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Despite extensive researches on manganites owing to widespread use in modern electronics, this class of metal oxides does not cease to surprise with its unique properties and new phenomena. Here we have studied structural and magnetic properties of non-Heisenberg manganite nanoparticles with a strong spin-electron coupling. During transition from low temperature ferromagnetic to high temperature paramagnetic state, the change in charge, valence and spin (magnetic moment) with the localization of eg-electrons on the manganese ions have been detected. With decrease in a temperature, the overstated effective magnetic moment of Mn ions in paramagnetic phase is reduced dramatically testifying to spin-dependent magnetism. The critical behavior of magnetization with determination of critical parameters near second-order phase transition has been studied comprehensively. Based on unusual behavior of temperature and field dependences of magnetic entropy change under different magnetic field, an additional influence of superparamagnetism of nanoparticles on the magnetocaloric effect has been found., Comment: Manuscript consists of 26 pages, 6 Figures. Supplementary Material consists of 37 pages, 11 Figures and 12 Tables