Designer ligands for beryllium.
We report the rational design of ligands that selectively bind beryllium. We selected two ligands to design Be based on binding polynulear species with a Be-O-Be motif: 2-hydroxyisophthalic acid (HIPA) and 2,3-dihydroxybenzoic acid (DHBA). All previous work has focused on BeL or BeL2 species. The HIPA and DHBA have extremely high binding constants of 17.5 and 18.4, respectively. These ligands outcompete chromotropic acid, which has one the highest binding constants for Be reported in the literature for a simple BeL species. The binding of the second Be to form the Be-O-Be motif is so strong that polynuclear species predominates in solution down to micromolar concentrations. Both ligands show a fluorescence response in the presence of beryllium, making them promising candidates for fluorescence-based sensors. In the case of HIPA, there is a fluorescence shift, and in the case of DHBA, the presence of beryllium turns on the fluorescence by removing two OH bonds that otherwise lead to nonradiative decay. The most dramatic result is that DHBA selectively binds Be in the presence of a metal cocktail containing a 50-fold excess of Al, Fe, Cr, Cu, Zn, Cd, and Pb. This is the first time that such selectivity for beryllium has been demonstrated.
Keizer
Timothy S
TS
Chemistry Division (C-SIC, Mail Stop J514), Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA.
Sauer
Nancy N
NN
McCleskey
T Mark
TM
D001607:Berylliosis / Q000188:drug therapy; D001608:Beryllium / Q000737:chemistry*; D002614:Chelating Agents / Q000737:chemistry*; D062385:Hydroxybenzoates / Q000737:chemistry*; D007700:Kinetics; D008024:Ligands; D010795:Phthalic Acids / Q000737:chemistry*; D013050:Spectrometry, Fluorescence; D013056:Spectrophotometry, Ultraviolet
C492390:2-hydroxyisophthalic acid; D002614:Chelating Agents; D062385:Hydroxybenzoates; D008024:Ligands; D010795:Phthalic Acids; C009135:2,3-dihydroxybenzoic acid; D001608:Beryllium