A new and simple approach to chemical complexity. Application to the synthesis of natural products.

A new approach to describe the complexity of chemical structures is proposed. This index is simple and can be easily programmed. It derives from Whitlock's index and, despite its empirical character, provides results paralleling those obtained with the mathematical Bertz index.

Formation of grignard reagents from aryl halides: effective radical probes hint at a nonparticipation of dianions in the mechanism.

We have prepared highly efficient radical probes 2a-b involving the hex-5-enyl rearrangement. The reaction of 2a-b with active magnesium leads to the cyclized products 4a-b, providing a direct evidence of radical intermediates during the formation of aryl Grignard reagents. The variations of yields for cyclized products 4a-b as a function of structural modifications in 2a-b suggest that the intervention of dianions is not necessary to explain the observed results.

Photodynamic activities of silicon phthalocyanines against achromic M6 melanoma cells and healthy human melanocytes and keratinocytes.

Dichlorosilicon phthalocyanine (Cl2SiPc) and bis(tri-n-hexylsiloxy) silicon phthalocyanine (HexSiPc) have been evaluated in vitro as potential photosensitizers for photodynamic therapy (PDT) against the human amelanotic melanoma cell line M6. Each photosensitizer is dissolved in a solvent-PBS mixture, or entrapped in egg-yolk lecithin liposomes or in Cremophor EL micelles. The cells are incubated for 1 h with the sensitizer and then irradiated for 20 min, 1 h or 2 h (lambda > 480 nm, 10 mW cm-2).

ESR studies of a series of phthalocyanines. Mechanism of phototoxicity. Comparative quantitation of O2-. using ESR spin-trapping and cytochrome c reduction techniques.

ESR experiments with 2,2,6,6-tetramethyl-4-piperidone (4-oxo-TEMP) and the spin-trap 5,5-dimethyl pyrroline-N-oxide (DMPO) have been performed on a series of new phthalocyanines: the bis(tri-n-hexylsiloxy) silicon phthalocyanine ([(nhex)3SiO]2SiPc), the hexadecachloro zinc phthalocyanine (ZnPcCl16), the hexadecachloro aluminum phthalocyanine (AlPcCl16), the hexadecachloro aluminum phthalocyanine sulfate (HSO4AlPcCl16), whose photocytotoxicity has been studied against various leukemic and melanotic cell lines. Type I and Type II pathways occur simultaneously in DMF although the Type II seems to be prevalent. These results are not changed when the bis(tri-n-hexylsiloxy) silicon phthalocyanine is entrapped into liposomes.

Preferential photoinactivation of leukemia cells by aluminum phthalocyanine.

The efficacy of chloroaluminum phthalocyanine (AlPc) for photodynamic therapy (PDT) has been evaluated in vitro on acute myeloid leukemia (AML) cells, normal peripheral blood leukocytes (PBL) and mobilized peripheral blood stem cells (mPBSC). The selectivity of the treatment has been evaluated by mixing PBL and TF-1, an erythroleukemic cell line. Upon photoradiation, this photosensitizer leads to a significant and preferential photokilling of leukemia cells in comparison to normal cells.