A Tetraferrocenyl-Resorcinarene Cavitand as a Redox-Switchable Host of Ammonium Salts

Tetraannulation of a resorcinarene-octaamino cavitand with ferrocenecarboxaldehyde allows the preparation of a tetrabenzimidazole-resorcinarene cavitand with four ferrocenyl moieties directly linked to the C2 atom of the imidazole units. Oxidation of the four ferrocenyl moieties produces important structural modifications of the molecule, as indicated by DFT calculations performed for the neutral and tetraoxidized forms of the cavitand. By means of 1H NMR spectroscopic analysis, the encapsulating properties of the new tetraferrocenyl-resorcinarene cavitand toward a series of ammonium salts were evaluated, and a clear cutoff point in binding affinity with respect to size was observed. Cyclic voltammetric studies allowed us to estimate the relative association constants for the neutral and oxidized forms of the cavitand, thus indicating that the guest was bound to the neutral (reduced) state of the cavitand and was released from the oxidized form. These redox-addressable conformational and binding properties of the resorcinarene-tetraferrocenyl cavitand constitute all the necessary features of a redox-switchable molecular gripper. By means of mass-spectrometric analysis, we could unambiguously confirm the molar stoichiometry of the host–guest complex (1:1) and assess the strong guest encapsulation, as indicated by triggering the covalent coupling between host and guest in the gas phase.MEC of Spain (CTQ2011-24055/BQU and CTQ2014-54071-P) and the Universitat Jaume I (P11B2014-02

Semiprojectivity with and without a group action

The equivariant version of semiprojectivity was recently introduced by the first author. We study properties of this notion, in particular its relation to ordinary semiprojectivity of the crossed product and of the algebra itself. We show that equivariant semiprojectivity is preserved when the action is restricted to a cocompact subgroup. Thus, if a second countable compact group acts semiprojectively on a C*-algebra $A$, then $A$ must be semiprojective. This fails for noncompact groups: we construct a semiprojective action of the integers on a nonsemiprojective C*-algebra. We also study equivariant projectivity and obtain analogous results, however with fewer restrictions on the subgroup. For example, if a discrete group acts projectively on a C*-algebra $A$, then $A$ must be projective. This is in contrast to the semiprojective case. We show that the crossed product by a semiprojective action of a finite group on a unital C*-algebra is a semiprojective C*-algebra. We give examples to show that this does not generalize to all compact groups.Comment: 38 page

QM/MM molecular dynamics studies of metal binding proteins

Mixed quantum-classical (quantum mechanical/molecular mechanical (QM/MM)) simulations have strongly contributed to providing insights into the understanding of several structural and mechanistic aspects of biological molecules. They played a particularly important role in metal binding proteins, where the electronic effects of transition metals have to be explicitly taken into account for the correct representation of the underlying biochemical process. In this review, after a brief description of the basic concepts of the QM/MM method, we provide an overview of its capabilities using selected examples taken from our work. Specifically, we will focus on heme peroxidases, metallo-\u3b2-lactamases, a-synuclein and ligase ribozymes to show how this approach is capable of describing the catalytic and/or structural role played by transition (Fe, Zn or Cu) and main group (Mg) metals. Applications will reveal how metal ions influence the formation and reduction of high redox intermediates in catalytic cycles and enhance drug metabolism, amyloidogenic aggregate formation and nucleic acid synthesis. In turn, it will become manifest that the protein frame directs and modulates the properties and reactivity of the metalions