Alteration of the Axial Met Ligand to Electron Acceptor A0 in Photosystem I: An Investigation of Electron Transfer at Different Temperatures by Multifrequency Time-Resolved and CW EPR

The ambient temperature and low-temperature electron transfer properties of Photosystem I (PS I) from the M688N_PsaA and M668N_PsaB mutant strains of the cyanobacterium Synechocystis sp. PCC 6803 are studied using transient electron paramagnetic resonance (EPR) and continuous-wave (CW) EPR. The two mutations are expected to alter the midpoint potentials of, and the reorganization energies around, the primary electron chlorophyll acceptors A_0A and A_0B, which should lead to a change in the yield and/or rate of electron transfer to the phylloquinone acceptors A_1A and A_1B, respectively. At ambient temperature it is known that both quinone acceptors are active in electron transfer. At low temperature there are at least two fractions that undergo either reversible or irreversible electron transfer. The EPR data of the two PS I variants are used to investigate the relationship between these low-temperature fractions and the ambient temperature electron transfer pathway. The results show that mutation in the PsaA-branch increases the rate of $ {\text{A}}_{{1{\text{A}}}}^{. - } $ to F_X electron transfer at ambient temperature, while the corresponding mutation in the PsaB-branch has no effect on the electron transfer rate observable by transient EPR. An analysis of the complete time/field datasets from both variants suggests that the yield of electron transfer in the branch carrying the mutation is reduced. The mutations have no effect on the low-temperature CW EPR spectra of the iron–sulfur clusters if the samples are frozen under illumination but they both cause a decrease in the yield of reduced F_A and F_B if the samples are frozen in the dark and then illuminated. The PsaA-branch mutation greatly reduces the intensity and changes the polarization pattern of the radical pair $ {\text{P}}_{700}^{ + } {\text{A}}_{1}^{. - } $ . Possible causes of the changes in the polarization pattern are discussed and it is suggested that the mutations introduce structural heterogeneity in the vicinity of the A₀ binding site. No clear correlation between the yield of electron transfer in a particular branch and the yield of stable charge separation is found.     

Stability of {\text{SrCe}}_{{0.9}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} and {\text{SrZr}}_{{0.2}} {\text{Ce}}_{{0.7}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} under H2 atmospheres

Previous H₂ permeation tests showed a degradation of H₂ permeation flux with time. To understand the cause of degradation and develop a solution, the stability of $ {\text{SrCe}}_{{0.9}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} $ and $ {\text{SrZr}}_{{0.2}} {\text{Ce}}_{{0.7}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} $ samples were studied under dry and wet H₂ atmospheres. Total conductivity of $ {\text{SrCe}}_{{0.9}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} $ increased with time in dry H₂. The X-ray diffraction pattern of $ {\text{SrCe}}_{{0.9}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} $ after dry hydrogen atmosphere heat treatments show CeO₂ peaks indicating that $ {\text{SrCe}}_{{0.9}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} $ decomposes under dry H₂ atmospheres; scanning electron microscopy and energy dispersive X-ray spectroscopy analyses prove that decomposition proceeded along the grain boundaries. $ {\text{SrZr}}_{{0.2}} {\text{Ce}}_{{0.7}} {\text{Eu}}_{{0.1}} {\text{O}}_{{3 - \delta }} $ was investigated and demonstrated greater stability under dry hydrogen atmospheres. However, Zr substitution results in a tradeoff with electrical properties.     

Haag Duality and the Distal Split Property for Cones in the Toric Code

We prove that Haag duality holds for cones in the toric code model. That is, for a cone ??, the algebra ${\mathcal{R}_{\Lambda}}$ of observables localized in ?? and the algebra ${\mathcal{R}_{\Lambda^c}}$ of observables localized in the complement ?? ^c generate each other??s commutant as von Neumann algebras. Moreover, we show that the distal split property holds: if ${\Lambda_1 \subset \Lambda_2}$ are two cones whose boundaries are well separated, there is a Type I factor ${\mathcal{N}}$ such that ${\mathcal{R}_{\Lambda_1} \subset \mathcal{N} \subset \mathcal{R}_{\Lambda_2}}$ . We demonstrate this by explicitly constructing ${\mathcal{N}}$ .     

