Photophysics and redox behavior of chiral transition metal polymers

The absorption and emission spectra, excited-state lifetimes, quantum yields, and electrochemical measurements have been obtained for a new series of chiral complexes based on three different chiral 2,2':6',2' '-terpyridine ligands, (-)-ctpy, (-)-[ctpy-x-ctpy], and (-)-[ctpy-b-ctpy], with one, two, or multiple Ru metal centers. The room-temperature absorption and emission maxima of [[((-)-ctpy)Ru]-(-)-[ctpy-b-ctpy]-[Ru((-)-ctpy)]](PF(6))(4) and ((-)-[ctpy-b-ctpy])-[[Ru((-)-[ctpy-b-ctpy])](PF(6))(2)](n) were shifted to lower energies and also exhibited significantly longer luminescence lifetimes when compared to [Ru((-)-ctpy)(2)](PF(6))(2), [[((-)-ctpy)Ru]-(-)-[ctpy-x-ctpy]-[Ru((-)-ctpy)]](PF(6))(4), and ((-)-[ctpy-x-ctpy])-[[Ru((-)-[ctpy-x-ctpy])](PF(6))(2)](n). In terms of their electrochemical behavior, all of the complexes studied exhibited one Ru-centered and two ligand-centered redox waves and the [[((-)-ctpy)Ru]-(-)-[ctpy-x-ctpy]-[Ru((-)-ctpy)]](PF(6))(4), ((-)-[ctpy-x-ctpy])-[[Ru((-)-[ctpy-x-ctpy])](PF(6))(2)](n), and ((-)-[ctpy-b-ctpy])-[[Ru((-)-[ctpy-b-ctpy])](PF(6))(2)](n)() complexes were found to electrodeposit upon ligand-based reduction. The difference between the formal potentials of the Ru-centered and the first ligand-centered (least negative) waves corresponded linearly with the changes in the observed emission energies. The shifts in energy are discussed using a particle-in-a-box model, and the luminescence lifetimes are discussed in terms of the structure of the excited-state manifold.     

Recoil polarimetry with the Crystal Ball at MAMI

The spectrum and properties of the excited states of the nucleon are still poorly established despite decades of study. These proceedings describe new measurements of pseudo-scalar meson photoproduction at the Crystal Ball at MAMI, employing a new large acceptance nucleon recoil polarimeter. The double- and single-polarisation observables obtained will provide valuable and unique data to be used as part of the world effort to improve our knowledge of this fundamental spectrum.     

Precision measurements of strangeness photoproduction at threshold energies with the Crystal Ball at MAMI-C

The photoproduction of K＋ mesons from the nucleon provides important constraints on the nucleon excitation spectrum and at threshold energies challenges effective field theories based on chiral perturbation in the strange quark sector. Preliminary cross-section measurements for γ（P, K＋）A are presented at an unprecedented beam energy resolution. The data was collected at the MAMI-C facility in Mainz using the Crystal Ball Detector. A new method of K＋ detection was used in which the K＋ is tagged from its weak decay products in the detector crystals. This technique has application with other calorimeters at present and future hadron facilities.     

Measurement of the electric form factor of the neutron at Q2 = 0.3-0.8 (GeV/ c) 2 ⋆

The electric form factor of the neutron, G_E,n, has been measured at the Mainz Microtron by recoil polarimetry in the quasielastic D(¯e, e¯n)p reaction. Three data points have been extracted at squared four-momentum transfers Q ² = 0.3, 0.6 and 0.8 (GeV/c)². Corrections for nuclear binding effects have been applied.This revised version was published online in March 2005. In the previous version, the email address of one author was inadvertently assigned to multiple authors.     

Model of convergent extension in animal morphogenesis

We argue that energy minimization can explain the pattern of cell movements in the morphogenetic process known as convergent extension provided that the cell-cell adhesive energy has a certain type of anisotropy, which we describe. This single simple property suffices to cause the cell elongation, cell alignment, and lengthening of a cellular array that characterize convergent extension. We show that the final aspect ratio of the array of cells depends on the anisotropy and is independent of the initial configuration and of the degree of cell elongation.     

Intermolecular Regio‐ and Stereoselective Hetero‐[5+2] Cycloaddition of Oxidopyrylium Ylides and Cyclic Imines

We have developed the first intermolecular hetero‐[5+2] cycloaddition reaction between oxidopyrylium ylides and cyclic imines with excellent control of regio‐ and stereoselectivity. Surprisingly, divergent stereochemistry was observed depending on the substitution pattern of the oxidopyrylium ylide. This new reaction provides quick access to highly substituted nitrogen‐containing seven‐membered rings—azepanes. Notably, a broad range of oxidopyrylium ylides and cyclic imines participate in this novel hetero‐[5+2] cycloaddition reaction and the cycloadducts can be readily transformed into the core skeletons of bioactive natural products. DFT calculations revealed that the cycloaddition proceeds through a stepwise pathway and the imine nitrogen atom serves as the nucleophile to initiate the cycloaddition.     

Recoil polarimetry in meson photoproduction at MAMI

The nucleon excitation spectrum remains poorly known, with the masses, widths, EM couplings and even existence of many states not well established. A program of experiments using meson photoproduction off the nucleon is being carried out to improve this situation. A new large acceptance recoil polarimeter has been developed by the Edinburgh group for use in such reactions with the Crystal Ball at MAMI. This work summarizes the procedure used to measure recoil polarization with the new device and presents some preliminary results for the double polarization observable C_x in the reaction γp→pπ~0, compared to the current partial wave analysis.