Improved Stability and Photodynamic Activity of Water‐Soluble 5,15‐Diazaporphyrins Incorporated in β‐(1,3‐1,6)‐d‐Glucan with On‐Off Switch

Abstract

5,15-Diazaporphyrins, which have al arge absorption at wavelengths over 600 nm, were dissolved in water by complexf ormation with b-(1,3-1,6)-d-glucans. Aqueous solutions of these complexes were relativelys table compared with their trimethyl-b-cyclodextrin-complexed analogues. b-Glucan-complexed diazaporphyrins showed quenched fluorescencea nd had low singlet-oxygen-genera-tion abilities owing to random self-aggregation.H owever, external stimuli, such as the presenceo fl iposomes or intracellularu ptake, restored the fluorescence and singletoxygen-generation abilities of b-glucan-complexed diazaporphyrins. Consequently, b-glucan-complexed diazaporphyrins showedv ery high photodynamic activities toward HeLa cells.

Water Solubilization and Thermal Stimuli-Triggered Release of Porphyrin Derivatives Using Thermoresponsive Polysaccharide Hydroxypropyl Cellulose for Mitochondria-Targeted Photodynamic Therapy

“…Here, we have developed mechanochemical HSVM techniques using oligo-and polysaccharides for water solubilization. 27 HSVM techniques enable the solubilization of hydrophobic compounds, including fullerenes, 28 porphyrins, 29 and chlorines 15 in water. In addition, the hydrophobic compounds complexed with oligosaccharides and polysaccharides exhibit excellent photochemical properties in water for bioimaging and photodynamic activities against cancer cells.…”

Solubilization of Tetrahydroxyphenylchlorin in Water and Improved Photodynamic Activity after Complexation with Cyclic Oligo- and Polysaccharides

“…Porphyrin derivative complexes with aryl groups in the meso position can be easily obtained using TMeβCD or β-1,3 glucan via mechanochemical high-speed vibration milling (HSVM) without polar organic solvents. [9][10][11][12]21 The photodynamic activities of complexes prepared with aniline-and phenol-substituted porphyrin derivatives are much higher than that of tetraphenylporphyrin (3, Figure 1) due to more efficient intracellular uptake of the complexes by tumor cells. 9,11 This indicates the presence of phenol receptors on HeLa cells.…”

Mechanism toward Turn‐on of Polysaccharide‐Porphyrin Complexes for Fluorescence Probes and Photosensitizers in Photodynamic Therapy in Living Cells

“…Water‐soluble polysaccharides improve the solubility of hydrophobic guest molecules in water by forming cyclodextrin‐like complexes. Polysaccharide‐containing complexes are more effective than their cyclodextrin counterparts, as they can accommodate larger guest molecules such as polyaniline, [4] polythiophene, [5] fullerenes, [6–8] carbon nanotubes, [9–11] and porphyrins [12–14] . These complexes are typically formed via hydrophobic interactions.…”

“…Polysaccharide-containing complexes are more effective than their cyclodextrin counterparts, as they can accommodate larger guest molecules such as polyaniline, [4] polythiophene, [5] fullerenes, [6][7][8] carbon nanotubes, [9][10][11] and porphyrins. [12][13][14] These complexes are typically formed via hydrophobic interactions. Additionally, they provide notable medicinal benefits attributed to the interactions between the polysaccharides and the guest molecules.…”