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本文测定了2,4-二(α-亚氨基乙酸乙基)次卟啉Ⅸ和2,4-二(α-巯乙基)次卟啉Ⅸ的g因子、ΔH_(pp)、线型及自旋浓度;它们的ESR信号强度对微波功率的饱和效应及对温度的响应;同时测定了在不同温度下UV-辐照的ESR相对强度。发现它们的ESR由两种顺磁中心所贡献;卟啉环中的未偶非定域电子与环上的磁性核相互作用产生的超精细结构和卟啉与氧有关的自由基。与氧有关的自由基的ESR信号强度对微波功率的饱和效应与各化合物析出的等电点pH值有关;对温度的响应情况比较复杂;光化反应对与氧有关的自由基呈现零级动力学行为,整个反应受三态氧向激发态卟啉“活动范围”的扩散所控制。
In this paper, the g-factor, ΔH_ (pp), linear and the ratio of 2,4-bis (α-mercaptoethyl) porphyrin IX and 2,4- Spin concentration; the saturation effect of their ESR signal intensity on microwave power and its response to temperature; and the relative intensities of UV-irradiated ESR at different temperatures were measured simultaneously. Their ESRs were found to be contributed by two paramagnetic centers; hyperfine structures resulting from the interaction of non-delocalized electrons in the porphyrin ring with the magnetic nuclei on the ring and oxygen-related porphyrin free radicals. The saturation effect of the ESR signal intensity of the oxygen-related free radicals on the microwave power is related to the pH value of the isoelectric point precipitated by each compound; the response to the temperature is relatively complicated; the photochemical reaction presents zero-order motive force for the oxygen-related free radicals Learning behavior, the entire reaction by the three-state oxygen to excited state porphyrin “activity range” diffusion control.