PMADQUAT/PSt-PAA聚离子复合物聚集体增强卟啉和富勒烯类衍生物单重态氧产率

doi:10.7517/j.issn.1674-0475.2013.03.004

摘要/Abstract

摘要： 采用原子转移自由基聚合(ATRP)法合成了嵌段共聚物聚苯乙烯-聚丙烯酸叔丁酯(PSt-PtBuA), 在酸性条件下水解得到聚苯乙烯-聚丙烯酸(PSt-PAA), 利用核磁共振氢谱(¹HNMR)、凝胶渗透色谱(GPC)等对产物进行了表征. PSt-PAA在Tris-HCl缓冲溶液中(pH=7.0)形成临界聚集浓度(CAC)为0.015 g/L的聚集体. PSt-PAA与聚2-甲基丙烯酰氧基乙基三甲基氯化铵(PMADQUAT)可通过静电相互作用形成聚离子复合物(polyion complex, PIC), 当 m_(PMADQUAT)/m_(PSt-PAA)=3时, 形成的聚离子复合物的CAC为0.005 g/L. 动态光散射(DLS)和透射电镜(TEM)结果表明, 形成聚离子复合物后, 聚集体粒径变小. 聚合物形成聚集体可包载二乙二醇单甲醚修饰的C₇₀(MDG-C₇₀)、原卟啉(PPIX)、四苯基锌卟啉(ZnTPP)和四苯基卟啉(TPP)等光敏剂, 并增强光敏剂在缓冲溶液中的溶解度. 光照条件下, MDG-C₇₀、PPIX、ZnTPP和TPP在聚离子复合物聚集体m_(PMADQUAT)/m_(PSt-PAA)=3的溶液中的单重态氧量子产率分别是在PSt-PAA聚集体溶液中的1.64、2.63、2.60和2.20倍. 而在缓冲溶液中,由于光敏剂的聚集作用,未能检测到单重态氧的产生。研究结果表明,聚离子复合物聚集体能够包载光敏剂,是提高单重态氧产率的一个有效途径.

关键词: 聚离子复合物聚集体, 自组装, 富勒烯, 卟啉, 单重态氧

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

中图分类号:

O647

李海霞, 高云燕, 欧植泽, 金和林, 曹璐, 陈晨. PMADQUAT/PSt-PAA聚离子复合物聚集体增强卟啉和富勒烯类衍生物单重态氧产率[J]. 影像科学与光化学, 2013, 31(3): 197-207.

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.

