Photochemical & Related Thermal Mechanisms of Transition Metal Complexes

无机化学、生物无机化学和金属有机化学计划为加州大学圣巴巴拉分校化学系Peter C.Ford博士的光化学研究提供持续支持。将研究一氧化氮(NO)产生的光化学机制以及NO与生物无机感兴趣的金属中心之间的热反应动力学。将进行各种单核金属亚硝酰基和金属亚硝酸络合物的闪光和连续光解，特别强调化合物的分子设计，这些化合物可以作为根据需要将NO光化学输送到所需目标的前体。由卟啉或其他吸收红光的生色团构成的“天线”将与前体耦合，以允许通过单光子或双光子吸收机制对化合物的金属亚硝基部分进行低能量激发。化学还将扩展到产生亚硝酰氢化物(HNO)和氮氧基阴离子(NO-)的体系，这两种物种也可能具有生物重要性。当光被分子吸收时，分子获得的能量有时会引发化学反应。在这种情况下，前体分子解体，释放出一氧化氮(NO)和含有金属的副产品。因为NO是心血管系统的生物调节剂，也参与免疫反应，这种分子的受控释放具有许多潜在的医疗好处。这项基础性研究可能为光动力疗法和一氧化氮的其他用途带来新的策略。几名研究生将接受无机化学这一重要新领域的培训。

The Inorganic, Bioinorganic, and Organometallic Chemistry Program provides continued support for photochemical research by Dr. Peter C. Ford,Chemistry Department, University of California, Santa Barbara. The photochemical mechanisms of nitric oxide (NO) generation as well as the dynamics of thermal reactions between NO and metal centers of bioinorganic interest will be studied. Flash and continuous photolysis of various mononuclear metal nitrosyl and metal nitrito complexes will be conducted, placing particular emphasis on the molecular design of compounds that may serve as precursors for the photochemical delivery of NO to desired targets on demand. "Antennas" constructed of porphyrins or other chromophores that absorb red light will be coupled to the precursors to allow for low-energy excitation of the metal nitrosyl part of the compound by single photon or two photon absorption mechanisms. The chemistry will also be extended to systems that generate nitrosyl hydride (HNO) and nitroxyl anion (NO-), two species that also may have biological importance.When light is absorbed by a molecule, the energy that the molecule acquires sometimes initiates a chemical reaction. In this case, a precursor molecule disintegrates to release nitric oxide (NO) plus a metal-containing byproduct. Because NO is a bioregulator of the cardiovascular system as well as participating in immune responses, the controlled release of this molecule has many potential medical benefits. This fundamental study may lead to new strategies for photodynamic therapy and other uses of nitric oxide. Several graduate students will be trained in this important new area of inorganic chemistry.