Biosynthesis of the iron-guanylylpyridinol cofactor of [Fe]-hydrogenase in methanogenic archaea as elucidated by stable-isotope labeling

[Fe]-hydrogenase catalyzes the reversible hydride transfer from H(2) to methenyltetrahydromethanoptherin, which is an intermediate in methane formation from H(2) and CO(2) in methanogenic archaea. The enzyme harbors a unique active site iron-guanylylpyridinol (FeGP) cofactor, in which a low-spin Fe(II) is coordinated by a pyridinol-N, an acyl group, two carbon monoxide, and the sulfur of the enzyme's cysteine. Here, we studied the biosynthesis of the FeGP cofactor by following the incorporation of (13)C and (2)H from labeled precursors into the cofactor in growing methanogenic archaea and by subsequent NMR, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS), electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS) and IR analysis of the isolated cofactor and reference compounds. The pyridinol moiety of the cofactor was found to be synthesized from three C-1 of acetate, two C-2 of acetate, two C-1 of pyruvate, one carbon from the methyl group of l-methionine, and one carbon directly from CO(2). The metabolic origin of the two CO-ligands was CO(2) rather than C-1 or C-2 of acetate or pyruvate excluding that the two CO are derived from dehydroglycine as has previously been shown for the CO-ligands in [FeFe]-hydrogenases. A formation of CO from CO(2) via direct reduction catalyzed by a nickel-dependent CO dehydrogenase or from formate could also be excluded. When the cells were grown in the presence of (13)CO, the two CO-ligands and the acyl group became (13)C-labeled, indicating either that free CO is an intermediate in their synthesis or that free CO can exchange with these iron-bound ligands. Based on these findings, we propose pathways for how the FeGP cofactor might be synthesized.     

High-efficiency (7.2%) flexible dye-sensitized solar cells with Ti-metal substrate for nanocrystalline-TiO2 photoanode

High-efficiency flexible dye-sensitized solar cells were fabricated with a Ti-metal foil substrate for photo anode and using a Pt-electrodeposited counter electrode on ITO/polyethylene naphthalate (ITO/PEN); these devices were characterized by incident photon-to-current efficiency (IPCE), optical transmittance and electrical impedance spectroscopy.     

Direct coulomb and exchange interaction in artificial atoms

We determine contributions from the direct Coulomb and exchange interactions to the total interaction in artificial semiconductor atoms. We tune the relative strengths of the two interactions and measure them as a function of the number of confined electrons. The electrons tend to have parallel spins when they occupy nearly degenerate single-particle states. We use a magnetic field to adjust the single-particle-state degeneracy, and find that the spin configurations in an arbitrary magnetic field are well explained in terms of two-electron singlet and triplet states.     

Vertical quantum dots at high magnetic fields beyond the few-electron limit

We describe phenomena that can be studied in vertical quantum dot single electron transistors. Moving from the few-electron to the several- and many-electron regimes, features in the conductance peaks initially related to spin polarization evolve with magnetic field. This allows us to first probe the spin-flip region beyond the last single-particle crossing at low field, and then the formation and stability of the spin-polarized maximum density droplet at high field. According to a simple capacitance model, charge redistribution in the dot at higher magnetic fields is accompanied by abrupt changes in the area of the droplet.     

Noise correlations in a Coulomb-blockaded quantum dot

We report measurements of current noise auto- and cross correlation in a tunable quantum dot with two or three leads. As the Coulomb blockade is lifted at finite source-drain bias, the autocorrelation evolves from super- to sub-Poissonian in the two-lead case, and the cross correlation evolves from positive to negative in the three-lead case, consistent with transport through multiple levels. Cross correlations in the three-lead dot are found to be proportional to the noise in excess of the Poissonian value in the limit of weak output tunneling.     

Electron-spin manipulation and resonator readout in a double-quantum-dot nanoelectromechanical system

We demonstrate how magnetically coupling a nanomechanical resonator to a double quantum dot confining two electrons can enable the manipulation of a single electron spin and the readout of the resonator's natural frequency. When the Larmor frequency matches the resonator frequency, the electron spin in one of the dots can be selectively and coherently flipped by the magnetized oscillator. By simultaneously measuring the charge state of the two-electron double quantum dots, this transition can be detected thus enabling the natural frequency and displacement of the mechanical oscillator to be determined.     

Multifrequency TREPR Investigation of Excited-State ZnTPP/Nitroxide Radical Complexes

Multiple-frequency (X-band and W-band) time-resolved electron paramagnetic resonance spectra of Zn-tetraphenylporphyrin (ZnTPP) triplet states coordinated to two different stable nitroxide moieties are presented and discussed. The position of the pyrimidyl nitroxide relative to the ZnTPP plane is the only structural change made between the two complexes, from ortho to para. This changes the angle between the interacting orbitals of the three-spin system with only a minor change in the distance between the unpaired electron of the nitroxide and the TPP ring system. Changes in the electron spin polarization patterns at the two different frequencies of observation are discussed in terms of a radical?Ctriplet pair spin-state mixing model, including the intersystem crossing processes. It is determined that the inclusion of an additional spin-selective relaxation process to the computational model for the spectral shapes gives adequate reproduction of the experimental results using the same parameters at each frequency.     

Voltage-selective bidirectional polarization and coherent rotation of nuclear spins in quantum dots

We propose and demonstrate that the nuclear spins of the host lattice in GaAs double quantum dots can be polarized in either of two opposite directions, parallel or antiparallel to an external magnetic field. The direction is selected by adjusting the dc voltage. This nuclear polarization manifests itself by repeated controlled electron-nuclear spin scattering in the Pauli spin-blockade state. Polarized nuclei are also controlled by means of nuclear magnetic resonance. This Letter confirms that the nuclear spins in quantum dots are long-lived quantum states with a coherence time of up to 1 ms, and may be a promising resource for quantum-information processing such as quantum memories for electron spin qubits.     

Two-qubit gate of combined single-spin rotation and interdot spin exchange in a double quantum dot

A crucial requirement for quantum-information processing is the realization of multiple-qubit quantum gates. Here, we demonstrate an electron spin-based all-electrical two-qubit gate consisting of single-spin rotations and interdot spin exchange in a double quantum dot. A partially entangled output state is obtained by the application of the two-qubit gate to an initial, uncorrelated state. We find that the degree of entanglement is controllable by the exchange operation time. The approach represents a key step towards the realization of universal multiple-qubit gates.