Oxygen Activation by Mononuclear Mn, Co, and Ni Centers in Biology and Synthetic Complexes

The active sites of metalloenzymes that catalyze O2-dependent reactions generally contain iron or copper ions. However, several enzymes are capable of activating O2 at manganese or nickel centers instead, and a handful of dioxygenases exhibit activity when substituted with cobalt. This minireview summarizes the catalytic properties of oxygenases and oxidases with mononuclear Mn, Co, or Ni active sites, including oxalate-degrading oxidases, catechol dioxygenases, and quercetin dioxygenase. In addition, recent developments in the O2 reactivity of synthetic Mn, Co, or Ni complexes are described, with an emphasis on the nature of reactive intermediates featuring superoxo-, peroxo-, or oxo-ligands. Collectively, the biochemical and synthetic studies discussed herein reveal the possibilities and limitations of O2 activation at these three “overlooked” metals

Neutrino emissivities and bulk viscosity in neutral two-flavor quark matter

We study thermodynamic and transport properties for the isotropic color-spin-locking (iso-CSL) phase of two-flavor superconducting quark matter under compact star constraints within a NJL-type chiral quark model. Chiral symmetry breaking and the phase transition to superconducting quark matter leads to a density dependent change of quark masses, chemical potentials and diquark gap. A self-consistent treatment of these physical quantities influences on the microscopic calculations of transport properties. We present results for the iso-CSL direct URCA emissivities and bulk viscosities, which fulfill the constraints on quark matter derived from cooling and rotational evolution of compact stars. We compare our results with the phenomenologically successful, but yet heuristic 2SC+X phase. We show that the microscopically founded iso-CSL phase can replace the purely phenomenological 2SC+X phase in modern simulations of the cooling evolution for compact stars with color superconducting quark matter interior.Comment: 15 pages, 6 figures, references added, text improve

An Introduction to Conformal Ricci Flow

We introduce a variation of the classical Ricci flow equation that modifies the unit volume constraint of that equation to a scalar curvature constraint. The resulting equations are named the Conformal Ricci Flow Equations because of the role that conformal geometry plays in constraining the scalar curvature. These equations are analogous to the incompressible Navier-Stokes equations of fluid mechanics inasmuch as a conformal pressure arises as a Lagrange multiplier to conformally deform the metric flow so as to maintain the scalar curvature constraint. The equilibrium points are Einstein metrics with a negative Einstein constant and the conformal pressue is shown to be zero at an equilibrium point and strictly positive otherwise. The geometry of the conformal Ricci flow is discussed as well as the remarkable analytic fact that the constraint force does not lose derivatives and thus analytically the conformal Ricci equation is a bounded perturbation of the classical unnormalized Ricci equation. That the constraint force does not lose derivatives is exactly analogous to the fact that the real physical pressure force that occurs in the Navier-Stokes equations is a bounded function of the velocity. Using a nonlinear Trotter product formula, existence and uniqueness of solutions to the conformal Ricci flow equations is proven. Lastly, we discuss potential applications to Perelman's proposed implementation of Hamilton's program to prove Thurston's 3-manifold geometrization conjectures.Comment: 52 pages, 1 figur

A Synthetic Model of the Nonheme Iron–Superoxo Intermediate of Cysteine Dioxygenase

A nonheme Fe(II) complex (1) that models substrate-bound cysteine dioxygenase (CDO) reacts with O2 at −80 °C to yield a purple intermediate (2). Analysis with spectroscopic and computational methods determined that 2 features a thiolate-ligated Fe(III) center bound to a superoxide radical, mimicking the putative structure of a key CDO intermediate

Spectroscopic and Computational Studies of Reversible O\u3csub\u3e2\u3c/sub\u3e Binding by a Cobalt Complex of Relevance to Cysteine Dioxygenase

The substitution of non-native metal ions into metalloenzyme active sites is a common strategy for gaining insights into enzymatic structure and function. For some nonheme iron dioxygenases, replacement of the Fe(II) center with a redox-active, divalent transition metal (e.g., Mn, Co, Ni, Cu) gives rise to an enzyme with equal or greater activity than the wild-type enzyme. In this manuscript, we apply this metal-substitution approach to synthetic models of the enzyme cysteine dioxygenase (CDO). CDO is a nonheme iron dioxygenase that initiates the catabolism of L-cysteine by converting this amino acid to the corresponding sulfinic acid. Two mononuclear Co(II) complexes (3 and 4) have been prepared with the general formula [Co2+(TpR2)(CysOEt)] (R = Ph (3) or Me (4); TpR2 = hydrotris(pyrazol-1-yl)borate substituted with R-groups at the 3- and 5-positions, and CysOEt is the anion of L-cysteine ethyl ester). These Co(II) complexes mimic the active-site structure of substrate-bound CDO and are analogous to functional iron-based CDO models previously reported in the literature. Characterization with X-ray crystallography and/or 1H NMR spectroscopy revealed that 3 and 4 possess five-coordinate structures featuring facially-coordinating TpR2 and S,N-bidentate CysOEt ligands. The electronic properties of these high-spin (S = 3/2) complexes were interrogated with UV-visible absorption and X-band electron paramagnetic resonance (EPR) spectroscopies. The air-stable nature of complex 3 replicates the inactivity of cobalt-substituted CDO. In contrast, complex 4 reversibly binds O2 at reduced temperatures to yield an orange chromophore (4-O2). Spectroscopic (EPR, resonance Raman) and computational (density functional theory, DFT) analyses indicate that 4-O2 is a S = 1/2 species featuring a low-spin Co(III) center bound to an end-on (η1) superoxo ligand. DFT calculations were used to evaluate the energetics of key steps in the reaction mechanism. Collectively, these results have elucidated the role of electronic factors (e.g., spin-state, d-electron count, metal–ligand covalency) in facilitating O2 activation and S-dioxygenation in CDO and related models

