Design of redox/radical sensing molecules via Nitrile Imine-Mediated Tetrazole-ene Cycloaddition (NITEC)

The current study introduces a novel synthetic avenue for the preparation of profluorescent nitroxides via nitrile imine-mediated tetrazole-ene cycloaddition (NITEC). The photoinduced cycloaddition was performed under metal-free, mild conditions allowing the preparation of a library of the nitroxide functionalized pyrazolines and corresponding methoxyamines. High reaction rates and full conversion were observed, with the presence of the nitroxide having no significant impact on the cycloaddition performance. The formed products were investigated with respect to their photophysical properties in order to quantify their “switch on/off” behavior. The fluorescence quenching performance is strongly dependent on the distance between the chromophore and the free radical spin as demonstrated theoretically and experimentally. Highest levels of fluorescence quenching were achieved for pyrazolines with the nitroxide directly fused to the chromophore. Importantly, the pyrazoline profluorescent nitroxides were shown to efficiently act as sensors for redox/radical processes.

Observation of sea-salt fraction in sub-100 nm diameter particles at Cape Grim

Volatility-hygroscopicity tandem differential mobility analyzer measurements were used to infer the composition of sub-100 nm diameter Southern Ocean marine aerosols at Cape Grim in November and December 2007. This study focuses on a short-lived high sea spray aerosol (SSA) event on 7–8 December with two externally mixed modes in the Hygroscopic Growth Factor (HGF) distributions (90% relative humidity (RH)), one at HGF > 2 and another at HGF~1.5. The particles with HGF > 2 displayed a deliquescent transition at 73–75% RH and were nonvolatile up to 280°C, which identified them as SSA particles with a large inorganic sea-salt fraction. SSA HGFs were 3–13% below those for pure sea-salt particles, indicating an organic volume fraction (OVF) of up to 11–46%. Observed high inorganic fractions in sub-100 nm SSA is contrary to similar, earlier studies. HGFs increased with decreasing particle diameter over the range 16–97 nm, suggesting a decreased OVF, again contrary to earlier studies. SSA comprised up to 69% of the sub-100 nm particle number, corresponding to concentrations of 110–290 cm−3. Air mass back trajectories indicate that SSA particles were produced 1500 km, 20–40 h upwind of Cape Grim. Transmission electron microscopy (TEM) and X-ray spectrometry measurements of sub-100 nm aerosols collected from the same location, and at the same time, displayed a distinct lack of sea salt. Results herein highlight the potential for biases in TEM analysis of the chemical composition of marine aerosols.

Modernist 16-19 Business Education in a Postmodern world - critical evidence of business practice and business education in the cultural industries

This article examines the continued relevance of the 16-19 business education curriculum in the UK, stimulated by doubts expressed by Thomas (1996), over its continued relevance. We express a concern that business education needs, but is struggling, to respond to significant societal shifts in consumption and production strategies that do not sit easily within traditional theories of business practice currently underpinning 16-19 business education. We examine firstly, the extent to which a formal body of knowledge couched in a modernist discourse of facts and objectivity can cope with the changing and fluid developments in much current business practice that is rooted in the cultural and symbolic. Secondly, the extent to which both academic and vocational competences provide the means for students to develop a framework of critical understanding that can respond effectively to rapidly changing business environments.Findings are based on research conducted jointly by the University of Manchester and the Manchester Institute for Popular Culture at Manchester Metropolitan University. The growth of dynamism of the cultural industries sector - largely micro-businesses and small and medium sized enterprises (SMEs) -encapsulates forms of business knowledge, business language and business practice which may not immediately fit with the models provided within business education. Results suggest increasingly reflexive forms of consumption being met by similarly reflexive and flexible modes of production.Our evidence suggests that whilst modernist business knowledge is often the foundation for many 16-19 business education courses, these programmes of study/training do not usually reflect the activities of SME and micro-business practitioners in the cultural industries. Given the importance of cultural industries in terms of the production strategies required to meet increasingly reflexive markets, it is suggested that there may be a need to incorporate a postmodern approach to the current content and pedagogy; one that is contextual, cultural and discursive.

