RESUMO
The construction of molecular machines has captured the imagination of scientists for decades. Despite significant progress in the synthesis and studies of the properties of small-molecule components (smaller than 2-5 kilo Dalton), challenges regarding the incorporation of molecular components into real devices are still eminent. Nano-sized molecular machines operate the complex biological machinery of life, and the idea of mimicking the amazing functions using artificial nano-structures is intriguing. Both in small-molecule molecular machine components and in many naturally occurring molecular machines, mechanically interlocked molecules and structures are key functional components. In this work, we describe our initial efforts to interface mechanically-interlocked molecules and gold-nanoparticles (AuNPs); the molecular wire connecting the AuNPs is covered in an insulating rotaxane-layer, thus mimicking the macroscopic design of a copper wire. Taking advantage of recent progress in the preparation of supramolecular complexes of the cucurbit[7]uril (CB[7]) macrocycle, we have prepared a bis-thiol functionalised pseudo-rotaxane that enables us to prepare a AuNP-stoppered [2]rotaxane in water. The pseudo-rotaxane is held together extremely tightly (Ka > 1013 M-1), Ka being the association constant. We have studied the solution and gas phase guest-host chemistry using NMR spectroscopy, mass spectroscopy, and electrochemistry. The bis-thiol functionalised pseudo-rotaxane holds further a ferrocene unit in the centre of the rotaxane; this ferrocene unit enables us to address the system in detail with and without CB[7] and AuNPs using electrochemical methods.
RESUMO
Biotin[6]uril hexaesters represent a new class of anionophores which operate solely through C-H···anion interactions. The use of soft H-bond donors favors the transport of less hydrophilic anions (e.g., Cl(-), NO3(-)) over hard, stongly hydrated anions (e.g., HCO3(-) and SO4(2-)). Especially relevant is the selectivity between chloride and bicarbonate, the major inorganic anions in biological systems.
