Photoelectrochemistry with quinone radical anions: Kinetics of homogeneous redox catalysis

Cyclic voltammograms of quinones were recorded in acetonitrile in the presence of various substrates: carbonyl compounds, halobenzenes, Methyl Viologen and Neutral Red. When illuminated with light of λ >410 nm, catalytic waves were observed. From the ratio of the catalysed to uncatalysed peak current, electron transfer rate constants were calculated using the working curves of Saveant and coworkers. The values of these rate constants were compared with the values obtained by Shukla and Rusling for different systems using a similar method and with quenching rate constants calculated using Rehm-Weller-Marcus theory.

Photoelectrochemistry using quinone radical anions

The photoelectrochemistry of quinone radical anions has been demonstrated qualitatively by the photoassisted reduction of methyl viologen with benzoquinone and of neutral red with chloranil. Data were then collected for the estimation of quenching rate constants using Marcus-Weller theory. Reduction potentials of seven quinones were obtained in four solvents (and two aqueous mixtures) by cyclic voltammetry. The solvent effects on these potentials were studied by fitting them to the Taft relationship. The effects of proton donors were also noted. Absorption spectra of the radical anions were measured and the solvent effects noted and commented upon. From the molar absorption coefficients of the radical anions, the mean lifetimes of the excited states were estimated. Fluorescence spectra were obtained for anthraquinone and naphthaquinone radical anions and excitation energies were calculated. These values were estimated for the other quinones. Values of redox potentials for the excited radical anions were thence obtained. The Gibbs energies of the electron transfers between the excited quinone radical anions and the various substrates were obtained and hence the Gibbs energies of activation were calculated using the Marcus equation. The quenching rate constants were calculated using the Rehm-Weller equation and plotted vs. ΔG giving a characteristic Marcus plot including some data in the inverted region. The significance of the inverted region is discussed.

A fluorescence model of the C3 radical in comets

Theoretical resonance fluorescence calculations are presented of the triatomic C3 radical and are compared with observations of the C3 emission in comets Hale-Bopp and de Vico. A theoretical model of the C3 vibration-rotational structure in the A1Piu - X1Sigmag + electronic system is introduced. The model takes into account the detailed structure of the bending mode nu2 which is responsible for the emission of the 4050 Å group. A total of 1959 levels are considered, with 515 levels in the ground state. The main effort is to model high-resolution spectra of the 4050 Å emission in comets C/1995 O1 Hale-Bopp and 122P/1995 S1 de Vico. The agreement between observed and theoretical spectra is good for a value of the dipole moment derivative of dmu/dr ~ 2.5 Debye Å-1. The modeled C3 emission exhibits a pronounced Swings effect. Based on observations made with William Herschel Telescope operated on the island of La Palma by the Isaac Newton Group in the Spanish Observatorio del Roque de los Muchachos of the Instituto de Astrofisica de Canarias, and on observations made at the McDonald Observatory, which is operated by the University of Texas at Austin, USA.

The Impact of Colleague Peer Review on the Radiotherapy Treatment Planning Process in the Radical Treatment of Lung Cancer

AIMS: Modern radiotherapy uses techniques to reliably identify tumour and reduce target volume margins. However, this can potentially lead to an increased risk of geographic miss. One source of error is the accuracy of target volume delineation (TVD). Colleague peer review (CPR) of all curative-intent lung cancer plans has been mandatory in our institution since May 2013. At least two clinical oncologists review plans, checking treatment paradigm, TVD, prescription dose tumour and critical organ tolerances. We report the impact of CPR in our institution.

MATERIALS AND METHODS: Radiotherapy treatment plans of all patients receiving radical radiotherapy were presented at weekly CPR meetings after their target volumes were reviewed and signed off by the treating consultant. All cases and any resultant change to TVD (including organs at risk) or treatment intent were recorded in our prospective CPR database. The impact of CPR over a 13 month period from May 2013 to June 2014 is reported.

RESULTS: One hundred and twenty-two patients (63% non-small cell lung carcinoma, 17% small cell lung carcinoma and 20% 'clinical diagnosis') were analysed. On average, 3.2 cases were discussed per meeting (range 1-8). CPR resulted in a change in treatment paradigm in 3% (one patient proceeded to induction chemotherapy, two patients had high-dose palliative radiotherapy). Twenty-one (17%) had a change in TVD and one (1%) patient had a change in dose prescription. In total, 6% of patients had plan adjustment after review of dose volume histogram.

