Fluorescent sensors for Hg 2+ are demonstrating their potential in a variety of fields such as environmental and biological applications. The review focuses on the recent development of rhodamine derivatives in which the spirolactam (non-fluorescent) to ring-opened amide (fluorescent) process was utilized and on the development of BODIPY derivatives in which the photoinduced electron transfer (PET) process was utilized. New trends in the immobilization of the molecular probes on solid supports, as polymers and/ or nanostructures, have been emphasized. The different recognition mechanisms used for the signal responses have been analyzed. The spectroscopic properties, reaction media, analytical parameters, interferences by other ions and practical applications have been summarized.Arsenio Muñoz de la Peña received his PhD (1981) degree at the University of Extremadura, Badajoz, Spain. He held post-doctoral positions at the
This article summarizes a series of recent and simple experiments to produce optically active substances from achiral precursors. These symmetry-breaking processes include either autocatalytic crystallization or asymmetric autocatalysis, and provide new insights into the origin of biomolecular homochirality. In addition, support from an extraterrestrial origin of chiral molecules has also come from recent findings.
The archetypal Cu(I)-catalyzed alkyne-azide click cycloaddition (CuAAC) has been explored thoroughly via density functional calculations, modeling copper nuclei with the LANL2DZ basis set and aqueous environments with CPCM solvation. All the mechanistic proposals, ranging from the intermediacy of copper acetylides to π-complexes and multinuclear clusters have been compared. The known features of the CuAAC reaction such as the observed second order kinetics for the Cu(I) species and the marked regioselectivity have been taken into account. The calculated energy barriers point to the intermediacy of copper(i) acetylides with two metal centers, in agreement with the observed kinetics, which exhibit barriers of 10.1 kcal mol(-1) and 13.7 kcal mol(-1) for the 1,4- and 1,5-regiochemistries, respectively, thus accounting for the marked regioselectivity of the copper catalyzed azide-alkyne cycloaddition. The copper acetylide versus π-complexes dilemma has also been experimentally addressed through the click reaction of benzyl azide and isotopically labeled phenylacetylene. The total proton/deuterium exchange in the afforded triazole demonstrates the formation of a copper acetylide intermediate during the transformation.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.