Intelligence collective et démocratie en Politique, III, 11

À l’heure où les limites du modèle de la démocratie représentative traditionnelle apparaissent de plus en plus évidentes, on a pu défendre, dans la littérature récente, un modèle sensiblement différent : celui d’une démocratie épistémique, tirant parti, par le mécanisme de la délibération inclusive, d’une forme d’intelligence collective qui serait disséminée à travers les agents d’une collectivité. Or, les partisans d’une telle approche se réclament souvent d’un argument qu’on trouve sous la plume d’Aristote en Politique, III, 11. L’objectif de cette étude est d’examiner la légitimité d’une telle filiation, en examinant de manière comparative les arguments modernes en faveur de la démocratie épistémique délibérative et le texte aristotélicien. Un tel travail permet de nuancer la portée du recours à Aristote dans les justifications épistémiques de la démocratie : d’une part, le mécanisme auquel songe Aristote dans le texte de la Politique ne saurait se ramener à une forme quelconque de délibération inclusive ; et, d’autre part, l’argument épistémique se trouve restreint par la mise en évidence des limites intrinsèques du régime démocratique. Plutôt que la source d’une position moderne en faveur de la démocratie, on trouverait alors chez Aristote l’occasion de penser le danger concret qui guette tout modèle délibératif : c’est-à-dire, la confiscation du débat public par une minorité de démagogues, qui empêche la collectivité de tirer parti de la diversité cognitive qu’elle contient.

High resolution optogalvanic spectrum of N2-rotational structure of (11, 7) band in the first positive system

High resolution optogalvanic spectrum of the (11, 7) band in the first positive system of nitrogen molecule has been recorded from 17179 to 17376 cm- 1. Assignment of 432 rotational lines belonging to the 27 branches of this band has been carried out.

"Alkaline Lipase Production by Marine Bacillus smithii BTMS 11"

Considering the potential of marine environment present study was designed for the screening and isolation of a potential salt tolerant. alkaline and thennotolerant lipase producing bacteria from the costal belts of South India and consequent development of ideal bioprocess for industrial production, purification characterisation and evaluation of the potential of the lipase enzyme for various industrial applications 1. Screening and isolation of a potential lipase producing bacteria. 2. Optimization of various physicochemical factors in Submerged fennentation for the production of alkaline lipase 3. Purification ofthe lipase enzyme 4. Characterisation of the enzyme 5. Evaluation of the enzyme for various industrial applications

Detergent compatible alkaline lipase produced by marine Bacillus smithii BTMS 11

Bacillus smithii BTMS 11, isolated from marine sediment, produced alkaline and thermostable lipase. The enzyme was purified to homogeneity by ammonium sulfate precipitation and ion exchange chromatography which resulted in 0.51 % final yield and a 4.33 fold of purification. The purified enzyme was found to have a specific activity of 360 IU/mg protein. SDS-PAGE analyses, under non-reducing and reducing conditions, yielded a single band of 45 kDa indicating the single polypeptide nature of the enzyme and zymogram analysis using methylumbelliferyl butyrate as substrate confirmed the lipolytic activity of the protein band. The enzyme was found to have 50 C and pH 8.0 as optimum conditions for maximal activity. However, the enzyme was active over wide range of temperatures (30–80 C) and pH (7.0–10.0). Effect of a number of metal salts, solvents, surfactants, and other typical enzyme inhibitors on lipase activity was studied to determine the novel characteristics of the enzyme. More than 90 % of the enzyme activity was observed even after 3 h of incubation in the presence of commercial detergents Surf, Sunlight, Ariel, Henko, Tide and Ujala indicating the detergent compatibility of B. smithii lipase. The enzyme was also found to be efficient in stain removal from cotton cloths. Further it was observed that the enzyme could catalyse ester synthesis between fatty acids of varying carbon chain lengths and methanol with high preference for medium to long chain fatty acids showing 70 % of esterification. Results of the study indicated scope for application of this marine bacterial lipase in various industries

Ferrocene-Based Pyridylphosphine Ligands – Coordination Chemistry of Group 10, 11 and 12 Metals

English: The present thesis describes the synthesis of 1,1’-ferrocendiyl-based pyridylphosphine ligands, the exploration of their fundamental coordination chemistry and preliminary experiments with selected complexes aimed at potential applications. One main aspect is the synthesis of the bidentate ferrocene-based pyridylphosphine ligands 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene, 1-(Pyrid-3-yl)-1’-diphenylphosphinoferrocene and 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene. A specific feature of these ligands is the ball-bearing like flexibility of the ferrocenebased backbone. An additional flexibility element is the rotation around the C–C single bonds. Consequently, the donor atoms can realise a wide range of positions with respect to each other and are therefore able to adapt to the coordination requirements of different metal centres. The flexibility of the ligand also plays a role in another key aspect of this work, which concerns the coordination mode, i. e. bridging vs. chelating. In addition to the flexibility, also the position of the donor atoms to each other is important. This is largely affected by the position of the pyridyl nitrogen (pyrid-2-yl vs. pyrid-3-yl) and the methylen group in 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene. Another interesting point is the combination of a soft phosphorus donor atom with a harder nitrogen donor atom, according to the HSAB principle. This combination generates a unique binding profile, since the pi-acceptor character of the P site is able to stabilise a metal centre in a low oxidation state, while the nitrogen sigma-donor ability can make the metal more susceptible to oxidative addition reactions. A P,N-donor combination can afford hemilabile binding profiles, which would be ideal for catalysis. Beyond 1,2-substituted ferrocene derivatives, which are quite successful in catalytic applications, 1,1’-derivatives are rather underrepresented. While a low-yield synthetic pathway to 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene was already described in the literature [I. R. Butler, Organometallics 1992, 11, 74.], it was possible to find a new, improved and simplified synthetic pathway. Both other ligands were unknown prior to this work. Satisfactory results in the synthesis of 1-(Pyrid-3-yl)-1’-diphenylphosphinoferrocene could be achieved by working in analogy to the new synthetic procedure for 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene. The synthesis of 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene has been handled by the group of Prof. Petr Stepnicka from Charles University, Prague, Czech Republic. The synthesis of tridentate ligands with an analogous heterodentate arrangement, was investigated briefly as a sideline of this study. The major part of this thesis deals with the fundamental coordination chemistry towards transition metals of the groups 10, 11 and 12. Due to the well-established catalytic properties of analogous palladium complexes, the coordination chemistry towards palladium (group 10) is of particular interest. The metals zinc and cadmium (group 12) are also of substantial importance because they are redox-inert in their divalent state. This is relevant in view of electrochemical investigations concerning the utilisation of the ligands as molecular redox sensors. Also mercury and the monovalent metals silver and gold (group 11) are included because of their rich coordination chemistry. It is essential to answer questions concerning aspects of the ligands’ coordination mode bearing in mind the HSAB principle.