Targeting intermediates of [FeFe]-hydrogenase by CO and CN vibrational signatures

In this work, we employ density functional theory to assign vibrational signatures of [FeFe]-hydrogenase intermediates to molecular structures. For this purpose, we perform an exhaustive analysis of structures and harmonic vibrations of a series of CN and CO containing model clusters of the [FeFe]-hydrogenase enzyme active site considering also different charges, counterions, and solvents. The pure density functional BP86 in combination with a triple-ζ polarized basis set produce reliable molecular structures as well as harmonic vibrations. Calculated CN and CO stretching vibrations are analyzed separately. Scaled vibrational frequencies are then applied to assign intermediates in [FeFe]-hydrogenase's reaction cycle. The results nicely complement the previous studies of Darensbourg and Hall, and Zilberman et al. The infrared spectrum of the H(ox) form is in very good agreement with the calculated spectrum of the Fe(I)Fe(II) model complex featuring a free coordination site at the distal Fe atom, as well as, with the calculated spectra of the complexes in which H(2) or H(2)O are coordinated at this site. The spectrum of H(red) measured from Desulfovibrio desulfuricans is compatible with a mixture of a Fe(I)Fe(I) species with all terminal COs, and a Fe(I)Fe(I) species with protonated dtma ligand, while the spectrum of H(red) recently measured from Chlamydomonas reinhardtii is compatible with a mixture of a Fe(I)Fe(I) species with a bridged CO, and a Fe(II)Fe(II) species with a terminal hydride bound to the Fe atom.     

Resonance and rotation numbers for planar Hamiltonian systems: Multiplicity results via the Poincaré-Birkhoff theorem

In the general setting of a planar first order system

(0.1)     

Exact and approximate solutions for the dilute Ising model

The ground state energy and entropy of the dilute mean field Ising model is computed exactly by a single order parameter as a function of the dilution coefficient. An analogous exact solution is obtained in the presence of a magnetic field with random locations. Results lead to a complete understanding of the geography of the associated random graph. In particular, we give the size of the giant component (continent) and the number of isolated clusters of connected spins of all given size (islands). We also compute the average number of bonds per spin in the continent and in the islands. Then, we tackle the problem of solving the dilute Ising model at strictly positive temperature. In order to obtain the free energy as a function of the dilution coefficient and the temperature, it is necessary to introduce a second order parameter. We are able to find out the exact solution in the paramagnetic region and exactly determine the phase transition line. In the ferromagnetic region we provide a solution in terms of an expansion with respect to the second parameter which can be made as accurate as necessary. All results are reached in the replica frame by a strategy which is not based on multi-overlaps.     

The "bridge" game: role of the fourth player in chiral recognition

A new team player: The "three-point interaction" model, which is usually employed to rationalize chiral recognition, does not account for the amazing enantioselectivity measured for the receptors of many proteic acceptors. Gas-phase experiments have indicated that at least a fourth "player" must be considered: the rigidity that a receptor opposes to distortions of its cavity resulting from noncovalent interactions with a chiral molecule (see picture).     

Fabrication of nanostructured silver substrates for surface-enhanced Raman spectroscopy

Four nanostructured Ag substrates have been fabricated with different surface morphologies and tested with surface-enhanced Raman scattering (SERS) experiments by adsorption of adenine. Their SERS efficiency has been compared and related to the surface roughness resulting from atomic force microscopy measurements. Chemical etching of silver by thiourea/Fe(III)nitrate produces homogeneously roughened plates, exhibiting the largest three-dimensional surface and the best SERS enhancement. They mostly exhibit surface protrusions with sizes around 200 nm, thus matching the best condition for obtaining SERS enhancement by laser excitation at 785 nm. This is quite important in the case of biomolecules, whose samples often present strong fluorescence bands, which usually are not observed with red-shifted exciting lines. Moreover, these Ag platforms, owing to their uniform nanostructured surfaces, are suitable for obtaining reproducible results from microRaman investigation. In conclusion, the present nanofabrication of Ag surfaces allows obtaining SERS-active substrates, which combine high reproducibility and sensitivity and can be successfully employed in the molecular recognition of different organic ligands or biomolecules like nucleic acids and proteins.     

Scenarios in the experimental response of a vibro-impact single-degree-of-freedom system and numerical simulations

Nonlinear Dynamics - In this paper, possible scenarios within the experimental dynamic response of a vibro-impact single-degree-of-freedom system, symmetrically constrained by deformable and...     

Unbalanced Unicyclic and Bicyclic Graphs with Extremal Spectral Radius

Czechoslovak Mathematical Journal - A signed graph Γ is a graph whose edges are labeled by signs. If Γ has n vertices, its spectral radius is the number ?(Γ):=...     

Naturally Occurring5-[(2-Thienyl)Ethynyl] Thiophene-2-Carbal-Dehyde Through a Short Synthesis of Diarylacetylenes

Title compound and related diarylacetylenes were synthesized via a one-pot procedure starting from aryliodide and trimethylsilylacetylene.