was no substantial statistical difference between the two manager types (clinical and non-clinical) across the five profiles. Conclusion This paper demonstrated that managers that came from clinical backgrounds have similar ethical decision-making profiles to non-clinically trained managers. This is an important finding in terms of manager development and how organisations understand the various approaches of managerial decision-making across the different ethical profiles.

Fluorescent probe and NMR studies of the aggregation of bile salts in aqueous solution

The binding of the fluorescent probes 1-anilino-8-naphthalene sulfonate and dansyl cadaverine to the sodium salts of cholic, deoxycholic and dehydrocholic acids has been investigated. Enhanced probe solubilisation accompanies aggregation. Monitoring of fluorescence intensities as a function of bile salt concentration permits the detection of primary micelle formation, as well as secondary association. The transition concentrations obtained by fluorescence are in good agreement with values determined for the critical micelle concentrations, by other methods. Differences in the behaviour of cholate and deoxycholate have been noted. Fluorescence polarisation studies of 1,6-diphenyl-1,3,5-hexatriene solubilised in bile salt micelles suggest a higher microviscosity for the interior of the deoxycholate micelle as compared to cholate. 1H NMR studies of deoxycholate over the range 1–100 mg/ml suggest that micelle formation leads to a greater immobilisation of the C18 and C19 methyl groups as compared to the C21 methyl group. Well resolved 13C resonances are observed for all three steroids even at high concentration. Both fluorescence and NMR studies confirm that dehydrocholate does not aggregate.

Affective Sensing: Vision Impairment and Implications for Spatial Enquiry

Recent interest in affect and the body have mobilised a contemporary review of aesthetics and phenomenology within architecture to unpack how environments affect spatial experience. Emerging spatial studies within the neurosciences, and their implications for architectural research as raised by architectural theorists has been well supported by a raft of scientists and institutions. Although there has been some headway in spatial studies of the vision impaired (Cattaneo et al., 2011) to understand the role of their non-visual systems in assisting navigation and location, little is discussed in terms of their other abilities in sensing particular qualities of space which impinge upon emotion and wellbeing. This research explores, through published studies and constructed spatial interviews, the affective perception of the vision impaired and how further interplay between this research and the architectural field can contribute new knowledge regarding space and affect. The research aims to provide background of current and potential cross disciplinary research and highlight the role wearable technologies can play in enhancing knowledge of affective spatial experience.

Syntheses and Self-Assembling Characteristics of Amphiphilic Star Diblock Copolymers

Uusien polymeeripohjaisten teknologioiden ja materiaalien myötä räätälöityjen polymeerien tarve on kasvanut. Viime vuosituhannen lopussa kehitetyt kontrolloidut polymerointimenetelmät ovat avanneet uusia mahdollisuuksia paitsi monimutkaisten polymeerien synteesiin, myös itsejärjestyvyyteen perustuvien funktionaalisten nanorakenteiden suunnitteluun ja valmistukseen. Nämä voivat jäljitellä luonnossa esiintyviä rakenteita, joita muodostavat esimerkiksi lipidit ja proteiinit. Itsejärjestyvät molekyylit ovat usein amfifiilisiä eli ne koostuvat hydrofiilisistä ja hydrofobisista osista ja polymeereissä nämä osat voivat olla omina lohkoinaan, jolloin puhutaan amfifiilisistä lohko- tai blokkikopolymeereistä. Riippuen järjestyneiden rakenteiden koostumuksesta ja muodosta, amfifiilisiä blokkikopolymeerejä on tutkittu tai jo käytetty nanoteknologiassa, elastomeereissä, voiteluaineissa, pinta-aktiivisina aineina, lääkkeenannostelussa, maaleissa, sekä elektroniikka-, kosmetiikka- ja elintarviketeollisuudessa. Tavallisimmin käytetyt amfifiiliset blokkikopolymeerit ovat olleet lineaarisia, mutta viime aikoina tutkimus on suuntautunut kohti monimutkaisempia rakenteita. Tällaisia ovat esimerkiksi tähtipolymeerit. Tähtimäisissä polymeereissä miselleille tyypillinen ydin-kuori-rakenne säilyy hyvin alhaisissakin polymeerikonsentraatioissa, koska polymeeriketjut ovat kiinni toisissaan yhdessä pisteessä. Siten ne ovat erityisen kiinnostavia tutkimuskohteita erilaisten hydrofobisten orgaanisten yhdisteiden sitomiseksi ja vapauttamiseksi. Tässä työssä on tarkasteltu amfifiilisten tähtipolymeerien itsejärjestymistä vesiliuoksissa sekä kokeellisesti ja tietokonesimulaatioin. Työ koostuu kahdesta osasta: tähtipolymeerien synteesistä makrosyklisillä initiaattoreilla ja amfifiilisten tähtimäisten blokkikopolymeerien ominaisuuksien tutkimisesta.

