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.
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(01):119127. |
[2] | Chelushkin PS;Lysenko EA;Bronich TK;Eisenberg A;Kabanov VA;Kabanov AV .Polyion complex nanomaterials from block polyelectrolyte micelles and linear polyelectrolytes of opposite charge. 2. Dynamic properties[J].The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical,2008(26):7732-7738. |
[3] | Park JS;Akiyama Y;Yamasaki Y;Kataoka K .Preparation and characterization of polyion complex micelles with a novel thermosensitive poly(2-isopropyl-2-oxazoline) shell via the complexation of oppositely charged block ionomers[J].Langmuir: The ACS Journal of Surfaces and Colloids,2007(26):138-146. |
[4] | Anraku, Y;Kishimura, A;Oba, M;Yamasaki, Y;Kataoka, K .Spontaneous Formation of Nanosized Unilamellar Polyion Complex Vesicles with Tunable Size and Properties[J].Journal of the American Chemical Society,2010(5):1631-1636. |
[5] | Ohya, Y.;Takeda, S.;Shibata, Y.;Ouchi, T.;Kano, A.;Iwata, T.;Mochizuki, S.;Taniwaki, Y.;Maruyama, A. .Evaluation of polyanion-coated biodegradable polymeric micelles as drug delivery vehicles[J].Journal of Controlled Release: Official Journal of the Controlled Release Society,2011(1):104-110. |
[6] | Weihang Ji;David Panus;R. Noelle Palumbo .Poly(2-aminoethyl methacrylate) with Well-Defined Chain Length for DNA Vaccine Delivery to Dendritic Cells[J].Biomacromolecules,2011(12):4373-4385. |
[7] | Atsushi Tamura;Motoi Oishi;Yukio Nagasaki .Enhanced Cytoplasmic Delivery of siRNA Using a Stabilized Polyion Complex Based on PEGylated Nanogels with a Cross-Linked Polyamine Structure[J].Biomacromolecules,2009(7):1818-1827. |
[8] | Zhang GD.;Harada A.;Nishiyama N.;Jiang DL.;Koyama H.;Aida T.;Kataoka K. .Polyion complex micelles entrapping cationic dendrimer porphyrin: effective photosensitizer for photodynamic therapy of cancer[J].Journal of Controlled Release: Official Journal of the Controlled Release Society,2003(2):141-150. |
[9] | Ideta R;Tasaka F;Jang WD;Nishiyama N;Zhang GD;Harada A;Yanagi Y;Tamaki Y;Aida T;Kataoka K .Nanotechnology-based photodynamic therapy for neovascular disease using a supramolecular nanocarrier loaded with a dendritic photosensitizer[J].Nano letters,2005(12):2426-2431. |
[10] | Niedermair, Fabian;Sandholzer, Martina;Kremser, Gabriele;Slugovc, Christian .Solution Self-Assembly and Photophysics of Platinum Complexes Containing Amphiphilic Triblock Random Copolymers Prepared by ROMP[J].Organometallics,2009(9):2888-2896. |
[11] | Wen-Chung Wu;Ching-Yi Chen;Yanqing Tian;Sei-Hum Jang;Yuning Hong;Yang Liu;Rongrong Hu;Ben Zhong Tang;Yi-Ting Lee;Chin-Ti Chen;Wen-Chang Chen;Alex K.-Y. Jen .Enhancement of Aggregation-Induced Emission in Dye-Encapsulating Polymeric Micelles for Bioimaging[J].Advanced functional materials,2010(9):1413-1423. |
[12] | Herlambang, S.;Kumagai, M.;Nomoto, T.;Horie, S.;Fukushima, S.;Oba, M.;Miyazaki, K.;Morimoto, Y.;Nishiyama, N.;Kataoka, K. .Disulfide crosslinked polyion complex micelles encapsulating dendrimer phthalocyanine directed to improved efficiency of photodynamic therapy[J].Journal of Controlled Release: Official Journal of the Controlled Release Society,2011(3):449-457. |
[13] | Tsai,H.-C.;Tsai,C.-H.;Lin,S.-Y.;Jhang,C.-R.;Chiang,Y.-S.;Hsiue,G.-H. .Stimulated release of photosensitizers from graft and diblock micelles for photodynamic therapy[J].Biomaterials,2012(6):1827-1837. |
[14] | Nishiyama N;Morimoto Y;Jang WD .Design and development of dendrimer photosensitizer-incorporated polymeric micelles for enhanced photodynamic therapy.[J].Advanced drug delivery reviews,2009(4):327-338. |
[15] | Duncan R .Polymer conjugates for tumour targeting and intracytoplasmic delivery.The EPR effect as a commongateway[J].Pharmaceutical Science & Technology Today,1999,2(11):441-449. |
[16] | Maeda H;Bharate GY;Daruwalla J .Polymeric drugs for efficient tumor-targeted drug delivery based on EPR-effect.[J].European journal of pharmaceutics and biopharmaceutics: official journal of Arbeitsgemeinschaft fuer Pharmazeutische Verfahrenstechnik e.V,2009(3):409-419. |
