Synthesis Of Saddle-type Cobalt Porphyrins And Their Regulation To NO Moiety

Nitric oxide?NO?plays a role in signaling and regulating cellular functions in the body for Cardiovascular disease and many cancers.Binding to NO is a common phenomenon that contains both heme and collinocyclic proteins.It is a systematic project to artificially simulate the binding,transfer and transformation of hemoglobin Binding to NO.In this paper,a series of saddle distortion cobalt porphyrins?P-Cos?and it coordination with NO?P-Co-NOs?were synthesized.the structure of model compounds was studied by X-single crystal diffraction spectroscopy and infrared vibration spectroscopy.In order to realize the artificial regulation of NO molecule,We have Using Electron Paramagnetic Resonance and hydrogen nuclear magnetic resonance?NMR?spectroscopy,DFT theoretical calculation and ultraviolet-visible spectra and cyclic voltammograms electrochemical,respectively discusses the influence of the big ring distortion to molecular magnetism,the changes of orbital energy level of Co-NO moieties,the molecular oxidation reducing performance.In order to control the distortion of porphyrins,In this paper,two groups of alkyl bands containing different quantities of methylene?-OCH₂O-?were used to connect the meso adjacent to the large ring.Thus,the control of the degree of distortion of the large ring is achieved by controlling the number of methylene?-CH₂-?.subsequently,we using this way construct a model of the modified cobalt porphyrins with NO.Through the study of this model compounds,we found that when the macrocycle distortion in the saddle cobalt porphyrin causes the N₄ core constriction to a certain extent.Then,it can change the CoNO moieties of the{CoNO}⁸ compound.including:1)making NO_bentent are converted to a NO_linear,2)changing coupling of d electrons,3)changing the way of d-?Orbital hybridization,4)making An electron or charge transfer and redox.The macrocycle distortion will finally make to convert from(Co^II)^+·-NO^·to Co^III-NO^-of the{CoNO}⁸compound.This reaction shows that the conversion of electrophilic NO^·to nucleophilic NO^-is feasible only by virtue of the core contraction of saddled porphyrins.It is suggested that the binding,transfer,transformation and dissociation process of hemoglobin to NO in biological body is regulated by heme structure distortion.Therefore,the research results of this paper provide relevant theoretical and experimental support for understanding the interaction mechanism between NO and certain enzyme and heme.