Engineering tyrosine-based electron flow pathways in proteins: The case of aplysia myoglobin

Tyrosine residues can act as redox cofactors that provide an electron transfer ("hole-hopping") route that enhances the rate of ferryl heme iron reduction by externally added reductants, for example, ascorbate. Aplysia fasciata myoglobin, having no naturally occurring tyrosines but 15 phenylalanines that can be selectively mutated to tyrosine residues, provides an ideal protein with which to study such through-protein electron transfer pathways and ways to manipulate them. Two surface exposed phenylalanines that are close to the heme have been mutated to tyrosines (F42Y, F98Y). In both of these, the rate of ferryl heme reduction increased by up to 3 orders of magnitude. This result cannot be explained in terms of distance or redox potential change between donor and acceptor but indicates that tyrosines, by virtue of their ability to form radicals, act as redox cofactors in a new pathway. The mechanism is discussed in terms of the Marcus theory and the specific protonation/deprotonation states of the oxoferryl iron and tyrosine. Tyrosine radicals have been observed and quantified by EPR spectroscopy in both mutants, consistent with the proposed mechanism. The location of each radical is unambiguous and allows us to validate theoretical methods that assign radical location on the basis of EPR hyperfine structure. Mutation to tyrosine decreases the lipid peroxidase activity of this myoglobin in the presence of low concentrations of reductant, and the possibility of decreasing the intrinsic toxicity of hemoglobin by introduction of these pathways is discussed. © 2012 American Chemical Society

Universal subspaces for compact Lie groups

For a representation of a connected compact Lie group G in a finite dimensional real vector space U and a subspace V of U, invariant under a maximal torus of G, we obtain a sufficient condition for V to meet all G-orbits in U, which is also necessary in certain cases. The proof makes use of the cohomology of flag manifolds and the invariant theory of Weyl groups. Then we apply our condition to the conjugation representations of U(n), Sp(n), and SO(n) in the space of $n\times n$ matrices over C, H, and R, respectively. In particular, we obtain an interesting generalization of Schur's triangularization theorem.Comment: 20 page

A new genus for a rare African vespertilionid bat: insights from South Sudan

A new genus is proposed for the strikingly patterned African vespertilionid "Glauconycteris" superba Hayman, 1939 on the basis of cranial and external morphological comparisons. A review of the attributes of a newly collected specimen from South Sudan (a new country record) and other museum specimens of "Glauconycteris" superba suggests that "Glauconycteris" superba is markedly distinct ecomorphologically from other species classified in Glauconycteris and is likely the sister taxon to Glauconycteris sensu stricto. The recent capture of this rarely collected but widespread bat highlights the need for continued research in tropical sub-Saharan Africa and in particular, for more work in western South Sudan, which has received very little scientific attention. New country records for Glauconycteris cf. poensis (South Sudan) and Glauconycteris curryae (Gabon) are also reported.DeeAnn M. Reeder, Kristofer M. Helgen, Megan E. Vodzak, Darrin P. Lunde, Imran Ejotr

A Population of Taphromysis louisianae (Banner); (Crustacea: Mysidae) in a Clermont County Ohio River Wetland

Author Institution: Department of Biological and Environmental Sciences, Morehead State UniversityA reproducing population of Taphromysis louisianae was found in a shallow freshwater tributary of the Ohio River in Clermont County, OH throughout 1990-91. The nearest distribution record is in Louisiana. Therefore, this is the first record of this normally brackish water species in the Ohio River Basin. Analysis of habitat reveals that the population prefers shallow water (< 1 m) with leafy, high organic matter (about 8% of the soil dry weight) substrate. At the Ohio discovery site salinity was below limits of detection; the average pH was 6.5, and the mean dissolved oxygen concentration was 10 mg I1. This is in contrast to the higher salinity habitat of this species in bays and ditches of tidal areas. Because of distance and physiochemical disparities between the Gulf Coast and Ohio habitats, it is suggested that the isolated inland population exhibits characteristics of the early stages of speciation

Graded Hecke algebras for disconnected reductive groups

We introduce graded Hecke algebras H based on a (possibly disconnected) complex reductive group G and a cuspidal local system L on a unipotent orbit of a Levi subgroup M of G. These generalize the graded Hecke algebras defined and investigated by Lusztig for connected G. We develop the representation theory of the algebras H. obtaining complete and canonical parametrizations of the irreducible, the irreducible tempered and the discrete series representations. All the modules are constructed in terms of perverse sheaves and equivariant homology, relying on work of Lusztig. The parameters come directly from the data (G,M,L) and they are closely related to Langlands parameters. Our main motivation for considering these graded Hecke algebras is that the space of irreducible H-representations is canonically in bijection with a certain set of "logarithms" of enhanced L-parameters. Therefore we expect these algebras to play a role in the local Langlands program. We will make their relation with the local Langlands correspondence, which goes via affine Hecke algebras, precise in a sequel to this paper.Comment: Theorem 3.4 and Proposition 3.22 in version 1 were not entirely correct as stated. This is repaired in a new appendi

On the elliptic nonabelian Fourier transform for unipotent representations of p-adic groups

In this paper, we consider the relation between two nonabelian Fourier transforms. The first one is defined in terms of the Langlands-Kazhdan-Lusztig parameters for unipotent elliptic representations of a split p-adic group and the second is defined in terms of the pseudocoefficients of these representations and Lusztig's nonabelian Fourier transform for characters of finite groups of Lie type. We exemplify this relation in the case of the p-adic group of type G_2.Comment: 17 pages; v2: several minor corrections, references added; v3: corrections in the table with unipotent discrete series of G

Enhanced acoustic mode coupling resulting from an internal solitary wave approaching the shelfbreak in the South China Sea

Author Posting. © Acoustical Society of America, 2013. This article is posted here by permission of Acoustical Society of America for personal use, not for redistribution. The definitive version was published in Journal of the Acoustical Society of America 133 (2013): 1306-1319, doi:10.1121/1.4789358.Internal waves and bathymetric variation create time- and space-dependent alterations in the ocean acoustic waveguide, and cause subsequent coupling of acoustic energy between propagating normal modes. In this paper, the criterion for adiabatic invariance is extended to the case of an internal solitary wave (ISW) encountering a sloping bathymetry (i.e., continental shelfbreak). Predictions based on the extended criterion for adiabatic invariance are compared to experimental observations from the Asian Seas International Acoustics Experiment. Using a mode 1 starter field, results demonstrate time-dependent coupling of mode 1 energy to higher adjacent modes, followed by abrupt coupling of mode 5–7 energy to nonadjacent modes 8–20, produces enhanced mode coupling and higher received levels downrange of the oceanographic and bathymetric features. Numerical simulations demonstrate that increasing ISW amplitude and seafloor slope enhance the coupling of energy to adjacent and nonadjacent modes. This enhanced coupling is the direct result of the simultaneous influence of the ISW and its proximity to the shelfbreak, and, compared to the individual effect of the ISW or shelfbreak, has the capacity to scatter 2–4 times the amount of acoustic energy from below the thermocline into the upper water column beyond the shelfbreak in realistic environments.The ASIAEX and NLIWI experiments were supported jointly by the National Science Council of Taiwan and the U.S. Office of Naval Research