Site-Selective Orbital Interactions in an Ultrathin Iron-Carbene Photosensitizer Film
JOURNAL OF PHYSICAL CHEMISTRY A
Authors: Temperton, Robert H.; Rosemann, Nils W.; Guo, Meiyuan; Johansson, Niclas; Fredin, Lisa A.; Prakash, Om; Warnmark, Kenneth; Handrup, Karsten; Uhlig, Jens; Schnadt, Joachim; Persson, Petter
Abstract
We present the first experimental study of the frontier orbitals in an ultrathin film of the novel hexa-carbene photosensitizer [Fe(btz)(3)](3+), where btz is 3,3'-dimethyl-1,1'-bis(p-tolyl)-4,4'-bis(1,2,3-triazol-5-ylidene). Resonant photoelectron spectroscopy (RPES) was used to probe the electronic structure of films where the molecular and oxidative integrities had been confirmed with optical and X-ray spectroscopies. In combination with density functional theory calculations, RPES measurements provided direct and site-selective information about localization and interactions of occupied and unoccupied molecular orbitals. Fe 2p, N 1s, and C 1s measurements selectively probed the metal, carbene, and side-group contributions revealing strong metal-ligand orbital mixing of the frontier orbitals. This helps explain the remarkable photophysical properties of iron-carbenes in terms of unconventional electronic structure properties and favorable metal-ligand bonding interactions-important for the continued development of these type of complexes toward light-harvesting and light-emitting applications.
Tuning the selectivity of a commercial cyanine nucleic acid dye for preferential sensing of hybrid telomeric G-quadruplex DNA
SENSORS AND ACTUATORS B-CHEMICAL
Authors: Wang, Yu-Qing; Hu, Ming-Hao; Guo, Rui-Jun; Chen, Shuo-Bin; Huang, Zhi-Shu; Tan, Jia-Heng
Abstract
Recent years have witnessed an ever-increasing interest in G-quadruplexes for diagnostic and therapeutic applications. This calls for the development of highly selective probes that can differentiate a particular structure among large quantities of G-quadruplexes. However, to this day, there are few probes that show satisfactory selectivity for a particular G-quadruplex structure. In this study, we engineered a new probe called TO-BTZ by introducing an additional benzothiazole moiety on a commercial cyanine dye thiazole orange (TO). Such a modification of TO significantly tuned its selectivity toward the hybrid telomeric G-quadruplex DNA by specifically targeting the unique binding site formed near the 5'-end G-quartet. Such specific interactions disassembled the TO-BTZ H-aggregate to its monomers and further hindered the molecular rotation of the TO-BTZ monomer, thus leading to fluorescence enhancement. Furthermore, we observed that TO-BTZ has the potential to sense telomeric G-quadruplexes in cells. Taken together, this work will shed light on the search for a new generation of probes that can distinguish between different G-quadruplex structures. (C) 2018 Elsevier B.V. All rights reserved.