CONCLUSION: The introduction of CPR in our centre has resulted in a change in a component of the treatment plan for 27% of patients receiving curative-intent lung radiotherapy. We recommend CPR as a mandatory quality assurance step in the planning process of all radical lung plans.

Reclaiming the Radical in Universal Human Rights: Universality as Universalisation

The universality of human rights has been a fiercely contested issue throughout their history. This article contributes to scholarly engagements with the universality of human rights by proposing a re-engagement with this concept in a way that is compatible with the aims of radical politics. Instead of a static attribute or characteristic of rights this article proposes that universality can be thought of as, drawing from Judith Butler, an ongoing process of universalisation. Universality accordingly emerges as a site of powerful contest between competing ideas of what human rights should mean, do or say, and universal concepts are continually reworked through political activity. This leads to a differing conception of rights politics than traditional liberal approaches but, moreover, challenges such approaches. This understanding of universality allows human rights to come into view as potentially of use in interrupting liberal regimes and, crucially, opens possibilities to reclaim the radical in rights.

After the Critique of Rights: For a Radical Democratic Theory and Practice of Human Rights

The critique of human rights has proliferated in critical legal thinking over recent years, making it clear that we can no longer uncritically approach human rights in their liberal form. In this article I assert that after the critique of rights one way human rights may be productively re-engaged in radical politics is by drawing from the radical democratic tradition. Radical democratic thought provides plausible resources to rework the shortcomings of liberal human rights, and allows human rights to be brought within the purview of a wider political project adopting a critical approach to current relations of power. Building upon previous re-engagements with rights using radical democratic thought, I return to the work of Ernesto Laclau and Chantal Mouffe to explore how human rights may be thought as an antagonistic hegemonic activity within a critical relation to power, a concept which is fundamentally futural, and may emerge as one site for work towards radical and plural democracy. I also assert, via Judith Butler's model of cultural translation, that a radical democratic practice of human rights may be advanced which resonates with and builds upon already existing activism, thereby holding possibilities to persuade those who remain sceptical as to radical re-engagements with rights.

Rydberg structure associated with core-excited autoionizing states of the LiH radical

We have investigated inner-shell excitation of the LiH + molecular ion by electron impact within several different collision models to delineate Rydberg autoionizing resonance structure associated with the LiH + (1σ2σ 2 2 Σ + ) core-excited threshold. The minimal representation requires only the retention of the 1σ and 2σ molecular orbitals, in which the core-excited state involves the promotion of a single electron into the 2σ orbital. This model is extended to include two further representations, in which both the 3σ and 4σ orbitals obtained from a self-consistent field calculation improve target representation, correlation and support additional autoionization channels. This affects the autoionization widths and to a lesser degree the positions of the LiH (1σ2σ 2 n s, n p 1,3 Σ + ) resonance series. Comparing our work with calculations on the counterpart atomic Be system assists in the assignment of the core-excited molecular resonance states. The results from our investigation provide helpful insights into the study of inner-shell transitions produced by electron or photon impact in more complex diatomic molecules.

