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Fluorescence Study of Nanoparticles Formed by Diblock Copolymer

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Title: Fluorescence Study of Nanoparticles Formed by Diblock Copolymer
Author(s): Chou, Hao-Wei
Contributor: University of Helsinki, Faculty of Science, none
Discipline: none
Degree program: Master's Programme in Chemistry and Molecular Sciences
Specialisation: Polymer Materials Chemistry
Language: English
Acceptance year: 2019
Diblock copolymers, poly(lactide)-block-poly(2-isopropyl-2-oxazoline) (PiPOx-b-PLA) and n-octadecyl poly(2-isopropyl-2-oxazoline) (PiPOx-C18), were characterized using the steady-state fluorescence with two fluorescence probes, pyrene and (1,6-diphenyl-l,3,4-hexatriene) (DPH), to investigate the core structure of the particles formed by the polymers. The two enantiomers of PiPOx-b-PLA, which are PiPOx-PLLA and PiPOx-PDLLA, reflected very different features in terms of polarity of the micellar core and the partitioning equilibrium constants of pyrene (Kv). This suggests that the core of the particles formed by PiPOx-PDLLA has higher polarity due to high water content in the range of the polymer concentrations from 0.03 g/L to 3 g/L, and more pyrene molecules are bound to the particles. Furthermore, the core of the particles formed by PiPOx-PDLLA reveals rigidity lower than that of PiPOx-PLLA, which is supported by the low anisotropy value (r) of DPH. r did not change upon heating from 15 ⁰C to 65 ⁰C for the PiPOx-PLLA particles. A slight decrease of r occurred above 50 ⁰C for the PiPOx-PDLLA particle. The PiPOx-C18 micelles exhibit higher critical micellar concentration (CMC), smaller Kv, and softer core in comparison to the PiPOx-b-PLA micelles. These differences owe to the nature of the alkyl chain end. Loading and release of a hydrophobic drug, curcumin, to/from the PiPOx-PLLA and PiPOx-PDLLA micelles were investigated by means of the steady-state fluorescence. The release test was conducted using the dialysis bag method. The PiPOx-PDLLA particles encapsulated more curcumin with encapsulation efficiency (EE) value being 98% while the curcumin-to-polymer ratio was 1:20. Curcumin intake of the PiPOx-PLLA particles was lower under the same condition (EE = 56%). The PiPOx-PDLLA particles show excellent ability of trapping curcumin. PiPOx-PDLLA bear 70% of curcumin inside the dialysis bag after 50 h, whereas 40% of curcumin was discharged from dispersions of PiPOx-PLLA. Precipitation of curcumin was observed in presence of PiPOx-PLLA in 4 days. No curcumin precipitating from the PiPOx-PDLLA dispersion occurred and a decrease in the intensity of curcumin owed to the degradation of curcumin. Finally, all the phenomena observed are well illustrated by the hypothesis of the morphology of the particles formed by PiPOx-PLLA and PiPOx-PDLLA. The particle formed by PiPOx-PDLLA consists of a loose hydrophobic core with hydrated tails extending to the aqueous phase, whereas the core of PiPOx-PLLA particle is dense.

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