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The neighbouring effect of isosorbide and its epimers in their reactions with dimethyl carbonate

Fabio Aricò, Pietro Tundo (corresponding) (2014)
Abstract The reactions of isosorbide and its epimers, isomannide and isoidide, with dimethyl carbonate have been herein investigated as easy access to bio-based products by a free-halogen chemistry approach. Isosorbide and its epimers show a different reactivity in bimolecular nucleophilic substitution with dimethyl carbonate (DMC). Carboxymethylation reaction was carried out in the presence of DMC and a weak base resulting in the high-yielding synthesis of dicarboxymethyl derivatives. Isomannide was the most reactive anhydro sugar due to the less sterically hindered exo position of the OH groups. On the other hand, methylation of isosorbide and its epimers, conducted in the presence of a strong base and DMC, showed the higher reactivity of the endo hydroxyl group, isoidide being the most reactive epimer. This result has been ascribed to the neighboring effect due to the combination of the oxygen in β-position and the intramolecular hydrogen bond within the anhydro sugar structure. Methylation reactions were also conducted in autoclave at high temperature with the amphoteric catalyst hydrotalcite using DMC as reagent and solvent. In this case, the reactivity of the epimers resulted quite differently with isosorbide being the most reactive reagent possibly as a result of the structure of hydrotalcite comprising of both acidic and basic sites. The neighboring effect was observed with good evidence in these methylation reactions.
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The Spherical Nucleic Acids mRNA Detection Paradox

From the 1950s onwards, our understanding of the formation and intracellular trafficking of membrane vesicles was informed by experiments in which cells were exposed to gold nanoparticles and their uptake and localisation, studied by electron microscopy. In the last decade, building on progress in the synthesis of gold nanoparticles and their controlled functionalisation with a large variety of biomolecules (DNA, peptides, polysaccharides), new applications have been proposed, including the imaging and sensing of intracellular events. Yet, as already demonstrated in the 1950s, uptake of nanoparticles results in confinement within an intracellular vesicle which in principle should preclude sensing of cytosolic events. To study this apparent paradox, we focus on a commercially available nanoparticle probe that detects mRNA through the release of a fluorescently-labelled oligonucleotide (unquenching the fluorescence) in the presence of the target mRNA. Using electron, fluorescence and photothermal microscopy, we show that the probes remain in endocytic compartments and that they do not report on mRNA level. We suggest that the validation of any nanoparticle-based probes for intracellular sensing should include a quantitative and thorough demonstration that the probes can reach the cytosolic compartment.
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Review of ‘Student Evaluations of Teaching (Mostly) Do Not Measure Teaching Effectiveness’

    Rated 4.5 of 5. Mine Cetinkaya-Rundel on 2016-03-06 (2016)

This article presents findings from two studies on the effectiveness of student evaluations of teaching as a measure of teaching effectiveness. First study is from a five-year natural experiment at a French university (23,011 evaluations of 379 instructors by 4,423 students in six mandatory …

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Review of ‘Indandiazocines: Unidirectional molecular switches’

    Rated 4.5 of 5. Martin Suhm on 2016-02-15 (2015)
Sets the stage for calculations and experiments on molecular machines exploiting this chromophore
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Ultraviolet Fe II Emission in Fainter Quasars: Luminosity Dependences, and the Influence of Environments

, , (2016)
We investigate the strength of ultraviolet Fe II emission in fainter quasars compared with brighter quasars for 1.0 ~ 25 Ang. there is a universal (i.e. for quasars in general) strengthening of W2400 with decreasing intrinsic luminosity, L3000. (2) In conjunction with previous work by Clowes et al., we find that there is a further, differential, strengthening of W2400 with decreasing L3000 for those quasars that are members of Large Quasar Groups (LQGs). (3) We find that increasingly strong W2400 tends to be associated with decreasing FWHM of the neighbouring Mg II {\lambda}2798 broad emission line. (4) We suggest that the dependence of W2400 on L3000 arises from Ly{\alpha} fluorescence. (5) We find that stronger W2400 tends to be associated with smaller virial estimates from Shen et al. of the mass of the central black hole, by a factor ~ 2 between the ultrastrong emitters and the weak. Stronger W2400 emission would correspond to smaller black holes that are still growing. The differential effect for LQG members might then arise from preferentially younger quasars in the LQG environments.
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Gravitational bending angle of light for finite distance and the Gauss-Bonnet theorem

, , (2016)
We discuss a possible extension of calculations of the bending angle of light in a static, spherically symmetric and asymptotically flat spacetime to a non-asymptotically flat case. We examine a relation between the bending angle of light and the Gauss-Bonnet theorem by using the optical metric. A correspondence between the deflection angle of light and the surface integral of the Gaussian curvature may allow us to take account of the finite distance from a lens object to a light source and a receiver. Using this relation, we propose a method for calculating the bending angle of light for such cases. Finally, this method is applied to two examples of the non-asymptotically flat spacetimes to suggest finite-distance corrections: Schwarzschild-de Sitter (Kottler) solution to the Einstein equation and an exact solution in Weyl conformal gravity.