Solution and structural characterization of iron(II) complexes with ortho-halogenated phenolates: insights into potential substrate binding modes in hydroquinone dioxygenases

The new ligand cis,cis-1,3,5-tris-(E)-(tolylideneimino)cyclohexane (TACH-o-tolyl) forms a 1:1 complex with iron(II). Addition of substituted phenolates forms 1:1:1 ligand:iron:phenolate complexes, which have been characterized both in the solid state and in solution. There is complete binding of the phenolate to the complex only when there are ortho-halogens on the phenolate. The tertiary complexes with ortho-halo-substituted phenolates exhibit short Fe-halogen distances, and the complex containing a non-coordinating but similarly sized ortho-methyl phenolate has a significantly different conformation and coordination geometry. Therefore, it is likely that the metal-halogen interaction stabilizes the complexes. The iron(II)-halogen interaction in these complexes may explain the substrate specificity of PcpA and LinE, enzymes that preferentially bind phenols and hydroquinones containing halogen substituents in ortho positions.     

Atomic imaging of the monolayer nucleation and unpinning of a compound semiconductor surface during atomic layer deposition

The reaction of trimethyl aluminum on the group III rich reconstructions of InAs(0 0 1) and In(0.53)Ga(0.47)As(0?0?1) is observed with scanning tunneling microscopy/spectroscopy. At high coverage, a self-terminated ordered overlayer is observed that provides the monolayer nucleation density required for subnanometer thick transistor gate oxide scaling and removes the surface Fermi level pinning that is present on the clean InGaAs surface. Density functional theory simulations confirm that an adsorbate-induced reconstruction is the basis of the monolayer nucleation density and passivation.     

Time resolved velocity measurements of unsteady systems using spiral imaging

Although biomolecular dynamics has been investigated using NMR for at least 40 years, only in the past 20 years have internal motions been characterized at atomic resolution throughout proteins and nucleic acids. This development was made possible by multidimensional heteronuclear NMR approaches that provide near complete sequential signal assignments of uniformly labeled biomolecules. Recent methodological advances have enabled characterization of internal dynamics on timescales ranging from picoseconds to seconds, both in solution and in the solid state. The size, complexity and functional significance of biomolecules investigated by NMR continue to grow, as do the insights that have been obtained about function. In this article I review a number of recent advances that have made such studies possible, and provide a few examples of where NMR either by itself or in combination with other approaches has paved the way to a better understanding of the complex relationship between dynamics and biomolecular function. Finally, I discuss prospects for further advances in this field.     

Thermographic signal reconstruction for vibrothermography

Vibrothermography, also known as thermosonics or sonic infrared, is a method of nondestructive evaluation that finds cracks or delaminations from the heat given off in response to vibration. In vibrothermography, finding cracks requires identifying and localizing pulsed surface and subsurface heat sources from a time sequence of infrared images. Traditionally this identification involves manually stepping through and studying the images. Careful observation of the heating and subsequent cooling is needed to distinguish cracks from false indications. In this paper, we present an algorithm that reduces the entire time sequence to a single static plot. The plot uses only a few coefficients per pixel to reconstruct the original sequence; this is possible because the reduction is based on a physical model. As an added bonus, the algorithm reduces noise and improves sensitivity. A single false-color image summarizes all the information from the entire sequence, simplifying the task of identifying cracks.     

X-ray standing waves and scanning electron microscopy — Energy dispersive X-ray emission spectroscopy study of gold nanoparticles

A systematic characterization of mono-disperse nanoparticles with nominal diameters of 25 nm, 46 nm, 73 nm, 100 nm, 115 nm, and 250 nm was performed using X-ray standing waves (XSW). The samples were prepared on Si-wafer pieces and analyzed at DELTA synchrotron facility at beamline BL8 under grazing incidence geometry of the primary radiation. Additionally, SEM-EDX inspections of single particles as well as population-density checks were conducted. Particles with smaller diameters were able be characterized by XSW while the larger ones were not completely covered by the interference field produced by the provided 15 keV monochromatic radiation of BL8. The results of the measurements were compared with those of numerical simulations. The extension of the interference field perpendicular to the Si-wafer reflector was determined to be 83 nm ± 4 nm.     

Causal phase-space approach to fermion theories understood through Cliford algebras

A Wigner-Moyal phase-space approach is developed for the Dirac and Feynman-Gell-Mann equations. The role of spinors as primitive elements of the spacetime and phase-space Clifford algebras is emphasized. A conserved phase-space current is constructed.     

Conductivity of electrolytes and their mixtures: The aqueous HCl-MgCl2 system at low concentrations

The Onsager-Fuoss-Chen theory of conductance for mixtures has been explored and compared with experimental results for the system HCl−MgCl₂−H₂O from 5×10⁻⁵ to 0.02 mol-kg⁻¹ of water. In the theory, the higher order term O(ka) which involves the ion size parameter has been replaced by a linear term with an empirical constant. The theory including the additional linear term agrees well with the experimental results. The mixture effect on the equivalent conductance is small, but on the individual ionic mobilities is substantial.     

Long-range acoustic scattering from a shallow-water mud-volcano cluster

Analysis of reverberation measurements in the Straits of Sicily shows high intensity, discrete, scattered returns 10-20 dB above background reverberation. These returns are due to scattering from mud volcanoes. The reverberation from the mud volcanoes at ranges of 15-22 km is reasonably consistent over these spatial scales (i.e., kilometers) and temporal scales of several hours; measurements separated by 4 years are also similar. Statistical characterization indicates that the reverberation associated with a mud-volcano cluster is strongly non-Rayleigh and that the reverberation can be characterized by a single (shape) parameter, roughly independent of frequency. The non-Rayleigh statistics, with a concomitant increase in the probability of false alarm, indicate that mud volcanoes are a likely source of clutter. Mean target strengths were estimated at 1-11 dB over 160-1400 Hz and are consistent with target strengths measured during a different year at short (direct-path) ranges. Accumulated evidence points to small (order 10 m diameter and several meters high) carbonate chimneys on the mud-volcano edifice as the scattering mechanism as opposed to the edifice itself or scattering from gas bubbles in the water column. Thus, the results represent acoustic scattering from mud volcanoes in a quiescent state.