Formation of the heterocumulene anion SCCCN- by a cyano migration from the radical anion of 1,2-dicyanoethylenedithiolate

The anionic heterocumulene SCCCN- was generated in the gas phase by collisional activation of the radical anion of 1,2-dicyanoethylenedithiolate. The mechanism of this reaction, as well as the structures of neutral and anionic products, was investigated by hybrid density functional theory (DFT) calculations. Dissociation to form SCCCN- and SCN is proposed to occur by a radical directed cyano migration reaction, with calculations suggesting this is the lowest energy fragmentation pathway available to the precursor anion. In contrast, the even-electron protonated 1,2-dicyanoethylenedithiolate anion fragmented by loss of HCN.

'What's on your mind?' Writing on Facebook as a tool for self-formation

In the context of modern western psychologised, techno-social hybrid realities, where individuals are incited constantly to work on themselves and perform their self-development in public, the use of online social networking sites (SNSs) can be conceptualised as what Foucault has described as a ‘technique of self’. This article explores examples of status updates on Facebook to reveal that writing on Facebook is a tool for self-formation with historical roots. Exploring examples of self-writing from the past, and considering some of the continuities and discontinuities between these age-old practices and their modern translations, provides a non-technologically deterministic and historically aware way of thinking about the use of new media technologies in modern societies that understands them to be more than mere tools for communication.

All the worldwide web's a stage : teenage girls' self-presentation and identities formation through status updates

This study investigates grade eight girls’ use of status updates on Facebook in order to create identities online. Using sociologist Erving Goffman’s theory of self-presentation as a framework, Jones and Pittman’s subsequent strategies of self-presentation are used to discover the ways in which teenage girls use status updates in order to create identities online and manage audience impressions. Using a mixed methods design, the results showed that, while existing self-presentation strategies persist, social networking has created new means of self-presentation. This study adds to a growing pool of research regarding teens’ engagement with social networking websites to form identities.

Using pulse transit delay in Z-scan to discriminate between excited-state absorption and other nonlinear processes in ZnO nanocones

We report a new approach that uses the single beam Z-scan technique, to discriminate between excited state absorption (ESA) and two and three photon nonlinear absorption. By measuring the apparent delay or advance of the pulse in reaching the detector, the nonlinear absorption can be unambiguously identified as either instantaneous or transient. The simple method does not require a large range of input fluences or sophisticated pulse-probe experimental apparatus. The technique is easily extended to any absorption process dependent on pulse width and to nonlinear refraction measurements. We demonstrate in particular, that the large nonlinear absorption in ZnO nanocones when exposed to nanosecond 532 nm pulses, is due mostly to ESA, not pure two-photon absorption.

Becoming a pharmacist : the role of curriculum in professional identity formation

Objective To understand how the formal curriculum experience of an Australian undergraduate pharmacy program supports students’ professional identity formation. Methods A qualitative ethnographic study was conducted over four weeks using participant observation and examined the ‘typical’ student experience from the perspective of a pharmacist. A one-week period of observation was undertaken with each of the four year groups (that is, for years one to four) comprising the undergraduate curriculum. Data were collected through observation of the formal curriculum experience using field notes, a reflective journal and informal interviews with 38 pharmacy students. Data were analyzed thematically using an a priori analytical framework. Results Our findings showed that the observed curriculum was a conventional curricular experience which focused on the provision of technical knowledge and provided some opportunities for practical engagement. There were some opportunities for students to imagine themselves as pharmacists, for example, when the lecture content related to practice or teaching staff described their approach to practice problems. However, there were limited opportunities for students to observe pharmacist role models, experiment with being a pharmacist or evaluate their professional identities. While curricular learning activities were available for students to develop as pharmacists e.g. patient counseling, there was no contact with patients and pharmacist academic staff tended to role model as educators with little evidence of their pharmacist selves. Conclusion These findings suggest that the current conventional approach to the curriculum design may not be fully enabling learning experiences which support students in successfully negotiating their professional identities. Instead it appeared to reinforce their identities as students with a naïve understanding of professional practice, making their future transition to professional practice challenging.

Mechanical influences on endothelial cell network formation in vitro

While both the restoration of the blood supply and an appropriate local mechanical environment are critical for uneventful bone healing, their influence on each other remains unclear. Human bone fracture haematomas (<72h post-trauma) were cultivated for 3 days in fibrin matrices, with or without cyclic compression. Conditioned medium from these cultures enhanced the formation of vessel-like networks by HMEC-1 cells, and mechanical loading further elevated it, without affecting the cells’ metabolic activity. While haematomas released the angiogenesis-regulators, VEGF and TGF-β1, their concentrations were not affected by mechanical loading. However, direct cyclic stretching of the HMEC-1 cells decreased network formation. The appearance of the networks and a trend towards elevated VEGF under strain suggested physical disruption rather than biochemical modulation as the responsible mechanism. Thus, early fracture haematomas and their mechanical loading increase the paracrine stimulation of endothelial organisation in vitro, but direct periodic strains may disrupt or impair vessel assembly in otherwise favourable conditions.