Polymer Protected Gold Nanoparticles

Polymer protected gold nanoparticles have successfully been synthesized by both "grafting-from" and "grafting-to" techniques. The synthesis methods of the gold particles were systematically studied. Two chemically different homopolymers were used to protect gold particles: thermo-responsive poly(N-isopropylacrylamide), PNIPAM, and polystyrene, PS. Both polymers were synthesized by using a controlled/living radical polymerization process, reversible addition-fragmentation chain transfer (RAFT) polymerization, to obtain monodisperse polymers of various molar masses and carrying dithiobenzoate end groups. Hence, particles protected either with PNIPAM, PNIPAM-AuNPs, or with a mixture of two polymers, PNIPAM/PS-AuNPs (i.e., amphiphilic gold nanoparticles), were prepared. The particles contain monodisperse polymer shells, though the cores are somewhat polydisperse. Aqueous PNIPAM-AuNPs prepared using a "grafting-from" technique, show thermo-responsive properties derived from the tethered PNIPAM chains. For PNIPAM-AuNPs prepared using a "grafting-to" technique, two-phase transitions of PNIPAM were observed in the microcalorimetric studies of the aqueous solutions. The first transition with a sharp and narrow endothermic peak occurs at lower temperature, and the second one with a broader peak at higher temperature. In the first transition PNIPAM segments show much higher cooperativity than in the second one. The observations are tentatively rationalized by assuming that the PNIPAM brush can be subdivided into two zones, an inner and an outer one. In the inner zone, the PNIPAM segments are close to the gold surface, densely packed, less hydrated, and undergo the first transition. In the outer zone, on the other hand, the PNIPAM segments are looser and more hydrated, adopt a restricted random coil conformation, and show a phase transition, which is dependent on both particle concentration and the chemical nature of the end groups of the PNIPAM chains. Monolayers of the amphiphilic gold nanoparticles at the air-water interface show several characteristic regions upon compression in a Langmuir trough at room temperature. These can be attributed to the polymer conformational transitions from a pancake to a brush. Also, the compression isotherms show temperature dependence due to the thermo-responsive properties of the tethered PNIPAM chains. The films were successfully deposited on substrates by Langmuir-Blodgett technique. The sessile drop contact angle measurements conducted on both sides of the monolayer deposited at room temperature reveal two slightly different contact angles, that may indicate phase separation between the tethered PNIPAM and PS chains on the gold core. The optical properties of amphiphilic gold nanoparticles were studied both in situ at the air-water interface and on the deposited films. The in situ SPR band of the monolayer shows a blue shift with compression, while a red shift with the deposition cycle occurs in the deposited films. The blue shift is compression-induced and closely related to the conformational change of the tethered PNIPAM chains, which may cause a decrease in the polarity of the local environment of the gold cores. The red shift in the deposited films is due to a weak interparticle coupling between adjacent particles. Temperature effects on the SPR band in both cases were also investigated. In the in situ case, at a constant surface pressure, an increase in temperature leads to a red shift in the SPR, likely due to the shrinking of the tethered PNIPAM chains, as well as to a slight decrease of the distance between the adjacent particles resulting in an increase in the interparticle coupling. However, in the case of the deposited films, the SPR band red-shifts with the deposition cycles more at a high temperature than at a low temperature. This is because the compressibility of the polymer coated gold nanoparticles at a high temperature leads to a smaller interparticle distance, resulting in an increase of the interparticle coupling in the deposited multilayers.

