The light-induced photolysis of [Zn-(NTAdeCage)] − generates a temporally controlled burst of Zn 2+ , which is rapidly chelated in situ by the free ligand Zincon 2− . The [Zn(Zincon)] 2− coordination progress is monitored using absorption spectroscopy in bulk aqueous buffer and reverse micelle environments. The [Zn-(NTAdeCage)] − photocage and free ligand Zincon 2− have different reverse micelle locations that affect the [Zn(Zincon)] 2− formation at the nanoscale compared to the bulk aqueous buffer. The formation of [Zn-(Zincon)] 2− in a bulk aqueous buffer is more efficient despite the released Zn 2+ and Zincon 2− being physically closer within reverse micelles. The observed reduction of complex formation is attributed to the interfacial partitioning of Zincon 2− , distinct from the Zn 2+ photocage in the water pool, requiring diffusion for the species to meet to form [Zn(Zincon)] 2− . This work introduces a proof-of-concept methodology to experimentally measure fast chelation reactions in confined spaces and thus provides an approach to exploring cellular responses.
Vanadium salts and coordination compounds have desirable cellular anticancer effects, and although they have been investigated in detail as a potential treatment for diabetes, less attention has been given to the anticancer effects. The inhibition of some signal transduction enzymes is known, and studies of the metabolism and activation pathways both in vitro and in vivo are important for future investigations and development of vanadium's role as a new potential drug. In addition, a new approach has demonstrated that the enhancement of oncolytic viruses using vanadium salts and coordination complexes for immunotherapy is very promising. Some differences exist between this approach and current antidiabetic and anticancer studies because vanadium(iv) complexes have been found to be most potent in the latter approach, but the few compounds investigated with oncolytic viruses show that vanadium(v) systems are more effective. We conclude that recent studies demonstrate effects on signal transduction enzymes and anticancer pathways, thus suggesting potential applications of vanadium as anticancer agents in the future both as standalone treatments as well as combination therapies.
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