Perturbations of Spatially Closed Bianchi III Spacetimes

Motivated by the recent interest in dynamical properties of topologically nontrivial spacetimes, we study linear perturbations of spatially closed Bianchi III vacuum spacetimes, whose spatial topology is the direct product of a higher genus surface and the circle. We first develop necessary mode functions, vectors, and tensors, and then perform separations of (perturbation) variables. The perturbation equations decouple in a way that is similar to but a generalization of those of the Regge--Wheeler spherically symmetric case. We further achieve a decoupling of each set of perturbation equations into gauge-dependent and independent parts, by which we obtain wave equations for the gauge-invariant variables. We then discuss choices of gauge and stability properties. Details of the compactification of Bianchi III manifolds and spacetimes are presented in an appendix. In the other appendices we study scalar field and electromagnetic equations on the same background to compare asymptotic properties.Comment: 61 pages, 1 figure, final version with minor corrections, to appear in Class. Quant. Gravi

Picosecond time-resolved energy transfer within C-phycocyanin aggregates of Mastigocladus laminosus

We have investigated by picosecond absorption experiments how the size of C-phycocyanin aggregates from Mastigocladus laminosus influences the excitation energy transfer kinetics. Going from C-phycocyanin monomers to trimers the lifetime of the faster energy transfer component decreased from 57 ± 4 to 27 ± 4 ps over most of the wavelength range (580–645 nm) studied. This change was interpreted as the opening of fast transfer channels (α-84 → β-84 and/or β-84 → β-84) between two adjacent monomers in the trimeric unit. The 57 ps lifetime is probably due mainly to the β-155 → β-84 energy transfer step. The intermediate lifetime decreased from about 300 ps in the monomer to 100–120 ps in the trimer. The former is believed to be dominated by the equilibration process α-84 a3 β-84, while the latter probably represents the time required for the excitation energy to reach thermodynamic equilibrium within the trimer. The lifetime of the longest components was about 1 ns in both systems. This indicates that the chromophores in these C-phycocyanin complexes are more exposed to non-radiative processes (like, for instance, isomerization) compared to the chromophores in intact phycobilisomes, where this lifetime typically is about 1.8 ns. The anisotropy relaxation closely followed the isotropic lifetimes in both systems. The anisotropy after the initial fast relaxation, r(∞), was 0.29 ± 0.04 in monomers and decreased to 0.15 ± 0.03 in trimers. Measurements of the steady-state fluorescence excitation anisotropy gave the same results within the experimental error

Head-up transition behavior of pilots with and without head-up display in simulated low-visibility approaches

To quantify head-up transition behavior with and without a flightpath type head-up display, eight rated B-727 pilots each flew 31 manual and coupled approaches in a simulator with B-727 dynamics and collimated model board external scene. Data were also obtained on the roll played by the head-up display in the coupled-to-manual transition. Various wind shears, low visibilities, and ceilings were tested along with unexpected misalignment between the runway and head-up display symbology. The symbolic format used was a conformal scene. Every pilot except one stayed head-up, flying with the display after descending below the ceiling. Without the display and as altitude decreased, the number of lookups from the instrument panel decreased and the duration of each one increased. No large differences in mean number or duration of transitions up or down were found during the head-up display runs comparing the no-misalignment with the lateral instrument landing system offset misalignment runs. The head-up display led to fewer transitions after the pilot made a decision to land or execute a missed approach. Without the display, pilots generally waited until they had descended below the ceiling to look outside the first time, but with it several pilots looked down at their panel at relatively high altitudes (if they looked down at all). Manual takeover of control was rapid and smooth both with and without the display which permitted smoother engine power changes

Thermal Conductivity of Single Wall Carbon Nanotubes: Diameter and Annealing Dependence

The thermal conductivity, k(T), of bulk single-wall carbon nanotubes (SWNT's) displays a linear temperature dependence at low T that has been attributed to 1D quantization of phonons. To explore this issue further, we have measured the k(T) of samples with varying average tube diameters. We observe linear k(T) up to higher temperatures in samples with smaller diameters, in agreement with a quantization picture. In addition, we have examined the effect of annealing on k(T). We observe an enhancement in k(T) for annealed samples which we attribute to healing of defects and removal of impurities. These measurements demonstrate how the thermal properties of an SWNT material can be controlled by manipulating its intrinsic nanoscale properties.Comment: Proc. of the XV. Int. Winterschool on Electronic Properties of Novel Materials, Kirchberg/Tirol, Austria, 200