Effects of Interfacial Interactions on Electrocatalytic Activity of Cytochrome c Oxidase in Biomimetic Lipid Membranes on Gold Electrodes.

Effects of interfacial interactions on the electrocatalytic activity of protein-tethered bilayer lipid membranes (ptBLMs) containing cytochrome c oxidase (CcO) for the oxygen reduction reaction are studied by using protein film electrochemistry and surface-enhanced infrared absorption (SEIRA) spectroscopy. Mammalian CcO was immobilized on a gold electrode via self-assembled monolayers (SAMs) of mixed alkanethiols. The protein orientation on the electrode is controlled by SAM-CcO interactions and is critical to the cytochrome c (cyt c) binding. The CcO-phospholipid and CcO-cyt c interactions modulate the electrocatalytic activity of CcO, and more densely packed ptBLMs show higher electrocatalytic activity. Our study indicates that spectroscopic and electrochemical studies of ptBLMs can provide insights into the effects of relatively weak protein-protein and protein-lipid interactions on the enzymatic activity of transmembrane enzymes.

Materials design of Kitaev spin liquids beyond the Jackeli-Khaliullin mechanism.

The Kitaev spin liquid provides a rare example of well-established quantum spin liquids in more than one dimension. It is obtained as the exact ground state of the Kitaev spin model with bond-dependent anisotropic interactions. The peculiar interactions can be yielded by the synergy of spin-orbit coupling and electron correlations for specific electron configuration and lattice geometry, which is known as the Jackeli-Khaliullin mechanism. Based on this mechanism, there has been a fierce race for the materialization of the Kitaev spin liquid over the last decade, but the candidates have been still limited mostly to 4d- and 5d-electron compounds including cations with the low-spin d 5 electron configuration, such as Ir4+ and Ru3+. Here we discuss recent efforts to extend the material perspective beyond the Jackeli-Khaliullin mechanism, by carefully reexamining the two requisites, formation of the j eff = 1/2 doublet and quantum interference between the exchange processes, for not only d- but also f-electron systems. We present three examples: the systems including Co2+ and Ni3+ with the high-spin d 7 electron configuration, Pr4+ with the f 1-electron configuration, and polar asymmetry in the lattice structure. In particular, the latter two are intriguing since they may realize the antiferromagnetic Kitaev interactions, in contrast to the ferromagnetic ones in the existing candidates. This partial overview would stimulate further material exploration of the Kitaev spin liquids and its topological properties due to fractional excitations.