A novel photosensitizer based on hypocrellin B activated by cysteine over-expressed in cancer cells.

L-Cysteine (Cys)-activatable photosensitizer 3 was designed and synthesized based on hypocrellin B (1). Cys is a novel tumor-associated biomarker. 3 exhibited negligible photosensitizing ability without Cys. However, when 1 was released from 3 by reaction with Cys, the photosensitizing activity was restored. Furthermore, 3 showed selective and effective photo-cytotoxicity against only cancer cells such as HeLa and A549 cells that highly express Cys when irradiated with 660 nm light, which is inside the phototherapeutic window.

Photo-induced glycosylation using the edible polyphenol curcumin.

Photo-induced glycosylations of trichloroacetimidate donors and alcohols using an edible polyphenol, curcumin, were examined under visible photo-irradiation (470 nm). It was found, for the first time, that these glycosylations proceed smoothly under mild reaction conditions to give the corresponding glycosides in high yields. In addition, the present glycosylation method was applicable to a wide range of trichloroacetimidate donors and alcohol acceptors and showed high chemoselectivity over glycosyl phosphite, phosphate, (N-phenyl)trifluoroacetimidate, fluoride, glycal and thioglycoside.

Designed Mannosylerythritol Lipid Analogues Exhibiting Both Selective Cytotoxicity Against Human Skin Cancer Cells and Recovery Effects on Damaged Skin Cells.

Mannosylerythritol lipids (MELs) are a class of amphipathic molecules bearing a hydrophilic 4-O-ß-D-mannopyranosyl-D-erythritol skeleton. Here, we designed and synthesized four kinds of MEL analogues R-MEL-A ([2R,3S]-erythritol type), S-mannosylthreitol lipid (MTL)-A ([2S,3S]-threitol type), R-MTL-A ([2R,3R]-threitol type), and α-S-MEL-A ([2S,3R]-erythritol type) using our previously reported boron-mediated aglycon delivery (BMAD) method and a neighboring group assisted glycosylation method. The selective cytotoxicity of the target compounds against cancer cells was evaluated, with R-MTL-A showing the highest selective cytotoxicity against human skin squamous carcinoma HSC-5 cells. Our findings suggest that R-MTL-A induces necrosis-like cell death against HSC-5 cells by decreasing cell membrane fluidity. R-MTL-A also exhibits an efficient recovery effect on damaged skin cells, indicating that R-MTL-A has potential as a lead compound for new cosmeceuticals with both cancer cell-selective toxicity and recovery effects on damaged skin cells.

Total Synthesis of Mannosylerythritol Lipids and Structure-Function Relationship Studies.

Mannosylerythritol lipid (MEL) has attracted much attention as an environmentally benign and biocompatible material in many research fields due to its significant biochemical and physiological properties. However, heterogeneity always exists in MEL obtained from microbial products with respect to the chain length of the fatty acids. In this context, the total synthesis of the 20 members of MEL was effectively and stereoselectively achieved using our boron-mediated aglycon delivery (BMAD) method. In addition, structure-function relationship (SFR) studies of antibacterial activity, self-assembling properties, and recovery effects on damaged skin cells have been conducted, and these results are introduced in this mini-review article.