Developing an evolutionary/ecological approach in enterprise education

This paper presents an ecological/evolutionary approach to enterprise education. Ecological approaches are used at the University of Tasmania to heighten the awareness of students to a raft of difficult to observe environmental factors associated with developing enterprising ideas. At Sheffield University, the discovery and exploitation of entrepreneurial opportunities is viewed as a co-evolving system of emerging business ideas, and routines/heuristics respectively. It is argued that using both approaches enables students to develop a greater awareness of their situated environment, and ultimately the degree of fit between their learning process and a changing external world. The authors argue that in order to improve the chances of longer-term survival what is needed is a new level of organisation where the individual is capable of developing a representation of the external world that he or she can use to sense the appropriateness of local decisions. This reinterpretation of events allows individuals to step back and examine the broader consequences of their actions through the interpretation and anticipation of feedback from the environment. These approaches thus seek to develop practice-based heuristics which individuals can use to make sense of their lived experiences, as they learn to evolve in an increasingly complex world.

Reactive state selectivity in photodimerization through micellar counter-ion effects: photodimerization of acenaphthylenes

Photodimerization of acenaphthylene and 5,6-dichloroacenaphthylene solubilized in sodium dodecylsulphate (SDS), cetyltrimethylammonium chloride (CTAC), dodecyltrimethylammonium chloride (DTAC), cetyltrimethylammonium bromide (CTAB) and Triton X-100 micelles gives a mixture of cis and trans dimers. The magnitude of the cis:trans ratio is sensitive to the type of micelle used. In CTAB micelles the heavy atom effect of the bromide counter-ions leads to an increased triplet-derived trans dimer yield, whereas in micelles with light atom counter-ions (CTAC, DTAC and SDS) the singlet-derived cis dimer predominates.

Distance dependence of fluorescence resonance energy transfer

Deviations from the usual R (-6) dependence of the rate of fluorescence resonance energy transfer (FRET) on the distance between the donor and the acceptor have been a common scenario in the recent times. In this paper, we present a critical analysis of the distance dependence of FRET, and try to illustrate the non R (-6) type behaviour of the rate for the case of transfer from a localized electronic excitation on the donor, a dye molecule to three different energy acceptors with delocalized electronic excitations namely, graphene,two-dimensional semiconducting sheet and the case of such a semiconducting sheet rolled to obtain a nanotube. We use simple analytic models to understand the distance dependence in each case.

Ligand Specificity of Group I Biotin Protein Ligase of Mycobacterium tuberculosis

Background: Fatty acids are indispensable constituents of mycolic acids that impart toughness & permeability barrier to the cell envelope of M. tuberculosis. Biotin is an essential co-factor for acetyl-CoA carboxylase (ACC) the enzyme involved in the synthesis of malonyl-CoA, a committed precursor, needed for fatty acid synthesis. Biotin carboxyl carrier protein (BCCP) provides the co-factor for catalytic activity of ACC. Methodology/Principal Findings: BPL/BirA (Biotin Protein Ligase), and its substrate, biotin carboxyl carrier protein (BCCP) of Mycobacterium tuberculosis (Mt) were cloned and expressed in E. coli BL21. In contrast to EcBirA and PhBPL, the similar to 29.5 kDa MtBPL exists as a monomer in native, biotin and bio-5'AMP liganded forms. This was confirmed by molecular weigt profiling by gel filtration on Superdex S-200 and Dynamic Light Scattering (DLS). Computational docking of biotin and bio-5'AMP to MtBPL show that adenylation alters the contact residues for biotin. MtBPL forms 11 H-bonds with biotin, relative to 35 with bio-5'AMP. Docking simulations also suggest that bio-5'AMP hydrogen bonds to the conserved `GRGRRG' sequence but not biotin. The enzyme catalyzed transfer of biotin to BCCP was confirmed by incorporation of radioactive biotin and by Avidin blot. The K-m for BCCP was similar to 5.2 mu M and similar to 420 nM for biotin. MtBPL has low affinity (K-b = 1.06 x 10(-6) M) for biotin relative to EcBirA but their K-m are almost comparable suggesting that while the major function of MtBPL is biotinylation of BCCP, tight binding of biotin/bio-5'AMP by EcBirA is channeled for its repressor activity. Conclusions/Significance: These studies thus open up avenues for understanding the unique features of MtBPL and the role it plays in biotin utilization in M. tuberculosis.