The development of an effective and efficient dispute resolution processes for strata scheme disputes in peninsular Malaysia

Dispute resolution in strata schemes in Peninsular Malaysia should focus on more than just "settlement." The quality of the outcome, its sustainability and its relevance in supporting the basic principles of a good neighbourhood and self-governance in a strata scheme are also fundamental. Based on the comprehensive law movement, this thesis develops a theoretical framework for strata scheme disputes within the parameters of therapeutic jurisprudence, preventive law, alternative dispute resolution (ADR) and problem-solving courts. The therapeutic orientation of this model offers approaches that promote positive communication between disputing parties, preserve neighbour relations and optimise people's psychological and emotional well-being.

Research participation by people with intellectual disability and mental health issues : an examination of the processes of consent

Balancing the demands of research and ethics is always challenging and even more so when recruiting vulnerable groups. Within the context of current legislation and international human rights declarations, it is strongly advocated that research can and must be undertaken with all recipients of health care services. Research in the field of intellectual disability presents particular challenges in regard to consenting processes. This paper is a critical reflection and analysis of the complex processes undertaken and events that occurred in gaining informed consent from people with intellectual disability to participate in a study exploring their experiences of being an inpatient in mental health hospitals within Aotearoa/New Zealand. A framework based on capacity, information and voluntariness is presented with excerpts from the field provided to explore consenting processes. The practical implications of the processes utilised are then discussed in order to stimulate debate regarding clearer and enhanced methods of gaining informed consent from people with intellectual disability.

Potential interstellar molecules : Formation of neutral C6CO from C6CO- in the gas phase

Computations at the RCCSD(T)/aug-cc-pVDZ//B3LYP/6-31G* level of theory indicate that neutral C6CO is a stable species. The ground state of this neutral is the singlet cumulene oxide :C=C=C=C=C=C=C=O. The adiabatic electron affinity and dipole moment of singlet C6CO are 2.47 eV and 4.13 D, respectively, at this level of theory. The anion (C6CO)(-.) should be a possible precursor to this neutral. It has been formed by an unequivocal synthesis in the ion source of a mass spectrometer by the S(N)2(Si) reaction between (CH3)(3)Si-C=C-C=C-C=C-CO-CMe3 and F- to form C-=C-C=C-C=C-CO-CMe3 which loses Me3C in the source to form C6CO-.. Charge stripping of this anion by vertical Franck-Condon oxidation forms C6CO, characterised by the neutralisation-reionisation spectrum (-NR+) of C6CO-., which is stable during the timeframe of this experiment (10(-6) s), Copyright (C) 2000 John Wiley & Sons, Ltd.

Effect of culture conditions and calcium phosphate coating on ectopic bone formation

This study investigated the effect of a calcium phosphate (CaP) coating onto a polycaprolactone melt electrospun scaffold and in vitro culture conditions on ectopic bone formation in a subcutaneous rat model. The CaP coating resulted in an increased alkaline phosphatase activity (ALP) in ovine osteoblasts regardless of the culture conditions and this was also translated into higher levels of mineralisation. A subcutaneous implantation was performed and increasing ectopic bone formation was observed over time for the CaPcoated samples previously cultured in osteogenic media whereas the corresponding non-coated samples displayed a lag phase before bone formation occurred from 4 to 8 weeks post-implantation. Histology and immunohistochemistry revealed bone fill through the scaffolds 8 weeks post-implantation for coated and non-coated specimens and that ALP, osteocalcin and collagen 1 were present at the ossification front and in the bone tissues. Vascularisation in the vicinity of the bone tissues was also observed indicating that the newly formed bone was not deprived of oxygen and nutrients.We found that in vitro osteogenic induction was essential for achieving bone formation and CaP coating accelerated the osteogenic process. We conclude that high cell density and preservation of the collagenous and mineralised extracellular matrix secreted in vitro are factors of importance for ectopic bone formation.

Making YAWL and SmartPM interoperate : managing highly dynamic processes by exploiting automatic adaptation features

In the last years, the trade-o between exibility and sup- port has become a leading issue in work ow technology. In this paper we show how an imperative modeling approach used to de ne stable and well-understood processes can be complemented by a modeling ap- proach that enables automatic process adaptation and exploits planning techniques to deal with environmental changes and exceptions that may occur during process execution. To this end, we designed and imple- mented a Custom Service that allows the Yawl execution environment to delegate the execution of subprocesses and activities to the SmartPM execution environment, which is able to automatically adapt a process to deal with emerging changes and exceptions. We demonstrate the fea- sibility and validity of the approach by showing the design and execution of an emergency management process de ned for train derailments.

