Alkyl radical geometry controls geminate cage recombination in alkylcobalamins

Abstract: The radical pair that results from photolysis of adenosylcob(II1)alamin (AdoCbl"') undergoes primary geminate recombination with a first-order rate constant of 1 x lo9 s-l. In contrast, methylcob(II1)alamin (CH3Cbl"') and aristeromicylcob(II1)alamin (AriCblII', the carbocyclic analogue of AdoCbl"' in which the ribofuranose ring oxygen has been replaced with a methylene group) does not undergo primary geminate recombination. The ribofwanose group enables a high rate of geminate recombination in the [Ado' Cbl"'] radical pair. This may be due to a stereoelectronic (p-anomeric) effect that maintains a pyramidal geometry at the 5'-carbon of the 5'-deoxyadenosyl radical, or it may be due to hindered rotation about the C4t-C5, bond such that /?-elimination to the olefin is prevented. Recombination in the geminate singlet radical pair is in competition with diffusive escape to form a solvent-separated radical pair. Hyperfine coupling from Co" promotes intersystem crossing to the triplet radical pair (Chagovetz, A. M.; Grissom, C. B. J. Am. Chem. SOC. 1993, 115, 12152). Recombination of the [CH3' Cbl"] radical pair is not prevented by a lack of intersystem crossing, as neither unlabeled or I3C-labeled CH3Cbl"' undergoes geminate recombination. There is only a small difference in the rate of diffusive recombination in the solvent cage for AdoCbl"', AriCbl"', and CH3Cbl"' following photolysis: 2.01 x 10" s-l, 2.20 x lo4 s-l, and 1.16 x lo4 s-l. The rate of diffusive recombination is limited by productive collisions and not by radical geometry or intersystem crossing. The CF3' radical that results from photolysis of (trifluoromethyl)cob(III)alamin (CF3Cbl"') maintains its pyramidal geometry and undergoes faster diffusive recombination in the solvent cage at 51 x lo4 s-l. The C-Co bond dissociation enthalpy in AriCbl"' is 37 f 1.4 kcaymol. The profound difference in geminate recombination rates for AdoCbl"' and CH3Cbl"' is consistent with their different biological roles as enzymatic cofactors: AdoCbl"' is an initiator of radical chain chemistry in the active site, whereas CH3Cbl"' is a methyl group donor in an S~2-type process.

Film review : Citizen Murdoch?

It hasn’t been a good year for media barons. Actually, it’s not been a great century. In 2007 Baron Conrad Black was sent to jail in the US for embezzling his shareholders. Silvio Berlusconi’s grip on the Italian media hasn’t prevented a steady flow of allegations of sleaze and scandal since 2009, which have reduced him to a global laughing stock. And since July 2011, we have seen the dizzying fall of Rupert Murdoch and his son, James, from their positions of unquestioned (and unquestionable) authority at the helm of the world’s most powerful media empire.

Photocatalytic reduction of carbon dioxide to formic acid, formaldehyde, and methanol using dye-sensitized TiO2 film

A bifunctionalized TiO2 film containing a dye-sensitized zone and a catalysis zone is designed for visible-light photocatalytic reduction of CO2 to chemicals continuously. Charge separation can be accomplished with electron transferring to catalysis zone and positive charge transforming to anode. Highly efficient conversion of CO2 to formic acid, formaldehyde, and methanol is achieved through the transferring electrons on conduction bands (CB) of TiO2. Reduction of CO2 and O2 evolution take place in separated solutions on different catalysts. The separated solution carried out in this photo-reactor system can avoid CO2 reduction products being oxidized by anode. The yields of reduction products were enhanced remarkably by external electrical power. This study provides not only a new photocatalytic system but also a potential of renewable energy source via carbon dioxide.

Creativity is as important as literacy : making a film trailer responding to literature

The first part of the title is from Sir Ken Robinson (Robinson, 2009), the esteemed educator and champion of creativity in schools. Sometimes in the face of meeting the demands of time, timetabling, demanding administration tasks and teaching for high stakes testing accountability, we can find ourselves desperate for time to remember that English has always been one of the places in schools where creativity can flourish. English is a place for the play of the imagination. English teachers are the purveyors of narrative; the keepers and teachers of stories. The new Australian Curriculum: English, (Australian Curriculum and Assessment Reporting Authority (ACARA), 2012) asks us to be using ICT technologies in creative ways to tell those stories. The curriculum asks students to access texts receptively and to then speak about, write and create texts productively. There are so many interesting things to do with texts beyond word processing of print based resources. Responding to literature through media is always an alternative option to writing or simply speaking about it. In this paper my QUT pre-service student Chrystal Armitage describes how she made a mini story via a film trailer in response to a short story, ‘Turned’ (Gilman, 1987) in the unit, Literature in Secondary Teaching.

Policy measures for creating an integrated and brand-focused innovation system for film industries in shadow nations : an application to Australia's national film industry

Shadow nations face particular problems in constructing competitive film industries. Shadow nations refer to nations whose relative competitiveness suffers from easy product substitutability by products initiated, produced and distributed by powerful actors, such as media conglomerates located in Hollywood. The dominant literature has so far neglected the developing policy recommendations for dealing explicitly with the challenges of shadow nations. This paper aims to develop and apply a normative model for the development of film industries in shadow nations. The model integrates insights from innovation system studies and place branding. The developed model is applied to the Australian film industry as Australia represents a typical shadow nation within the film industry.

