4.6 Article

Cyclodextrin carriers of positively charged porphyrin sensitizers

Journal

ORGANIC & BIOMOLECULAR CHEMISTRY
Volume 7, Issue 18, Pages 3797-3804

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/b908772a

Keywords

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Funding

  1. Czech Science Foundation [203/08/0831, 203/07/1424]
  2. Ministry of Education, Youth and Sports of the Czech Republic [MSM 0021620857]

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The cationic sensitizer 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP) forms supramolecular complexes with native, per-methylated, sulfonated and dimethyl-sulfonated cyclodextrins (CDs). Binding interactions were proved by NMR, mass spectra, capillary zone electrophoresis, UV-Vis and. uorescence spectroscopy. The 2D-NMR experiments on native CDs indicate that the interaction of TMPyP with the external CD surface is the dominant binding mode. The high binding affinity of TMPyP towards sulfonated CDs is due to electrostatic interactions. Binding is accompanied by an increase of the TMPyP basicity. Whereas beta CD does not affect the lifetime of the TMPyP triplet states, binding with sulfonated CDs causes the protonation of the TMPyP triplet states even in neutral solution. The diprotonated anionic sensitizer 5,10,15,20-tetrakis(4-sulfonatophenyl) porphyrin (TPPSH22+) forms host-guest complexes with native beta CD and gamma CD, similarly as in its non-protonated state. The positive charge of pyrrole nitrogen atoms does not significantly influence the mode of the interaction. In contrast to TMPyP, the lifetimes of the triplet states of bound TPPSH22+ to native CDs increase.

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