Encapsulate Porphyrin or Fullerene Derivatives in PMADQUAT/PSt-PAA Polyion Complex Aggregates for Enhanced Singlet Oxygen Yields

doi:10.7517/j.issn.1674-0475.2013.03.004

Abstract

Abstract: The polystyrene-poly(tert-butyl acrylate) (PSt-PtBuA) block copolymer was synthesized using atom transfer radical polymerization (ATRP) method, and the polystyrene-poly(acrylic acid) (PSt-PAA) was obtained by the hydrolysis of PSt-PtBuA under acidic condition. The copolymers are characterized with proton nuclear magnetic resonance (¹HNMR) and gel permeation chromatography (GPC). The polymer PSt-PAA can form aggregates in the buffer solution of Tris-HCl (pH=7.0), with the critical aggregation concentration (CAC) of 0.015 g/L. The polyion complex (PIC) aggregates can be formed between poly-2-[(methacryloyloxy)-ethyl]trimethylammonium chloride (PMADQUAT) and PSt-PAA through electrostatic interaction. When the weight ratio of PMADQUAT:PSt-PAA is 3:1, the CAC of aggregates becomes 0.005 g/L. Dynamic light scattering (DLS) and transmission electron microscope (TEM) results indicate that the particle diameters become smaller after forming PIC aggregates. The photosensitizers, such as diethyleneglycolmonomethylether modified fullerene (MDG-C₇₀), protoporphyrin (PPIX), zinc-meso-tetraphenylporphine (ZnTPP) and 5,10,15,20-tetraphenylporphin (TPP) can be encapsulated into the polymer aggregates, thereby enhancing their solubility in the buffer solution. Under irradiation, the yields of singlet oxygen of MDG-C₇₀, PPXI, ZnTPP and TPP in PIC aggregates are 1.64, 2.63, 2.60 and 2.20 times, respectively, compared with that in PSt-PAA aggregates. The singlet oxygen is not detected in the buffer solutions of these photosensitizers, due to the aggregation of photosensitizer. These results suggest that encapsulation of photosensitizer in PIC aggregates is one of the effective ways to enhance singlet oxygen yield of photosensitizer.

Key words: polyion complex aggregates, self-assembly, fullerene, porphyrin, singlet oxygen

CLC Number:

O647

LI Hai-xia, GAO Yun-yan, OU Zhi-ze, JIN He-lin, CAO Lu, CHEN Chen. Encapsulate Porphyrin or Fullerene Derivatives in PMADQUAT/PSt-PAA Polyion Complex Aggregates for Enhanced Singlet Oxygen Yields[J]. Imaging Science and Photochemistry, 2013, 31(3): 197-207.

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