A Cucurbit[8]uril 2:2 Complex with a Negative pKa Shift

A viologen derivative carrying a benzimidazole group ( V-P-I ²⁺; viologen–phenylene–imidazole V-P-I ) can be dimerized in water using cucurbit[8]uril (CB[8]) in the form of a 2:2 complex resulting in a negative shift of the guest pK_a, by more than 1 pH unit, contrasting with the positive pK_a shift usually observed for CB-based complexes. Whereas 2:2 complex protonation is unclear by NMR, silver cations have been used for probing the accessibility of the imidazole groups of the 2:2 complexes. The protonation capacity of the buried imidazole groups is reduced, suggesting that CB[8] could trigger proton release upon 2:2 complex formation. The addition of CB[8] to a solution containing V-P- I ³⁺ indeed released protons as monitored by pH-metry and visualized by a coloured indicator. This property was used to induce a host/guest swapping, accompanied by a proton transfer, between V-P-I ³⁺ ⋅ CB[7] and a CB[8] complex of 1-methyl-4-(4-pyridyl)pyridinium. The origin of this negative pK_a shift is proposed to stand in an ideal charge state, and in the position of the two pH-responsive fragments inside the two CB[8] which, alike residues engulfed in proteins, favour the deprotonated form of the guest molecules. Such proton release triggered by a recognition event is reminiscent of several biological processes and may open new avenues toward bioinspired enzyme mimics catalyzing proton transfer or chemical reactions.     

An Efficient Preparation of 2,6-Di-t-Butyl-1,4-Benzoquinone

A convenient and high yielding preparation of 2,6-di-t-butyl-1,4-benzoquinone from the iron-catalyzed oxidation of 2,4,6-tri-t-butylphenol with t-butyl hydroperoxide (TBHP) under acidic conditions is reported.     

A PDE based and interpolation-free framework for modeling the sifting process in a continuous domain

The empirical mode decomposition (EMD) is a powerful tool in signal processing. Despite its algorithmic origin making its theoretical analysis and formulation very difficult, a few recent works has contributed to its theoretical framework. Herein, the former local mean is formulated in a more convenient way by introducing operators to calculate local upper and lower envelopes. This enables the use of differential calculus and other classical calculations on the new local mean. Based on its more accurate formulation, a partial differential equation (PDE) consistency result is provided to approximate the sifting process iterations, without any envelope interpolation. In addition, a new stopping criterion based on the introduced local mean is proposed. This new criterion is a local measure and resolves the null integral conservative property of the previous derived PDE, which made any signal having a null integral be a PDE-based mode. Moreover, the δ inner model parameter is now linked to the signal intrinsic properties, providing to the latter a physical meaning and making the proposed model keep the auto-adaptive property of the EMD. New decomposition modes are now analytically and fully characterized, and also interpolation free. Finally, properties of the interpolation free PDE model are presented. Results obtained with our proposed approach by explicit computations thanks to the eigendecomposition of the Laplacian operator, and also by numerical resolution of the derived PDE, show noticeable improvements for both stationary and non stationary signals, in comparison to the former EMD algorithm.     

Sono and electrochemical synthesis and characterization of copper core–silver shell nanoparticles

Cu–Ag core–shell nanopowders have been prepared by ultrasound-assisted electrochemistry followed by a displacement reaction. The composition of the particles has been determined by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX). The XRD patterns versus time displacement show that higher are the silver peaks intensities, weaker are the copper ones. That exhibits the progressive recovering of copper by silver. EDX results and quartz crystal microbalance results indicate that various reaction mechanisms are implied in this process. Transmission electron microscopy (TEM) points out variable nanometric diameter grain and some small agglomerates. Elemental mapping obtained by electron energy-loss spectroscopy (EELS) underlines the core–shell structure.     

Study of Electrical Conductivity of Para-Toluene Sulfonic Acid Doped Polyaniline/Polyester-Based Polyurethane Blends in the S-Band Frequency Range

Conducting polymer blends were prepared using polyaniline doped with para- toluene sulfonic acid (PTSA-PANI) and a polyester polyol-based polyurethane (PU). The morphological, thermal and dielectric properties of the PTSA-PANI/PU blends in the frequency range of 1–5 GHz (S band) were investigated. It was found that the morphology of the samples was affected by the PTSA-PANI loading, resulting in the formation of agglomerates and pathways when above 10 wt%. The thermal stability of the composites was improved with increased PTSA-PANI loading. The electrical conductivity percolation threshold was obtained at 2.5% of PTSA-PANI loading and the electrical conductivity reached the value of 0.13 S/m at a PTSA-PANI loading of 30 wt%. The obtained results for the PTSA-PANI/PU blends prepared indicate a high potential for their successful use in electrical and electromagnetic applications.     

Synthesis of azafluorenones and related compounds using deprotocupration–aroylation followed by intramolecular direct arylation

The efficiency of the deprotocupration–aroylation of 2-chloropyridine using lithiocuprates prepared from CuX (X=Cl, Br) and LiTMP (TMP=2,2,6,6-tetramethylpiperidido, 2 equiv) was investigated. CuCl was identified as a more suitable copper source than CuBr for this purpose. Different diaryl ketones bearing a halogen at the 2 position of one of the aryl groups were synthesized in this way from azines and thiophenes. These were then involved in palladium-catalyzed ring closure: substrates underwent expected CH-activation-type arylation to afford fluorenone-type compounds, and were also subjected to cyclization reactions leading to xanthones, notably in the presence of oxygen-containing substituents or reagents.     

Synthesis and Structural Assignment of 1-O-Acetyl-2,3,5-tri-O-benzoyl-4-(thymin-1-yl)-α-l-lyxofuranose

Abstract

Analogues of nucleosides in which the nucleobase is fixed onto the C-4 of the sugar moiety are generally prepared either from 4,5-unsaturated sugar derivatives or via a formaldehyde condensation.¹ We tested the furanosyl bromide reactivity of 1 ² towards a series of nucleophiles, mostly azides or cyanides, without success. Conversely, the nucleosidation of 1 using 5-methyl-2,4-bis(trimethyl-silyloxy)pyrimidine in the presence of stannic chloride took place at the second anomeric position (C-4) and led to the isolation in acceptable yield (47%) of a unique anomer 2 (Scheme 1).