The complexation of the macrocyclic cavitand cucurbit[7]uril (Q7) with a series of amino acids (AA) with different side chains (Asp, Asn, Gln, Ser, Ala, Val, and Ile) is investigated by ESI-MS techniques. The 1:1 [Q7 + AA + 2H]²⁺ adducts are observed as the base peak when equimolar Q7:AA solutions are electrosprayed, whereas the 1:2 [Q7 + 2AA + 2H]²⁺ dications are dominant when an excess of the amino acid is used. A combination of ion mobility mass spectrometry (IM-MS) and DFT calculations of the 1:1 [Q7 + AA + 2H]²⁺ (AA = Tyr, Val, and Ser) adducts is also reported and proven to be unsuccessful at discriminating between exclusion or inclusion-type conformations in the gas phase. Collision induced dissociation (CID) revealed that the preferred dissociation pathways of the 1:1 [Q7 + AA + 2H]²⁺ dications are strongly influenced by the identity of the amino acid side chain, whereas ion molecule reactions towards N-butylmethylamine displayed a common reactivity pattern comprising AA displacement. Special emphasis is given on the differences between the gas-phase behavior of the supramolecular adducts with amino acids (AA = Asp, Asn, Gln, Ser, Ala, Val, and Ile) and those featuring basic (Lys and Arg) and aromatic (Tyr and Phe) side chains.

The formation of lead dioxide PbO₂, an important corrosion product in drinking water distribution systems with lead-bearing plumbing materials, has been hypothesized to involve Pb(III) intermediates, but their nature and formation mechanisms remain unexplored. This study employed the electrochemical (EC) method of rotating ring disk electrode (RRDE) and quantum chemical (QC) simulations to examine the generation of intermediates produced during the oxidation of Pb(II) to PbO₂. RRDE data demonstrate that PbO₂ deposition and reduction involves at least two intermediates. One of them is a soluble Pb(III) species that undergoes further transformations to yield immobilized PbO₂ nanoparticles. The formation of this intermediate in EC system is mediated by hydroxyl radicals (OH^•), as was evidenced by the suppression of intermediates formation in the presence of the OH^• scavenger para-chlorobenzoic acid. QC simulations confirmed that the oxidation of Pb(II) by OH^• proceeds via Pb(III) species. These results show that Pb(III) intermediates play an important role in the reactions determining transitions between Pb(II) and Pb(IV) species and could impact lead release in drinking water.

Impact of thiacalix[4]arene-calix[4]arene scaffolds on structure and luminescence of Tb³⁺ complexes.