Characterization of a putative sensory [FeFe]-hydrogenase provides new insight into the role of the active site architecture

[FeFe]-hydrogenases are known for their high rates of hydrogen turnover, and are intensively studied in the context of biotechnological applications. Evolution has generated a plethora of different subclasses with widely different characteristics. The M2e subclass is phylogenetically distinct from previously characterized members of this enzyme family and its biological role is unknown. It features significant differences in domain- and active site architecture, and is most closely related to the putative sensory [FeFe]-hydrogenases. Here we report the first comprehensive biochemical and spectroscopical characterization of an M2e enzyme, derived from Thermoanaerobacter mathranii. As compared to other [FeFe]-hydrogenases characterized to-date, this enzyme displays an increased H₂ affinity, higher activation enthalpies for H⁺/H₂ interconversion, and unusual reactivity towards known hydrogenase inhibitors. These properties are related to differences in active site architecture between the M2e [FeFe]-hydrogenase and “prototypical” [FeFe]-hydrogenases. Thus, this study provides new insight into the role of this subclass in hydrogen metabolism and the influence of the active site pocket on the chemistry of the H-cluster.

Characterization of a group D putative sensory [FeFe]-hydrogenase reveals how the active site can be tuned to decrease CO inhibition and increase stability of a reduced H-cluster while retaining the ability to catalyze H⁺/H₂ interconversion.     

Studies on the chemistry of 1,4-oxazines. 18. Synthesis of tricyclic 1,4-benzoxazines via nucleophilic substitution of activated precursors

Starting from activated benzoxazines 1 and 2 new synthetic pathways to the tricyclic compounds 4, 9, 12 and 16 are described. Reaction of the hydrazides 17a,b with thionylchloride leads to the novel thiatriazolo-benzoxazines 18a,b .     

Density functional theory calculations for the hydrogen evolution reaction in an electrochemical double layer on the Pt(111) electrode

We present results of density functional theory calculations on a Pt(111) slab with a bilayer of water, solvated protons in the water layer, and excess electrons in the metal surface. In this way we model the electrochemical double layer at a platinum electrode. By varying the number of protons/electrons in the double layer we investigate the system as a function of the electrode potential. We study the elementary processes involved in the hydrogen evolution reaction, 2(H(+) + e(-)) --> H(2), and determine the activation energy and predominant reaction mechanism as a function of electrode potential. We confirm by explicit calculations the notion that the variation of the activation barrier with potential can be viewed as a manifestation of the Br?nsted-Evans-Polanyi-type relationship between activation energy and reaction energy found throughout surface chemistry.     

Superpositioned dielectrophoresis for enhanced trapping efficiency

One of the major applications for dielectrophoresis is selective trapping and fractionation of particles. If the surrounding medium is of low conductivity, the trapping force is high, but if the conductivity increases, the attraction decreases and may even become negative. However, high-conductivity media are essential when working with biological material such as living cells. In this paper, some basic calculations have been performed, and a model has been developed which employs both positive and negative dielectrophoresis in a channel with interdigitated electrodes. The finite element method was utilized to predict the trajectories of Escherichia coli bacteria in the superpositioned electrical fields. It is shown that a drastic improvement of trapping efficiency can be obtained in this way, when a high conductivity medium is employed.     

Effect of pressure on luminescence properties of Sm3+ ions in potassium niobate tellurite glass

Emission spectra and decay properties of the ⁴G_5/2 level of Sm³⁺ ions in TeO₂+K₂O+Nb₂O₅ glass have been measured as a function of pressure upto 14.6 GPa at room temperature. A progressive red shift in the barycentres of ⁴G_5/2→⁶H_J (J=9/2, 7/2 and 5/2) emission bands and increase in splitting of these bands have been observed with increasing pressure. The luminescence decay profile of the ⁴G_5/2 level at ambient condition shows a nearly single exponential nature and with increase in pressure it becomes gradually non-exponential associated with a decrease in lifetime. The non-exponential decay curves are well-fitted to the Inokuti–Hirayama model for S=6, indicating that the interaction for cross-relaxation energy transfer between Sm³⁺ ions is of dipole–dipole type. The results obtained after release of pressure reveal that there is a small hysteresis.     

Control of the Interface Between Electron‐Hole and Electron‐Ion Plasmas: Hybrid Semiconductor‐Gas Phase Devices as a Gateway for Plasma Science

Coupling electron‐hole (e^–‐ h⁺) and electron‐ion plasmas across a narrow potential barrier with a strong electric field provides an interface between the two plasma genres and a pathway to electronic and photonic device functionality. The magnitude of the electric field present in the sheath of a low temperature, nonequilibrium microplasma is sufficient to influence the band structure of a semiconductor region in immediate proximity to the solid‐gas phase interface. Optoelectronic devices demonstrated by leveraging this interaction are described here. A hybrid microplasma/semiconductor photodetector, having a Si cathode in the form of an inverted square pyramid encompassing a neon microplasma, exhibits a photosensitivity in the ～420–1100 nm region as high as 3.5 A/W. Direct tunneling of electrons into the collector and the Auger neutralization of ions arriving at the Si surface appear to be facilitated by an n ‐type inversion layer at the cathode surface resulting from bandbending by the microplasma sheath electric field. Recently, an npn plasma bipolar junction transistor (PBJT), in which a low temperature plasma serves as the collector in an otherwise Si device, has also been demonstrated. Having a measured small signal current gain h_fe as large as 10, this phototransistor is capable of modulat‐ing and extinguishing the collector plasma with emitter‐base bias voltages <1 V. Electrons injected into the base when the emitter‐base junction is forward‐biased serve primarily to replace conduction band electrons lost to the collector plasma by secondary emission and ion‐enhanced field emission in which ions arriving at the base‐collector junction deform the electrostatic potential near the base surface, narrowing the potential barrier and thereby facilitating the tunneling of electrons into the collector. Of greatest significance, therefore, are the implications of active, plasma/solid state interfaces as a new frontier for plasma science. Specifically, the PBJT provides the first opportunity to control the electronic properties of a material at the boundary of, and interacting with, a plasma. By specifying the relative number densities of free (conduction band) and bound (valence band) electrons at the base‐collector interface, the PBJT's emitter‐base junction is able to dictate the rates of secondary electron emission (including Auger neutralization) at the semiconductor‐plasma interface, thereby offering the ability to vary at will the effective secondary electron emission coefficient for the base surface (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Experimental observation of the bifurcation dynamics of an intrinsic localized mode in a driven 1D nonlinear lattice

Linear response spectra of a driven intrinsic localized mode in a micromechanical array are measured as it approaches two fundamentally different kinds of bifurcation points. A linear phase mode associated with this autoresonant state softens in frequency and its amplitude grows as the upper frequency bifurcation point is approached, similar to the soft-mode kinetic transition for a single driven Duffing resonator. A lower frequency bifurcation point occurs when the four-wave-mixing partner of this same phase mode intercepts the top of the extended wave branch, initiating a second kinetic transition process.