CuproCleav-1, a first generation photocage for Cu+

Abstract

By utilizing thioether ligands, CuproCleav-1 stabilizes Cu(+) complexes in aqueous solution and releases the guest metal ion upon photolysis of the nitrobenzyl group. The photocage has an apparent K(d) of 54 pM for Cu(+), and metal ion release has been demonstrated using the fluorescent sensor CS1.

Chemical Communication between Molecules

“…The o ‐nitrobenzyl system undergoes a photoreaction, yielding the release of the metal ion. Similar irreversible metal ion release has been shown for other o ‐nitrobenzyl caged compounds or by using light as a stimulus in conjugation with photosensitized singlet‐oxygen formation …”

“…[11,39] The Zn 2 + source consisted of ac oordination complex with ap hotocleavable ligand system (15). The o-nitrobenzyl system undergoes ap hotoreaction,y ieldingt he releaseo ft he metal ion.S imilar irreversible metal ion release has been shown for other o-nitrobenzyl caged compounds [40,41] or by using light as as timulus in conjugation with photosensitized singletoxygenf ormation. [42] Notably,t he light-induced release of metal ions can be performed with reversibly operating systems.…”

Chemical Communication between Molecules

“…The o ‐nitrobenzyl system undergoes a photoreaction, yielding the release of the metal ion. Similar irreversible metal ion release has been shown for other o ‐nitrobenzyl caged compounds or by using light as a stimulus in conjugation with photosensitized singlet‐oxygen formation …”

“…[11,39] The Zn 2 + source consisted of ac oordination complex with ap hotocleavable ligand system (15). The o-nitrobenzyl system undergoes ap hotoreaction,y ieldingt he releaseo ft he metal ion.S imilar irreversible metal ion release has been shown for other o-nitrobenzyl caged compounds [40,41] or by using light as as timulus in conjugation with photosensitized singletoxygenf ormation. [42] Notably,t he light-induced release of metal ions can be performed with reversibly operating systems.…”

Isothermal Titration Calorimetry for Characterizing the Zinc(II)‐Binding Properties of Photocaged Complexes with Micromolar Affinity

“…When photocages lack a spectroscopic response upon metal ion binding, the most common technique is competitive binding titration with an optically active chelator. CuproCleav‐1, a photocage for Cu + that does not show a spectral response when titrated with Cu + , required competitive binding titrations with the fluorescent sensor CS1 to determine the binding affinity [26] . By titrating [Cu(CS1)] + with CuproCleav‐1 the removal of Cu + from the sensor could be monitored by a decrease in fluorescence intensity.…”

A Zinc(II) Photocage Based on a Decarboxylation Metal Ion Release Mechanism for Investigating Homeostasis and Biological Signaling

“…Alternatively, photolytically breaking a carbon‐heteroatom bond provides compounds that release metal ions through the reduction of chelate effects. The Cleav class of photocaged complexes can effectively buffer and release Ca 2+ ,13 Cu 2+/1+ ,14, 15 or Zn 2+ depending on the ligand design 16. 17…”

Chemical Communication between Molecules

“…The o ‐nitrobenzyl system undergoes a photoreaction, yielding the release of the metal ion. Similar irreversible metal ion release has been shown for other o ‐nitrobenzyl caged compounds or by using light as a stimulus in conjugation with photosensitized singlet‐oxygen formation …”

“…[11,39] The Zn 2 + source consisted of ac oordination complex with ap hotocleavable ligand system (15). The o-nitrobenzyl system undergoes ap hotoreaction,y ieldingt he releaseo ft he metal ion.S imilar irreversible metal ion release has been shown for other o-nitrobenzyl caged compounds [40,41] or by using light as as timulus in conjugation with photosensitized singletoxygenf ormation. [42] Notably,t he light-induced release of metal ions can be performed with reversibly operating systems.…”

Isothermal Titration Calorimetry for Characterizing the Zinc(II)‐Binding Properties of Photocaged Complexes with Micromolar Affinity

“…When photocages lack a spectroscopic response upon metal ion binding, the most common technique is competitive binding titration with an optically active chelator. CuproCleav‐1, a photocage for Cu + that does not show a spectral response when titrated with Cu + , required competitive binding titrations with the fluorescent sensor CS1 to determine the binding affinity [26] . By titrating [Cu(CS1)] + with CuproCleav‐1 the removal of Cu + from the sensor could be monitored by a decrease in fluorescence intensity.…”

A Zinc(II) Photocage Based on a Decarboxylation Metal Ion Release Mechanism for Investigating Homeostasis and Biological Signaling

“…Alternatively, photolytically breaking a carbon‐heteroatom bond provides compounds that release metal ions through the reduction of chelate effects. The Cleav class of photocaged complexes can effectively buffer and release Ca 2+ ,13 Cu 2+/1+ ,14, 15 or Zn 2+ depending on the ligand design 16. 17…”

Chemical Communication between Molecules

“…The o ‐nitrobenzyl system undergoes a photoreaction, yielding the release of the metal ion. Similar irreversible metal ion release has been shown for other o ‐nitrobenzyl caged compounds or by using light as a stimulus in conjugation with photosensitized singlet‐oxygen formation …”

“…[11,39] The Zn 2 + source consisted of ac oordination complex with ap hotocleavable ligand system (15). The o-nitrobenzyl system undergoes ap hotoreaction,y ieldingt he releaseo ft he metal ion.S imilar irreversible metal ion release has been shown for other o-nitrobenzyl caged compounds [40,41] or by using light as as timulus in conjugation with photosensitized singletoxygenf ormation. [42] Notably,t he light-induced release of metal ions can be performed with reversibly operating systems.…”

Isothermal Titration Calorimetry for Characterizing the Zinc(II)‐Binding Properties of Photocaged Complexes with Micromolar Affinity

“…When photocages lack a spectroscopic response upon metal ion binding, the most common technique is competitive binding titration with an optically active chelator. CuproCleav‐1, a photocage for Cu + that does not show a spectral response when titrated with Cu + , required competitive binding titrations with the fluorescent sensor CS1 to determine the binding affinity [26] . By titrating [Cu(CS1)] + with CuproCleav‐1 the removal of Cu + from the sensor could be monitored by a decrease in fluorescence intensity.…”

A Zinc(II) Photocage Based on a Decarboxylation Metal Ion Release Mechanism for Investigating Homeostasis and Biological Signaling

“…Alternatively, photolytically breaking a carbon‐heteroatom bond provides compounds that release metal ions through the reduction of chelate effects. The Cleav class of photocaged complexes can effectively buffer and release Ca 2+ ,13 Cu 2+/1+ ,14, 15 or Zn 2+ depending on the ligand design 16. 17…”