A simple method for using sound pulses to harvest protein crystals from a commercially available crystallization plate is described. Crystals can be grown using conventional vapor-diffusion methods and then individually harvested or serially combined with a chemical library such as a fragment library.
Metallothioneins (MTs) are a ubiquitous class of small cysteine-rich metal-binding proteins involved in metal homeostasis and detoxification with highly versatile metal binding properties. Despite the long-standing association of MT with M 3 S 3 and M 4 S 5 metal clusters, synthetic complexes with these core architectures are exceptionally rare. Here, we demonstrate an approach to synthesizing and characterizing aggregates of group 12 metal ions with monocyclic M 3 S 3 cores in acetonitrile solution without the protection of a protein. Multidentate monothiol ligand N,N-bis(2-pyridylmethyl)-2-aminoethanethiol (L1H) provided [Cd 3 (L1) 3 ](ClO 4 ) 3 (1), the first structurally characterized nonproteinaceous aggregate with a metallothionein-like monocyclic Cd 3 S 3 core. In addition, [Zn 3 (L1) 3 ](ClO 4 ) 3 •4CH 3 CN (2•4CH 3 CN) was characterized by X-ray crystallography. The complex cations of 1 and 2 had comparable structures despite being nonisomorphic. Variable temperature and concentration 1 H NMR were used to investigate aggregation equilibria of 1, 2, and a precipitate with composition "Hg(L1)(ClO 4 )" (3). Cryogenic 1 H NMR studies of 3 revealed a J( 199 Hg 1 H) coupling constant pattern consistent with an aggregate possessing a cyclic core. ESI-MS was used for gas-phase characterization of 1−3, as well as mixed-metal [M 2 M′(L1) 3 (ClO 4 ) 2 ] + ions prepared in situ by pairwise acetonitrile solution combinations of the group 12 complexes of L1. Access to synthetic variants of metallothionein-like group 12 aggregates provides an additional approach to understanding their behavior.
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