Mean fluorescence lifetime and its error

Mean excited-state lifetime is one of the fundamental fluorescence characteristics and enters as an important parameter into numerous calculations characterizing molecular interactions, such as e.g. FRET or fluorescence quenching. Our experiments demonstrated that the intensity-weighted mean fluorescence lifetime is very robust characteristic, in contrast to the amplitude-weighted one, which value is dependent on the data quality and particularly on the used fitting model. For the first time, we also report the procedure for the error estimation for both the intensity- and amplitude-weighted mean fluorescence lifetimes. Furthermore, we present a method for estimation of the mean fluorescence lifetime directly from the fluorescence-decay curve recorded by TCSPC (Time-Correlated Single-Photon Counting) method. For its simplicity and low computational demands, it could be a useful tool in the high-throughput applications, such as FACS, FLIM-FRET or HPLC detectors.     

Regioselective Hydration of Alkynes by Iron(III) Lewis/Brønsted Catalysis

The triflimide iron(III) salt [Fe(NTf₂)₃] promotes the direct hydration of terminal and internal alkynes with very good Markovnikov regioselectivities and high yields. The enhanced carbophilic Lewis acidity of the Fe^III cation mediated by the weakly‐coordinating triflimide anion is crucial for the catalytic activity. The iron(III) metal salt can be recycled in the form of the OPPh₃/[Fe(NTf₂)₃] system with similar activity and selectivity. However, spectroscopic and kinetic studies show that [Fe(NTf₂)₃] hydrolyzes under the reaction conditions and that catalytically less active Brønsted species are formed, which points to a Lewis/Brønsted co‐catalysis. This triflimide‐based catalytic system is regioselective for the hydration of internal aryl‐alkynes and opens the door to a new synthetic route to alkyl ketophenones. As a proof of concept, the synthesis of two antipsychotics Haloperidol and Melperone, with general butyrophenone‐like structure, is shown.