Amidine-appended ferrocene derivatives form a supramolecular assembly with Ru(ii)(bpy-COOH) (L)22+ complexes (bpy-COOH is 4-CO2H-4'-CH3-bpy and L = bpy, 2,2'-bipyridine or btfmbpy, 4,4'-bis (trifluoromethyl)-2,2'-bipyridine). Steady-state, time-resolved spectroscopy and kinetic isotope effects establish that the metal-to-ligand charge transfer excited states of the Ru(ii) complexes are quenched...

Homologous to bacteriorhodopsin and even more to proteorhodopsin, xanthorhodopsin is a light-driven proton pump that, in addition to retinal, contains a noncovalently bound carotenoid with a function of a light-harvesting antenna. We determined the structure of this eubacterial membrane protein-carotenoid complex by X-ray diffraction, to 1.9-A resolution. Although it contains 7 transmembrane he...

The electron and proton transfer in phenol-imidazole-base systems (base = NH(2)(-) or OH(-)) were investigated by density-functional theory calculations. In particular, the role of bridge imidazole on the electron and proton transfer was discussed in comparison with the phenol-base systems (base = imidazole, H(2)O, NH(3), OH(-), and NH(2)(-)). In the gas phase phenol-imidazole-base system, the ...

A combination of first-principles density functional theory calculations and a search over structures is used to predict the stability of a proton-transfer modification of ammonia monohydrate with space group P4∕nmm. The phase diagram is calculated with the Perdew-Burke-Ernzerhof (PBE) density functional, and the effects of a semi-empirical dispersion correction, zero point motion, and finite t...

The mechanism of base to base intermolecular proton shuttling occurring in the excited state proton transfer reaction between 7-hydroxy-4-(trifluoromethyl)coumarin (CouOH) and concentrated 1-methylimidazole base (1-MeId) in toluene solution is disclosed here by means of a computational approach based on Density Functional Theory (DFT) and Time Dependent DFT (TD-DFT). These methods allow us to c...

A ruthenium(II) complex with two 4,4'-bis(trifluoromethyl)-2,2'-bipyridine chelates and a 2-(2'-pyridyl)imidazole ligand was synthesized and characterized by electrochemical and optical spectroscopic means. The respective complex has the potential to act as a combined electron-proton donor when promoted to its long-lived (3)MLCT excited state with visible light. The possibility of proton-couple...

The excited-state proton transfer (ESPT) via proton transfer wires in green fluorescent protein (GFP) plays an important role on the spectroscopic of GFP. In this work, we use the proton transfer wires and the chromophore complex to simulate the tautomer structures of neutral state and the intermediate state in wt-GFP. And we employ the time-dependent density functional theory combined with the...

We report time-resolved mid-IR kinetics for the ultrafast acid-base reaction between photoexcited 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS), and acetate at three concentrations (0.5, 1.0, and 2.0 M) and three temperatures (5, 30, and 65 degrees C) in liquid D(2)O. The observed proton-transfer kinetics agree quantitatively, over all times (200 fs-500 ps), with an extended Smol...

A highly conserved histidine-rich region with unknown function was recognized in the large subunit of [NiFe] hydrogenases. The HxHxxHxxHxH sequence occurs in most membrane-bound hydrogenases, but only two of these histidines are present in the cytoplasmic ones. Site-directed mutagenesis of the His-rich region of the T. roseopersicina membrane-attached Hyn hydrogenase disclosed that the enzyme a...

The excited-state intramolecular proton transfer (ESIPT) is reviewed for several benchmark systems [o-hydroxybenzaldehyde (OHBA), salicylic acid and 2-(2′-hydroxyphenyl)-benzothiazole (HBT)] in order to verify the applicability of the time-dependent density functional theory (TDDFT) and the resolution-of-the-identity approximate second-order coupled cluster (RI-CC2) methods. It was found that t...