Dual-function multilayers for the photodelivery of nitric oxide and singlet oxygen

In this contribution we report the design, preparation and characterization of bichromophoric Langmuir-Schäfer multilayer films which enable the simultaneous generation of nitric oxide (NO) and singlet oxygen (1)O(2) ((1)Delta(g)). They are achieved by exploiting effective interfacial electrostatic interactions between the floating film of a cationic amphiphilic nitric oxide (NO) photodonor and an anionic porphyrin dissolved in the water subphase. The morphology and the spectroscopic features of the floating films at the water-air interface are inspected by Brewster angle microscopy and UV/Vis reflection spectroscopy, respectively. Multilayer films containing both the chromogenic centres are obtained by horizontal lifting deposition onto hydrophobized quartz substrates and are characterized by steady-state UV/Vis absorption, fluorescence and laser flash photolysis. The anionic porphyrin units are entangled into the films network mainly in their monomeric forms and no significant intra and inter-chromophoric interaction occur in the excited state, preserving the photochemical independency of the two photoactive units in the multilayers. The capability of the bichromophoric films to delivery NO and singlet oxygen, (1)O(2) ((1)Delta(g)), under light excitation is unambiguously demonstrated by the direct and in real time monitoring of these transient species using an ultrasensitive electrode and a time-resolved infrared luminescence apparatus, respectively.