A viscous lock-exchange gravity current corresponds to the reciprocal exchange of two fluids of different densities in a horizontal channel. The resulting front between the two fluids spreads as the square root of time, with a diffusion coefficient reflecting the buoyancy, viscosity, and geometrical configuration of the current. On the other hand, an autocatalytic reaction front between a reactant and a product may propagate as a solitary wave, namely, at a constant velocity and with a stationary concentration profile, resulting from the balance between molecular diffusion and chemical reaction. In most systems, the fluid left behind the front has a different density leading to a lock-exchange configuration. We revisit, with a chemical reaction, the classical situation of lock-exchange. We present an experimental analysis of buoyancy effects on the shape and the velocity of the iodate arsenous acid autocatalytic reaction fronts, propagating in horizontal rectangular channels and for a wide range of aspect ratios (1/3 to 20) and cylindrical tubes. We do observe stationary-shaped fronts, spanning the height of the cell and propagating along the cell axis. Our data support the contention that the front velocity and its extension are linked to each other and that their variations scale with a single variable involving the diffusion coefficient of the lock-exchange in the absence of chemical reaction. This analysis is supported by results obtained with lattice Bathnagar-Gross-Krook (BGK) simulations Jarrige et al. [Phys. Rev. E 81, 06631 (2010)], in other geometries (like in 2D simulations by Rongy et al. [J. Chem. Phys. 127, 114710 (2007)] and experiments in cylindrical tubes by Pojman et al. [J. Phys. Chem. 95, 1299 (1991)]), and for another chemical reaction Schuszter et al. [Phys. Rev. E 79, 016216 (2009)].
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http://dx.doi.org/10.1063/1.3507899 | DOI Listing |
Proc Natl Acad Sci U S A
January 2025
California Institute for Quantitative Biosciences, University of California, Berkeley, CA 94720.
Polysaccharide monooxygenase (PMO) catalysis involves the chemically difficult hydroxylation of unactivated C-H bonds in carbohydrates. The reaction requires reducing equivalents and will utilize either oxygen or hydrogen peroxide as a cosubstrate. Two key mechanistic questions are addressed here: 1) How does the enzyme regulate the timely and tightly controlled electron delivery to the mononuclear copper active site, especially when bound substrate occludes the active site? and 2) How does this electron delivery differ when utilizing oxygen or hydrogen peroxide as a cosubstrate? Using a computational approach, potential paths of electron transfer (ET) to the active site copper ion were identified in a representative AA9 family PMO from (PMO9E).
View Article and Find Full Text PDFJ Org Chem
January 2025
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China.
Pd-catalyzed C4-selective alkynylation of indoles was established by employing glycine as a transient directing group. This reaction exhibits high regioselectivity with the tolerance of a wide scope of functional groups to afford diverse alkynylated indoles in moderate to good yields. Moreover, the readily accessible scale-up synthesis and further decorations to achieve multifunctionalized indoles demonstrate the synthetic potential of this protocol.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
School of Chemistry and Chemical Engineering, Hainan University, Haikou 570228, China.
A recruiting rate () of 0.1-5 s has been proposed as the criterion for super-resolution spontaneously blinking rhodamines. Accurate prediction of the recruiting rate () of rhodamines is very important for developing spontaneously blinking rhodamines.
View Article and Find Full Text PDFInorg Chem
January 2025
School of Chemistry and Chemical Engineering, and Institute for Innovative Materials and Energy, Yangzhou University, 180 Si-Wang-Ting Road, Yangzhou 225002, China.
The interaction between electrocatalytic active centers and their support is essential to the electrocatalytic performance, which could regulate the electronic structure of the metal centers but requires precise design. Herein, we report on covalent grafting of graphene quantum dots (GQDs) on stepped TiO as a support to anchoring cobalt phosphide nanoparticles (CoP/GQD/S-TiO) for electrocatalytic hydrogen evolution reaction (HER). The covalent ester bonds between GQDs and TiO endow enlarged anchoring sites to achieve highly dispersed electroactive CoP nanoparticles but, more importantly, provide an efficient electron-transfer pathway from TiO to GQDs which could regulate the electronic structure of CoP.
View Article and Find Full Text PDFChemistry
January 2025
Wuhan University of Technology - Mafangshan Campus: Wuhan University of Technology, School of Material Science and Engineeringl, CHINA.
NiFe layered double hydroxide (LDH) currently are the most efficient catalysts for the oxygen evolution reaction (OER) in alkaline environments. However, the development of high-performance low cost OER electrocatalysts using straightforward strategies remains a significant challenge. In this study, we describe an innovative microbial mineralization-based method for in situ-induced preparation of NiFe LDH nanosheets loaded on nickel foam and demonstrate that this material serves as an efficient oxygen evolution electrocatalyst.
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