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Reactive Oxygen Species Generation on Nanoparticulate Material  191








                                   86
                                   87
                                   83




                              80
                               82 or 83
                                              97  98  94  103


                                                       104







        Figure 5.23  Major photosensitization pathways for C 60 . Numbers vide supra and vide
        infra refer to the primary reaction pathways shown in this figure and Figure 5.22.

        1
         C (Eq. 94). The triplet state is also susceptible to self-quenching (Eq. 97)
          60
                                            0
        via interaction with the ground state ( C ) and triplet-triplet annihi-
                                              60
                                                        3
        lation (Eq. 98) via interaction with another triplet ( C ). Type I sensi-
                                                          60
        tization (Eq. 103) occurs when the triplet state comes in contact with
        a donor molecule that has a more negative reduction potential than
         3                          ?2
        ( C ). The resulting radical (C 60 ) can then pass the electron to ground-
           60
        state oxygen to form superoxide (Eq. 104). An illustration of these main
        fullerene photosentization pathways is shown in Figure 5.23.
          In general, conditions that lead to ROS generation can be grouped into
        four categories in which reaction pathways are most directly related and
        in many cases have been investigated together:
        1. Ground-state Fullerene: Excitation and Decay (Eqs. 80, 81, 82)
        2. Intersystem Crossing: Fullerene Triplet-state Formation (Eqs. 83,
           86, 87)
        3. Fullerene Triplet Quenching: Type II Photosensitization (Eqs. 97, 98, 94)
        4. Fullerene Triplet Reduction: Type I Photosensitization (Eqs. 103, 104).

        Each of these groups of reaction pathways are affected by changes in
        fullerene functionality and aggregation state, such as those produced to
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