Formation of specialized propagules resistant to desiccation and cryopreservation in the threatened moss Ditrichum plumbicola (ditrichales, bryopsida)

Background and Aims Successful cryopreservation of bryophytes is linked to intrinsic desiccation tolerance and survival can be enhanced by pre-treatment with abscisic acid (ABA) and sucrose. The pioneer moss Ditrichum plumbicola is naturally subjected to desiccation in the field but showed unexpectedly low survival of cryopreservation, as well as a poor response to pre-treatment. The effects of the cryopreservation protocol on protonemata of D. plumbicola were investigated in order to explore possible relationships between the production in vitro of cryopreservation-tolerant asexual propagules and the reproductive biology of D. plumbicola in nature. Methods Protonemata were prepared for cryopreservation using a four-step protocol involving encapsulation in sodium alginate, pre-treatment for 2 weeks with ABA and sucrose, desiccation for 6 h and rapid freezing in liquid nitrogen. After each stage, protonemata were prepared for light and electron microscopy and growth on standard medium was monitored. Further samples were prepared for light and electron microscopy at intervals over a 24-h period following removal from liquid nitrogen and re-hydration. Key Results Pre-treatment with ABA and sucrose caused dramatic changes to the protonemata. Growth was arrested and propagules induced with pronounced morphological and cytological changes. Most cells died, but those that survived were characterized by thick, deeply pigmented walls, numerous small vacuoles and lipid droplets in their cytoplasm. Desiccation and cryopreservation elicited no dramatic cytological changes. Cells returned to their pre-dehydration and cryopreservation state within 2 h of re-hydration and/or removal from liquid nitrogen. Regeneration was normal once the ABA/sucrose stimulus was removed. Conclusions The ABA/sucrose pre-treatment induced the formation of highly desiccation- and cryopreservation-tolerant propagules from the protonemata of D. plumbicola. This parallels behaviour in the wild, where highly desiccation-tolerant rhizoids function as perennating organs allowing the moss to endure extreme environmental conditions. An involvement of endogenous ABA in the desiccation tolerance of D. plumbicola is suggested.

Mass spectrometric study of the dissociation of Group XI metal complexes with fatty acids and glycerolipids : Ag2H+ and Cu2H+ ion formation in the presence of a double bond

Results of mass spectrometric studies are reported for the collisional dissociation of Group XI (Cu, Ag, Au) metal ion complexes with fatty acids (palmitic, oleic, linoleic and a-linolenic) and glycerolipids. Remarkably, the formation of M2H+ ions (M = Cu, Ag) is observed as a dissociation product of the ion complexes containing more than one metal cation and only if the lipid in the complex contains a double bond. Ag2H+ is formed as the main dissociation channel for all three of the fatty acids containing double bonds that were investigated while Cu2H+ is formed with one of the fatty acids and, although abundant, is not the dominant dissociation channel. Also. Cu(I) and Ag(I) ion complexes were observed with glycerolipids (including triacylglycerols and glycerophospholipids) containing either saturated or unsaturated fatty acid substituents. Interestingly. Ag2H+ ion is formed in a major fragmentation channel with the lipids that are able to form the complex with two metal cations (triacylglycerols and glycerophosphoglycerols), while lipids containing a fixed positive charge (glycerophospocholines) complex only with a single metal cation. The formation of Ag2H+ ion is a significant dissociation channel from the complex ion Ag-2(L-H)(+) where L = Glycerophospholipid (GP) (18:1/18:1). Cu(I) also forms complexes of two metal cations with glycerophospholipids but these do not produce Cu2H+ upon dissociation. Rather organic fragments, not containing Cu(I), are formed, perhaps due to different interactions of these metal cations with lipids resulting from the much smaller ionic radius of Cu(I) compared to Ag(I) (C).

Conversion of neutral C2COC2 to C4CO. potential interstellar molecules

Both [C4CO]−· and [C2COC2]−· are formed in the ion source of a VG ZAB 2HF mass spectrometer by the respective processes HO− + Me3Si–CC–CC–CO–CMe3 → [C4CO]−· + Me3SiOH + Me3C·, and Me3Si–CC–CO–CC–SiMe3 + SF6 + e → [C2COC2]−· + 2Me3SiF + SF4. The second synthetic pathway involves a double desilylation reaction similar to that first reported by Squires. The two radical anion isomers produce different and characteristic charge reversal spectra upon collisional activation. In contrast, following collision induced charge stripping, both radical anions produce neutral C4CO as evidenced by the identical neutralisation reionisation (−NR+) spectra. The exclusive rearrangement of C213COC2 to C413CO indicates that 12C–O bond formation is not involved in the reaction. Ab initio calculations (at the RCCSD(T)/aug-cc-pVDZ//B3LYP/6-31G∗ level of theory) have been used to investigate the reaction coordinates on the potential surfaces for both singlet and triplet rearrangements of neutral C2COC2. Singlet C2COC2 is less stable than singlet C4CO by 78.8 kcal mol−1 and requires only 8.5 kcal mol−1 of additional energy to effect conversion to C4CO by a rearrangement sequence involving three C–C ring opening/cyclisation steps.