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.     

Energy dependence of the 6Li + 16O elastic scattering versus that of 7Li + 16O

The European Physical Journal A - Existing data for the 6Li + 16O elastic scattering at $ E_{c.m.}=3.27$ -36.8MeV were analyzed within the optical model and coupled-reaction-channels method. The...     

A Galois-Theoretic Approach to the Covering Theory of Quandles

The purpose of this article is to clarify the relationship between the algebraic notion of quandle covering introduced by M. Eisermann and the categorical notion of covering arising from Galois theory. A crucial role is played by the adjunction between the variety of quandles and its subvariety of trivial quandles.