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.     

Regulation of glutamatergic signalling by PACAP in the mammalian suprachiasmatic nucleus

Background  

Previous studies indicate that light information reaches the suprachiasmatic nucleus (SCN) through a subpopulation of retinal ganglion cells that contain both glutamate and pituitary adenylyl cyclase activating peptide (PACAP). While the role of glutamate in this pathway has been well studied, the involvement of PACAP and its receptors are only beginning to be understood. Speculating that PACAP may function to modulate how neurons in the suprachiasmatic nucleus respond to glutamate, we used electrophysiological and calcium imaging tools to examine possible cellular interactions between these co-transmitters.     

Elastic response of an orthogonally reinforced plate

This paper develops a three-dimensional fully elastic analytical model of a solid plate that has two sets of embedded, equally spaced stiffeners that are orthogonal to each other. The dynamics of the solid plate are based on the Navier–Cauchy equations of motion of an elastic body. This equation is solved with unknown wave propagation coefficients at two locations, one solution for the volume above the stiffeners and the second solution for the volume below the stiffeners. The forces that the stiffeners exert on the solid body are derived using beam and bar equations of motion. Stress and continuity equations are then written at the boundaries and these include the stiffener forces acting on the solid. A two-dimensional orthognalization procedure is developed and this produces an infinite number of double indexed algebraic equations. These are all written together as a global system matrix. This matrix can be truncated and solved resulting in a solution to the wave propagation coefficients which allows the systems displacements to be determined. The model is verified by comparison to thin plate theory and finite element analysis. An example problem is formulated. Convergence of the series solution is discussed. The frequency limitations of the model are examined.     

Self-similarities in the frequency-amplitude space of a loss-modulated CO2 laser

We show the standard two-level continuous-time model of loss-modulated CO2 lasers to display the same regular network of self-similar stability islands known so far to be typically present only in discrete-time models based on mappings. Our results suggest that the two-parameter space of class B laser models and that of a certain class of discrete mappings could be isomorphic.     

Analysis of isotopic signals in the Danube River water at Tulln,Austria, based on daily grab samples in 2012

Results of stable isotope measurements (δ²H, δ¹⁸O) of daily grab samples, taken from the Danube River at Tulln (river km 1963) during 2012, show seasonal and short-term variations depending on the climatic/hydrological conditions and changes in the catchment area (temperature changes, heavy rains and snow melt processes). Isotope ratios in river water clearly reflect the isotopic composition of precipitation water in the catchment area since evaporation influences play a minor role. Average δ²H and δ¹⁸O values in 2012 are?78‰ and?11.0‰, respectively, deuterium excess averages 10‰. The entire variation amounts to 1.8‰ in δ¹⁸O and 15‰ in δ²H. Quick changes of the isotopic composition within a few days emphasise the necessity of daily sampling for the investigation of hydrological events, while monthly grab sampling seems sufficient for the investigation of long-term hydro-climatic trends. ³H results show peaks (half-width 1–2 days, up to about 150 TU) exceeding the regional environmental level of about 9 TU, probably due to releases from nuclear power plants.     

Sensitization of spinal cord nociceptive neurons with a conjugate of substance P and cholera toxin

Background  

Several investigators have coupled toxins to neuropeptides for the purpose of lesioning specific neurons in the central nervous system. By producing deficits in function these toxin conjugates have yielded valuable information about the role of these cells. In an effort to specifically stimulate cells rather than kill them we have conjugated the neuropeptide substance P to the catalytic subunit of cholera toxin (SP-CTA). This conjugate should be taken up selectively by neurokinin receptor expressing neurons resulting in enhanced adenylate cyclase activity and neuronal firing.     

Growth inside a corner: the limiting interface shape

We investigate the growth of a crystal that is built by depositing cubes inside a corner. The interface of this crystal approaches a deterministic growing limiting shape in the long-time limit. Building on known results for the corresponding two-dimensional system and accounting for basic three-dimensional symmetries, we conjecture a governing equation for the evolution of the interface profile. We solve this equation analytically and find excellent agreement with simulations of the growth process. We also present a generalization to arbitrary spatial dimension.     

Steady inter and intra-annual decrease in the vocalization frequency of Antarctic blue whales

Time averaged narrow-band noise near 27 Hz produced by vocalizations of many distant Antarctic blue whales intensifies seasonally from early February to late October in the ocean off Australia's South West. Spectral characteristics of long term patterns in this noise band were analyzed using ambient noise data collected at the Comprehensive Nuclear-Test-Ban Treaty hydroacoustic station off Cape Leeuwin, Western Australia over 2002-2010. Within 7 day averaged noise spectra derived from 4096-point FFT (～0.06 Hz frequency resolution), the -3-dB width of the spectral peak from the upper tone of Antarctic blue whale vocalization was about 0.5 Hz. The spectral frequency peak of this tonal call was regularly but not gradually decreasing over the 9 years of observation from ～27.7 Hz in 2002 to ～26.6 Hz in 2010. The average frequency peak steadily decreased at a greater rate within a season at 0.4-0.5 Hz/season but then in the next year recovered to approximately the mean value of the previous season. A regression analysis showed that the interannual decrease rate of the peak frequency of the upper tonal call was 0.135 ± 0.003 Hz/year over 2002-2010 (R(2) ≈ 0.99). Possible causes of such a decline in the whale vocalization frequency are considered.