Femtosecond relaxation kinetics of highly excited \mathrm{M}_{\mathrm{Na}}^{**} states in CaF2 at 3.2 eV and 4.7 eV

Femtosecond (fs) laser pulses at variable delay times allowed us to track the fast non-radiative transitions between the manifold of highly excited $\mathrm{M}_{\mathrm{Na}}^{**}$ states to the lower lying fluorescent $\mathrm{M}_{\mathrm{Na}}^{*}$ state in CaF₂. Two distinct $\mathrm{M}_{\mathrm{Na}}^{**}$ states of the manifold at 3.16?eV ( $\mathrm{M}_{\mathrm{Na}2}^{**}$ ) and 4.73?eV ( $\mathrm{M}_{\mathrm{Na}3}^{**}$ ) were populated using the second (SH) and third harmonics (TH) of fs laser light at 785?nm. The population kinetics of the fluorescent $\mathrm{M}_{\mathrm{Na}}^{*}$ state in the 2?eV excitation energy range was revealed by depleting its fluorescence centered at 740?nm using fundamental near infrared (NIR) fs laser pulses. The related time constants for $\mathrm{M}_{\mathrm{Na}2,3}^{**}{\sim}{>} \mathrm{M}_{\mathrm{Na}}^{*}$ relaxation amounted to 1.0±0.14?ps and 3.0±0.3?ps upon SH and TH excitation, respectively.     

Singular $$ \mathcal{R}$$ -Matrices and Drinfeld's Comultiplication

We compute the $\mathcal{R}$ -matrix which intertwines two dimensional evaluation representations with Drinfeld comultiplication for ${\text{U}}_q \left( {\widehat{{\text{sl}}}_{\text{2}} } \right)$ . This $\mathcal{R}$ -matrix contains terms proportional to the δ-function. We construct the algebra $A\left( \mathcal{R} \right)$ generated by the elements of the matrices L^±(z) with relations determined by $\mathcal{R}$ . In the category of highest-weight representations, there is a Hopf algebra isomorphism between $A\left( \mathcal{R} \right)$ and an extension $\overline {\text{U}} _q \left( {\widehat{{\text{sl}}}_{\text{2}} } \right)$ of Drinfeld's algebra.     

Invariant Measures for Dissipative Dynamical Systems: Abstract Results and Applications

In this work we study certain invariant measures that can be associated to the time averaged observation of a broad class of dissipative semigroups via the notion of a generalized Banach limit. Consider an arbitrary complete separable metric space X which is acted on by any continuous semigroup {S(t)} _{t ?? 0}. Suppose that {S(t)} _{t ?? 0} possesses a global attractor ${\mathcal{A}}$ . We show that, for any generalized Banach limit LIM _{T ?? ??} and any probability distribution of initial conditions ${\mathfrak{m}_0}$ , that there exists an invariant probability measure ${\mathfrak{m}}$ , whose support is contained in ${\mathcal{A}}$ , such that $$\int_{X} \varphi(x) {\rm d}\mathfrak{m}(x) = \underset{t \rightarrow \infty}{\rm LIM}\frac{1}{T} \int_0^T \int_X \varphi(S(t) x) {\rm d}\mathfrak{m}_0(x) {\rm d}t,$$ for all observables ?? living in a suitable function space of continuous mappings on X. This work is based on the framework of Foias et?al. (Encyclopedia of mathematics and its applications, vol 83. Cambridge University Press, Cambridge, 2001); it generalizes and simplifies the proofs of more recent works (Wang in Disc Cont Dyn Syst 23(1?C2):521?C540, 2009; Lukaszewicz et?al. in J Dyn Diff Eq 23(2):225?C250, 2011). In particular our results rely on the novel use of a general but elementary topological observation, valid in any metric space, which concerns the growth of continuous functions in the neighborhood of compact sets. In the case when {S(t)} _{t ?? 0} does not possess a compact absorbing set, this lemma allows us to sidestep the use of weak compactness arguments which require the imposition of cumbersome weak continuity conditions and thus restricts the phase space X to the case of a reflexive Banach space. Two examples of concrete dynamical systems where the semigroup is known to be non-compact are examined in detail. We first consider the Navier-Stokes equations with memory in the diffusion terms. This is the so called Jeffery??s model which describes certain classes of viscoelastic fluids. We then consider a family of neutral delay differential equations, that is equations with delays in the time derivative terms. These systems may arise in the study of wave propagation problems coming from certain first order hyperbolic partial differential equations; for example for the study of line transmission problems. For the second example the phase space is ${X= C([-\tau,0],\mathbb{R}^n)}$ , for some delay ?? > 0, so that X is not reflexive in this case.     