Thermal analysis of synthetic reevesite and cobalt substituted reevesite (Ni,Co)6Fe2(OH)16(CO3)•4H2O

The mineral reevesite and the cobalt substituted reevesite have been synthesised. The d(003) spacings of the minerals ranged from 7.54 to 7.95 Å. The maximum d(003) value occurred at around Ni:Co 0.4:0.6. This maximum in interlayer distance is proposed to be due to a greater number of carbonate anions and water molecules intercalated into the structure. The stability of the reevesite and cobalt doped reevesite was determined by thermogravimetric analysis. The maximum temperature of the reevesite occurs for the unsubstituted reevesite and is around 220°C. The effect of cobalt substitution results in a decrease in thermal stability of the reevesites. Four thermal decomposition steps are observed and are attributed to dehydration, dehydroxylation and decarbonation, decomposition of the formed carbonate and oxygen loss at ~807 °C. A mechanism for the thermal decomposition of the reevesite and the cobalt substituted reevesite is proposed.

Exercise intensity influences NEAT in overweight and obese adults

PURPOSE: To determine the effect of acute bouts of moderate- and high-intensity walking exercise on non-exercise activity thermogenesis (NEAT) in overweight and obese adults. ---------- METHOD: 16 participants performed a single bout of either moderate-intensity walking exercise (MIE) or high-intensity walking exercise (HIE) on two separate occasions. The MIE consisted of walking for 60 minutes on a motorized treadmill at 6 km.h. The 60-minute HIE session consisted of walking in 5-min intervals at 6 km.h and 10% grade followed by 5-min at 0% grade. NEAT was assessed by accelerometer on three days before, the day of, and three days following the exercise sessions. ---------- RESULTS: There was no significant difference in NEAT vector magnitude (counts.min) between the pre-exercise period (days 1-3) and the exercise day (day 4) for either MIE or HIE protocol. In addition, there was no change in NEAT during the three days following the MIE session, however NEAT increased by 16% on day 7 (post-exercise) compared with exercise day (P = 0.32). However during the post-exercise period following the HIE session, NEAT was increased by 25% on day 7 compared with the exercise day (P = 0.08), and by 30-33% compared with pre-exercise period (day 1, day 2 and day 3); P = 0.03, 0.03, 0.02, respectively. ---------- CONCLUSION: A single bout of either MIE or HIE did not alter NEAT on the exercise day or on the first two days following the exercise session. However, monitoring NEAT on a third day allowed the detection of a 48-h delay in increased NEAT after performing HIE. A longer-term intervention is needed to determine the effect of accumulated exercise sessions over a week on NEAT.

Synthesis and Raman spectroscopic characterisation of hydrotalcites based on the formula Ca6Al2(CO3)(OH)16· 4H2O

We have successfully synthesized hydrotalcites (HTs) contg. calcium, which are naturally occurring minerals. Insight into the unique structure of HTs has been obtained using a combination of X-ray diffraction (XRD) as well as IR and Raman spectroscopies. Calcium-contg. hydrotalcites (Ca-HTs) of the formula Ca4Al2(CO3)(OH)12·4H2O (2:1 Ca-HT) to Ca8Al2(CO3)(OH)20· 4H2O (4:1 Ca-HT) have been successfully synthesized and characterised by XRD and Raman spectroscopy. XRD has shown that 3:1 calcium HTs have the largest interlayer distance. Raman spectroscopy complemented with selected IR data has been used to characterize the synthesized Ca-HTs. The Raman bands obsd. at around 1086 and 1077 cm-1 were attributed to the ν1 sym. stretching modes of the (CO32-) units of calcite and carbonate intercalated into the HT interlayer. The corresponding ν3 CO32- antisym. stretching modes are found at around 1410 and 1475 cm-1.

