Determination of Kinetic Characteristics of Dissociation of Complexes Meta-Tetra(Hydroxyphenyl)Chlorine and Dextran-Poly-N-Isopropylacryl-amide Copolymer by Fluorescence Spectroscopy

The ability of the thermosensitive copolymer dextran-poly-N-isopropylacrylamide (D-PNIPAM) to bind and release the photosensitizer (PS) meta-tetra(hydroxyphenyl)chlorin (mTHPC) was investigated using fluorescence spectroscopy techniques. It is shown that the efficiency of mTHPC molecules sorption by the copolymer depends on its phase state: mTHPC is efficiently adsorbed by D-PNIPAM (copolymer in globular conformation) at temperatures above 34–35 C, but PS is practically not adsorbed on D-PNIPAM (copolymer in coil conformation) at temperatures below 34–35 C. The presence of additional structural rearrangements in the globule of D-PNIPAM under the action of high temperatures (above 45°C) was shown by the method of dynamic light scattering. Comparing the mTHPC dissociation rates from complexes with DPNIPAM formed at 37-60 °C and calculating the mTHPC release rate constants from the polymer globule were performed. It is shown that the high temperature of complexation (45–60 C) of mTHPC with DPNIPAM leads to almost a twofold increase in the rate of PS molecules release from the copolymer globule at physiological temperatures, compared to similar complexes formed at 37–40°C. The time required for thermally induced structural rearrangements in D-PNIPAM has been estimated. The globule-coil transition in the D-PNIPAM molecule caused by temperature decrease below 34–35°C takes less than a minute, while the reversibility of conformational changes in the copolymer globule when the medium temperature rises above 45°C requires about 150 min. The obtained results suggest that thermo-dependent conformational rearrangements in the D-PNIPAM copolymer can be used to efficiently regulate the rate of PS release in cellular and tissue systems.

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