We have designed a photolysis system in reverse micelles to study fast time-scale metal chelation by peptides within a membrane model system with the specificity to release metal ions at specific time by irradiation alone without having to manually add other solutions. Zn(II) ion release by photo-induced decarboxylation reactions of Zn(II)-nitriliotriacetate decarboxylation cage (Zn(II)-NTAdeCage) photo-complexes within confined spaces are governed by specific location of the compound and the charge compatibility of complex with the reverse micelle interface. Zn(II)-NTAdeCage has been shown in buffered aqueous solution (pH 7.5, 40 mM HEPES/100 mM KCl) to photolytically release Zn(II) with irradiation at 365 nm. The intact cage has a high affinity for Zn(II) and upon irradiation creates two photoproducts (iminodiacetic acid, m-nitrobenzaldehyde) which have little affinity for Zn(II). The current work shows successful photo-induced decarboxylation of the Zn(II)-NTAdeCage complex within AOT/isooctane reverse micelles (pH 7.5, 40 mM HEPES, 0.02 M AOT, w0 30, λirr355 nm). We observe the release of Zn(II) ions from Zn(II)-NTAdeCage complex by a decrease in the absorbance at 270 nm (Zn(II)-NTAdeCage) as the complex is degraded and the subsequent retrieval of Zn(II) by Zincon monosodium salt with peak growth at 620 nm of the Zn(II)-Zincon complex and peak loss at 470 nm (aqueous) or 540 nm (reverse micelle) of the free Zincon ligand in both aqueous buffered and reverse micelle systems.

Photolysis of a Zn(II)-nitriliotriacetate cage in AOT/isooctane reverse micelles

253rd National Meeting (2017)

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