Hemispherical Synthesis of L-Lysine dendrimers for Clustering of Functional Groups and developing new Functions.

游离基卟啉和锌(II)-卟啉以不同的方式结合成树枝状多聚(L-赖氨酸)，如杂乱、半球和双层。观察到8个锌(II)-卟啉以双层方式对16或32个自由基卟啉的610 nm发射有效猝灭(90%)。在树状大分子表面引入甲基紫精基团，构建了一种新型的电子转移体系。将锌(II)-卟啉和甲基紫精以不同的方式引入到树枝状聚L-赖氨酸S中。根据前人的报道合成了(Zn8/MV16)K14和(Zn8/MV8)K14。与未结合的卟啉/甲基紫精体系相比，两种树枝状大分子的荧光猝灭效率都提高了约6倍。此外，在三乙醇胺存在下，锌(II)-卟啉在(Zn8/Mv16)K14和(Zn8/Mv8)K14中的Soret带连续照射下，紫红色的树枝状大分子溶液变为亮蓝色，表明甲基紫精自由基离子的产生。利用6，10，16，20-tetrakis(4-amino-phenyl)porphyrin(TAP).设计并合成了以自由基和锌(II)为中心的树枝状聚(L赖氨酸)S(Fb1/Zn8)K4和(Zn1/Fb8)K4在DMF中，以(FB1)K4和8个当量的锌(II)-卟啉的混合物为参照，对树状大分子(FB1/Zn8)K4进行了荧光测量。锌(II)-卟啉的Q带在660 nm激发时，其610 nm处的发射被显著猝灭。相反，自由基卟啉在660 nm和720 nm处的发射显著增加。最有趣的是，610 nm发射的下降幅度和660 nm发射的增加幅度几乎是相同的。这一事实表明，能量转移是定量发生的。还对(Zn1/Fb8)K4进行了荧光测量，并与(Fb1/Zn8)K4进行了比较。

Free -base porphyrins and Zn(II)-porphyrins were combined to a dendritic poly(L-lysine) in various fashions such as scramble, hemisphere, and double strata. Efficient quenching (90%) of emission at 610 nm was observed from 8 Zn(II)-porphyrins to 16 or 32 free base porphyrins in double strata fashion. Methyl viologen groups were also combined to the surface of the dendrimer to built a novel electron transfer system.Clusters of Zn(II)-porphyrins and methyl viologen were introduced to dendritic poly(L-lysine)s in different manners. The synthesis of (Zn8/MV16)K14 and (Zn8/MV8)K14 were carried out according to previous reports. Both of the dendrimers showed about six times more efficient fluorescence quenching in comparison with the unbound porphyrin/methyl viologen system. Furthermore, the purple colored dendrimer solution turned brilliant blue on continuous irradiation of the Soret band of Zn(II)-porphyrin in (Zn8/MV16)K14 and (Zn8/MV8)K14 in the presence of triethanolamine indicating the generation of methyl viologen radical ion.Free-base and Zn(II)-porphyrin centered dendritic poly(L-lysine)s (Fbl/Zn8)K4 and (Znl/Fb8)K4 were designed and synthesized using 6,10,16,20-tetrakis(4-amino-phenyl)porphyrin(TAP). The dendrimer (Fbl/Zn8)K4) was subjected to fluorescence measurements with reference to a mixture of (Fb1)K4 and eight equivalents of Zn(II)-porphyrin in DMF. Upon excitation at 660 nm for Q band of Zn(II)-porphyrin, the emission at 610 nm from Zn(II)-porphyrin was significantly quenched. Instead, emission from free-base porphyrin at 660 nm and 720 nm increased significantly. Most interestingly, extent.of decrease in the emission at 610 nm and the extent of increase in emission at 660 nm were almost same. This fact suggests that energy transfer occurred quantitatively. Fluorescence measurement for (Zn1/Fb8)K4 was also performed and compared with (Fb1/Zn8)K4.