Comparison of intranasal and transcutaneous immunization for induction of protective immunity against chlamydia muridarum respiratory tract infection

Chlamydia pneumoniae causes a range of respiratory infections including bronchitis, pharyngitis and pneumonia. Infection has also been implicated in exacerbation/initiation of asthma and chronic obstructive pulmonary disease (COPD) and may play a role in atherosclerosis and Alzheimer's disease. We have used a mouse model of Chlamydia respiratory infection to determine the effectiveness of intranasal (IN) and transcutaneous immunization (TCI) to prevent Chlamydia lung infection. Female BALB/c mice were immunized with chlamydial major outer membrane protein (MOMP) mixed with cholera toxin and CpG oligodeoxynucleotide adjuvants by either the IN or TCI routes. Serum and bronchoalveolar lavage (BAL) were collected for antibody analysis. Mononuclear cells from lung-draining lymph nodes were stimulated in vitro with MOMP and cytokine mRNA production determined by real time PCR. Animals were challenged with live Chlamydia and weighed daily following challenge. At day 10 (the peak of infection) animals were sacrificed and the numbers of recoverable Chlamydia in lungs determined by real time PCR. MOMP-specific antibody-secreting cells in lung tissues were also determined at day 10 post-infection. Both IN and TCI protected animals against weight loss compared to non-immunized controls with both immunized groups gaining weight by day 10-post challenge while controls had lost 6% of body weight. Both immunization protocols induced MOMP-specific IgG in serum and BAL while only IN immunization induced MOMP-specific IgA in BAL. Both immunization routes resulted in high numbers of MOMP-specific antibody-secreting cells in lung tissues (IN > TCI). Following in vitro re-stimulation of lung-draining lymph node cells with MOMP; IFNγ mRNA increased 20-fold in cells from IN immunized animals (compared to non-immunized controls) while IFNγ levels increased 6- to 7-fold in TCI animals. Ten days post challenge non-immunized animals had >7000 IFU in their lungs, IN immunized animals <50 IFU and TCI immunized animals <1500 IFU. Thus, both intranasal and transcutaneous immunization protected mice against respiratory challenge with Chlamydia. The best protection was obtained following IN immunization and correlated with IFNγ production by mononuclear cells in lung-draining LN and MOMP-specific IgA in BAL.

Enlightening, balancing and transcending entrepreneurial orientation : the 4th annual EO3 research PDW

Entrepreneurial Orientation (EO) has a 30 year history as one of the most used concepts in entrepreneurship research. “Recent attention in formal sessions at the Academy of Management conference programs confirm Entrepreneurial Orientation as a primary construct with a majority of Entrepreneurship Division sponsored sessions devoted to studies using EO related measures”, as reported by the 2010 division program chair, Per Davidson (Roberts, 2010: 9). However, questions continue to be raised concerning over-dependence on parts of one strategic scale, possible inappropriate or under-theorized adaptations, and the lack of theoretical development on application and performance variance in emergent, organizational, and socioeconomic settings. One recent area of investigation in analysis, methods, theory and application concerns an “EO gestalt”, focusing on the family of EO-related measures and theory, rather than on one or more dimensions, in order to explore the theory and process of the Entrepreneurial Orientation phenomenon. The goals of the 4th Annual EO3 PDW are to enlighten researchers on the development of Entrepreneurial Orientation theory and related scales, balance the use of Entrepreneurial Orientation current knowledge with new research frontiers suggested by EO3 scholars’ questions, and transcend boundaries in the discoveries undertaken in the shared interdisciplinary and cross-cultural research agenda currently developing for Entrepreneurial Orientation concepts. Going into its forth year, the EO3 PDW has been pivotal in formalizing discussion, pushing research forward, and gaining insights from experienced and cutting edge scholars, as it provides a point of reference for coalescing research questions and findings surrounding this important concept.