title: Synthesis, photophysical properties and sugar-dependent in vitro photocytotoxicity of pyrrolidine-fused chlorins bearing S-glycosides.
abstract: Eight S-glycosylated 5,10,15,20-tetrakis(tetrafluorophenyl)porphyrins (1a', 1b', 1a and 1b (a: S-glucosylated, b: S-galactosylated)) and their 1,3-dipolar cycloadducts, i.e. chlorins 2a', 2b', 2a and 2b were prepared by nucleophilic substitution of the pentafluorophenyl groups with S-glycoside. These photosensitizers were characterized by (1)H, (13)C and (19)F NMR spectroscopies and elemental analysis. The photocytotoxicity of the S-glycosylated photosensitizers and the parent porphyrin (1) and chlorin (2) was examined in HeLa cells. Photosensitizers 1, 2, 1a', 1b', 2a' and 2b' showed no significant photocytotoxicity at the concentration of 0.5microM, while the deprotected photosensitizers 1a, 1b, 2a and 2b were photocytotoxic. The strong inhibition by sodium azide of the photocytotoxicity of these photosensitizers suggested that (1)O(2) is the main mediator. The S-glucosylated photosensitizers 1a and 2a showed higher photocytotoxicity than S-galactosylated 1b and 2b, respectively. The cellular uptake of 1a and 2a increased up to 24h, while that of 1b and 2b was saturated by 12h.
authors.affiliation: Graduate School of Materials Science, Nara Institute of Science and Technology, Ikoma, Nara, Japan. hirohara@ms.naist.jp
authors.forename: Shiho
authors.initials: S
authors.lastname: Hirohara
authors.forename: Makoto
authors.initials: M
authors.lastname: Obata
authors.forename: Hiroki
authors.initials: H
authors.lastname: Alitomo
authors.forename: Kohei
authors.initials: K
authors.lastname: Sharyo
authors.forename: Tsuyoshi
authors.initials: T
authors.lastname: Ando
authors.forename: Masao
authors.initials: M
authors.lastname: Tanihara
authors.forename: Shigenobu
authors.initials: S
authors.lastname: Yano
mesh_terms: D002241:Carbohydrates / Q000737:chemistry*; D045744:Cell Line, Tumor; D006027:Glycosides / Q000138:chemical synthesis* / Q000378:metabolism / Q000633:toxicity; D006367:HeLa Cells; D006801:Humans; D008027:Light; D017319:Photosensitizing Agents / Q000138:chemical synthesis* / Q000378:metabolism / Q000633:toxicity; D011166:Porphyrins / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism / Q000633:toxicity; D011759:Pyrrolidines / Q000737:chemistry*; D017382:Reactive Oxygen Species / Q000378:metabolism; D013997:Time Factors
chemical_list: D002241:Carbohydrates; D006027:Glycosides; D017319:Photosensitizing Agents; D011166:Porphyrins; D011759:Pyrrolidines; D017382:Reactive Oxygen Species; C006969:chlorin; C032519:pyrrolidine