Electrochemically driven efficient enzymatic conversion of CO2 to formic acid with artificial cofactors

Enzymatic reduction of CO2 to formic acid with the enzyme formate dehydrogenase (FDH) and a cofactor is a promising method for CO2 conversion and utilization. However, the natural cofactor nicotinamide adenine dinucleotide (NADH) shows some drawbacks such as a low reduction efficiency and forms isomers or dimers (1,6 - NADH or NAD dimer) in the regeneration reaction. To overcome them and to improve the production of formic acid, in this work, the artificial cofactors, i.e., the bipyridinium-based salts of methyl viologen (MV2+), 1,1’-dicarboxymethyl-4,4’-bipyridinium bromine (DC2+), and 1,1’-diaminoethyl-4,4’-bipyridinium bromine (DA2+), were used to replace NADH, and the effect of different functional groups on the electrochemical regeneration and catalytic performance in the enzymatic reaction was studied systematically. Also, studies using the natural cofactor NADH were carried out for comparison. It was found that the cofactor with amino groups showed the highest catalytic efficiency (kcat/Km) of 0.161 mM-1min-1, which is 536 times higher than that of the natural cofactor NADH. Molecular Dynamics simulations were conducted to give further molecular insight into the behavior of the cofactors. Analyzing the free energy profiles of the complexes between CO2 in the FDH active site with different artificial cofactors indicated that the artificial cofactor with the amino groups had the highest affinity for CO2, being consistent with the experimental observations

Structure and Spin Dynamics of La0.85_{0.85}Sr0.15_{0.15}MnO3_3

Neutron scattering has been used to study the structure and spin dynamics of La$_{0.85}$Sr$_{0.15}$MnO$_3$. The magnetic structure of this system is ferromagnetic below T_C = 235 K. We see anomalies in the Bragg peak intensities and new superlattice peaks consistent with the onset of a spin-canted phase below T_{CA} = 205 K, which appears to be associated with a gap at q = (0, 0, 0.5) in the spin-wave spectrum. Anomalies in the lattice parameters indicate a concomitant lattice distortion. The long-wavelength magnetic excitations are found to be conventional spin waves, with a gapless (< 0.02 meV) isotropic dispersion relation $E = Dq^2$. The spin stiffness constant D has a $T^{5/2}$ dependence at low T, and the damping at small q follows $q^4T^{2}$. An anomalously strong quasielastic component, however, develops at small wave vector above 200 K and dominates the fluctuation spectrum as T -> T_C. At larger q, on the other hand, the magnetic excitations become heavily damped at low temperatures, indicating that spin waves in this regime are not eigenstates of the system, while raising the temperature dramatically increases the damping. The strength of the spin-wave damping also depends strongly on the symmetry direction in the crystal. These anomalous damping effects are likely due to the itinerant character of the $e_g$ electrons.Comment: 8 pages (RevTex), 9 figures (encapsulated postscript

The Structure of Nanoscale Polaron Correlations in La1.2Sr1.8Mn2O7

A system of strongly-interacting electron-lattice polarons can exhibit charge and orbital order at sufficiently high polaron concentrations. In this study, the structure of short-range polaron correlations in the layered colossal magnetoresistive perovskite manganite, La1.2Sr1.8Mn2O7, has been determined by a crystallographic analysis of broad satellite maxima observed in diffuse X-ray and neutron scattering data. The resulting q=(0.3,0,1) modulation is a longitudinal octahedral-stretch mode, consistent with an incommensurate Jahn-Teller-coupled charge-density-wave fluctuations, that implies an unusual orbital-stripe pattern parallel to the directions.Comment: Reformatted with RevTe

Neutron and X-ray evidence of charge melting in ferromagnetic layered colossal magnetoresistance manganites