[17] | Jang WD;Nakagishi Y;Nishiyama N;Kawauchi S;Morimoto Y;Kikuchi M;Kataoka K .Polyion complex micelles for photodynamic therapy: Incorporation of dendritic photosensitizer excitable at long wavelength relevant to improved tissue-penetrating property[J].Journal of Controlled Release: Official Journal of the Controlled Release Society,2006(1):73-79. |
[18] | Raymond Bonnett .Photosensitizers of the Porphyrin and Phthalocyanine Series for Photodynamic Therapy[J].Chemical Society Reviews,1995(1):19-33. |
[19] | Henderson B W;Dougherty T J .How does photodynamic therapy work[J].Photochemistry and Photobiology,1992,55(01):145-157. |
[20] | Eiichi Nakamura;Hiroyuki Isobe .Functionalized Fullerenes in Water.The First 10 Years of Their Chemistry,Biology,and Nanoscience[J].Accounts of Chemical Research,2003(11):807-815. |
[21] | Arbogast J W;Foote C S .Chemistry of singlet oxygen.36.Singlet molecular oxygen (1△g) luminescence in solution following pulsed laser excitation.Solvent deuterium isotope effects on the lifetime of singlet oxygen[J].Journal of the American Chemical Society,1982,104(07):2069-2070. |
[22] | Vitaliy V. Khutoryanskiy;Piotr Kujawa;Zauresh S. Nurkeeva;Janusz M. Rosiak .Radiation Synthesis of Linear and Crosslinked Poly[2-(methacryloyloxy)ethyl]trimethylammonium Chloride and Complex Formation with Potassium Hexacyanoferrates (II, III) in Aqueous Solutions[J].Macromolecular chemistry and physics,2001(7):1089-1093. |
[23] | 高云燕,刘丽华,欧植泽,李嫕,杨国强,王雪松.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(02):495-501. |
[24] | Gao, Yunyan,Wang, Zhongli,Ou, Zhize,Li, Yi,Wang, Xuesong,Yang, Guoqiang.Regulation of Glucose Oxidase Activity through Interaction with Fullerene Derivatives[J].中国化学:英文版,2012(02):418-426. |
[25] | Zhang LF;Eisenberg A .MULTIPLE MORPHOLOGIES AND CHARACTERISTICS OF CREW-CUT MICELLE-LIKE AGGREGATES OF POLYSTYRENE-B-POLY(ACRYLIC ACID) DIBLOCK COPOLYMERS IN AQUEOUS SOLUTIONS[J].Journal of the American Chemical Society,1996(13):3168-3181. |
[26] | Hidetoshi Arimura;Yuichi Ohya;Tatsuro Ouchi .Formation of Core-Shell Type Biodegradable Polymeric Micelles from Amphiphilic Poly(aspartic acid)-block-Polylactide Diblock Copolymer[J].Biomacromolecules,2005(2):720-725. |
[27] | Dawei Zhang;Hao Zhang;Jun Nie .Synthesis and self-assembly behavior of pH-responsive amphiphilic copolymers containing ketal functional groups[J].Polymer international,2010(7):967-974. |
[28] | Miyamoto S.;Martinez GR.;Medeiros MHG.;Di Mascio P. .Singlet molecular oxygen generated from lipid hydroperoxides by the Russell mechanism: Studies using O-18-labeled linoleic acid hydroperoxide and monomol light emission measurements[J].Journal of the American Chemical Society,2003(20):6172-6179. |
[29] | Sayuri Miyamoto;Glaucia R. Martinez;Daniel Rettori;Ohara Augusto;Marisa H. G. Medeiros;Paolo Di Mascio .Linoleic acid hydroperoxide reacts with hypochlorous acid, generating peroxyl radical intermediates and singlet molecular oxygen[J].Proceedings of the National Academy of Sciences of the United States of America,2006(2):293-298. |
[30] | Yan Y;de Keizer A;Stuart MAC;Drechsler M;Besseling NAM .Stability of complex coacervate core micelles containing metal coordination polymer[J].The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical,2008(35):10908-10914. |
[31] | Ohya, Y.;Takeda, S.;Shibata, Y.;Ouchi, T.;Maruyama, A. .Preparation of highly stable biodegradable polymer micelles by coating with polyion complex[J].Macromolecular chemistry and physics,2010(16):1750-1756. |
[32] | Astafieva I;Zhong X F;Eisenberg A .Critical micellization phenomena in block polyelectrolyte solutions[J].Macromolecules,1993(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(05):1033-1040. |
[34] | Yang, H.;Hu, C.;Wu, X.;Chen, H.;Wang, J. .PH and salt effects on the aggregation behaviour of star polymer with G1 polyamidoamine core and terminal amphiphilic blocks[J].Supramolecular chemistry,2010(9/10):477-482. |
[35] | 谢洁,何慧珠.一种可生成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(03):212. |
[36] | Wang XS;Metanawin T;Zheng XY;Wang PY;Ali M;Vernon D .Structure-defined C-60/polymer colloids supramolecular nanocomposites in water[J].Langmuir: The ACS Journal of Surfaces and Colloids,2008(17):9230-9232. |
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