Structures and Reactivity Patterns of Group 9 Metallocorroles

Group 9 metallocorroles 1-M(PPh_3) and 1-M(py)_2 [M = Co(III), Rh(III), Ir(III); 1 denotes the trianion of 5,10,15-tris-pentafluorophenylcorrole] have been fully characterized by structural, spectroscopic, and electrochemical methods. Crystal structure analyses reveal that average metal−N(pyrrole) bond lengths of the bis-pyridine metal(III) complexes increase from Co (1.886 Å) to Rh (1.957 Å)/Ir (1.963 Å); and the average metal−N(pyridine) bond lengths also increase from Co (1.995 Å) to Rh (2.065 Å)/Ir (2.059 Å). Ligand affinities for 1-M(PPh_3) axial coordination sites increase dramatically in the order 1-Co(PPh_3) < 1-Rh(PPh_3) < 1-Ir(PPh_3). There is a surprising invariance in the M(+/0) reduction potentials within the five- and six-coordinate corrole series, and even between them; the average M(+/0) potential of 1-M(PPh_3) is 0.78 V vs Ag/AgCl in CH_2Cl_2 solution, whereas that of 1-M(py)_2 is 0.70 V under the same conditions. Electronic structures of one-electron-oxidized 1-M(py)_2 complexes have been assigned by analysis of electron paramagnetic resonance spectroscopic measurements: oxidation is corrole-centered for 1-Co(py)_2 (g = 2.008) and 1-Rh(py)_2 (g = 2.003), and metal-centered for 1-Ir(tma)_2 (g_(zz) = 2.489, g_(yy) = 2.010, g_(xx) = 1.884, g_(av) = 2.128) and 1-Ir(py)_2 (g_(zz) = 2.401, g_(yy) = 2.000, g_(xx) = 1.937, g_(av) = 2.113)

Nonclassical correlation in a multipartite quantum system: two measures and evaluation

There is a commonly recognized paradigm in which a multipartite quantum system described by a density matrix having no product eigenbasis is considered to possess nonclassical correlation. Supporting this paradigm, we define two entropic measures of nonclassical correlation of a multipartite quantum system. One is defined as the minimum uncertainty about a joint system after we collect outcomes of particular local measurements. The other is defined by taking the maximum over all local systems about the minimum distance between a genuine set and a mimic set of eigenvalues of a reduced density matrix of a local system. The latter measure is based on an artificial game to create mimic eigenvalues of a reduced density matrix of a local system from eigenvalues of a density matrix of a global system. Numerical computation of these measures for several examples is performed.Comment: v1: 10 pages, 8 figures, IOPART, v2: introduction modified, figure 7 replaced, v3: 10 pages, 10 figures, RevTeX4, major revision with an additional measure introduced, title changed (previous title: Non-classical correlation in a multi-partite quantum system reconsidered), to appear in Phys. Rev.

Outer-Sphere Effects on Reduction Potentials of Copper Sites in Proteins: The Curious Case of High Potential Type 2 C112D/M121E Pseudomonas aeruginosa Azurin

Redox and spectroscopic (electronic absorption, multifrequency electron paramagnetic resonance (EPR), and X-ray absorption) properties together with X-ray crystal structures are reported for the type 2 Cu^(II) C112D/M121E variant of Pseudomonas aeruginosa azurin. The results suggest that Cu^(II) is constrained from interaction with the proximal glutamate; this structural frustration implies a “rack” mechanism for the 290 mV (vs NHE) reduction potential measured at neutral pH. At high pH (~9), hydrogen bonding in the outer coordination sphere is perturbed to allow axial glutamate ligation to Cu^(II), with a decrease in potential to 119 mV. These results highlight the role played by outer-sphere interactions, and the structural constraints they impose, in determining the redox behavior of transition metal protein cofactors

Search for long lived charged massive particles in pp collisions at s-hat = 1.8TeV