Recent x-ray and neutron scattering studies have revealed static diffuse scattering due to polarons in the paramagnetic phase of the colossal magnetoresistive manganites La2-2xSr1+2xMn2O7, with x = 0.40 and 0.44. We show that the polarons exhibit short-range incommensurate correlations that grow with decreasing temperature, but disappear abruptly at the combined ferromagnetic and metal-insulator transition in the x = 0.40 system because of the sudden charge delocalization, while persisting at low temperature in the antiferromagnetic x = 0.44 system. The "melting" of the polaron ordering as we cool through T-C occurs with the collapse of the polaron scattering itself in the x = 0.40 system. This short-range polaron order is characterized by an ordering wave vector q = (0.3,0,1) that is almost independent of x for x greater than or equal to 0.38, and is consistent with a model of disordered stripes. (C) 2001 American Institute of Physics

Stripes Induced by Orbital Ordering in Layered Manganites

Spin-charge-orbital ordered structures in doped layered manganites are investigated using an orbital-degenerate double-exchange model tightly coupled to Jahn-Teller distortions. In the ferromagnetic phase, unexpected diagonal stripes at $x$=$1/m$ ($m$=integer) are observed, as in recent experiments. These stripes are induced by the orbital degree of freedom, which forms a staggered pattern in the background. A $\pi$-shift in the orbital order across stripes is identified, analogous to the $\pi$-shift in spin order across stripes in cuprates. At $x$=1/4 and 1/3, another non-magnetic phase with diagonal static charge stripes is stabilized at intermediate values of the $t_{\rm 2g}$-spins exchange coupling.Comment: reordering of figure

Optical Studies of a Layered Manganite La_{1.2}Sr_{1.8}Mn_2O_7 : Polaron Correlation Effect

Optical conductivity spectra of a cleaved ab-plane of a La_{1.2}Sr_{1.8}Mn_2O_7 single crystal exhibit a small polaron absorption band in the mid-infrared region at overall temperatures. With decreasing temperature (T) to Curie temperature (T_C), the center frequency of the small polaron band moves to a higher frequency, resulting in a gap-like feature, and that it collapses to a lower frequency below T_C. Interestingly, with decreasing T, the stretching phonon mode hardens above T_C and softens below T_C. These concurring changes of lattice and electronic structure indicate that short range polaron correlation exist above T_C but disappear with a magnetic ordering.Comment: 4 pages including 5 figures. submitted to Phys. Rev.

The phase-separated states in antiferromagnetic semiconductors with polarizable lattice

The possibility of the slab or stripe phase separation (alternating ferromagnetic highly- conductive and insulating antiferromagnetic layers) is proved for isotropic degenerate antiferromagnetic semiconductors. This type of phase separation competes with the droplet phase separation (ferromagnetic droplets in the antiferromagnetic host or vice versa). The interaction of electrons with optical phonons alone cannot cause phase-separated state with alternating highly-conductive and insulating regions but it stabilizes the magnetic phase separation. The magnetostriction deformation of the lattice in the phase-separated state is investigated.Comment: 17 Pages, 1 EPS Figur

Approach to the metal-insulator transition in La(1-x)CaxMnO3 (0<x<.2): magnetic inhomogeneity and spin wave anomaly

We describe the evolution of the static and dynamic spin correlations of La$_{1-x}$Ca$_x$MnO$_3$, for x=0.1, 0.125 and 0.2, where the system evolves from the canted magnetic state towards the insulating ferromagnetic state, approaching the metallic transition (x=0.22). In the x=0.1 sample, the observation of two spin wave branches typical of two distinct types of magnetic coupling, and of a modulation in the elastic diffuse scattering characteristic of ferromagnetic inhomogeneities, confirms the static and dynamic inhomogeneous features previously observed at x$<$0.1. The anisotropic q-dependence of the intensity of the low-energy spin wave suggests a bidimensionnal character for the static inhomogeneities. At x=0.125, which corresponds to the occurence of a ferromagnetic and insulating state, the two spin wave branches reduce to a single one, but anisotropic. At this concentration, an anomaly appears at {\bf q$_0$}=(1.25,1.25,0), that could be related to an underlying periodicity, as arising from (1.5,1.5,0) superstructures. At x=0.2, the spin-wave branch is isotropic. In addition to the anomaly observed at q$_0$, extra magnetic excitations are observed at larger q, forming an optical branch. The two dispersion curves suggest an anti-crossing behavior at some {\bf q$_0$'} value, which could be explained by a folding due to an underlying perodicity involving four cubic lattice spacings