226 research outputs found
Ion-Mobility Mass Spectrometry for the Rapid Determination of the Topology of Interlocked and Knotted Molecules.
A rapid screening method based on traveling-wave ion-mobility spectrometry (TWIMS) combined with tandem mass spectrometry provides insight into the topology of interlocked and knotted molecules, even when they exist in complex mixtures, such as interconverting dynamic combinatorial libraries. A TWIMS characterization of structure-indicative fragments generated by collision-induced dissociation (CID) together with a floppiness parameter defined based on parent- and fragment-ion arrival times provide a straightforward topology identification. To demonstrate its broad applicability, this approach is applied here to six Hopf and two Solomon links, a trefoil knot, and a [3]catenate.Deutsche Forschungsgemeinschaft (CRC 765 âMultivalencyâ).
Alexander von Humboldt Foundation.
Swiss National Science Foundation (PZ00P2_161270).
Fondation Wiener-Anspach
Switchable synchronisation of pirouetting motions in a redox-active [3]rotaxane
In this study, the crown/ammonium [3]rotaxane R2 is reported which allows a switchable synchronisation of wheel pirouetting motions. The rotaxane is composed of a dumbbell-shaped axle molecule with two mechanically interlocked macrocycles which are decorated with a redox-active tetrathiafulvalene (TTF) unit. Electrochemical, spectroscopic, and electron paramagnetic resonance experiments reveal that rotaxane R2 can be reversibly switched between four stable oxidation states (R2, R2Ë+, R22(Ë+), and R24+). The oxidations enable non-covalent, cofacial interactions between the TTF units in each stateâincluding a stabilised mixed-valence (TTF2)Ë+ and a radical-cation (TTFË+)2 dimer interactionâwhich dictate a syn (R2, R2Ë+, and R22(Ë+)) or anti (R24+) ground state co-conformation of the wheels in the rotaxane. Furthermore, the strength of these wheelâwheel interactions varies with the oxidation state, and thus electrochemical switching allows a controllable synchronisation of the wheelsâ pirouetting motions. DFT calculations explore the potential energy surface of the counter-rotation of the two interacting wheels in all oxidation states. The controlled coupling of pirouetting motions in rotaxanes can lead to novel molecular gearing systems which transmit rotational motion by switchable non-covalent interactions
Optically pure, water-stable metallo-helical âflexicateâ assemblies with antibiotic activity
The helicatesâchiral assemblies of two or more metal atoms linked by short or relatively rigid multidentate organic ligandsâmay be regarded as non-peptide mimetics of α-helices because they are of comparable size and have shown some relevant biological activity. Unfortunately, these beautiful helical compounds have remained difficult to use in the medicinal arena because they contain mixtures of isomers, cannot be optimized for specific purposes, are insoluble, or are too difficult to synthesize. Instead, we have now prepared thermodynamically stable single enantiomers of monometallic units connected by organic linkers. Our highly adaptable self-assembly approach enables the rapid preparation of ranges of water-stable, helicate-like compounds with high stereochemical purity. One such iron(II) âflexicateâ system exhibits specific interactions with DNA, promising antimicrobial activity against a Gram-positive bacterium (methicillin-resistant Staphylococcus aureus, MRSA252), but also, unusually, a Gram-negative bacterium (Escherichia coli, MC4100), as well as low toxicity towards a non-mammalian model organism (Caenorhabditis elegans)
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