Showing papers by "Shawn C. Burdette published in 2009"
TL;DR: The novel catechol-BODIPY dyad, 8-(3,4-dihydroxyphenyl)-2,6-bis(ethoxycarbonyl)-1,3,5,7-tetramethyl-4, 4-difluoro-4-bora-3a,4a-diaza-s-indacene (FerriBRIGHT) was rationally designed with the aid of computational methods and suggests
Abstract: The novel catechol−BODIPY dyad, 8-(3,4-dihydroxyphenyl)-2,6-bis(ethoxycarbonyl)-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (FerriBRIGHT) was rationally designed with the aid of computational methods. FerriBRIGHT could be prepared by standard one-pot synthesis of BODIPY fluorophores from 3,4-bis(benzyloxy)benzaldehyde (1) and 3,5-dimethyl-4-(ethoxycarbonyl)pyrrole (3); however, isolating the dipyrrin intermediate 8-[3,4-bis(benzyloxy)phenyl]-2,6-bis(ethoxycarbonyl)-1,3,5,7-tetramethyl-4,4-diaza-s-indacene (7) prior to reaction with excess BF3·OEt2 led to marked improvements in the isolated overall yield of the desired compound. In addition to these improvements in fluorophore synthesis, microwave-assisted palladium-catalyzed hydrogenolysis of benzyl ethers was used to reduce reaction times and catalyst loading in preparation of the desired compound. When FerriBRIGHT is exposed to excess FeCl3, CuCl2, [Co(NH3)5Cl]Cl2, 2,3-dichloro-5,6-dicyanobenzoquinone, or ceric ammonium nitrate in met...
103 citations
TL;DR: The synthesis and properties of ZinCleav-1, a cage for Zn(2+) that fragments upon photolysis, is reported, and it is expected to be the first in a class of caged complexes that will facilitate biological investigations.
Abstract: Caged complexes are metal ion chelators that release analytes when exposed to light of a specific wavelength. The synthesis and properties of ZinCleav-1, a cage for Zn2+ that fragments upon photolysis, is reported. The general uncaging strategy involves integrating a nitrobenzyl group on the backbone of the ligand so that a carbon-heteroatom bond is cleaved by the photoreaction. The caged complex was obtained using a new synthetic strategy involving a Strecker synthesis to prepare a key aldehyde intermediate. ZinCleav-1 has a Kd of 0.23 pM for Zn2+ as measured by competitive titration with [Zn(PAR)2] (PAR = 4-(2-pyridyl-2-azo) resorcinol). The quantum yield for ZinCleav-1 is 2.4% and 0.55% for the apo and Zn2+ complex, respectively. The ability of ZinCleav-1 to increase free [Zn2+] is calculated theoretically using the binding constants for the uncaged photoproducts, and demonstrated practically by using a fluorescent sensor to image the liberated Zn2+. Free Zn2+ may function as a neurotransmitter and hav...
43 citations
TL;DR: Two strategies were applied to the synthesis of ZinCast-1, a nitrobenzhydrol-based caged complex that upon photolysis exhibits a nearly 400-fold difference in binding for Zn(2+).
24 citations
TL;DR: Three different synthetic strategies were utilized in the construction of a novel class of macrocyclic containing o-nitrobenzhydrol group II cation cages.
20 citations