Methods for Preparing Metal Ion Photocages: Application to the Synthesis of CrownCast

Kennedy, Daniel P.; Gwizdala, Celina; Burdette, Shawn C.

doi:10.1021/ol900902z

Cited by 24 publications

(34 citation statements)

References 18 publications

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“…In the presence of metal ions, the quantum yields of all the CrownCast ligands increase slightly (Table 1), a typical property of this class of ligands 15,46. The metal ionsscreened correspond to those of the desired applications; therefore, Hg 2+ was selected for CrownCast‐2 and Pb 2+ for CrownCast‐3.…”

Section: Resultssupporting

confidence: 79%

“…In a preliminary communication, we described three synthetic routes to CrownCast‐1 15. The first utilizes the trimethylsilyl trifluoromethanesulfonate (TMSOTf) assisted electrophilic aromatic substitution reaction pioneered by Tsien and Zucker (Scheme , Entry A) 12.…”

Section: Resultsmentioning

confidence: 99%

“…Each CrownUnc was prepared in bulk by photolysis of the corresponding CrownCast to obtain the precise extinction coefficients of both the caged and uncaged ligand, which allows accurate measurements of the quantum yields by using spectrophotometric techniques. The quantum yields obtained for the two new apo‐CrownCast ligands are comparable to both CrownCast‐1 and other related nitrobenzhydrol derived cages 15,46…”

Section: Resultsmentioning

confidence: 99%

“…Macrocyclic crown ethers are among the most recognizable receptors for metal ions; numerous sensors and molecular devices exploit the unique properties of these ligands 17–23. Initially, we designed a cage that utilized a 13‐phenyl‐1,4,7,10‐tetraoxa‐13‐azacyclopentadecane receptor (A15C5, 2 ) to develop new synthetic strategies for preparing Cast ligands 15. The crown ether macrocycle was chosen as a surrogate for other ligands that could potentially be incompatible with some of the synthetic manipulations being screened.…”

Section: Introductionmentioning

confidence: 99%

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Buffering Heavy Metal Ions with Photoactive CrownCast Cages

et al. 2010

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Historically, caged compounds have been used to interrogate the biological activity of organic molecules by using light; however, R. Tsien and others have developed methodologies over the last three decades for using nitrobenzyl-derived caged complexes to study the signaling behavior of Ca 2+. A series of cation-selective N-phenyl-azamacrocyclic receptors integrated with a 4,5-dimethoxy-2-nitrobenzyl (DMNB) photoactive group act as cages for divalent metal ions. The uncaging mechanism of these complexes involves a photoreaction that converts the nitrobenzhydrol, which is para to the aniline nitrogen atom, into the corresponding nitrosobenzophenone. Resonance delocalization of the aniline into the distal carbonyl group of the photoproduct attenuates the ability of the nitrogen atom to interact with the guest. CrownCast-1 (3) utilizes a 13-phenyl-1,4,7,10-tetraoxa-13-azacyclopentadecane (A15C5, 2) receptor. Binding studies with CrownCast-1 revealed a modest selectivity for Ca 2+ ; however, differences in the measured binding affinity upon photolysis suggest that CrownCast-1 is better suited to cage

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Section: Resultssupporting

confidence: 79%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Buffering Heavy Metal Ions with Photoactive CrownCast Cages

et al. 2010

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“…0.005. [40] Zhang . [43] Die Reaktivität dieser Metallionen in vitro und in vivo vor und nach der Photolyse bleibt aber noch zu bestimmen.…”

Section: D-block-metallkäfigeunclassified

Schlüssel zum Öffnen photolabiler, metallhaltiger Käfige

Ciesienski

Franz

2010

Angewandte Chemie

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Photolabile metallhaltige Käfige sind Metallkomplexe, die bei Bestrahlung mit Licht geeigneter Wellenlänge eine Veränderung der Koordinationsumgebung erfahren. Dabei kann entweder der verkapselnde Ligand allein oder der gesamte Metallkomplex photoresponsiv sein. Die veränderten Koordinationseigenschaften photoresponsiver Komplexe können mehrere Auswirkungen haben: eine Freisetzung des koordinierten Metallions in seine Umgebung, eine veränderte Reaktivität des Metallzentrums oder die Abspaltung eines reaktiven Moleküls, das zuvor durch Bindung an das Metallzentrum passiviert war. Diese photoaktivierbaren Systeme können von Nutzen sein, um die Bioverfügbarkeit von Metallen oder ihren koordinierenden Liganden für das Studium biologischer Reaktionspfade oder für mögliche therapeutische Zwecke zu manipulieren.

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Photo‐release of Metal Ions in Living Cells

Gwizdala¹,

Burdette²

2014

Inorganic Chemical Biology

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Methods for Preparing Metal Ion Photocages: Application to the Synthesis of CrownCast

Cited by 24 publications

References 18 publications

Buffering Heavy Metal Ions with Photoactive CrownCast Cages

Buffering Heavy Metal Ions with Photoactive CrownCast Cages

Schlüssel zum Öffnen photolabiler, metallhaltiger Käfige

Photo‐release of Metal Ions in Living Cells

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