参考文献

[1] Matsumoto S, Christie R J, Nishiyama N, et al. Enviroment-responsive block copolymer micelles with a disulfide cross-linked core for enhanced siRNA delivery[J]. Biomacromolecules, 2009, 10(1): 119-127.
[2] Chelushkin P S, Lysenko E A, Bronich Y K, et al. Polyion complex nanomaterials from block polyelectrolyte micelles and linear polyelectrolytes of opposite charge. 2. dynamic properties[J]. J. Phys. Chem. B, 2008, 112(26): 7732-7738.
[3] Park J S, Akiyama Y, Yamasaki Y, et al. Preparation and characterization of polyion complex micelles with a novel thermosensitive poly(2-isopropyl-2-oxazoline) shell via the complexation of oppositely charged block lonomers[J]. Langmuir, 2007, 23(1): 138-146.
[4] Anraku Y, Kishimura A, Oba M, et al. Spontaneous formation of nanosized unilamellar polyion complex vesicles with tunable size and properties[J]. J. Am. Chem. Soc., 2010, 132(5): 1631-1636.
[5] Ohya Y, Takeda S, Shibata Y, et al. Evaluation of polyanion-coated biodegradable polymeric micelles as drug delivery vehicles[J]. J. Contr. Release, 2011, 155(1): 104-110.
[6] Ji W H, Panus D, Palumbo R N, et al. Poly(2-aminoethyl methacrylate) with well-defined chain length for DNA vaccine delivery to dendritic cells[J]. Biomacromolecules, 2011, 12(12): 4373-4385.
[7] Tamura A, Oishi M, Nagasaki Y. Enhanced cytoplasmic delivery of siRNA using a stabilized polyion complex based on PEGylated nanogels with a cross-linked polyamine structure[J]. Biomacromolecules, 2009, 10(7): 1818-1827.
[8] Zhang G D, Harada A, Nishiyama N, et al. Polyion complex micelles entrapping cationic dendrimer porphyrin: effective photosensitizer for photodynamic therapy of cancer[J]. J. Contr. Release, 2003, 93(2): 141-150.
[9] Ideta R, Tasaka F, Jang W D, et al. Nanotechnology-based photodynamic therapy for neovascular disease using a supramolecular nanocarrier loaded with a dendritic photosensitizer[J]. Nano Lett., 2005, 5(12): 2426-2431.
[10] Niedermair F, Sandholzer M, Kremser G, et al. Solution self-assembly and photophysics of platinum complexes containing amphiphilic triblock random copolymers prepared by ROMP[J]. Organometallics, 2009,28(9): 2888-2896.
[11] Wu W C, Chen C Y, Tian Y Q, et al. Enhancement of aggregation-induced emission in dye-encapsulating polymeric micelles for bioimaging[J]. Adv. Funct. Mater., 2010, 20(9): 1413-1423.
[12] Herlambang S, Kumagai M, Nomoto Y, et al. Disulfide crosslinked polyion complex micelles encapsulating dendrimer phthalocyanine directed to improved efficiency of photodynamic therapy. J. Contr. Release, 2011, 155(3): 449-457.
[13] Tsai H C, Tsai C H, Lin S Y, et al. Stimulated release of photosensitizers from graft and diblock micelles for photodynamic therapy[J]. Biomaterials, 2012, 33(6): 1827-1837.
[14] Nishiyama N, Morimoto Y, Jang W D, et al. Design and development of dendrimer photosensitizer-incorpora-ted polymeric micelles for enhanced photodynamictherapy[J]. Adv. Drug Del. Rev., 2009, 61(4): 327-338.
[15] Duncan R. Polymer conjugates for tumour targeting and intracytoplasmic delivery. The EPR effect as a common gateway[J]. Pharm. Sci. Technol. Today, 1999, 2(11): 441-449.
[16] Maeda H, Bharate G Y, Daruwalla J. Polymeric drugs for efficient tumor-targeted drug delivery based on EPR-effect[J].Eur. J. Pharm. Biopharm., 2009, 71(3): 409-419.
[17] Jang W D, Nakagishi Y, Nishiyama N, et al. Polyioncomplexmicelles for photodynamictherapy: incorporation of dendritic photosensitizer excitable at long wavelength relevant to improved tissue-penetrating property[J]. J. Contr. Release, 2006, 113(1): 73-79.
[18] Bonnett R. Photosensitizers of the porphyrin and phthalocyanine series for photodynamic therapy[J]. Chem. Soc. Rev., 1995, 24(1): 19-33.
