2018 (2) 2

Self-assambling nanocarriers for melanin delivery

N.M. Permyakova1, T.B. Zheltonozhskaya1, T.V. Beregova2, D.O. Klymchuk3, T. M. Falalyeyeva2

1Taras Shevchenko National University of Kyiv, Faculty of Chemistry, Department of Macromolecular Chemistry

60, Vladimirskaya str., Kyiv, 01033, Ukraine, permyakova@ukr.net

2Taras Shevchenko National University of Kyiv, ESC ”Institute of Biology”

2, Glushkova av, Kyiv, 03187, Ukraine

3M.G. Kholodny Institute of Botany NAS of Ukraine

2, Tereschenkovskaya str., Kyiv, 01601, Ukraine

Polym. J., 2018, 40, no. 2: 80-92

Section: Synthesis polymers.

Language: Ukrainian.

Abstract:

Micelles of asymmetric block copolymers based on poly(ethylene oxide) and poly(acrylic acid) have been used for encapsulation of the antiсancer drug eumelanin, which is the vital activity product of black yeast “Nadsoniella nigra sp. X-1. The detailed study of the chemical structure, solubility in water, electrochemical and absorption properties of this eumelanin sample was carried out using 1H NMR and FTIR spectroscopy and potentiometric titration. It is revealed the zwitter-ionic character of eumelanin macromolecules due to a presence the charged >NH2+ and -COO– groups in a solid EMel sample. So some excess (in 7 mol %) of secondary amine groups against carboxylic ones was determined. Acidic properties of both the groups were characterized. The values of pK0 were equaled to 4.44 and 9,27 for carboxylic and amine groups consequently. A strong compactization of eumelanin macromolecules in the pH>6 region, which is accompanied by a phase separation of the system, was established. Thus, it was shown that the state and solubility of melanin in aqueous medium is determined by a complex balance of electrostatic interactions and hydrogen bonds. The eumelanin encapsulation into micellar nanocarries and a state of the obtained drug/micelle systems, depending on the morphology and the size of nanocarriers, and also the method of encapsulation (ex situ or in situ) were studied by UV-Vis and FTIR spectroscopy. It was shown the essential influence a state of micellar systems, parameters of micellization process, sizes and morphology of micelles, nature and length of micellar “coronas” for  eumelanin connection. The actual state of the micellar system with encapsulated eumelanin was established by TEM. It was revealed that eumelanin could simultaneous interact with the surface of several micelles, which leads to changes in their size and morphology.

Key words: block copolymer, micelle, eumelanin, zwitter-ion, encapsulation.

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