A Selective Sulfide Oxidation Catalyzed by Heterogeneous Artificial Metalloenzymes Iron@NikA

Performing a heterogeneous catalysis with proteins is still a challenge. Herein, we demonstrate the importance of cross-linked crystals for sulfoxide oxidation by an artificial enzyme. The biohybrid consists of the insertion of an iron complex into a NikA protein crystal. The heterogeneous catalysts displays a better efficiency-with higher reaction kinetics, a better stability and expand the substrate scope compared to its solution counterpart. Designing crystalline artificial enzymes represents a good alternative to soluble or supported enzymes for the future of synthetic biology.     

Two-Photon Absorption and Cell Imaging of Fluorene-Functionalized Epicocconone Analogues

Epicocconone 1 is a natural chromophore isolated from the fungus Epicoccum nigrum that has shown applications in proteomics and fluorescent microscopy thanks to its unique pro-fluorescence properties. The modification of the skeleton of the natural product by replacing the triene side chain by a fluorenyl scaffold can noticeably increase the fluorophore's absorption coefficient. The synthesis of the analogues of the natural product has been made possible by the use of a palladium-catalyzed carbonylation reaction, allowing the construction of the β-keto-dioxinone key intermediate. Two-photon absorption cross-section measurements of the fluorenyl epicocconone analogues show a structure dependency with values ranging from 60 to 280 GM and live cell imaging show intense staining of intracellular vesicle-like structures around the nucleus.     

Quasipatterns versus superlattices resulting from the superposition of two hexagonal patterns

We present a short review of the experimental observations and mechanisms related to the generation of quasipatterns and superlattices by the Faraday instability with two-frequency forcing. We show how two-frequency forcing makes possible triad interactions that generate hexagonal patterns, twelvefold quasipatterns or superlattices that consist of two hexagonal patterns rotated by an angle α relative to each other. We then consider which patterns could be observed when α does not belong to the set of prescribed values that give rise to periodic superlattices. Using the Swift–Hohenberg equation as a model, we find that quasipattern solutions exist for nearly all values of α. However, these quasipatterns have not been observed in experiments with the Faraday instability for $\alpha \ne \mathrm{\pi }/6$. We discuss possible reasons and mention a simpler framework that could give some hint about this problem.     

Reducing the computational cost of NMR crystallography of organic powders at natural isotopic abundance with the help of 13C-13C dipolar couplings

Structure determination of functional organic compounds remains a formidable challenge when the sample exists as a powder. Nuclear magnetic resonance crystallography approaches based on the comparison of experimental and Density Functional Theory (DFT)-computed ¹H chemical shifts have already demonstrated great potential for structure determination of organic powders, but limitations still persist. In this study, we discuss the possibility of using ¹³C-¹³C dipolar couplings quantified on powdered theophylline at natural isotopic abundance with the help of dynamic nuclear polarization, to realize a DFT-free, rapid screening of a pool of structures predicted by ab initio random structure search. We show that although ¹³C-¹³C dipolar couplings can identify structures possessing long range structural motifs and unit cell parameters close to those of the true structure, it must be complemented with other data to recover information about the presence and the chemical nature of the supramolecular interactions.     

Structure–Property Relationships in Click‐Derived Donor–Triazole–Acceptor Materials

To shed light on intramolecular charge‐transfer phenomena in 1,2,3‐triazole‐linked materials, a series of 1,2,3‐triazole‐linked push–pull chromophores were prepared and studied experimentally and computationally. Investigated modifications include variation of donor and/or acceptor strength and linker moiety as well as regioisomers. Photophysical characterization of intramolecular charge‐transfer features revealed ambipolar behavior of the triazole linker, depending on the substitution position. Furthermore, non‐centrosymmetric materials were subjected to second‐harmonic generation measurements, which revealed the high nonlinear optical activity of this class of materials.     

3D electrogenerated chemiluminescence: from surface-confined reactions to bulk emission

Among luminescence techniques, electrogenerated chemiluminescence (ECL) provides a unique level of manipulation of the luminescent process by controlling the electrochemical trigger. Despite its attractiveness, ECL is by essence a 2D process where light emission is strictly confined to the electrode surface. To overcome this intrinsic limitation, we added a new spatial dimension to the ECL process by generating 3D ECL at the level of millions of micro-emitters dispersed in solution. Each single object is addressed remotely by bipolar electrochemistry and they generate collectively the luminescence in the bulk. Therefore, the entire volume of the solution produces light. To illustrate the generality of this concept, we extended it to a suspension of multi-walled carbon nanotubes where each one acts as an individual ECL nano-emitter. This approach enables a change of paradigm by switching from a surface-limited process to 3D electrogenerated light emission.     

Local convergence of generalized Mann iteration

The local convergence of generalized Mann iteration is investigated in the setting of a real Hilbert space. As application, we obtain an algorithm for estimating the local radius of convergence for some known iterative methods. Numerical experiments are presented showing the performances of the proposed algorithm. For a particular case of the Ezquerro-Hernandez method (Ezquerro and Hernandez, J. Complex., 25:343–361: 2009), the proposed procedure gives radii which are very close to or even identical with the best possible ones.     

Heuristics and lower bounds for minimizing fuel consumption in hybrid-electrical vehicles

In hybrid electric vehicles, the electrical powertrain system has multiple energy sources that it can gather power from to satisfy the propulsion power requested by the vehicle at each instant. This paper focusses on the minimization of the fuel consumption of such a vehicle, taking advantage of the different energy sources. Based on global optimization approaches, the proposed heuristics find solutions that best split the power requested between the multi-electrical sources available. A lower bounding procedure is introduced to validate the quality of the solutions. Computational results show a significant improvement over previous results from the literature in both the computing time and the quality of the solutions.