We describe here a study of the mobility of the alkoxy radical on a surface by detection of its recombination product. A novel method called symmetrical product recombination (SRP) uses an unsymmetrical peroxide that upon sensitized homolysis recombines to a symmetrical product [R'OOR → R'O↑ + OR → ROOR]. This allows for self-sorting of the radical to enhance the recombination path to a symmetrical product, which has been used to deduce surface migratory aptitude. SPR also provides a new opportunity for mechanistic studies of interfacial radicals, including monitoring competition between radical recombination versus surface hydrogen abstraction. This is an approach that might work for other surface-borne radicals on natural and artificial particles.
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http://dx.doi.org/10.1021/acs.jpcb.1c01099 | DOI Listing |
Langmuir
January 2025
CNNFM Lab, School of Mechanical Engineering, College of Engineering, University of Tehran, P.O. Box 11155-4563 Tehran, Iran.
This study investigates the impact of cell dynamics on mixing efficiency within a microfluidic droplet, emphasizing the relationship between cell motion, deformability, and resultant asymmetry in velocity and concentration fields. Simulations were conducted for droplets containing encapsulated cells at varying Peclet numbers ( = 100-800) and coupling constants ( = 0.0025, 0.
View Article and Find Full Text PDFJ Org Chem
January 2025
Department of Materials Science and Engineering, Institute of Science Tokyo, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8552, Japan.
A series of 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) derivatives with various heterocyclic moieties, including pyridine, carbazole, indole, and benzothiadiazole, was newly synthesized through a [2 + 2] cycloaddition-retroelectrocyclization reaction. Symmetric electron-rich 1,3-butadiynes with end-capped heterocyclic substituents were reacted with tetracyanoethylene (TCNE), yielding the target TCBD products in 60-80% yields under ambient or mild heating conditions. The thermal stability and optical and electrochemical properties of both 1,3-butadiyne precursors and the corresponding TCBD derivatives were investigated by using thermogravimetric analysis (TGA), UV-vis spectroscopy, and cyclic voltammetry (CV).
View Article and Find Full Text PDFNano Lett
January 2025
National Key Laboratory of Uranium Resources Exploration-Mining and Nuclear Remote Sensing, East China University of Technology, Nanchang 330013, China.
Efficient sacrificial-agent-free photosynthesis of HO from air and water represents the greenest, lowest-cost, most real-time avenue for HO production but remains a challenging issue. Here, we show a general and effective approach through a structural design on covalent organic frameworks (COFs) with asymmetric dual-function hybrid linkages for boosting the HO photosynthesis of the COFs. Through such design we can equip a COF with not only a catalytic active center but also a special function for isolating the D-A motif, which consequently endows the COF (CI-COF) built on asymmetric dual-function hybrid linkages with a significantly enhanced efficiency in the generation, transmission, and separation of photogenerated carriers, relative to the COF (II-COF and CC-COF) built on symmetric single-function single linkages.
View Article and Find Full Text PDFPhilos Trans A Math Phys Eng Sci
January 2025
IBM Research-Europe, 8803 Rüschlikon, Zurich, Switzerland.
Encryption and decryption of data with very low latency and high energy efficiency is desirable in almost every application that deals with sensitive data. The advanced encryption standard (AES) is a widely adopted algorithm in symmetric key cryptography with numerous efficient implementations. Nonetheless, in scenarios involving extensive data processing, the primary limitations on performance and efficiency arise from data movement between memory and the processor, rather than data processing itself.
View Article and Find Full Text PDFJ Chem Phys
January 2025
Theoretical and Computational Physics Section, Raja Ramanna Centre for Advanced Technology, Indore 452013, India.
The orbital-free density functional theory (OF-DFT) based method is a convenient tool to carry out electronic structure calculations scaling almost linearly with the number of electrons. However, the main impediment in the application of this method is the unavailability of the accurate form for the non-interacting kinetic energy functional in terms of electron density. The Pauli kinetic energy functional is the unknown part of the kinetic energy functional, and the corresponding Pauli potential appears in the governing Euler equation.
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