Electrospray Mass Spectrometry to Study Combinatorial iClick Reactions and Multiplexed Kinetics of [Ru(N 3 )(N∧N)(terpy)]PF 6 with Alkynes of Different Steric and Electronic Demand.
Tristan ZachFlorian GeyerBenjamin KiendlJan MößelerOlivier NguyenThomas SchmidpeterPatrick SchusterChristoph NagelUlrich SchatzschneiderPublished in: Inorganic chemistry (2023)
In a combinatorial approach, a family of ruthenium(II) azido complexes [Ru(N 3 )(N∧N)(terpy)]PF 6 with terpy = 2,2':6',2″-terpyridine and N∧N as a bidentate chelator derived from 2,2'-biypridine and its 4,4'-disubstituted derivatives, 2,2'-bipyrimidine, and 1,10-phenanthroline were reacted with different internal and terminal alkynes to give access to a total of 7 × 7 = 49 triazolato complexes in a room-temperature catalyst-free iClick reaction. The reactants were mixed in a repurposed high-performance liquid chromatography (HPLC) autosampler, and the reaction progress was monitored by direct injection into an electrospray mass spectrometer. The ratio of the peak intensities of [Ru(N 3 )(N∧N)(terpy)] + and [Ru(triazolato)(N∧N)(terpy)] + was converted to a colored heat map for facile visual inspection of the conversion ratio. By automated multiple injections of the reaction mixture in fixed time intervals and plotting peak intensities over reaction time, pseudo-first-order rate constants were easily determined. Finally, nonoverlapping isotope patterns of the azido starting materials and triazolato products enabled multiplexed parallel determination of rate constants for four different ruthenium(II) azido complexes from a single sample vial, thereby reducing experiment time by 75%.
Keyphrases
- mass spectrometry
- high performance liquid chromatography
- room temperature
- liquid chromatography
- solid phase extraction
- tandem mass spectrometry
- gas chromatography
- simultaneous determination
- high resolution
- energy transfer
- ionic liquid
- capillary electrophoresis
- highly efficient
- single cell
- reduced graphene oxide
- ms ms
- machine learning
- molecularly imprinted
- ultrasound guided
- platelet rich plasma
- carbon dioxide
- visible light