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).     

Molecular dynamics investigations on polishing of a silicon wafer with a diamond abrasive

During the final stages of polishing silicon wafers, much of the interactions between silicon and diamond abrasive takes place at the silicon asperities. These interactions, leading to material removal, were investigated in a MD simulation of polishing of a silicon wafer with a diamond abrasive under dry conditions. Simulations were conducted with silicon asperities of different geometries, different abrasive configurations, and polishing speeds. Under the conditions of polishing, the silicon atoms from the asperities were found to bond chemically to the surface of the diamond abrasive. Continued transverse motion of the diamond abrasive (relative to the silicon asperity) leads to tensile pulling, necking, and ultimate separation of the silicon asperity material instead of conventional material removal in polishing (chip formation) involving cutting/ploughing, which takes place in the absence of chemical bonding between the abrasive and the asperity material. This phenomenon has not been reported previously in the literature. The thrust and cutting forces initially increase due to the increase in the number of asperity atoms affected finally reaching a maximum. This is followed by a decrease of these forces due to tensile pulling and formation of individual strings followed by ultimate separation or breakage of the final string. The ratio of thrust force (F _z ) to the cutting force (F _x ), i.e. |(F _z /F _x )| was found to increase continuously to a maximum of ～0.8 followed by continuous decrease to ～0.25. This is in contrast to a more or less constant value of ～2 in the case of tools with rounded radii or tools with large negative rake angles, where material is removed in the form of chips ahead of the tool. Three regions of the asperity have been identified that are useful in the development of a phenomenological model for polishing that enables computation of material removal rates: (1) the region directly in front of the abrasive for which the probability of the removal of an asperity atom is close to unity, (2) the distant region where this probability is nearly zero, and (3) an intermediate region from which the probability of removal is close to half.