Effect of surfactants on the fluorescence spectra of water-soluble MEHPPV derivatives having grafted polyelectrolyte chains

Poly(2-methoxy-5-[2'-ethylhexyoxy]-1,4-phenylenevinylene) (MEHPPV) derivatives with polyacrylic acid (PAA) chains grafted onto their backbone were found to be water soluble, and they exhibited a dramatic increase in their fluorescence intensity in the presence of a variety of surfactants, even at concentrations far below their critical micelle concentrations (CMC). This increase was accompanied by a blue-shift in the emission maximum. These observations are rationalized based on the postulate that the backbone conformation of the conjugated polymer is modulated upon interaction of the surfactant molecules with the polyelectrolytic tethers, which in turn results in a significant depletion of intra-chain interchromophore interactions that are known to cause red-shifted emission bands with significantly lower emission yields.

Thermotropic and hydration studies of membranes formed from gemini pseudoglyceryl lipids possessing polymethylene spacers

Membrane formation from gemini pseudoglyceryl lipids bearing n-C14H29 and n-C16H33 chains has been reported. These lipid aggregates have been characterized using transmission electron microscopy (TEM), dynamic light scattering (DLS), high sensitivity differential scanning calorimetry (DSC), and Paldan fluorescence studies. The length of the spacer between the cationic ammonium headgroups has been varied from -(CH2)(3)- (propandiyl) to -(CH2)(12)- (dodecandiyl) in these lipids. All gemini lipids were found to generate stable suspensions in aqueous media. Electron microscopic studies revealed the smaller size of the gemini lipid aggregates as compared to their monomeric lipid counterparts. DLS measurements showed that the gemini lipid suspensions with a -(CH2)(8)- spacer length were bigger in size than that of other analogues. DSC studies suggest the unusual behavior of the gemini lipids bearing -(CH2)3- propanediyl spacer based lipids. These observations were consistent irrespective of the hydrocarbon chain lengths of the lipids. Paldan fluorescence based hydration studies showed that the hexadecyl chain based gemini lipid aggregates bearing a -(CH2)(12)- spacer were the most hydrated in their gel states among all the gemini lipid series investigated herein.

Purification, characterization and molecular cloning of a monocot mannose-binding lectin from Remusatia vivipara with nematicidal activity

A mannose-binding lectin (RVL) was purified from the tubers of Remusatia vivipara, a monocot plant by single-step affinity chromatography on asialofetuin-Sepharose 4B. RVL agglutinated only rabbit erythrocytes and was inhibited by mucin, asialomucin, asialofetuin and thyroglobulin. Lectin activity was stable up to 80A degrees C and under wide range of pH (2.0-9.3). SDS-PAGE and gel filtration results showed the lectin is a homotetramer of Mr 49.5 kDa, but MALDI analysis showed two distinct peaks corresponding to subunit mass of 12 kDa and 12.7 kDa. Also the N-terminal sequencing gave two different sequences indicating presence of two polypeptide chains. Cloning of RVL gene indicated posttranslational cleavage of RVL precursor into two mature polypeptides of 116 and 117 amino-acid residues. Dynamic light scattering (DLS) and gel filtration studies together confirmed the homogeneity of the purified lectin and supported RVL as a dimer with Mr 49.5 kDa derived from single polypeptide precursor of 233 amino acids. Purified RVL exerts potent nematicidal activity on Meloidogyne incognita, a root knot nematode. Fluorescent confocal microscopic studies demonstrated the binding of RVL to specific regions of the alimentary-tract and exhibited a potent toxic effect on M. incognita. RVL-mucin complex failed to interact with the gut confirming the receptor mediated lectin interaction. Very high mortality (88%) rate was observed at lectin concentration as low as 30 A mu g/ml, suggesting its potential application in the development of nematode resistant transgenic-crops.