Nickel(II) meso-hydroxyporphyrin complexes revisited: Palladium-catalysed synthesis, electronic structures of derived oxy radicals, and oxidative coupling to a dioxoporphodimethene dyad

We report the synthesis and characterisation of new examples of meso-hydroxynickel(II) porphyrins with 5,15-diphenyl and 10-phenyl-5,15-diphenyl/diaryl substitu- tion. The OH group was introduced by using carbonate or hydroxide as nucleophile by using palladium/phosphine cat- alysis. The NiPor OHs exist in solution in equilibrium with the corresponding oxy radicals NiPor OC. The 15-phenyl group stabilises the radicals, so that the 1H NMR spectra of {NiPor OH} are extremely broad due to chemical exchange with the paramagnetic species. The radical concentration for the diphenylporphyrin analogue is only 1%, and its NMR line-broadening was able to be studied by variable-tempera- ture NMR spectroscopy. The EPR signals of NiPor OC are con- sistent with somewhat delocalised porphyrinyloxy radicals, and the spin distributions calculated by using density func- tional theory match the EPR and NMR spectroscopic obser- vations. Nickel(II) meso-hydroxy-10,20-diphenylporphyrin was oxidatively coupled to a dioxo-terminated porphodimethene dyad, the strongly red-shifted electronic spectrum of which was successfully modelled by using time-dependent DFT calculations.

On the Epistemology of Narrative Theory: Narratology and Other Theories of Fictional Narrative

In this article, I propose to analyze narrative theory from an epistemological standpoint. To do so, I will draw upon both Genettian narratology and what I would call, following Shigeyuki Kuroda, “non-communicational” theories of fictional narrative. In spite of their very unequal popularity, I consider these theories as objective, or, in other words, as debatable and ripe for rational analyses; one can choose between them. The article is made up of three parts. The first part concerns the object of narrative theory, or the narrative as a constructed object, both in narratology (where narrative is likened to a narrative discourse) and in non-communicational narrative theories (where fictional narrative and discourse are mutually exclusive categories). The second part takes up the question of how the claims of these theories do or do not lend themselves to falsification. In particular, Gérard Genette’s claim that “every narrative is, explicitly or not, ‘in the first person’”, will be considered, through the lens of Ann Banfield’s theory of free indirect style. In the third part the reductionism of narrative theory will be dealt with. This leads to a reflection on the role of narrative theory in the analysis of fictional narratives.

Multivariate juggling probabilities

We consider refined versions of Markov chains related to juggling introduced by Warrington. We further generalize the construction to juggling with arbitrary heights as well as infinitely many balls, which are expressed more succinctly in terms of Markov chains on integer partitions. In all cases, we give explicit product formulas for the stationary probabilities. The normalization factor in one case can be explicitly written as a homogeneous symmetric polynomial. We also refine and generalize enriched Markov chains on set partitions. Lastly, we prove that in one case, the stationary distribution is attained in bounded time.

The central nervous control of walking in the locust, Schistocerca Americana

Rhythmic motor behaviors in all animals appear to be under the control of "central pattern generator" circuits, neural circuits which can produce output patterns appropriate for behavior even when isolated from their normal peripheral inputs. Insects have been a useful model system in which to study the control of legged terrestrial locomotion. Much is known about walking in insects at the behavioral level, but to date there has been no clear demonstration that a central pattern generator for walking exists. The focus of this thesis is to explore the central neural basis for locomotion in the locust, Schistocerca americana.

Rhythmic motor patterns could be evoked in leg motor neurons of isolated thoracic ganglia of locusts by the muscarinic agonist pilocarpine. These motor patterns would be appropriate for the movement of single legs during walking. Rhythmic patterns could be evoked in all three thoracic ganglia, but the segmental rhythms differed in their sensitivities to pilocarpine, their frequencies, and the phase relationships of motor neuron antagonists. These different patterns could be generated by a simple adaptable model circuit, which was both simulated and implemented in VLSI hardware. The intersegmental coordination of leg motor rhythms was then examined in preparations of isolated chains of thoracic ganglia. Correlations between motor patterns in different thoracic ganglia indicated that central coupling between segmental pattern generators is likely to contribute to the coordination of the legs during walking.

The work described here clearly demonstrates that segmental pattern generators for walking exist in insects. The pattern generators produce motor outputs which are likely to contribute to the coordination of the joints of a limb, as well as the coordination of different limbs. These studies lay the groundwork for further studies to determine the relative contributions of central and sensory neural mechanisms to terrestrial walking.

On the local Tamagawa number conjecture for Tate motives

There is a wonderful conjecture of Bloch and Kato that generalizes both the analytic Class Number Formula and the Birch and Swinnerton-Dyer conjecture. The conjecture itself was generalized by Fukaya and Kato to an equivariant formulation. In this thesis, I provide a new proof for the equivariant local Tamagawa number conjecture in the case of Tate motives for unramified fields, using Iwasawa theory and (φ,Γ)-modules, and provide some work towards extending the proof to tamely ramified fields.