We report a search for the production of long-lived charged massive particles in a data sample of 90   pb-1 of √s=1.8   TeV pp̅ collisions recorded by the Collider Detector at Fermilab. The search uses the muonlike penetration and anomalously high ionization energy loss signature expected for such a particle to discriminate it from backgrounds. The data are found to agree with background expectations, and cross section limits of O(1) pb are derived using two reference models, a stable quark and a stable scalar lepton

High-Potential C112D/M121X (X = M, E, H, L) Pseudomonas aeruginosa Azurins

Site-directed mutagenesis of Pseudomonas aeruginosa azurin C112D at the M121 position has afforded a series of proteins with elevated Cu^(II/I) reduction potentials relative to the CuII aquo ion. The high potential and low axial hyperfine splitting (Cu^(II) electron paramagnetic resonance A|) of the C112D/M121L protein are remarkably similar to features normally associated with type 1 copper centers

Approximating Spectral Impact of Structural Perturbations in Large Networks

Determining the effect of structural perturbations on the eigenvalue spectra of networks is an important problem because the spectra characterize not only their topological structures, but also their dynamical behavior, such as synchronization and cascading processes on networks. Here we develop a theory for estimating the change of the largest eigenvalue of the adjacency matrix or the extreme eigenvalues of the graph Laplacian when small but arbitrary set of links are added or removed from the network. We demonstrate the effectiveness of our approximation schemes using both real and artificial networks, showing in particular that we can accurately obtain the spectral ranking of small subgraphs. We also propose a local iterative scheme which computes the relative ranking of a subgraph using only the connectivity information of its neighbors within a few links. Our results may not only contribute to our theoretical understanding of dynamical processes on networks, but also lead to practical applications in ranking subgraphs of real complex networks.Comment: 9 pages, 3 figures, 2 table

Electron Transfer Reactivity of Type Zero Pseudomonas aeruginosa Azurin

Type zero copper is a hard-ligand analogue of the classical type 1 or blue site in copper proteins that function as electron transfer (ET) agents in photosynthesis and other biological processes. The EPR spectroscopic features of type zero Cu^(II) are very similar to those of blue copper, although lacking the deep blue color, due to the absence of thiolate ligation. We have measured the rates of intramolecular ET from the pulse radiolytically generated C3−C26 disulfide radical anion to the Cu^(II) in both type zero C112D/M121L and type 2 C112D Pseudomonas aeruginosa azurins in pH 7.0 aqueous solutions between 8 and 45 °C. We also have obtained rate/temperature (10−30 °C) profiles for ET reactions between these mutants and the wild-type azurin. Analysis of the rates and activation parameters for both intramolecular and intermolecular ET reactions indicates that the type zero copper reorganization energy falls in a range (0.9−1.1 eV) slightly above that for type 1 (0.7−0.8 eV), but substantially smaller than that for type 2 (>2 eV), consistent with XAS and EXAFS data that reveal minimal type zero site reorientation during redox cycling

The centred travelling salesman at high temperature

A recently formulated statistical mechanics method is used to study the phase transition occurring in a generalisation of the Traveling Salesman Problem (TSP) known as the centred TSP. The method shows that the problem has clear signs of a crossover, but is only able to access (unscaled) finite temperatures above the transition point. The solution of the problem using this method displays a curious duality

An evaluation of the Goddard Space Flight Center Library

The character and degree of coincidence between the current and future missions, programs, and projects of the Goddard Space Flight Center and the current and future collection, services, and facilities of its library were determined from structured interviews and discussions with various classes of facility personnel. In addition to the tabulation and interpretation of the data from the structured interview survey, five types of statistical analyses were performed to corroborate (or contradict) the survey results and to produce useful information not readily attainable through survey material. Conclusions reached regarding compatability between needs and holdings, services and buildings, library hours of operation, methods of early detection and anticipation of changing holdings requirements, and the impact of near future programs are presented along with a list of statistics needing collection, organization, and interpretation on a continuing or longitudinal basis