Melt textured Y123 bulk and thick film

YBa2Cu3O7-δ - 25mol%Y2BaCuO5 bars and thick films have been melt textured using a stationary furnace with a temperature gradient of 3 or 6°C/cm. Samples are heated above the peritectic reaction temperature and quenched to just above the solidification temperature and then slowly cooled below the solidification temperature. All bar shaped samples consist of 2-5 mm grains though the grain orientations strongly depend on the heat treatment conditions. The bar shows the maximum Jc of above 3,000 A/cm2, whereas the maximum Jc of 200 A/cm2 and Tczero of 88K are obtained for the thick film on (100) LaAlO3 single crystal.

The fishtown series

Fishtown is a series of mediated animated works which embody artistic conceptions of ambience and explore the interplay between foreground and background. The series draws upon a representation of natural patterns and rhythms in the ambient environment and is produced using a hybrid style of animation process that incorporates motion capture, dynamics and keyframe animation to construct a biomemtic peripheral rhythm. The display of the work is a crucial part of the project, and contributes a considerable amount to the reception of the work. Based on the ambient conceptions defined by Cage, Eno and Bizzocchi, ambient animation should incorporate some form of ambient display. As Eno (1978) states, it should be as ignorable as it is interesting. The ultimate intention is to place the work outside the gallery setting, to provide a more neutral ambient setting for the viewing of the work, and therefore the use of an ambient display is necessary if the work is to be situated in an ambient setting. Craig Walsh is a contemporary artist producing work for large scale projections in ambient settings. Completing Walsh's masterclass in 2011 (Tanawha Arts and Ecology Centre) has been an important factor in arriving at a strategy for the display of the Fishtown series. The most recent work in the Fishtown series was developed during a residency at the Crane Arts studios in Philadelphia USA in August 2012, and is comprised of a screen based animated work, utilizing large scale digital projection. Documentation of this work can be found at the Crane Arts Residency Website: http://cranearts.qcagriffith.com/crane-arts-residency-chris-denaro

Silver Gelatin Print: A group exhibition curated by Karen Milder that investigates and captures the traditional processes using photograms, liquid emulsion, toning, hand-colouring and film. Part of the Queensland Festival of Photography 4 (QFP4).

Pillar of salt: (3 hand-applied silver gelatin photographs) Statement: For women moving into new experiences and spaces, loss and hardship is often a price to be paid. These courageous women look back to things they have overcome in order to continue to grow.

Thin-film elemental analyses for precise characterization of minerals

The Analytical Electron Microscope (AEM), with which secondary X-ray emission from a thin (<150nm), electron-transparent material is measured, has rapidly become a versatile instrument for qualitative and quantitative elemental analyses of many materials, including minerals. With due regard for sources of error in experimental procedures, it is possible to obtain high spatial resolution (~20nm diameter) and precise elemental analyses (~3% to 5% relative) from many silicate minerals. In addition, by utilizing the orientational dependence of X-ray emission for certain multi-substituted crystal structures, site occupancies for individual elements within a unit cell can be determined though with lower spatial resolution. The relative ease with which many of these compositional data may be obtained depends in part on the nature of the sample, but, in general, is comparable to other solid state analytical techniques such as X-ray diffraction and electron microprobe analysis. However, the improvement in spatial resolution obtained with the AEM (up to two orders of magnitude in analysis diameter) significantly enhances interpretation of fine-grained assemblages in many terrestrial or extraterrestrial rocks.

Thin-film analyses of silicate standards at 200 kv : the effect of temperature on element loss

Preliminary data is presented on a detailed statistical analysis of k-factor determination for a single class of minerals (amphiboles) which contain a wide range of element concentrations. These amphiboles are homogeneous, contain few (if any) subsolidus microstructures and can be readily prepared for thin film analysis. In previous studies, element loss during the period of irradiation has been assumed negligible for the determination of k-factors. Since this phenomena may be significant for certain mineral systems, we also report on the effect of temperature on k-factor determination for various elements using small probe sizes (approx.20 nm).

Licensed to sell : product placement in the James Bond film series

As one of the longest running franchises in cinema history, and with its well-established use of product placements, the James Bond film series provides an ideal framework within which to measure and catalogue the number and types of products used within a particular timeframe. This case study will draw upon extensive content analysis of the James Bond film series in order to chart the evolution of product placement across the franchise's 50 year history.

First-principles prediction of metal-free magnetism and intrinsic half-metallicity in graphitic carbon nitride

Transition metal-free magnetism and half-metallicity recently has been the subject of intense research activity due to its potential in spintronics application. Here we, for the first time, demonstrate via density functional theory that the most recently experimentally realized graphitic carbon nitride (g-C4N3) displays a ferromagnetic ground state. Furthermore, this novel material is predicted to possess an intrinsic half-metallicity never reported to date. Our results highlight a new promising material toward realistic metal-free spintronics application.

The International Film and Television School in Cuba : for a stronger media culture in the global south

A little-known facet of Cuban internationalism is the Cuba shares in the education of young people who want to help build a stronger media culture that represents voices from the global South. Cuba was instrumental in the establishment and operation of the International Film and Television School at San Antonio de los Baños. The Cuban government provided the location and buildings for the school, and among the range of international media professionals who teach the students are selected Cuban professors from the Institute of the Arts, based n Havana. The International Film and Television School is supported by funding from Spain and other countries, and by the willingness of international media professionals to teach short courses for little more than an honorarium. Cuba used to provide full scholarships for student from the South to study a two-year course in film or television, but now charges fees for its three-year diploma course.