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

Observationally constrained modeling of sound in curved ocean internal waves: Examination of deep ducting and surface ducting at short range

Author Posting. © Acoustical Society of America, 2011. 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 130 (2011): 1173-1187, doi:10.1121/1.3605565.A study of 400 Hz sound focusing and ducting effects in a packet of curved nonlinear internal waves in shallow water is presented. Sound propagation roughly along the crests of the waves is simulated with a three-dimensional parabolic equation computational code, and the results are compared to measured propagation along fixed 3 and 6 km source/receiver paths. The measurements were made on the shelf of the South China Sea northeast of Tung-Sha Island. Construction of the time-varying three-dimensional sound-speed fields used in the modeling simulations was guided by environmental data collected concurrently with the acoustic data. Computed three-dimensional propagation results compare well with field observations. The simulations allow identification of time-dependent sound forward scattering and ducting processes within the curved internal gravity waves. Strong acoustic intensity enhancement was observed during passage of high-amplitude nonlinear waves over the source/receiver paths, and is replicated in the model. The waves were typical of the region (35 m vertical displacement). Two types of ducting are found in the model, which occur asynchronously. One type is three-dimensional modal trapping in deep ducts within the wave crests (shallow thermocline zones). The second type is surface ducting within the wave troughs (deep thermocline zones).Grants from the Office of Naval Research funded this work. Use of the vessels Ocean Researcher I and Ocean Researcher II in this experiment was funded by the Taiwan National Science Council

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

Impact of Grazing Management Strategies on Carbon Sequestration in a Semi-Arid Rangeland, USA

The effects of 12 years of grazing management strategies on carbon (C) distribution and sequestration were assessed on a semi-arid mixed-grass prairie in Wyoming, USA. Five grazing treatments were evaluated: non-grazed exclosures; continuous, season-long grazing at a light (22 steer-days ha-1) stocking rate; and, rotationally-deferred, short-duration rotation, and continuous, season-long grazing, all three at a heavy stocking rate (59 steer-days ha-1). Non-grazed exclosures exhibited a large buildup of dead plant material (72% of total aboveground plant matter) and forb biomass represented a large component (35%) of the plant community. Stocking rate, but not grazing strategy, changed plant community composition and decreased surface litter. Light grazing decreased forbs and increased cool-season mid-grasses, resulting in a highly diversified plant community and the highest total production of grasses. Heavy grazing increased warm-season grasses at the expense of the cool-season grasses, which decreased total forage production and opportunity for early season grazing. Compared to the exclosures, all grazing treatments resulted in significantly higher levels of C (6000-9000 kg ha-1) in the surface 15 cm of the soil. Higher levels of soil C with grazing are likely the result of faster litter decomposition and recycling, and redistribution of C within the 0-60 cm plant-soil system. Grazing at an appropriate stocking rate had beneficial effects on plant composition, forage production, and soil C sequestration. Without grazing, deterioration of the plant-soil system is indicated

Alternatively spliced variants of the cell adhesion molecule CD44 and tumour progression in colorectal cancer.

Increased expression of alternatively spliced variants of the CD44 family of cell adhesion molecules has been associated with tumour metastasis. In the present study, expression of alternatively spliced variants of CD44 and their cellular distribution have been investigated in human colonic tumours and in the corresponding normal mucosa, in addition to benign adenomatous polyps. The expression of CD44 alternatively spliced variants has been correlated with tumour progression according to Dukes' histological stage. CD44 variant expression was determined by immunohistochemisty using monoclonal antibodies directed against specific CD44 variant domains together with RT-PCR analysis of CD44 variant mRNA expression in the same tissue specimens. We demonstrate that as well as being expressed in colonic tumour cells, the full range of CD44 variants, CD44v2-v10, are widely expressed in normal colonic crypt epithelium, predominantly in the crypt base. CD44v6, the epitope which is most commonly associated with tumour progression and metastasis, was not only expressed by many benign colonic tumours, but was expressed as frequently in normal basal crypt epithelium as in malignant colonic tumour cells, and surprisingly, was even absent from some metastatic colorectal tumours. Expression of none of the CD44 variant epitopes was found to be positively correlated with tumour progression or with colorectal tumour metastasis to the liver, results which are inconsistent with a role for CD44 variants as indicators of colonic cancer progression

Horizontally Issuing Diffusion Flames Characterized by OH-PLIF and Visualizations

Planar laser induced fluorescence and flame visualizations characterized the effect of buoyancy on the behavior of the combustion zone of diffusion jet flames which issued from horizontally-oriented tubes into ambient air. The study focused on the mixing characteristics of propane and ethylene at Reynolds numbers ranging from 300 to 1500 in the near field of the jet (up to X/D=9) and Froude numbers ranging as low as 0.36, based on cold-flow gas properties and conditions. Performing the study with a variety of fuel tube diameters enabled independent control of Froude and Reynolds numbers. The PLIF visualizations revealed the presence of the hydroxyl radical in the mixing layer for all cases. The hydroxyl concentrations were consistently higher in the upper portion of the mixing layer, indicative of more vigorous mixing in this region. The visualizations also revealed the evolution of polycyclic aromatic hydrocarbons which were initially spatially segregated from the portion of the reaction zone containing the hydroxyl radical. The polycyclic aromatic hydrocarbons initiate in fuel-rich regions nearer to the jet core than the hydroxyl radical, though the two regions eventually combine well downstream of the tube exit. Both the hydroxyl radical and the polycyclic aromatic hydrocarbons were more prominent on the upper side of the jet flame. Both propane and ethylene fuels led to qualitatively similar features of the flow field, indicating the important role played by the buoyancy-influenced fluid dynamics of the combustion products. The resulting cross sectional PLIF images were used to produce a three-dimensional representation of the reaction zone, indicating the jet spread and trajectory. The data was empirically correlated and found to collapse when based on the Froude number consistent with the density and temperature of a fully-reacted stoichiometric mixture. Complementary visualizations provided additional insight into the trajectory of the jet flame and revealed features of the reaction zone farther from the tube exit