TY - JOUR
T1 - Synthesis and characterization of highly photoresponsive fullerenyl dyads with a close chromophore antenna-C60 contact and effective photodynamic potential
AU - Chiang, Long Y.
AU - Padmawar, Prashant A.
AU - Rogers-Haley, Joy E.
AU - So, Grace
AU - Canteenwala, Taizoon
AU - Thota, Sammaiah
AU - Tan, Loon Seng
AU - Pritzker, Kenneth
AU - Huang, Ying Ying
AU - Sharma, Sulbha K.
AU - Kurup, Divya Balachandran
AU - Hamblin, Michael R.
AU - Wilson, Brian
AU - Urbas, Augustine
PY - 2010
Y1 - 2010
N2 - We report the synthesis of a new class of photoresponsive C 60-DCE-diphenylaminofluorene nanostructures and their intramolecular photoinduced energy and electron transfer phenomena. Structural modification was made by chemical conversion of the keto group in C60(>DPAF-C n) to a stronger electron-withdrawing 1,1-dicyanoethylenyl (DCE) unit leading to C60(>CPAF-Cn) with an increased electronic polarization of the molecule. The modification also led to a large bathochromic shift of the major band in visible spectrum giving measureable absorption up to 600 nm and extended the photoresponsive capability of C60-DCE-DPAF nanostructures to longer red wavelengths than C60(>DPAF-C n). Accordingly, C60(>CPAF-Cn) may allow 2γ-PDT using a light wavelength of 1000-1200 nm for enhanced tissue penetration depth. Production efficiency of singlet oxygen by closely related C60(>DPAF-C2M) was found to be comparable with that of tetraphenylporphyrin photosensitizer. Remarkably, the 1O2 quantum yield of C60(>CPAF-C2M) was found to be nearly 6-fold higher than that of C60(>DPAF-C2M), demonstrating the large light-harvesting enhancement of the CPAF-C2M moiety and leading to more efficient triplet state generation of the C 60> cage moiety. This led to highly effective killing of HeLa cells by C60(>CPAF-C2M) via photodynamic therapy (200 J cm-2 white light). We interpret the phenomena in terms of the contributions by the extended π-conjugation and stronger electron-withdrawing capability associated with the 1,1-dicyanoethylenyl group compared to that of the keto group.
AB - We report the synthesis of a new class of photoresponsive C 60-DCE-diphenylaminofluorene nanostructures and their intramolecular photoinduced energy and electron transfer phenomena. Structural modification was made by chemical conversion of the keto group in C60(>DPAF-C n) to a stronger electron-withdrawing 1,1-dicyanoethylenyl (DCE) unit leading to C60(>CPAF-Cn) with an increased electronic polarization of the molecule. The modification also led to a large bathochromic shift of the major band in visible spectrum giving measureable absorption up to 600 nm and extended the photoresponsive capability of C60-DCE-DPAF nanostructures to longer red wavelengths than C60(>DPAF-C n). Accordingly, C60(>CPAF-Cn) may allow 2γ-PDT using a light wavelength of 1000-1200 nm for enhanced tissue penetration depth. Production efficiency of singlet oxygen by closely related C60(>DPAF-C2M) was found to be comparable with that of tetraphenylporphyrin photosensitizer. Remarkably, the 1O2 quantum yield of C60(>CPAF-C2M) was found to be nearly 6-fold higher than that of C60(>DPAF-C2M), demonstrating the large light-harvesting enhancement of the CPAF-C2M moiety and leading to more efficient triplet state generation of the C 60> cage moiety. This led to highly effective killing of HeLa cells by C60(>CPAF-C2M) via photodynamic therapy (200 J cm-2 white light). We interpret the phenomena in terms of the contributions by the extended π-conjugation and stronger electron-withdrawing capability associated with the 1,1-dicyanoethylenyl group compared to that of the keto group.
UR - http://www.scopus.com/inward/record.url?scp=77953554467&partnerID=8YFLogxK
U2 - 10.1039/c0jm00037j
DO - 10.1039/c0jm00037j
M3 - Article
AN - SCOPUS:77953554467
SN - 0959-9428
VL - 20
SP - 5280
EP - 5293
JO - Journal of Materials Chemistry
JF - Journal of Materials Chemistry
IS - 25
ER -