Identification of a Two-Coordinate Iron(I)-Oxalate Complex.

Exotic oxidation states of the first-row transition metals have recently attracted much interest. In order to investigate the oxidation states of a series of iron-oxalate complexes, an aqueous solution of iron(III) nitrate and oxalic acid was studied by infrared free liquid matrix-assisted laser desorption/ionization as well as ionspray mass spectrometry. Here, we show that iron is not only detected in its common oxidation states +II and +III, but also in its unusual oxidation state +I, detectable in both positive-ion and in negative-ion modes, respectively.

Discriminating Abiotic and Biotic Fingerprints of Amino Acids and Fatty Acids in Ice Grains Relevant to Ocean Worlds.

Identifying and distinguishing between abiotic and biotic signatures of organic molecules such as amino acids and fatty acids is key to the search for life on extraterrestrial ocean worlds. Impact ionization mass spectrometers can potentially achieve this by sampling water ice grains formed from ocean water and ejected by moons such as Enceladus and Europa, thereby exploring the habitability of their subsurface oceans in spacecraft flybys. Here, we extend previous high-sensitivity laser-based analog experiments of biomolecules in pure water to investigate the mass spectra of amino acids and fatty acids at simulated abiotic and biotic relative abundances.

Analog Experiments for the Identification of Trace Biosignatures in Ice Grains from Extraterrestrial Ocean Worlds.

Reliable identification of biosignatures, such as amino acids, fatty acids, and peptides, on extraterrestrial ocean worlds is a key prerequisite for space missions that search for life or its emergence on these worlds. One promising approach is the use of high-performance impact ionization mass spectrometers to sample water ice grains emerging from ocean-bearing moons such as Europa or Enceladus. A predecessor of such detectors, the Cosmic Dust Analyzer on board the Cassini spacecraft, has proven to be very successful in analyzing inorganic and organic ocean constituents and with that characterizing the habitability of Enceladus ocean.

Analogue spectra for impact ionization mass spectra of water ice grains obtained at different impact speeds in space.

Rationale: Detecting ice grains with impact ionization mass spectrometers in space provides information about the compositions of ice grains and their sources. Depending on the impact speeds of the ice grains onto the metal target of a mass spectrometer, ionization conditions can vary substantially, resulting in changes to the appearance of the resulting mass spectra.

Methods: Here we accurately reproduce mass spectra of water ice grains, recorded with the Cosmic Dust Analyzer (CDA) on board the Cassini spacecraft at typical impact speeds ranging between 4 km/s to 21 km/s, with a laboratory analogue experiment.

Macromolecular organic compounds from the depths of Enceladus.

Saturn's moon Enceladus harbours a global water ocean , which lies under an ice crust and above a rocky core . Through warm cracks in the crust a cryo-volcanic plume ejects ice grains and vapour into space that contain materials originating from the ocean. Hydrothermal activity is suspected to occur deep inside the porous core, powered by tidal dissipation .

Modular Synthesis of Dipyrroloquinolines: A Combined Synthetic and Mechanistic Study.

A straightforward synthesis of [1,2-a][3',2'-c]dipyrroloquinolines has been developed generating up to eight new σ-bonds and five new stereogenic centers in a simple and modular one-pot operation. Generally good to excellent yields and moderate to good stereoselectivities in favor of the all-cis stereoisomer were observed. A detailed investigation combining synthetic studies, analytical measurements, and theoretical calculations has been conducted to elucidate the reaction mechanism using ESI- and liquid-beam IR-laser desorption mass spectrometry as well as DFT calculations.

Liquid Beam Desorption Mass Spectrometry for the Investigation of Continuous Flow Reactions in Microfluidic Chips.

In this work, we present the combination of microfluidic chips and mass spectrometry employing laser-induced liquid beam ionization/desorption. The developed system was evaluated with respect to stable beam generation and laser parameters as well as solvent compatibility. The device was exemplarily applied to study a vinylogous Mannich reaction performed in continuous flow on chip.

A Complex Catalytic Reaction Caught in the Act: Intermediates and Products Sampling Online by Liquid μ-Beam Mass Spectrometry and Theoretical Modeling.

Liquid-beam IR-laser desorption mass spectrometry has been used to monitor the reactants, intermediates, and products of a complex organic signature reaction in real time on multiple timescales directly from the liquid phase. The reaction was chosen because it has advantages in medicinal chemistry applications, and the three-component, modular construction provides a means to generate molecular diversity rapidly. Under Lewis acid catalysis, a vinylogous Mannich reaction was monitored as it generated a δ-amino-α-silyloxy-α,β-unsaturated ester, which upon hydrolysis to the corresponding α-keto ester spontaneously reacted in a [3+2] cycloannulation to the final pyrrolo[2,1-b]benzoxazole.