Conformational selection of glycomimetics at enzyme catalytic sites: experimental demonstration of the binding of distinct high-energy distorted conformations of C-, S-, and O-glycosides by E. Coli beta-galactosidases

We show that the conformational features of the molecular complexes of E. coli beta-galactosidase and O-glycosides may differ from those formed with closely related compounds in their chemical nature, such as C- and S-glycosyl analogues. In the particular case presented here, NMR and ab initio quantum mechanical results show that the 3D-shapes of the ligand/inhibitor within the enzyme binding site depend on the chemical nature of the compounds. In fact, they depend on the relative size of the stereoelectronic barriers for chair deformation or for rotation around Phi glycosidic linkage.     

Single production of fourth-family quarks at the LHC

We study the single production of fourth-family quarks through the process pp→Q′jX at the Large Hadron Collider (LHC). We have calculated the decay widths and branching ratios of the fourth-family quarks (b′ and t′) in the mass range 300–800 GeV. The cross sections for the signal and background processes have been calculated in a Monte Carlo framework. It is shown that the LHC can discover single t′ and b′ quarks if the CKM matrix elements |V _t′q |,|V _qb′|≳0.01.     

The effect of rate of stimulation on perception of spectral shape by cochlear implantees

The effect of rate of stimulation on spectral shape perception was measured in six users of the Nucleus CI24 cochlear implant. Three spectral shapes were created by using three profiles of current across seven electrode positions. Each current profile was replicated in three stimuli that interleaved stimulus pulses across the seven electrodes with cycle rates (rate per electrode) of 450, 900, and 1800 Hz. The stimulus space resulting from a multidimensional scaling experiment showed a clear dimension related to the rate of stimulation that was orthogonal to the dimension related to the spectral shapes. A second experiment was performed with the same subjects to investigate whether the perceptual dimension related to rate in Experiment 1 could be attributed to different perceptual flatness of the profiles at different rates. In Experiment 2, the rate of stimulation was fixed at 900 Hz and three profiles were created for each spectral shape that differed in flatness. This experiment did not, however, result in an independent perceptual dimension related to the flatness of the profile. In conclusion, rate of stimulation provided an independent perceptual dimension in the multiple-electrode stimuli, in spite of the rates being not discriminable or barely discriminable in single-electrode stimulation.     

Head-to-head bisbenzazole derivatives as antiproliferative agents: design,synthesis, in vitro activity,and SAR analysis

Molecular Diversity - In the present work, a series of bisbenzazole derivatives were designed and synthesized as antiproliferative agents. The antiproliferative activity of these compounds was...     

A modified Newton-Jarratt’s composition

A reduced composition technique has been used on Newton and Jarratt’s methods in order to obtain an optimal relation between convergence order, functional evaluations and number of operations. Following this aim, a family of methods is obtained whose efficiency indices are proved to be better for systems of nonlinear equations.     

Analytical perfect fluid perturbation for the matter dominated epoch

We present the analytical solution to the linear evolution equation of a one component Friedmann perturbation using an equation of state of the form p = (1/3)μσ²(t), where μ is the mass density and σ(t) is the root mean square (rms) velocity in the matter dominated epoch. It is assumed that this rms velocity depends only on the time coordinate and decreases as 1/a, a being the expansion factor of the Friedmann background. The evolution equations are written for scales below the horizon using the longitudinal gauge. The general solution, in the coordinate space, of the evolution equation for the scalar mode is obtained. In the case of spherical symmetry, this solution is expressed in terms of unidimensional integrals of the initial conditions: the initial values of the Newtonian potential and its first time derivative. This perfect fluid solution is a good approximation to the evolution of warm dark matter perturbations obtained by solving the Vlasov’s equation for collisionless particles.     

Imaging the Magnetic Reversal of Isolated and Organized Molecular‐Based Nanoparticles using Magnetic Force Microscopy

In the race towards miniaturization in nanoelectronics, magnetic nanoparticles (MNPs) have emerged as potential candidates for their integration in ultrahigh‐density recording media. Molecular‐based materials open the possibility to design new tailor‐made MNPs with variable composition and sizes, which benefit from the intrinsic properties of these materials. Before their implementation in real devices is reached, a precise organization on surfaces and a reliable characterization and manipulation of their individual magnetic behavior are required. In this paper, it is demonstrated how molecular‐based MNPs are accurately organized on surfaces and how the magnetic properties of the individual MNPs are detected and tuned by means of low‐temperature magnetic force microscopy (LT‐MFM) with variable magnetic field. The magnetization reversal on isolated and organized MNPs is investigated; in addition, the temperature dependence of their magnetic response is evaluated.     

Observation and mechanistic study of facile C-O bond formation between a well-defined aryl-copper(III) complex and oxygen nucleophiles

A well-defined macrocyclic aryl–Cu(III) complex (2) reacts readily with a variety of oxygen nucleophiles, including carboxylic acids, phenols and alcohols, under mild conditions to form the corresponding aryl esters, biaryl ethers and alkyl aryl ethers. The relationship between these reactions and catalytic C-O coupling methods is demonstrated by the reaction of the macrocyclic aryl–Br species with acetic acid and p-fluorophenol in the presence of 10 mol% Cu(I). An aryl-Cu(III)-Br species 2(Br) was observed as an intermediate in the catalytic reaction. Investigation of the stoichiometric C-O bond-forming reactions revealed nucleophile-dependent changes in the mechanism. The reaction of 2 with carboxylic acids revealed a positive correlation between the log(k(obs)) and the pK(a) of the nucleophile (less-acidic nucleophiles react more rapidly), whereas a negative correlation was observed with most phenols (more-acidic phenols react more rapidly). The latter trend resembles previous observations with nitrogen nucleophiles. With carboxylic acids and acidic phenols, UV-visible spectroscopic data support the formation of a ground-state adduct between 2 and the oxygen nucleophile. Collectively, kinetic and spectroscopic data support a unified mechanism for aryl-O coupling from the Cu(III) complex, consisting of nucleophile coordination to the Cu(III) center, deprotonation of the coordinated nucleophile, and C-O (or C-N) reductive elimination from Cu(III).