A Zinc(II) Photocage Based on a Decarboxylation Metal Ion Release Mechanism for Investigating Homeostasis and Biological Signaling.
Metal ion signaling in biology has been studied extensively with ortho-nitrobenzyl photocages; however, the low quantum yields and other optical properties are not ideal for these applications. We describe the synthesis and characterization of NTAdeCage, the first member in a new class of Zn(2+) photocages that utilizes a light-driven decarboxylation reaction in the metal ion release mechanism. NTAdeCage binds Zn(2+) with sub-pM affinity using a modified nitrilotriacetate chelator and exhibits an almost 6 order of magnitude decrease in metal binding affinity upon uncaging. In contrast to other metal ion photocages, NTAdeCage and the corresponding Zn(2+) complex undergo efficient photolysis with quantum yields approaching 30 %. The ability of NTAdeCage to mediate the uptake of (65) Zn(2+) by Xenopus laevis oocytes expressing hZIP4 demonstrates the viability of this photocaging strategy to execute biological assays.
Department of Chemistry and Biochemistry, Worcester Polytechnic Institute, 100 Institute Road, Worcester, MA 01609-2280 (USA).
Prem N
PN
Basa
Department of Chemistry and Biochemistry, Worcester Polytechnic Institute, 100 Institute Road, Worcester, MA 01609-2280 (USA).
Sagar
S
Antala
Department of Chemistry and Biochemistry, Worcester Polytechnic Institute, 100 Institute Road, Worcester, MA 01609-2280 (USA).
Robert E
RE
Dempski
Department of Chemistry and Biochemistry, Worcester Polytechnic Institute, 100 Institute Road, Worcester, MA 01609-2280 (USA). scburdette@wpu.edu.
Shawn C
SC
Burdette
D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D003653:Decarboxylation; D006706:Homeostasis; D007477:Ions / Q000737:chemistry; D010782:Photolysis; D017319:Photosensitizing Agents / Q000138:chemical synthesis / Q000737:chemistry*; D015398:Signal Transduction; D015032:Zinc / Q000737:chemistry*
D056831:Coordination Complexes; D007477:Ions; D017319:Photosensitizing Agents; D015032:Zinc
X-ray diffraction; cage compounds; coordination compounds; photolysis; zinc