S,S-Chiral Linker Induced U Shape with a Syn-facial Sensitizer and Photocleavable Ethene Group

GHOSH, GOUTAM; BELH, SARAH J.; CHIEMEZIE, CALLISTUS; WALALAWELA, NILUKSHA; GHOGARE, ASHWINI A.; VIGNONI, MARIANA; THOMAS, ANDRÉS H.; MCFARLAND, SHERRI A.; GREER, EDYTA M.; GREER, ALEXANDER

PHOTOCHEMISTRY AND PHOTOBIOLOGY

WILEY-BLACKWELL PUBLISHING, INC

Año: 2019 vol. 95 p. 293 - 305

0031-8655

There is a major need for light-activated materials for the release of sensitizers and drugs. Considering the success of chiral columns for the separation of enantiomer drugs, we synthesized an S,S-chiral linker system covalently attached to silica with a sensitizer ethene near the silica surface. First, the silica surface was modified to be aromatic rich, by replacing 70% of the surface groups with (3-phenoxypropyl)silane. We then synthesized a 3-component conjugate [chlorin sensitizer, S,S-chiral cyclohexane and ethene building blocks] in 5 steps with a 13% yield, and covalently bound the conjugate to the (3-phenoxypropyl)silane-coated silica surface. We hypothesized that the chiral linker would increase exposure of the ethene site for enhanced 1O2-based sensitizer release. However, the chiral linker caused the sensitizer conjugate to adopt a U shape due to favored 1,2-diaxial substituent orientation; resulting in a reduced efficiency of surface loading. Further accentuating the U shape was π?π stacking between the (3-phenoxypropyl)silane and sensitizer. Semiempirical calculations and singlet oxygen luminescence data provided deeper insight into the sensitizer´s orientation and release. This study has lead to insight on modifications of surfaces for drug photorelease and can help lead to the development of miniaturized photodynamic devices.