On the Quasi-linear Elliptic PDE {-\nabla \cdot ( \nabla{u}/ \sqrt{1-| \nabla{u} |^2}) = 4 \pi \sum_k a_k \delta_{s_k}} in Physics and Geometry

It is shown that for each finite number N of Dirac measures ${\delta_{s_n}}$ supported at points ${s_n \in {\mathbb R}^3}$ with given amplitudes ${a_n \in {\mathbb R} \backslash\{0\}}$ there exists a unique real-valued function ${u \in C^{0, 1}({\mathbb R}^3)}$ , vanishing at infinity, which distributionally solves the quasi-linear elliptic partial differential equation of divergence form ${-\nabla \cdot ( \nabla{u}/ \sqrt{1-| \nabla{u} |^2}) = 4 \pi \sum_{n=1}^N a_n \delta_{s_n}}$ . Moreover, ${u \in C^{\omega}({\mathbb R}^3\backslash \{s_n\}_{n=1}^N)}$ . The result can be interpreted in at least two ways: (a) for any number N of point charges of arbitrary magnitude and sign at prescribed locations s _n in three-dimensional Euclidean space there exists a unique electrostatic field which satisfies the Maxwell-Born-Infeld field equations smoothly away from the point charges and vanishes as |s| ?? ??; (b) for any number N of integral mean curvatures assigned to locations ${s_n \in {\mathbb R}^3 \subset{\mathbb R}^{1, 3}}$ there exists a unique asymptotically flat, almost everywhere space-like maximal slice with point defects of Minkowski spacetime ${{\mathbb R}^{1, 3}}$ , having lightcone singularities over the s _n but being smooth otherwise, and whose height function vanishes as |s| ?? ??. No struts between the point singularities ever occur.     

Finite W-Superalgebras and Truncated Super Yangians

Let ${Y_{m|n}^{\ell}}$ be the super Yangian of general linear Lie superalgebra for ${\mathfrak{gl}_{m|n}}$ . Let ${e \in \mathfrak{gl}_{m\ell|n\ell}}$ be a “rectangular” nilpotent element and ${\mathcal{W}_e}$ be the finite W-superalgebra associated to e. We show that ${Y_{m|n}^{\ell}}$ is isomorphic to ${\mathcal{W}_e}$ .     

Oxidation of Pyrite Grains: A Mössbauer Spectroscopy and Mineral Magnetism Study

Fe²⁺ in pyrite is found in a low-spin d⁶ configuration, a necessary condition for diamagnetic and semi-conducting properties of material. The semi-conducting property of pyrite has been studied since the time when pyrite was used as a rectifier in early radios. Pyrite posses the highest possible crystal field stabilisation energy and offers a better altemative as solar material compared to Si-based materials. Unfortunately, pyrite is difficult to study due to its inherent deviation from stoichiometry and its ease of oxidation. Since pyrite and its oxidation products are all Fe-bearing phases, combining Mössbauer spectroscopy with mineral magnetic methods provides enough information to monitor the oxidation of pyrite in air and identify the different phases produced and their relation to different experimental parameters. For mm-sized grain samples, heating FeS₂ at temperatures between 450 °C and 650 °C five different mineral assemblages are identified. FeS₂ is oxidized to α-Fe₂O₃ along two separate routes: $${\text{FeS}}_{2} \to {\text{FeSO}}_{4} \to \varepsilon {\text{ - Fe}}_{2} {\text{O}}_{3} \to \alpha {\text{ - Fe}}_{2} {\text{O}}_{3} ;\;{\text{and}}$$ $${\text{FeS}}_{2} \to {\text{FeSO}}_{4} \to {\text{Fe}}_{2} {\left( {{\text{SO}}4} \right)}_{3} \to \beta {\text{ - Fe}}_{2} {\text{O}}_{3} \to \alpha {\text{ - Fe}}_{2} {\text{O}}_{3} $$      

Weyl’s Law and Connes’ Trace Theorem for Noncommutative Two Tori

We prove the analogue of Weyl’s law for a noncommutative Riemannian manifold, namely the noncommutative two torus ${\mathbb{T}_{\theta}^{2}}$ equipped with a general translation invariant conformal structure and a Weyl conformal factor. This is achieved by studying the asymptotic distribution of the eigenvalues of the perturbed Laplacian on ${\mathbb{T}_{\theta}^{2}}$ . We also prove the analogue of Connes’ trace theorem by showing that the Dixmier trace and a noncommutative residue coincide on pseudodifferential operators of order ?2 on ${\mathbb{T}_{\theta}^{2}}$ .     