[19] Henderson B W, Dougherty T J. How does photodynamic therapy work[J]. Photochem. Photobiol., 1992, 55(1): 145-157.
[20] Nakamura E, Isobe H. Functionalized fullerenes in water. The first 10 years of their chemistry, biology, and nanoscience[J].Acc. Chem. Res., 2003, 36(11): 807-815.
[21] Arbogast J W, Foote C S. Chemistry of singlet oxygen. 36. Singlet molecular oxygen (¹Δg) luminescence in solution following pulsed laser excitation. Solvent deuterium isotope effects on the lifetime of singlet oxygen[J]. J. Am. Chem. Soc., 1982, 104(7): 2069-2070.
[22] Khutoryanskiy V V, Kujawa P, Nurkeeva Z S, et al. Radiation synthesis of linear and crosslinked polytrimethylammonium chloride and complex formation with potassium hexacyanoferrates (II, III) in aqueous solutions[J]. Macromol. Chem. Phys., 2001, 202(7): 1089-1093.
[23] 高云燕, 刘丽华, 欧植泽, 等. 胆固醇修饰富勒烯/γ-环糊精包结复合物的生物活性[J]. 物理化学学报, 2010, 26(2): 495-501. Gao Y Y, Liu L H, Ou Z Z, et al. Biological activity of a cholesterol modified fullerene γ-cyclodextrin inclusion complex[J]. Acta Phys. Chim. Sin., 2010, 26(2): 495-501.
[24] Gao Y Y, Wang Z L, Ou Z Z, et al. Regulation of glucose oxidase activity through interaction with fullerene derivatives[J]. Chin. J. Chem., 2012, 30(2): 418-426.
[25] Zhang L F, Eisenberg A. Multiple morphologies and characteristics of "Crew-Cut" micelle-like aggregates of polystyrene-b-poly(acrylic acid) diblock copolymers in aqueous solutions[J]. J. Am. Chem. Soc., 1996, 118(13): 3168-3181.
[26] Arimura H, Ohya Y, Ouchi T, et al. Formation of core-shell type biodegradable polymeric micelles from amphiphilic poly(aspartic acid)-block-polylactide diblock copolymer[J].Biomacromolecules, 2005, 6(2): 720-725.
[27] Zhang D W, Zhang H, Nie J, et al. Synthesis and self-assembly behavior of pH-responsive amphiphilic copolymers containing ketal functional groups[J]. Polym. Int., 2010, 59(7): 967-974.
[28] Miyamoto S, Martinez G R, Medeiros M G, et al. Singlet molecular oxygen generated from lipid hydroperoxides by the russell mechanism: studies using ¹⁸O-labeled linoleic acid hydroperoxide and monomol light emission measurements[J]. J. Am. Chem. Soc., 2003, 125(20): 6172-6179.
[29] Miyamoto S, Martinez G R, Rettori D, et al. Linoleic acid hydroperoxide reacts with hypochlorous acid, generating peroxyl radical intermediates and singlet molecular oxygen[J]. Proc. Nat. Acad. Sci. USA, 2006, 103(2): 293-298.
[30] Yan Y, Keizer A, Stuart M C, et al. Stability of complex coacervate core micelles containing metal coordination polymer[J]. J. Phys. Chem. B, 2008, 112(35): 10908-10914.
[31] Ohya Y, Takeda S, Shibata Y, et al. Preparation of highly stable biodegradable polymer micelles by coating with polyion complex[J]. Macromol. Chem. Phys., 2010, 211(16): 1750-1756.
[32] Astafieva I, Zhong X F, Eisenberg A. Critical micellization phenomena in block polyelectrolyte solutions[J]. Macromolecule, 1993, 26(26): 7339-7352.
[33] Wilhelm M, Zhao C L, Wang Y C, et al. Poly(styrene-ethylene oxide) block copolymer micelle formation in water: a fluorescence probe study[J]. Macromolecules, 1991, 24(5): 1033-1040.
[34] Yang H, Hu C C, Wu X, Chen H B, et al. pH and salt effects on the aggregation behavior of star polymer with G1 polyamidoamine core and terminal amphiphilic blocks[J]. Supramol. Chem., 2010, 22(9): 477-482.
[35] 谢洁, 何慧珠. 一种可生产单重态氧的新型光敏剂-类卟啉大环金属配合物[J]. 感光科学与光化学, 1996, 14(3): 212-217. Xie J, He H Z. New photosensitizers for efficient production of singlet oxygen-porphyrin-like macrocycle metal complexes[J]. Photographic Science and Photochemistry, 1996, 14(3): 212-217.
[36] Wang X S, Metanawin T, Zheng X Y, et al.Structure-defined C60/polymer colloids supramolecular nanocomposites in water [J]. Langmuir, 2008, 24(17): 9230-9232.