N.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Kosygina St. 4, 119991 Moscow, Russia.
Institute for Regenerative Medicine, Sechenov University, Trubetskaya St. 8-2, 119991 Moscow, Russia.
Molecules. 2022 Oct 11;27(20):6796. doi: 10.3390/molecules27206796.
The influence of chitosan (CS) and amphiphilic polymers (AP: pluronic F108 and polyvinylpyrrolidone (PVP)) on the photocatalytic activity of rose bengal (RB) in a model reaction of tryptophan photo-oxidation in phosphate-buffered saline (PBS) was studied. It was shown that in the presence of CS, the effective rate constant of tryptophan photo-oxidation catalyzed by RB in PBS solution decreases by a factor of two. This is due to the ionic interaction of the RB with the chitosan. Rose bengal in a slightly acidic environment (pH 4.5) passes into a neutral lactone form, which sharply reduces the photosensitizing properties of the dye. It was demonstrated that the introduction of AP into a solution containing RB and CS prevents direct interaction between RB and CS. This is evidenced by the presence of photocatalytic activity of the dye in the RB-AP-CS systems, as well as bathochromic shifts of the main absorption bands of the dye, and an increase in the optical density and luminescence intensity of the RB when AP is introduced into a buffer solution containing RB and chitosan. The presence of RB-CS and RB-AP interaction in aqueous and PBS media is confirmed by the increase in the degree of fluorescence anisotropy () of these binary systems. In an aqueous solution, the value of for the RB-F108-CS system decreases by a factor of 3.5 (compared to the value of for the RB-CS system), which is associated with the localization of the dye in pluronic micelles. In PBS, the fluorescence anisotropy is practically the same for all systems, which is related to the stability of the dye structure in this medium. The presence of interaction between RB and AP in aqueous solutions was confirmed by the proton NMR method. In addition, the formation of RB-F108 macromolecular complexes, which form associates during solution concentration (in particular, during evaporation), was shown by AFM. Such RB-AP-CS systems may be promising for practical application in the treatment of local foci of infections by aPDT.
壳聚糖 (CS) 和两亲聚合物 (AP:泊洛沙姆 F108 和聚乙烯吡咯烷酮 (PVP)) 对吖啶黄 (RB) 在磷酸盐缓冲盐水 (PBS) 中色氨酸光氧化模型反应中的光催化活性的影响进行了研究。结果表明,在 CS 的存在下,RB 在 PBS 溶液中催化色氨酸光氧化的有效速率常数降低了一倍。这是由于 RB 与壳聚糖的离子相互作用。在微酸性环境 (pH 4.5) 中,吖啶黄转化为中性内酯形式,这大大降低了染料的光敏性质。研究表明,将 AP 引入含有 RB 和 CS 的溶液中可以防止 RB 和 CS 之间的直接相互作用。这可以通过在 RB-AP-CS 体系中存在染料的光催化活性以及染料的主要吸收带的红移,以及在向含有 RB 和壳聚糖的缓冲溶液中引入 AP 时染料的光密度和发光强度的增加来证明。在水相和 PBS 介质中,RB-CS 和 RB-AP 相互作用的存在通过这些二元体系的荧光各向异性度 () 的增加得到证实。在水溶液中,与 RB-CS 体系的 值相比,RB-F108-CS 体系的值降低了 3.5 倍(与 RB-CS 体系的 值相比),这与染料在普朗尼克胶束中的定位有关。在 PBS 中,所有体系的荧光各向异性几乎相同,这与染料在该介质中的结构稳定性有关。通过质子 NMR 法证实了 RB 和 AP 在水溶液中存在相互作用。此外,通过 AFM 显示了 RB-F108 大分子复合物的形成,这些复合物在溶液浓缩(特别是在蒸发过程中)期间形成缔合物。这些 RB-AP-CS 体系在局部感染病灶的 aPDT 治疗中可能具有应用前景。