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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 ‘Global assessment of exposure to faecal contamination through drinking water based on a systematic review’

    Rated 5 of 5. Dasapta Erwin Irawan on 2016-05-24 (2014)
Recommended article. More related Asian researchers should read this.
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Review of ‘Marrying Medicine and Materials: Artemisinin (Qinghaosu) Particle is Soft Enough for Scratching Hard SiC Wafer in Water’

    Rated 5 of 5. Yanquan Geng on 2016-05-18 (2016)

In general, this is a well written and interesting article which needs to be published. In this work, the authors presented a novel method for polishing SiC wafers effectively even in pure water using artemisinin (Qinghaosu) crystals. AFM was employed to conduct scratching tests to demonstrate …

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Signatures of topological Josephson junctions

, , (2016)
Quasiparticle poisoning and diabatic transitions may significantly narrow the window for the experimental observation of the \(4\pi\)-periodic \(dc\) Josephson effect predicted for topological Josephson junctions. Here, we show that switching current measurements provide accessible and robust signatures for topological superconductivity which persist in the presence of quasiparticle poisoning processes. Such measurements provide access to the phase-dependent subgap spectrum and Josephson currents of the topological junction when incorporating it into an asymmetric SQUID together with a conventional Josephson junction with large critical current. We also argue that pump-probe experiments with multiple current pulses can be used to measure the quasiparticle poisoning rates of the topological junction. The proposed signatures are particularly robust, even in the presence of Zeeman fields and spin-orbit coupling, when focusing on short Josephson junctions. Finally, we also consider microwave excitations of short topological Josephson junctions which may complement switching current measurements.
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The Hidden Convexity of Spectral Clustering

, , (2016)
In recent years, spectral clustering has become a standard method for data analysis used in a broad range of applications. In this paper we propose a new class of algorithms for multiway spectral clustering based on optimization of a certain "contrast function" over the unit sphere. These algorithms, partly inspired by certain Independent Component Analysis techniques, are simple, easy to implement and efficient. Geometrically, the proposed algorithms can be interpreted as hidden basis recovery by means of function optimization. We give a complete characterization of the contrast functions admissible for provable basis recovery. We show how these conditions can be interpreted as a "hidden convexity" of our optimization problem on the sphere; interestingly, we use efficient convex maximization rather than the more common convex minimization. We also show encouraging experimental results on real and simulated data.