A photoreactive small-molecule probe for 2-oxoglutarate oxygenases

2-oxoglutarate (2-OG)-dependent oxygenases have diverse roles in human biology. The inhibition of several 2-OG oxygenases is being targeted for therapeutic intervention, including for cancer, anemia, and ischemic diseases. We report a small-molecule probe for 2-OG oxygenases that employs a hydroxyquinoline template coupled to a photoactivable crosslinking group and an affinity-purification tag. Following studies with recombinant proteins, the probe was shown to crosslink to 2-OG oxygenases in human crude cell extracts, including to proteins at endogenous levels. This approach is useful for inhibitor profiling, as demonstrated by crosslinking to the histone demethylase FBXL11 (KDM2A) in HEK293T nuclear extracts. The results also suggest that small-molecule probes may be suitable for substrate identification studies.     

Toward scale‐free like behavior under increasing cognitive load

To understand how cognition and response selection processes might emerge from dynamic brain systems, we analyzed reaction times during the performance of both a working memory task and a choice reaction time task at different levels of “cognitive load.” Our findings suggest a continuous transition—tuned by load—from random behavior toward scale‐free like behavior as an expanding connectivity process in a network poised near a critical point. © 2012 Wiley Periodicals, Inc. Complexity, 2012     

Nanocomposites of titania and hybrid matrix with high refractive index

A sol–gel route for TiO₂ nanocrystals (NCs) synthesis has been developed at low temperature without surfactants. Synthetic and processing parameters have been optimized to maximize particles’ colloidal stability and crystallinity. The obtained TiO₂ NCs can be homogeneously dispersed in a sol–gel derived organic–inorganic hybrid material, resulting in homogeneous composite films when prepared by spin coating. High refractive index films were obtained with high TiO₂ NCs loading and good transparency. Furthermore, TiO₂ colloidal solutions can be used for depositing porous crystalline films, whose structural evolution has been followed under different annealing treatments. Nanocrystals were characterized by UV–Vis absorption, TEM, FT-Raman, and XRD techniques, while nanocomposite and TiO₂ films were analyzed by SEM, TEM, and spectroscopic ellipsometry.     

An easy and versatile approach for the regioselective de-O-benzylation of protected sugars based on the I2/Et3 SiH combined system

The use of cheap and easy to handle reagents, such as I(2) and Et(3) SiH, at low temperature allows the regioselective removal of benzyl protecting groups from highly O-benzylated carbohydrates. The observed regioselectivity is dependent on the nature of the precursor, the least accessible carbinol often being liberated. A mechanistic investigation reveals that in situ generated HI is the promoter of the process, whereas the regioselectivity appears to be mainly controlled by steric effects. However, the presence of an electron withdrawing acyl protecting group can switch the regioselectivity to favour deprotection of the carbinol position farthest from the ester group. The protocol is experimentally simple and provides straightforward access in useful yields to a wide range of partially protected mono- and disaccharide building blocks that are valuable for the synthesis of either biologically useful oligosaccharides or highly functionalised chiral compounds. Partially protected sugars thus obtained can also be coupled in situ with a glycosyl donor, as illustrated by the one-pot synthesis of a Lewis X mimic from fully protected precursors.     

Large scale dissipation and filament instability in two-dimensional turbulence

Coherent vortices in two-dimensional turbulence induce far-field effects that stabilize vorticity filaments and inhibit the generation of new vortices. We show that the large-scale energy sink often included in numerical simulations of statistically stationary two-dimensional turbulence reduces the stabilizing role of the vortices, leading to filament instability and to continuous formation of new coherent vortices. This counterintuitive effect sheds new light on the mechanisms responsible for vortex formation in forced-dissipated two-dimensional turbulence, and it has significant impact on the temporal evolution of the vortex population in freely decaying turbulence. The time dependence of vortex statistics in the presence of a large-scale energy sink can be approximately described by a modified version of the scaling theory developed for small-scale dissipation.     

Power semiconductor laser diode arrays characterization

Nowadays, power semiconductor laser diode arrays are becoming a widespread source for a large variety of industrial applications. In particular, the availability of low-cost high-power laser diode arrays makes their use possible in the industrial context for material cutting, welding, diagnostics and processing. In the above applications, the exact control of the beam quality plays a very important role because it directly affects the reliability of the final result. In this paper, we present two different approaches useful for the characterization of the beam quality in laser diode arrays. The first one, starting from total intensity measurements on planes orthogonal to the beam propagation path, is able to deduce the working conditions of each laser setting up the array. The second one is aimed at the measurement of a global quality factor of the array itself; to this end, the empirical extension of the M² concept to composite beams is presented along with some experimental results. As the first technique is especially intended for the non-destructive detection of design problems in the array itself and in the bias circuitry, the second one represents a powerful tool for the rapid on-line diagnostics of the laser beam during its use.     

Gas-phase enantioselectivity of chiral amido[4]resorcinarene receptors

Diastereomeric proton-bound [1(L)HA]+ complexes between selected amino acids (A=phenylglycine (Phg), tryptophan (Trp), tyrosine methyl ester (TyrOMe), threonine (Thr), and allothreonine (AThr)) and a chiral amido[4]resorcinarene receptor (1(L)) display a significant enantioselectivity when undergoing loss of the amino acid guest A by way of the enantiomers of 2-aminobutanes (B) in the gas phase. The enantioselectivity of the B-to-A displacement is ascribed to a combination of thermodynamic and kinetic factors related to the structure and the stability of the diastereomeric [1(L)HA]+ complexes and of the reaction transition states. The results of the present and previous studies allow classification of the [1(L)HA]+ complexes in three main categories wherein: i) guest A does not present any additional functionalities besides the amino acid one (alanine (Ala), Phg, and phenylalanine (Phe)); ii) guest A presents an additional alcohol function (serine (Ser), Thr, and AThr); and iii) guest A contains several additional functionalities on its aromatic ring (tyrosine (Tyr), TyrOMe, Trp, and 3,4-dihydroxyphenylalanine (DOPA)). Each category exhibits a specific enantioselectivity depending upon the predominant [1(L)HA]+ structures and the orientation of the 2-aminobutane reactant in the relevant adducts observed. The results may contribute to the understanding of the exceptional selectivity and catalytic properties of enzyme mimics towards unsolvated biomolecules.     

Dispersion and mixing in quasigeostrophic turbulence

The dynamics of passive Lagrangian tracers in three-dimensional quasigeostrophic turbulence is studied numerically and compared with the behavior of two-dimensional barotropic turbulence. Despite the different Eulerian properties of the two flows, the Lagrangian dynamics of passively advected tracers in three-dimensional quasigeostrophic turbulence is very similar to that of barotropic turbulence. In both systems, coherent vortices play a major role in determining the mixing and dispersion properties. This work indicates that recent results on particle dynamics in barotropic, two-dimensional turbulence carry over to more realistic baroclinic flows, such as those encountered in the large-scale dynamics of the atmosphere and ocean.     

On the possibility of simplifying the thermoelastic equation

By some very simple algebraic manipulations, it is shown as the linear thermoelastic equation can be solved by looking for the solutions of much simpler vectorial equations. As an example the displacements of the reflecting surface of a mirror illuminated by a high power laser beam have been evaluated.

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Sommario Utilizzando alcuni semplici passaggi algebrici, viene mostrato come l'equazione degli spostamenti termoelastici possa essere risolta cercando le soluzioni di equazioni vettoriali molto più semplici. Come esempio vengono calcolate le deformazioni della superficie riflettente di uno specchio investito da un fascio laser di grande potenza.