Study of Light Hypernuclei by the (e,e′K +) Reaction

We have been performing Λ hypernuclear spectroscopic experiments by the (e,e′K ⁺) reaction since 2000 at Thomas Jefferson National Accelerator Facility (JLab). The (e,e′K ⁺) experiment can achieve a few 100 keV (FWHM) energy resolution compared to a few MeV (FWHM) by the (K ^?, π ^?) and (π ⁺, K ⁺) experiments. Therefore, more precise Λ hypernuclear structures can be investigated by the (e,e′K ⁺) experiment. ${^{7}_{\Lambda}{\rm He}}$ , ${^{9}_{\Lambda}{\rm Li}}$ , ${^{10}_{\Lambda}{\rm Be}}$ , ${^{12}_{\Lambda}{\rm B}}$ , ${^{28}_{\Lambda}{\rm Al}}$ , and ${^{52}_{\Lambda}{\rm V}}$ were measured in the experiment at JLab Hall-C. In addition, ${^{9}_{\Lambda}{\rm Li}}$ , ${^{12}_{\Lambda}{\rm B}}$ , and ${^{16}_{\Lambda}{\rm N}}$ were measured in the experiment at JLab Hall-A.     

High-field EPR, ENDOR and ELDOR on bacterial photosynthetic reaction centers

We report on recent 95 and 360 GHz high-field electron paramagnetic resonance (EPR), electron-nuclear double resonance (ENDOR) and pulsed electron-electron double resonance (PELDOR) studies of wild-type and mutant reaction centers (RCs) from the photosynthetic bacteriumRhodobacter sphaeroides. Taking advantage of the excellent spectral and temporal resolution of EPR at 95 and 360 GHz, the electron-transfer (ET) cofactors radical ions and spin-correlated radical pairs were characterized by theirg- and hyperfine-tensor components, their anisotropicT ₂ relaxation as well as by the dipolar interaction between P ₈₆₅ ^?+ Q _A ^?? radical pairs. The goal of these studies is to better understand the dominant factors determining the specificity and directionality of transmembrane ET processes in photosynthetic RC proteins. In particular, our multifrequency experiments elucidate the subtle cofactor-protein interactions, which are essential for fine-tuning the ET characteristics, e.g., the unidirectionality of the light-induced ET pathways along the A branch of the RC protein. By our high-field techniques, frozen-solution RCs of novel site-specific single and double mutants ofR. sphaeroides were studied to modulate the ET characteristics, e.g., even to the extent that dominant B branch ET prevails. The presented multifrequency EPR work culminates in first 360 GHz ENDOR results from organic nitroxide radicals as well as in first 95 GHz high-field PELDOR results from orientationally selected spin-polarized radical pairs P ₈₆₅ ^?+ Q _A ^?? , which allow to determine the full geometrical structure of the pairs even in frozen-solution RCs.     

A stable and easily sintering {\text{BaCe}}_{0.7} {\text{Sn}}_{0.1} {\text{Gd}}_{0.2} {\text{O}}_{3 - \delta } electrolyte for solid oxide fuel cells

${\text{BaCe}}_{0.7} {\text{Sn}}_{0.1} {\text{Gd}}_{0.2} {\text{O}}_{3 - \sigma } $ (BCSG) and ${\text{BaCe}}_{0.8} {\text{Gd}}_{0.2} {\text{O}}_{3 - \sigma } $ (BCG) powders were prepared by solid-state reaction method. After exposure in 5% CO₂?+?5% H₂O?+?90% N₂ at 500 °C for 5 h, the BCSG powders were hardly affected while the BCG powders decomposed into CeO₂ and BaCO₃ phases. Moreover, the relative density of BCSG reaches 97%, while the BCG just displays 91% after sintering at 1,400 °C. The BCSG displays a conductivity of 0.01 S/cm at 700 °C in humid hydrogen, which is quite close to 0.012 S/cm for BCG. A fuel cell with BCSG exhibits 1.02 V for open circuit voltage, 420 mW/cm² for peak performance and 0.23 Ω cm² for interfacial resistance at 700 °C, respectively.     

