Trinuclear Schiff base complexes with uranium(V) and copper(II) or zinc(II) ions

Treatment of the uranium(IV) complexes [{ML¹(py)}₂U^IV] (M = Cu, Zn; L¹ = N,N′-bis(3-hydroxysalicylidene)-1,3-propanediamine) with silver nitrate in pyridine led to the formation of the corresponding cationic uranium(V) species which were found to be thermally unstable and were converted back into the parent U^IV complexes; no electron transfer was observed in solution between the U^IV and U^V compounds. In the crystals of [{ML¹(py)}₂U^IV][{ML¹(py)}₂U^V][NO₃], the neutral U^IV and cationic U^V species are clearly identified by the distinct U–O distances. Similar reaction of [{ZnL²(py)}₂U^IV] [L² = N,N′-bis(3-hydroxysalicylidene)-1,4-butanediamine] with AgNO₃ gave crystals of [{ZnL²(py)}U^V{ZnL²(py)₂}][NO₃] but the copper counterpart was not isolated. Crystals of [{ZnL¹(py)}₂U^V][OTf] · THF (OTf = OSO₂CF₃) were obtained fortuitously from the reaction of [Zn(H₂L¹)] and U(OTf)₃.     

A Water Molecule Triggers Guest Exchange at a Mono-Zinc Centre Confined in a Biomimetic Calixarene Pocket: a Model for Understanding Ligand Stability in Zn Proteins

In this study, the ligand exchange mechanism at a biomimetic Zn^II centre, embedded in a pocket mimicking the possible constrains induced by a proteic structure, is explored. The residence time of different guest ligands (dimethylformamide, acetonitrile and ethanol) inside the cavity of a calix[6]arene-based tris(imidazole) tetrahedral zinc complex was probed using 1D EXchange SpectroscopY NMR experiments. A strong dependence of residence time on water content was observed with no exchange occurring under anhydrous conditions, even in the presence of a large excess of guest ligand. These results advocate for an associative exchange mechanism involving the transient exo-coordination of a water molecule, giving rise to 5-coordinate Zn^II intermediates, and inversion of the pyramid at the Zn^II centre. Theoretical modelling by DFT confirmed that the associative mechanism is at stake. These results are particularly relevant in the context of the understanding of kinetic stability/lability in Zn proteins and highlight the key role that a single water molecule can play in catalysing ligand exchange and controlling the lability of Zn^II in proteins.     

Entanglement Dynamics and Symmetry Breaking in Symmetric four Qubits GHZ- and W-type States Coupled to Classical Random Telegraph Noise in Mixed Environments

A system of three non-interacting qubits is used as a quantum probe to classify three classical non-Gaussian noises namely, the static noise (SN), colored noise (pink and brown spectrum) and random telegraph noise (RTN), according to their detrimental effects on the evolution of entanglement of the latter. The probe system is initially prepared in the GHZ state and coupled to the noises in independent environments. Seven configurations for the qubit-noise coupling (QNC) are considered. To estimate the destructive influence of each kind of noise, the tripartite negativity is employed to compare the evolution of entanglement in these QNC configurations to each other with the same noise parameters. It is shown that the evolution of entanglement is drastically impacted by the QNC configuration considered as well as the properties of the environmental noises and that the SN is more detrimental to the survival of entanglement than the RTN and colored noise, regardless of the Markov or non-Markov character of the RTN and the spectrum of the colored noise. On the other hand, it is shown that pink noise is more fatal to the system than the RTN and that the situation is totally reversed in the case of brown noise. Finally, it is demonstrated that these noises, in descending order of destructive influence, can be classified as follows: SN > pink noise > RTN > brown noise.

     

Uncertainty quantification in a chemical system using error estimate-based mesh adaption

This paper describes a rigorous a posteriori error analysis for the stochastic solution of non-linear uncertain chemical models. The dual-based a posteriori stochastic error analysis extends the methodology developed in the deterministic finite elements context to stochastic discretization frameworks. It requires the resolution of two additional (dual) problems to yield the local error estimate. The stochastic error estimate can then be used to adapt the stochastic discretization. Different anisotropic refinement strategies are proposed, leading to a cost-efficient tool suitable for multi-dimensional problems of moderate stochastic dimension. The adaptive strategies allow both for refinement and coarsening of the stochastic discretization, as needed to satisfy a prescribed error tolerance. The adaptive strategies were successfully tested on a model for the hydrogen oxidation in supercritical conditions having 8 random parameters. The proposed methodologies are however general enough to be also applicable for a wide class of models such as uncertain fluid flows.     

Tetrathiafulvalene-annulated dipyrrolylquinoxaline: the effect of fluoride on its optical and electrochemical behaviors

A tetrathiafulvalene donor has been annulated to 2,3-di(1H-2-pyrrolyl)quinoxaline affording a new chemosensor 1, which shows a unique optical selectivity and reactivity for the fluoride ion over other anions in CH₂Cl₂ leading to a colorimetric response. Electrochemical polymerization of 1 occurred in the presence of fluoride.     

Growth Rates and Explosions in Sandpiles

We study the abelian sandpile growth model, where n particles are added at the origin on a stable background configuration in ? ^d . Any site with at least 2d particles then topples by sending one particle to each neighbor. We find that with constant background height h≤2d?2, the diameter of the set of sites that topple has order n ^1/d . This was previously known only for h<d. Our proof uses a strong form of the least action principle for sandpiles, and a novel method of background modification. We can extend this diameter bound to certain backgrounds in which an arbitrarily high fraction of sites have height 2d?1. On the other hand, we show that if the background height 2d?2 is augmented by 1 at an arbitrarily small fraction of sites chosen independently at random, then adding finitely many particles creates an explosion (a sandpile that never stabilizes).     

A Combined Kinetic and Thermodynamic Approach for the Interpretation of Continuous‐Flow Heterogeneous Catalytic Processes

The heterogeneous proline‐catalyzed aldol reaction was investigated under continuous‐flow conditions by means of a packed‐bed microreactor. Reaction‐progress kinetic analysis (RPKA) was used in combination with nonlinear chromatography for the interpretation, under synthetically relevant conditions, of important mechanistic aspects of the heterogeneous catalytic process at a molecular level. The information gathered by RPKA and nonlinear chromatography proved to be highly complementary and allowed for the assessment of optimal operating variables. In particular, the determination of the rate‐determining step was pivotal for optimizing the feed composition. On the other hand, the competitive product inhibition was responsible for the unexpected decrease in the reaction yield following an apparently obvious variation in the feed composition. The study was facilitated by a suitable 2D instrumental arrangement for simultaneous flow reaction and online flow‐injection analysis.