Specific Interaction with Cardiolipin Triggers Functional Activation of Dynamin-Related Protein 1

Dynamin-Related Protein 1 (Drp1), a large GTPase of the dynamin superfamily, is required for mitochondrial fission in healthy and apoptotic cells. Drp1 activation is a complex process that involves translocation from the cytosol to the mitochondrial outer membrane (MOM) and assembly into rings/spirals at the MOM, leading to membrane constriction/division. Similar to dynamins, Drp1 contains GTPase (G), bundle signaling element (BSE) and stalk domains. However, instead of the lipid-interacting Pleckstrin Homology (PH) domain present in the dynamins, Drp1 contains the so-called B insert or variable domain that has been suggested to play an important role in Drp1 regulation. Different proteins have been implicated in Drp1 recruitment to the MOM, although how MOM-localized Drp1 acquires its fully functional status remains poorly understood. We found that Drp1 can interact with pure lipid bilayers enriched in the mitochondrion-specific phospholipid cardiolipin (CL). Building on our previous study, we now explore the specificity and functional consequences of this interaction. We show that a four lysine module located within the B insert of Drp1 interacts preferentially with CL over other anionic lipids. This interaction dramatically enhances Drp1 oligomerization and assembly-stimulated GTP hydrolysis. Our results add significantly to a growing body of evidence indicating that CL is an important regulator of many essential mitochondrial functions.

An exploratory ecosystem model of the Bay of Bengal Large Marine Ecosystem

The study's aim was to develop and ecosystem model of the Bay of Bengal built with Ecopath and Ecoism software.The Ecopath model was built to represent 1978 and synthesise available population dynamics and fisheries data. A preliminary Ecoism was set up to explore interactions between functional groups and the impact of fishing.

An exploratory ecosystem model of the Bay of Bengal Large Marine Ecosystem

The study's aim was to develop and ecosystem model of the Bay of Bengal built with Ecopath and Ecoism software.The Ecopath model was built to represent 1978 and synthesise available population dynamics and fisheries data. A preliminary Ecoism was set up to explore interactions between functional groups and the impact of fishing.

Application of Dempster-Shafer evidence theory to unsupervised classification in multisource remote sensing

The aim of this paper is to show that Dempster-Shafer evidence theory may be successfully applied to unsupervised classification in multisource remote sensing. Dempster-Shafer formulation allows for consideration of unions of classes, and to represent both imprecision and uncertainty, through the definition of belief and plausibility functions. These two functions, derived from mass function, are generally chosen in a supervised way. In this paper, the authors describe an unsupervised method, based on the comparison of monosource classification results, to select the classes necessary for Dempster-Shafer evidence combination and to define their mass functions. Data fusion is then performed, discarding invalid clusters (e.g. corresponding to conflicting information) thank to an iterative process. Unsupervised multisource classification algorithm is applied to MAC-Europe'91 multisensor airborne campaign data collected over the Orgeval French site. Classification results using different combinations of sensors (TMS and AirSAR) or wavelengths (L- and C-bands) are compared. Performance of data fusion is evaluated in terms of identification of land cover types. The best results are obtained when all three data sets are used. Furthermore, some other combinations of data are tried, and their ability to discriminate between the different land cover types is quantified

Les Tritons de Th?ophile

Sibona, Bruno, 'Les Tritons de Th?ophile', L'Esprit cr?ateur - Literature and Ecology (2006) 46(2) pp.17-32

A feasibility study evaluating docetaxel-based sequential and combination regimens in the adjuvant therapy of node-positive breast cancer

BACKGROUND AND PURPOSE: Docetaxel is an active agent in the treatment of metastatic breast cancer. We evaluated the feasibility of docetaxel-based sequential and combination regimens as adjuvant therapies for patients with node-positive breast cancer. PATIENTS AND METHODS: Three consecutive groups of patients with node-positive breast cancer or locally-advanced disease, aged < or = 70 years, received one of the following regimens: a) sequential A-->T-->CMF: doxorubicin 75 mg/m2 q 3 weeks x 3, followed by docetaxel 100 mg/m2 q 3 weeks x 3, followed by i.v. CMF days 1 + 8 q 4 weeks x 3; b) sequential accelerated A-->T-->CMF: A and T were administered at the same doses q 2 weeks; c) combination therapy: doxorubicin 50 mg/m2 + docetaxel 75 mg/m2 q 3 weeks x 4, followed by CMF x 4. When indicated, radiotherapy was administered during or after CMF, and tamoxifen started after the end of CMF. RESULTS: Seventy-nine patients have been treated. Median age was 48 years. A 30% rate of early treatment discontinuation was observed in patients receiving the sequential accelerated therapy (23% during A-->T), due principally to severe skin toxicity. Median relative dose-intensity was 100% in the three treatment arms. The incidence of G3-G4 major toxicities by treated patients, was as follows: skin toxicity a: 5%; b: 27%; c: 0%; stomatitis a: 20%; b: 20%; c: 3%. The incidence of neutropenic fever was a: 30%; b: 13%; c: 48%. After a median follow-up of 18 months, no late toxicity has been reported. CONCLUSIONS: The accelerated sequential A-->T-->CMF treatment is not feasible due to an excess of skin toxicity. The sequential non accelerated and the combination regimens are feasible and under evaluation in a phase III trial of adjuvant therapy.