Theoretical study of collision and collision-free radiative lifetimes of {{\text{S}}_2}\left( {{{\text{B}}^3}\Sigma_{\text{u}}^{-} \left( {{\upsilon^{\prime}} = 0 - 9} \right)} \right)

We calculate multireference configuration-interaction wavefunctions and the potential-energy curves for the $ {B^3}\Sigma_u^{-} $ and $ {X^3}\Sigma_g^{-} $ states of the collision-free S₂ molecule and the T-shape collision complex S₂?CHe using cc-pVQZ basis sets. We obtain the transition dipole moments of the $ {{\text{S}}_2}\left( {{B^3}\Sigma_u^{-} \to {X^3}\Sigma_g^{-} } \right) $ and the Franck?CCondon factors between the vibrational levels of this two states. We evaluate the radiative lifetimes of $ {{\text{S}}_2}\left( {{B^3}\Sigma_u^{-} \left( {{\upsilon^{\prime}} = 0 - 9} \right)} \right) $ levels of the collision complex and the collision-free molecule and compare them with the experiments. The collision provides little change in the radiative lifetimes of $ {{\text{S}}_2}\left( {{B^3}\Sigma_u^{-} \left( {{\upsilon^{\prime}} = 0 - 9} \right)} \right) $ according to the previous calculations. We obtain excellent agreement between the theoretical results and the experiments. The data calculated are very useful in the study of the microwave-driven high-pressure sulfur lamp and an S₂ laser pumped by a transverse fast discharge.     

Investigations on the superhyperfine parameters for Cr3+ in the fluorides

The superhyperfine parameters A′ and B′ for Cr³⁺ ions in K₂NaGaF₆, K₂NaCrF₆, KMgF₃ and CsCdF₃ are theoretically studied from the cluster approach. In the present treatments, the orbital admixture coefficients and the unpaired spin densities in 2s, $ 2{\text{p}}_{\sigma } $ and $ 2{\text{p}}_{\pi } $ 2 fluorine orbitals are obtained in a uniform way. The experimental A′ and B′ are reasonably explained, and the unpaired spin densities for the 2s, 2pσ and 2pπ orbitals of the ligand F^? are also compared with those in the previous works.     

Regularity for Eigenfunctions of Schr?dinger Operators

We prove a regularity result in weighted Sobolev (or Babu?ka?CKondratiev) spaces for the eigenfunctions of certain Schr?dinger-type operators. Our results apply, in particular, to a non-relativistic Schr?dinger operator of an N-electron atom in the fixed nucleus approximation. More precisely, let ${\mathcal{K}_{a}^{m}(\mathbb{R}^{3N},r_S)}$ be the weighted Sobolev space obtained by blowing up the set of singular points of the potential ${V(x) = \sum_{1 \le j \le N} \frac{b_j}{|x_j|} + \sum_{1 \le i < j \le N} \frac{c_{ij}}{|x_i-x_j|}}$ , ${x \in \mathbb{R}^{3N}}$ , ${b_j, c_{ij} \in \mathbb{R}}$ . If ${u \in L^2(\mathbb{R}^{3N})}$ satisfies ${(-\Delta + V) u = \lambda u}$ in distribution sense, then ${u \in \mathcal{K}_{a}^{m}}$ for all ${m \in \mathbb{Z}_+}$ and all a ?? 0. Our result extends to the case when b _j and c _ij are suitable bounded functions on the blown-up space. In the single-electron, multi-nuclei case, we obtain the same result for all a?<?3/2.     

Level-Rank Duality via Tensor Categories

We give a new way to derive branching rules for the conformal embedding $$(\hat{\mathfrak{sl}}_n)_m\oplus(\hat{\mathfrak{sl}}_m)_n\subset(\hat{\mathfrak{sl}}_{nm})_1. $$ In addition, we show that the category ${\mathcal{C}(\hat{\mathfrak{sl}}_n)_m^0}$ of degree zero integrable highest weight ${(\hat{\mathfrak{sl}}_n)_m}$ -representations is braided equivalent to ${\mathcal{C}(\hat{\mathfrak{sl}}_m)_n^0}$ with the reversed braiding.     

Subfactors of Index Less Than 5, Part 3: Quadruple Points

One major obstacle in extending the classification of small index subfactors beyond ${3 +\sqrt{3}}$ is the appearance of infinite families of candidate principal graphs with 4-valent vertices (in particular, the ??weeds?? ${\mathcal{Q}}$ and ${\mathcal{Q}'}$ from Part 1 (Morrison and Snyder in Commun. Math. Phys., doi:10.1007/s00220-012-1426-y, 2012). Thus instead of using triple point obstructions to eliminate candidate graphs, we need to develop new quadruple point obstructions. In this paper we prove two quadruple point obstructions. The first uses quadratic tangles techniques and eliminates the weed ${\mathcal{Q}'}$ immediately. The second uses connections, and when combined with an additional number theoretic argument it eliminates both weeds ${\mathcal{Q}}$ and ${\mathcal{Q}'}$ . Finally, we prove the uniqueness (up to taking duals) of the 3311 Goodman-de la Harpe-Jones subfactor using a combination of planar algebra techniques and connections.