An Electrochemical Approach to and the Physical Consequences of Preparing Nanostructures from Gold Nanorods with Smooth Ends

We have developed a method to smooth the end sections of nanowires and nanograps generated via the On-Wire Lithography process and studied these rods with optical spectroscopies and theoretical modeling (Discrete Dipole Approximation). The first step of the smoothing process is a reductive one aimed at controlling the diffusion and migration of metal ions to the growing nanorod surface by adjusting the applied potential and concentration of the metal ions in the growth solution. A second oxidative smoothing step, based in part on the energetic differences between topologically rough and smooth surfaces, is used to further smooth the nanorod. The RMS roughness can be reduced over five fold to approximately 5 nm. The properties of these smoothed rods were investigated by empirical and theoretical methods, where it was found the smoothed rods have sharper plasmon resonances and decreased SERS intensity.     

Simple compact quantum groups I

The notion of simple compact quantum group is introduced. As non-trivial (noncommutative and noncocommutative) examples, the following families of compact quantum groups are shown to be simple: (a) The universal quantum groups Bu(Q) for Q∈GL(n,C) satisfying , n?2; (b) The quantum automorphism groups Aaut(B,τ) of finite-dimensional C^∗-algebras B endowed with the canonical trace τ when dim(B)?4, including the quantum permutation groups Aaut(Xn) on n points (n?4); (c) The standard deformations Kq of simple compact Lie groups K and their twists , as well as Rieffel's deformation KJ.     

Free products of compact quantum groups

We construct and study compact quantum groups from free products ofC ^*-algebras. In this connection, we discover two mysterious classes of natural compact quantum groups,A _u (m) andA _o (m). TheA _u (m)'s (respectivelyA _o (m)'s) are non-isomorphic to each other for differentm's, and are not obtainable by the ordinary quantization method. We also clarify some basic concepts in the theory of compact quantum groups.     

Tertiary amine mediated aerobic oxidation of sulfides into sulfoxides by visible-light photoredox catalysis on TiO2

The selective oxidation of sulfides into sulfoxides receives much attention due to industrial and biological applications. However, the realization of this reaction with molecular oxygen at room temperature, which is of importance towards green and sustainable chemistry, remains challenging. Herein, we develop a strategy to achieve the aerobic oxidation of sulfides into sulfoxides by exploring the synergy between a tertiary amine and titanium dioxide via visible-light photoredox catalysis. Specifically, titanium dioxide can interact with triethylamine (TEA) to form a visible-light harvesting surface complex, preluding the ensuing selective redox reaction. Moreover, TEA, whose stability was demonstrated by a turnover number of 32, plays a critical role as a redox mediator by shuttling electrons during the oxidation of sulfide. This work suggests that the addition of a redox mediator is highly functional in establishing visible-light-induced reactions via heterogeneous photoredox catalysis.     

Surprisingly Long‐Range Surface‐Enhanced Raman Scattering (SERS) on Au–Ni Multisegmented Nanowires

Very long range surface‐enhanced Raman scattering is observed from a nickel nanowire that is separated by 120 nm from a pair of gold nanodisks. The excitation of the surface‐plasmon resonance (SPR) from the gold nanodisk pair generates an enhanced electromagnetic field near the nickel segment (SEM, left), leading to Raman intensity greater than the nickel alone (right).

     

Mechanism of chromyl chloride epoxidation

Modern electronic structure methods including complete active space perturbation theory to second order (CASPT2), and a range of density functional (DFT) methods are used to characterize the intermediates and transition states associated with ethylene epoxidation by chromyl chloride. A novel zwitterionic direct addition pathway is characterized which, when coupled with a dinuclear complex, exothermically produces epoxide through a pathway with a small kinetic barrier.