RESUMO
Photoactive molecular junctions, based on 4 nm thick diarylethene (DAE) and 5 nm thick bisthienylbenzene (BTB) layers, were fabricated by electrochemical deposition. Total thickness was around 9 nm, that is, above the direct tunneling limit and in the hopping regime. The DAE units were switched between their open and closed forms. The DAE/BTB bilayer structure exhibits new electronic functions combining photoswitching and photorectification. The open form of DAE/BTB shows low conductance and asymmetric I-V curves while the closed form shows symmetric I-V curves and high conductance. More importantly, unprecedented ON/OFF current ratios of over 10â¯000 at 1 V were reproducibly measured.
Assuntos
EletrônicaRESUMO
In order to develop original water soluble antagonists of X-linked inhibitor of apoptosis protein (XIAP), a novel bicyclic scaffold was designed based on 8,5-fused bicyclic lactam. During its preparation, a spontaneous rearrangement from 8,5- to 7,5-fused bicyclic lactam was observed and confirmed by MS and NMR analyses, in particular the HMBC spectra. DFT calculations were performed to understand the corresponding mechanism. It was finally prevented through changing the reaction order in the synthesis route and a Smac mimetic with this core structure, ZJ-1 was successfully obtained. The structure of this new bicyclic scaffold was well confirmed by HRMS and NMR (1H, 13C, NOESY) analyses. ZJ-1 presented in addition a binding affinity to XIAP-BIR3, nearly 6â times better than that of AVPI, similar to the reported SM-128 in an inâ vitro fluorescence polarization (FP) assay. This preliminary result suggests that this new bicyclic scaffold could be very attractive in the development of novel anticancer agents targeting XIAP.