The First Water-Soluble Copper(I) Calix[6]arene Complex Presenting a Hydrophobic Ligand Binding Pocket: A Remarkable Model for Active Sites in Metalloenzymes

Abstract

Remarkable stabilization of a copper(i) center is evident in the tris(sulfonated) calixarene‐based complex shown. This complex is truly biomimetic as it is soluble in water and also has a free valence where CO can bind. Thus it imitates the first coordination sphere encountered in copper enzymes and the hydrophobic microenvironment of the active site.

Atomically precise Au144(SR)60 nanoclusters (R = Et, Pr) are capped by 12 distinct ligand types of 5-fold equivalence and display gigantic diastereotopic effects

“…Very recently, we studied Au 38 (SCn) 24 capped by propanethiolates ( n = 3) and butanethiolates ( n = 4) and found that α-CH 2 signals split by up to 0.67 (C3) and 0.69 ppm (C4), the β-CH 2 by 0.023 (C3) and 0.085 ppm (C4), and the γ-CH 2 by 0.029 ppm (C4) 41. These chirality-related diastereotopic effects are very large also in the context of many other molecular systems 52–54. Comparatively, the effect observed for the α-CH 2 signals in Au 144 (SC2) 60 can thus be easily defined as gigantic, being as large as 2.88 ppm and with a methylene proton resonance found at the very large downfield value of 7.87 ppm.…”

Imidazole and Triazole Coordination Chemistry for Antifouling Coatings

“…Moreover, only free ions of Cu 2+ and Cu + are considered to be bioavailable [73][74][75]. A lot of recent focus in the catalysis and microbiology community is addressing Cu + stabilization by altering the Cu 2+ /Cu + redox potential via the proper choice of ligand environment, both with respect to chemistry and geometry (see Section 2) [76][77][78][79]. Here, the ligand environment in copper proteins, including both the Cu(I) [77][78][79] and the Cu(II) [79][80][81][82][83][84][85][86][87][88][89][90][91][92][93][94] oxidation statse, is a continuous source of inspiration.…”

Interactions of Calix[n]arenes with Nucleic Acids

“…The cavitand application may even be extended by using two calixarene cups that are linked together at one of the rims to form a molecular capsule which completely surrounds its target [16][17][18]. Calixarenes have also been used to mimic metallo-enzyme active sites, acting as a coordination core and hydrophobic pocket [19]. One of the major advantages connected with calixarenes is the synthetic ease to generate multivalent ligands.…”