Spectroscopy and reactivity of a photogenerated tryptophan radical in a structurally defined protein environment

Near-UV irradiation of structurally characterized [Re(I)(CO)3(1,10-phenanthroline)(Q107H)](W48F/Y72F/H83Q/Y108W)AzM(II) [Az = Pseudomonas aeruginosa azurin, M = Cu, Zn]/[Co(NH3)5Cl]Cl2 produces a tryptophan radical (W108*) with unprecedented kinetic stability. After rapid formation (k = 2.8 x 106 s-1), the radical persists for more than 5 h at room temperature in the folded ReAzM(II) structure. The absorption spectrum of ReAz(W108*)M(II) exhibits maxima at 512 and 536 nm. Oxidation of K4[Mo(CN)8] by ReAz(W108*)Zn(II) places the W108*/W108 reduction potential in the protein above 0.8 V vs NHE.     

Synthesis and structure of iron(iii) diamine-bis(phenolate) complexes

The structures and properties of six new iron(iii) diamine-bis(phenolate) complexes are reported. Reaction of anhydrous FeX(3) salts (where X = Cl or Br) with the diprotonated tripodal tetradentate ligands 2-pyridylamino-N,N-bis(2-methylene-4-methyl-6-tert-butylphenol), H(2)[L(1)], and N,N-dimethyl-N',N'-bis(2-methylene-4-methyl-6-tert-butylphenol)ethylenediamine, H(2)[L(2)], produces the trigonal bipyramidal iron(iii) complexes, [L(1)]FeCl , [L(1)]FeBr , [L(2)]FeCl and [L(2)]FeBr . Reaction of FeX(3) with the related linear tetradentate ligand N,N'-bis(4,6-tert-butyl-2-methylphenol)-N,N'-bismethyl-1,2-diaminoethane, H(2)[L(3)], generates square pyramidal iron(iii) complexes, [L(3)]FeCl and [L(3)]FeBr . Complexes have been characterized using electronic absorption spectroscopy and magnetometry. Single crystal X-ray molecular structures have been determined for complexes 1, 3, 5 and 6.     

Limitations of the scalp-hair biologic monitor in assessing selenium status in epidemiological investigations

Scalp hair is routinely used to assess exposure to toxic trace elements and nutritional status of some required trace elements. The advantages and disadvantages of hair as a biologic monitor have been comprehensively discussed in the literature for many years. Among the concerns is distinguishing between exogenous and endogenous contributions. Nested in this issue is the longitudinal distribution of a trace element along the hair strand. The typical observation for many elements of interest is that the element concentration increases from the root end to the distal end; and this is attributed to continuing contamination from exogenous sources. In this study we used neutron activation analysis to measure 14 trace elements in 6 mm segments of full-length scalp hair from three healthy members of the same household having light-urban environmental exposure. To extend the data set for selenium, we included three adult female subjects with longer than average scalp hair. From these trace-element concentrations we calculated the root-to-distal end ratios as a profile diagnostic of trace-element distributions. Ratios fall into three diagnostic categories, >1, ≈1, and <1 corresponding to profiles having decreasing root-to-distal concentrations, unchanging concentrations, and increasing concentrations, respectively. Of the 14 elements measured, only Se has R > 1, Zn and S have R ≈ 1, and the remaining 11 elements all have R < 1 in the order: As > I > Hg ≈ Au ≈ Mg ≈ Mn ≈ Sb ≈ Ca > Cu > Al ≈ Ag. R _Se is greater than 1 and increases with hair length (P = 0.02) corresponding to a continuous longitudinal loss of Se in stark and puzzling contrast to the other elements measured. An analogous loss of Se in the nail monitor was not observed leading us to conclude that the nail is less prone to misclassification of selenium status in epidemiological studies.     

Hamiltonian Type Properties in Claw-Free $$P_5$$-Free Graphs

A graph G on n vertices is said to be (k, m)-pancyclic if every set of k vertices in G is contained in a cycle of length r for each integer r in the set \(\{ m, m + 1, \ldots , n \}\). This property, which generalizes the notion of a vertex pancyclic graph, was defined by Faudree et al. in (Graphs Combin 20:291–310, 2004). The notion of (k, m)-pancyclicity provides one way to measure the prevalence of cycles in a graph. Broersma and Veldman showed in (Contemporary methods in graph theory, BI-Wiss.-Verlag, Mannheim, Wien, Zürich, pp 181–194, 1990) that any 2-connected claw-free \(P_5\)-free graph must be hamiltonian. In fact, every non-hamiltonian cycle in such a graph is either extendable or very dense. We show that any 2-connected claw-free \(P_5\)-free graph is (k, 3k)-pancyclic for each integer \(k \ge 2\). We also show that such a graph is (1, 5)-pancyclic. Examples are provided which show that these results are best possible. Each example we provide represents an infinite family of graphs.     

A novel enantioselective synthetic route to omuralide analogues with the potential for species selectivity in proteasome inhibition

[reaction in text] The building blocks shown can be combined for an enantioselective construction of the simplified omuralide analogue 4 in nine steps, with the use of (R)-atrolactic acid as a recoverable chiral controller.     

Geometric modeling and analysis of detonation cellular stability

A geometric model with a low computational complexity capable of simulating detonation behavior in physical systems is proposed. In support of the geometric model development, a series of cylindrical 1D simulations with a variable size initiation kernel are performed in hydrogen-oxygen mixtures. From these 1D simulations a detonation cell stabilization mechanism is identified. The stabilization mechanism is predicated on the size of the gap between the pressure and temperature fronts at the point where the average pressure front velocity along one cell length is equal to the CJ velocity. This gap, in a multidimensional detonation, is the ignition kernel of a subsequent blast, and dictates the formation of the subsequent cell. Serial analysis of blasts in this context leads to a unique stable blast kernel size for any mixture, which, within the uncertainty of the initial kernel state, can predict the experimental cell length for mixtures considered in this study. Using a tabulation of the 1D simulations as an input, a formulation and sample results of the geometric model are shown. The geometric model can reproduce both qualitative and quantitative features of experimental detonation cellular structure.