Formação cívica e formação de professores: limites e potencialidades

A reorganização curricular do Ensino Básico de 2001 representou uma mudança de paradigma: uma aposta na flexibilidade, na integração e na autonomia. Uma das principais inovações desta reforma foi a criação de áreas curriculares não disciplinares, entre elas a Formação Cívica. Uma década volvida qual o impacto desta decisão? Estudos anteriores revelaram o uso administrativo e burocrático da Formação Cívica, ao serviço do Diretor de Turma e das suas responsabilidades de gestão da turma e resolução de conflitos. Num cenário de defraudamento das expetativas iniciais depositadas neste domínio não disciplinar e convencidos que estávamos da importância de potenciar espaços reais de promoção da Cidadania nas escolas desencadeámos um estudo de modelização dupla investigação-formação que nos permitisse compreender qual o papel da formação de professores neste domínio e os respetivos limites e potencialidades da Formação Cívica. Com base no pressuposto de que a ação de qualquer professor em contexto de sala de aula depende do conhecimento profissional que possui acerca de um determinado domínio curricular e reconhecendo a ausência de mecanismos de formação específica para a concretização dos tempos letivos de Formação Cívica, estruturámos o nosso trabalho com o intuito de contribuir para a construção de conhecimento sobre a natureza da formação de professores em Formação Cívica. Realizado no contexto da formação contínua de professores, o presente estudo desenvolveu-se em duas etapas fundamentais que se foram interligando entre momentos de investigação, reflexão, formação, recolha e análise de dados. A abordagem metodológica que se delineou para todas as fases assumiu um cariz qualitativo e crítico-interpretativo. Numa primeira fase, realizámos um estudo exploratório que nos permitiu identificar conceções, práticas e contextos no domínio da Formação Cívica. Selecionámos uma escola no distrito de Aveiro e entrevistámos 10 professores do 3.º CEB, coordenação e direção da escola, analisámos documentos oficiais e observámos aulas. Concluímos que a operacionalização da Formação Cívica está refém de um conjunto de condicionalismos, entre eles: a ausência de orientações curriculares; a sobreposição de funções do Diretor de Turma; o não reconhecimento das funções pedagógicas de uma área não disciplinar; a ausência de preparação científica e pedagógica dos professores responsáveis por este tempo letivo. A segunda fase do estudo contemplou a conceção, desenvolvimento, implementação e avaliação de um percurso formativo projetado com base nos resultados do estudo exploratório e da revisão da literatura realizada para o efeito. O percurso formativo, desenvolvido na modalidade de Oficina de Formação (OF), envolveu e alicerçou-se no potencial das tecnologias (participação numa comunidade online; criação de blogues; desenvolvimento de recursos digitais) e envolveu sete professores. Dos professores participantes na OF, foram analisados em detalhe o percurso formativo de três professoras de diferentes escolas do ensino básico e com diferentes níveis de experiência letiva em Formação Cívica. A realização deste percurso formativo permitiu-nos: i) identificar processos de reconstrução do conceito de cidadania e do lugar da Formação Cívica; ii) identificar uma visão mais alargada e transformadora da Formação Cívica ao invés de abordagens restritas de cariz administrativo; ii) analisar a importância da partilha de experiências, do feedback, do suporte e da reflexão no processo formativo para o desenvolvimento das práticas pedagógico-didáticas; iv) conceptualizar o conhecimento profissional docente associado à Formação Cívica. Consideramos que este estudo contribui para a necessária reflexão sobre o espaço e o papel da Educação para a Cidadania no sistema educativo Português, assim como para o debate da afirmação da Formação Cívica (com esta ou outra designação mas necessariamente com novos contornos), em particular no currículo do ensino básico. Sustentamos ainda a importância fundamental da formação contínua (de carácter ativo e reflexivo) e da construção partilhada do conhecimento para o desenvolvimento profissional dos professores de Formação Cívica, necessário para dar resposta aos desafios da Educação para a Cidadania.

Teaching Toward Utopia: Promise, Provocation, and Pain in Pedagogies of Radical Imagination

Thesis (Ph.D.)--University of Washington, 2014

Radical interiors: Cindy Sherman's ‘Sex pictures’ and Kathy Acker's 'My mother: demonology'

In 1989, the American visual artist Cindy Sherman produced her ‘Sex Pictures’, a number of photographic images of two medical mannequins whose bodies had been dismembered and reconstructed to form abstract configurations that alluded to pornographic poses. Sherman's series was a response to the National Endowment for the Arts controversy, in which American artists such as Andres Serrano and the late Robert Mapplethorpe, whose work was considered obscene by the Republican Congress, were censored. Many artists in the culture-war period had their grants rescinded. The American avant-garde writer Kathy Acker published My Mother: Demonology in 1993. A prominent concern of Acker's in the work is what she termed her ‘writing freedom’ in a climate of cultural expurgation by the Republican elite. In particular, Acker was worried that she was ‘internalizing certain censorships’. This article addresses Sherman's and Acker's work in a comparative context to explore, through the theoretical work of Julia Kristeva, the ways in which their responses to a climate of political censorship can be read as forms of intimate revolt. Kristeva's notion of ejection—the act of placing something beyond the scope of the possible—transpires as ‘a condition of art's creation’ in Sherman's and Acker's work. Acker and Sherman use the pornographic reference in their work to disrupt and dislocate the narrative and image from convention in order to de-eroticize the body, against heteronormativity's terms, and empower the female sex organs. Eversion—that is, in Sherman's and Acker's works, the act of turning the institutional and maternal body inside out—emerges as a mode of resistance to the danger of the writer and the artist internalizing cultural restrictions. The everted body creates a site of radical interiority which becomes the (impossible) site for the radical (re-)embodiment of the feminine subject.