Conformational preferences driven by the C-methyl substituent in chelated o-diphenylphosphino-alpha-methyl-N,N-dimethylbenzylamine rhodium complexes

The stereochemistry of the chelate rings of a number of rhodium aminophosphine complexes is studied by NMR spectroscopy. The similarity in the variable-temperature behavior for the different compounds is consistent with them having in common highly preferred chelate ring conformations. The six-membered metallacycle of coordinated (R)-PN (PN = o-diphenylphosphino-alpha-methyl-N,N-dimethylbenzylamine) adopts a delta conformation in the solid state. NMR experiments indicate that this conformation is strongly favored in solution as well. The preferred sense of helicity is imposed by the absolute configuration of the stereogenic carbon atom on the ligand, which exerts an important steric control. The complex [Rh(TFB)((C(6)H(4)CHMeNMe(2))(2)P(C(6)H(4)CHMeNHMe(2)))](BF(4))(2).H(2)O.Me(2)CO crystallizes in the monoclinic space group P2(1) with a = 12.0548(11) A, b = 16.139(2) A, c = 12.1804(10) A, beta = 100.742(9) degrees, Z = 4.     

Contents to Volume 123 (2000)

Authors Index

Contents to Volume 123 (2000)     

Development of Nanosensors and Bioprobes

We describe the development and application of nanosensors having bioreceptor probes for bioanalysis. The nanoprobes were fabricated with optical fibers pulled down to tips having distal end sizes of approximately 30–60nm. The use of two different types of receptors was investigated. Fiberoptic nanoprobes were covalently bound either with bioreceptors, such as antibodies, or with other receptors, such as cyclodextrins that are selective for the size and chemical structure of the analyte molecules. Theoretical calculations were performed to model the binding of beta-cyclodextrin with pyrene and 5,6-benzoquinoline, and to illustrate the possibility of comparing experimental data with theoretical data. The antibody-based nanoprobe was used for in situ measurements of benzopyrene tetrol in single cells. The performance of the nanosensor is illustrated by intracellular measurements performed on a rat liver epithelial cell line (Clone 9) used as the model cell system. The usefulness and potential of these nanotechnology-based biosensors in biological research and applications are discussed.     

Synthèse et étude de modèles de NADH à noyaux accolés en série pyrrolo[2,3-b] et [3,2-b]pyridines

Pyrrolo[2,3-b] and [3,2-b]pyridines derivatives, precursors for annealated NADH models have been prepared. Several methods for building a pyridinic annealates ring have been used starting from 2- or 3-aminopyrrole. The corresponding dihydropyridine structure leads to highly reactive NADH models compounds and are very much more stable than common models.     

Electrically pumped two-dimensional Bragg grating lasers

We demonstrate electrically pumped InGaAsP two-dimensional Bragg grating (2DBG) lasers with two line defects. The 2DBG structure uses a weak 2D index perturbation surface grating to control the optical modes in the plane of the wafer. Measurements of the 2DBG lasers show that modal control in both the longitudinal and transverse directions is due to the gratings and defects. The 2DBG lasers are promising candidates for single-mode, high power, and high efficiency large-area lasers.     

Microcanonical modeling of the thermokinetic method

A microcanonical analysis of the thermokinetic method is performed using statistical rate calculations based on orbiting transition state theory in order to model a proton transfer process: MH(+) + B(i) --> M + B(i)H(+). The reaction efficiency is calculated as a function of the difference in zero point energy of reactants and products. Several models of reactions were investigated in order to simulate situations where the base of interest M exhibits loss of entropy upon protonation of up to approximately 40 J mol(-1) K(-1). It is shown that the standard thermokinetic method would predict correct 298 K gas phase basicities, GB(298)(M), even for polydentate molecules M, if experiments are conducted at this temperature. Proton affinity, PA(298)(M), and protonation entropy may be obtained by the thermokinetic method only in special circumstances such as, for example, experiments conducted at various temperatures.     

The essentially tame local Langlands correspondence, I

Let be a non-Archimedean local field (of characteristic or ) with finite residue field of characteristic . An irreducible smooth representation of the Weil group of is called essentially tame if its restriction to wild inertia is a sum of characters. The set of isomorphism classes of irreducible, essentially tame representations of dimension is denoted . The Langlands correspondence induces a bijection of with a certain set of irreducible supercuspidal representations of . We consider the set of isomorphism classes of certain pairs , called ``admissible', consisting of a tamely ramified field extension of degree and a quasicharacter of . There is an obvious bijection of with . Using the classification of supercuspidal representations and tame lifting, we construct directly a canonical bijection of with , generalizing and simplifying a construction of Howe (1977). Together, these maps give a canonical bijection of with . We show that one obtains the Langlands correspondence by composing the map with a permutation of of the form , where is a tamely ramified character of depending on . This answers a question of Moy (1986). We calculate the character in the case where is totally ramified of odd degree.