Photochemical Delivery and Metal Mediated Reactions of Nitrogen Oxides and other Bioactive Small Molecules

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This award in the Chemistry of Life Processes (CLP) program supports continuing fundamental research by Professor Peter C. Ford at the University of California, Santa Barbara into how transition metal centers define the biological chemistry of nitric oxide (NO) and other small molecules that play key regulatory roles in mammalian physiology. These studies will also explore photochemical strategies using new nanomaterials for delivering such species to specific targets. It is now broadly known that NO, nitrogen oxide derivatives such as nitrite ion, carbon monoxide (CO) and several other simple molecular species have profound roles in controlling certain physiological functions including the cardiovascular system, wound healing, immune response to pathogens, etc. In nearly all such cases, the chemical reactions with metal centers, such as hemoglobin and other iron and copper containing proteins, is essential to the physiological effects. One goal of the current research is to define and to understand the relevant biochemistry of these metal--small molecule interactions. The techniques employed are reaction kinetics and modern analytical methods as well as theoretical computations. Another goal is to design, prepare and test new molecular and nano-scaled assemblies that that can be used with light to deliver such bioregulators to targeted tissues for the purpose of affecting the viability of the target. By using light as the triggering mechanism one can control the location, timing, and dosages of bioregulator release. Along this line, the UCSB group has developed new systems where nano-sized semiconductor quantum dots (QDs) serve as templates for carrying the small molecule precursors while simultaneously acting as the antennas for light absorption for triggering. On-going studies will refine these assemblies and study their effectivity. From a broader perspective, the UCSB studies will develop fundamental chemical understanding of these bioregulatory molecules that must underlie potential development of new therapeutic applications. The research performed under this award also serves as a template for training undergraduate, graduate and postdoctoral students in the nuances of creative scholarship. This also extends to local K-12 schools, since members of the Ford group have participated actively in scientific outreach programs. Undergraduates leaving the group have entered graduate and medical school programs and Ph.D. and postdoctoral graduates have assumed responsible roles in industry, government and academia, thereby contributing to the US scientific manpower pool.