Methylation-dependent T cell immunity to Mycobacterium tuberculosis heparin-binding hemagglutinin.

Although post-translational modifications of protein antigens may be important componenets of some B cell epitopes, the determinants of T cell immunity are generally nonmodified peptides. Here we show that methylation of the Mycobacterium tuberculosis heparin-binding hemagglutinin (HBHA) by the bacterium is essential for effective T cell immunity to this antigen in infected healthy humans and in mice. Methylated HBHA provides high levels of protection against M. tuberculosis challenge in mice, whereas nonmethylated HBHA does not. Protective immunity induced by methylated HBHA is comparable to that afforded by vaccination with bacille Calmette et Guérin, the only available anti-tuberculosis vaccine. Thus, post-translational modifications of proteins may be crucial for their ability to induce protective T cell-mediated immunity against infectious diseases such as tuberculosis.

Human dendritic cell maturation and cytokine secretion upon stimulation with Bordetella pertussis filamentous haemagglutinin.

In addition to antibodies, Th1-type T cell responses are also important for long-lasting protection against pertussis. However, upon immunization with the current acellular vaccines, many children fail to induce Th1-type responses, potentially due to immunomodulatory effects of some vaccine antigens, such as filamentous haemagglutinin (FHA). We therefore analysed the ability of FHA to modulate immune functions of human monocyte-derived dendritic cells (MDDC). FHA was purified from pertussis toxin (PTX)-deficient or from PTX- and adenylate cyclase-deficient Bordetella pertussis strains, and residual endotoxin was neutralized with polymyxin B. FHA from both strains induced phenotypic maturation of human MDDC and cytokine secretion (IL-10, IL-12p40, IL-12p70, IL-23 and IL-6). To identify the FHA domains responsible for MDDC immunomodulation, MDDC were stimulated with FHA containing a Gly→Ala substitution at its RGD site (FHA-RAD) or with an 80-kDa N-terminal moiety of FHA (Fha44), containing its heparin-binding site. Whereas FHA-RAD induced maturation and cytokine production comparable to those of FHA, Fha44 did not induce IL-10 production, but maturated MDDC at least partially. Nevertheless, Fha44 induced the secretion of IL-12p40, IL-12p70, IL-23 and IL-6 by MDDC, albeit at lower levels than FHA. Thus, FHA can modulate MDDC responses in multiple ways, and IL-10 induction can be dissociated from the induction of other cytokines.

Proper-motion binaries in the Hipparcos catalogue: comparison with radial velocity data

Context. This paper is the last in a series devoted to the analysis of the binary content of the Hipparcos Catalogue. Aims. The comparison of the proper motions constructed from positions spanning a short (Hipparcos) or long time (Tycho-2) makes it possible to uncover binaries with periods of the order of or somewhat larger than the short time span (in this case, the 3 yr duration of the Hipparcos mission), since the unrecognised orbital motion will then add to the proper motion. Methods. A list of candidate proper motion binaries is constructed from a carefully designed χ2 test evaluating the statistical significance of the difference between the Tycho-2 and Hipparcos proper motions for 103 134 stars in common between the two catalogues (excluding components of visual systems). Since similar lists of proper-motion binaries have already been constructed, the present paper focuses on the evaluation of the detection efficiency of proper-motion binaries, using different kinds of control data (mostly radial velocities). The detection rate for entries from the Ninth Catalogue of Spectroscopic Binary Orbits (SB9) is evaluated, as well as for stars like barium stars, which are known to be all binaries, and finally for spectroscopic binaries identified from radial velocity data in the Geneva-Copenhagen survey of F and G dwarfs in the solar neighbourhood. Results. Proper motion binaries are efficiently detected for systems with parallaxes in excess of ∼20 mas, and periods in the range 1000-30 000 d. The shortest periods in this range (1000-2000 d, i.e. once to twice the duration of the Hipparcos mission) may appear only as DMSA/G binaries (accelerated proper motion in the Hipparcos Double and Multiple System Annex). Proper motion binaries detected among SB9 systems having periods shorter than about 400 d hint at triple systems, the proper-motion binary involving a component with a longer orbital period. A list of 19 candidate triple systems is provided. Binaries suspected of having low-mass (brown-dwarf-like) companions are listed as well. Among the 37 barium stars with parallaxes larger than 5 mas, only 7 exhibit no evidence for duplicity whatsoever (be it spectroscopic or astrometric). Finally, the fraction of proper-motion binaries shows no significant variation among the various (regular) spectral classes, when due account is taken for the detection biases. © ESO 2007.