A Framework for Characterizing Structural Uncertainty in Large-Eddy Simulation Closures

Motivated by the sizable increase of available computing resources, large-eddy simulation of complex turbulent flow is becoming increasingly popular. The underlying filtering operation of this approach enables to represent only large-scale motions. However, the small-scale fluctuations and their effects on the resolved flow field require additional modeling. As a consequence, the assumptions made in the closure formulations become potential sources of incertitude that can impact the quantities of interest. The objective of this work is to introduce a framework for the systematic estimation of structural uncertainty in large-eddy simulation closures. In particular, the methodology proposed is independent of the initial model form, computationally efficient, and suitable to general flow solvers. The approach is based on introducing controlled perturbations to the turbulent stress tensor in terms of magnitude, shape and orientation, such that propagation of their effects can be assessed. The framework is rigorously described, and physically plausible bounds for the perturbations are proposed. As a means to test its performance, a comprehensive set of numerical experiments are reported for which physical interpretation of the deviations in the quantities of interest are discussed.     

Fluorescent macrocyclic chemosensor for Zn(II) detection at alkaline pH values

ABSTRACT

The new macrocyclic ligand L (28,29-dimethoxy-27-oxa-8,11,14,17,25,26-hexaazatetracyclo[22.2.1.1(2,6).1(19,23)]nonacosa-2,4,6(28),19,21,23(29),24,26(1)-octaene) has been synthesised. It contains a tetramine chain and the 2,5-bis(2-methoxy-3-metyl-phenyl)-1,3,4-oxadiazole (PPD-OMe) chromophore, acting as coordinating and sensing units, respectively.

The fluorescent emission of L depends on the pH being highly fluorescent at pH = 2 and not emitting from pH >10. The studies highlighted that L is a PET mediated emitting chemosensor, being the PET effect regulated by the degree of the tetraamine protonation.

L coordinates metal ions (Cu(II), Zn(II) and Cd(II)) in water giving rise to an OFF-ON fluorescent response for the presence of Zn(II) ion thus signalling its presence in the medium. This response is particularly notable at pH = 9 allowing to extend the Zn(II) sensing also in the alkaline pH field.     

Study of the initial stage of manganese dioxide electrodeposition on a rotating ring-disk electrode

The initial stage of electrodeposition of manganese dioxide has been studied on the platinum disk electrode and on the ring-disk electrode. Two current maxima were observed on the anodic voltammograms. It has been shown that the first rise in the current is associated with the formation of manganese dioxide (MD) nuclei on the electrode surface, and the second with their growth at the border between MnO₂ and bare platinum due to an increase in the perimeter of the nuclei. Electrodeposition on bare platinum proceeds at a higher rate than on the surface of growing MD. This is explained by the difference in the reaction mechanisms on these substrates. The first stage of the process on the growing MD is the chemisorption of Mn(II) ions with the formation of Mn(III) ions, which are then electrochemically oxidized to MD. Chemisorption is the slowest step in the whole process.     

Bottom-up Solution Synthesis of Graphene Nanoribbons with Precisely Engineered Nanopores

The incorporation of nanopores into graphene nanostructures has been demonstrated as an efficient tool in tuning their band gaps and electronic structures. However, precisely embedding the uniform nanopores into graphene nanoribbons (GNRs) at the atomic level remains underdeveloped especially for in-solution synthesis due to the lack of efficient synthetic strategies. Herein we report the first case of solution-synthesized porous GNR ( pGNR ) with a fully conjugated backbone via the efficient Scholl reaction of tailor-made polyphenylene precursor ( P1 ) bearing pre-installed hexagonal nanopores. The resultant pGNR features periodic subnanometer pores with a uniform diameter of 0.6 nm and an adjacent-pores-distance of 1.7 nm. To solidify our design strategy, two porous model compounds ( 1 a , 1 b ) containing the same pore size as the shortcuts of pGNR , are successfully synthesized. The chemical structure and photophysical properties of pGNR are investigated by various spectroscopic analyses. Notably, the embedded periodic nanopores largely reduce the π-conjugation degree and alleviate the inter-ribbon π–π interactions, compared to the nonporous GNRs with similar widths, affording pGNR with a notably enlarged band gap and enhanced liquid-phase processability.     

Crosslinked Hyaluronic Acid with Liposomes and Crocin Confers Cytoprotection in an Experimental Model of Dry Eye

Dry eye disease (DED) is a multifactorial condition caused by tear deficiency and accompanied by ocular surface damage. Recent data support a key role of oxidative and inflammatory processes in the pathogenesis of DED. Hyaluronic acid (HA) is widely used in artificial tears to treat DED by improving ocular hydration and reducing surface friction. Crocin (Cr), the main constituent of saffron, is a renowned compound that exhibits potent antioxidant and anti-inflammatory effects. The present study was undertaken to assess the viscosity and muco-adhesiveness of a photoactivated formulation with crosslinked HA (cHA), Cr, and liposomes (cHA-Cr-L). Our aim was also to evaluate whether cHA-Cr-L may exert cytoprotective effects against oxidative and inflammatory processes in human corneal epithelial cells (HCECs). Viscosity was measured using a rotational rheometer, and then the muco-adhesiveness was evaluated. Under hyperosmolarity (450 mOsm), the HCECs were treated with cHA-Cr-L. Interleukin-1β (IL-1β) and tumor necrosis factor α (TNFα) were quantified by quantitative real-time polymerase chain reaction (RT-qPCR). The levels of reactive oxygen species (ROS) were measured using the DCF assay. The combined action of cHA-Cr-L produced a higher viscosity and muco-adhesiveness compared to the control. The anti-inflammatory effect of cHA-Cr-L was achieved through a significant reduction of IL-1β and TNFα (p < 0.001). The results also showed that cHA-Cr-L reduces ROS production under conditions of hyperosmolarity (p < 0.001). We conclude that cHA-Cr-L has potential as a therapeutic agent in DED, which should be further investigated.