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A photolabile ligand for light-activated release of caged copper.

Publication ,  Journal Article
Ciesienski, KL; Haas, KL; Dickens, MG; Tesema, YT; Franz, KJ
Published in: Journal of the American Chemical Society
September 2008

A photosensitive caged copper complex has been prepared from a tetradentate ligand (H2cage) composed of two pyridyl-amide arms connected by a photoreactive nitrophenyl group. H2cage binds Cu2+ in aqueous solution with a stability constant (log beta) of 10.8, which corresponds to a KD of 16 pM at pH 7.4. The neutral Cu2+ complex, [Cu(OH2)(cage)], crystallizes as a distorted trigonal bipyramid coordinated by two amide and two pyridyl N atoms, with a water molecule bound in the trigonal plane. Photolysis with 350 nm UV light cleaves the ligand backbone to release photoproducts with significantly diminished affinity for Cu2+, thereby uncaging the metal ion. When coordinated as the caged complex, copper has diminished reactivity to produce hydroxyl radicals from Fenton-like reaction mixtures containing hydrogen peroxide and ascorbic acid. Postphotolysis, uncaged copper promotes hydroxyl radical formation under the same conditions. The strategy of caging copper is promising for applications where light could be used to trigger release of copper as a pro-oxidant to increase oxidative stress or as a tool to release copper intracellularly to study mechanisms of copper trafficking.

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Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

September 2008

Volume

130

Issue

37

Start / End Page

12246 / 12247

Related Subject Headings

  • Pyridines
  • Photolysis
  • Oxidation-Reduction
  • Organometallic Compounds
  • Ligands
  • Kinetics
  • Hydrogen-Ion Concentration
  • General Chemistry
  • Crystallography, X-Ray
  • Copper
 

Citation

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Ciesienski, K. L., Haas, K. L., Dickens, M. G., Tesema, Y. T., & Franz, K. J. (2008). A photolabile ligand for light-activated release of caged copper. Journal of the American Chemical Society, 130(37), 12246–12247. https://doi.org/10.1021/ja8047442
Ciesienski, Katie L., Kathryn L. Haas, Marina G. Dickens, Yohannes T. Tesema, and Katherine J. Franz. “A photolabile ligand for light-activated release of caged copper.Journal of the American Chemical Society 130, no. 37 (September 2008): 12246–47. https://doi.org/10.1021/ja8047442.
Ciesienski KL, Haas KL, Dickens MG, Tesema YT, Franz KJ. A photolabile ligand for light-activated release of caged copper. Journal of the American Chemical Society. 2008 Sep;130(37):12246–7.
Ciesienski, Katie L., et al. “A photolabile ligand for light-activated release of caged copper.Journal of the American Chemical Society, vol. 130, no. 37, Sept. 2008, pp. 12246–47. Epmc, doi:10.1021/ja8047442.
Ciesienski KL, Haas KL, Dickens MG, Tesema YT, Franz KJ. A photolabile ligand for light-activated release of caged copper. Journal of the American Chemical Society. 2008 Sep;130(37):12246–12247.
Journal cover image

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

September 2008

Volume

130

Issue

37

Start / End Page

12246 / 12247

Related Subject Headings

  • Pyridines
  • Photolysis
  • Oxidation-Reduction
  • Organometallic Compounds
  • Ligands
  • Kinetics
  • Hydrogen-Ion Concentration
  • General Chemistry
  • Crystallography, X-Ray
  • Copper