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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (06): 731-738. 上一篇    下一篇

研究论文

负载芳基苄醚树枝形酞菁锌聚合物纳米粒子的合成及其离体光动力活性

阙寿林1，彭亦如*,1，张宏1，陈莉莉1，黄丽珊1，刘建生1，陈奎治1，吴松一2   

  1. (1福建师范大学化学与材料学院 福建省高分子材料重点实验室 福州 350007)
    (2福建医科大学附属第一医院 福州 350005)
  • 投稿日期:2010-06-11 修回日期:2010-10-14 发布日期:2010-11-15
  • 通讯作者: 彭亦如 E-mail:yirupeng@fjnu.edu.cn
  • 基金资助:

    国家自然科学基金项目;卫生部科学研究基金;福建省科技厅重点项目;福建省自然科学基金

Synthesis and Characterization of Polyion Complex Micelle Loaded with Zinc(II) Phthalocyanine Bearing Poly(aryl benzyl ether) Dendrimer

Que Shoulin1 Peng Yiru*,1 Zhang Hong1 Chen Lili1 Huang Lishan1 Liu Jiansheng1 Chen Kuizhi1 Wu Songyi2   

  1. (1 College of Chemistry and Materials Science, Fujian Normal University, Fujian Provincial Key Laboratory of Polymer Materials, Fuzhou 350007)
    (2 The Affiliated First Hospital of Fujian Medical University, Fuzhou 350005)
  • Received:2010-06-11 Revised:2010-10-14 Published:2010-11-15
  • Contact: Yi-Ru PENG E-mail:yirupeng@fjnu.edu.cn

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首先将对氰基溴化苄与3,5-二羟基苯甲醇通过Frétchet反应合成芳基苄醚树枝分子3,5-[二-(4 -氰基苯甲氧基)]苯甲醇(1), 1与4-硝基邻苯二甲腈合成前驱物4-{3 ,5 -[二-(4 -氰基苯甲氧基)]}苯甲氧基邻苯二甲腈(3), 然后3在乙酸锌, 1,8-二氮杂二环(5,4,0)-7-十一烯(DBU)和正戊醇存在下合成以氰基为端基的芳基苄醚树形酞菁锌配合物四-{3,5-[二- (4 -氰基苯甲氧基)-苯甲氧基]}锌酞菁(4), 最后4在氢氧化钠中水解制备以羧基为端基的芳基苄醚树形酞菁锌四-{3,5-[二- (4 -羧基苯甲氧基)-苯甲氧基]}锌酞菁(5). 采用元素分析、IR, 1H NMR, ESI-MS和MALDI-TOF-MS对上述化合物的结构进行了表征. 带有负电荷的5与两嵌段共聚物聚乙二醇单甲醚-聚L-赖氨酸(PEG-b-PLL) (6)通过静电作用自组装成负载5的聚合物纳米粒子(5/m). AFM和TEM表明5/m为直径约为100 nm的核壳结构纳米粒子. 通过紫外光谱和荧光光谱法研究了5和5/m的光物理性质: 5包裹入聚合物胶束后, 5/m的Q带最大吸收峰强度增加, 位置红移, 荧光强度增加, 荧光寿命减少. 不同孵育时间HUVEC细胞(人体静脉内皮细胞)的5和5/m的药代动力学和MTT法研究表明: 与自由酞菁5相比, 5/m摄取率增加, 提前1 h达到最大浓度而且细胞抑制率也大大增加.

关键词: 芳基苄醚树枝酞菁锌, 聚乙二醇单甲醚-聚L-赖氨酸, 聚合物纳米粒子, 静电自组装, 合成, 表征

3,5-Di-(4 -cyanobenzyloxy)benzyl alcohol (1) was synthesized by reaction of 3,5-di-hydroxybenzyl alcohol with 4-cyanobenzyl bromide. 4-(3 ,5 -hydroxybenzyloxy)phthalonitrile (3) was obtained by reacation of 1 with 4-nitrophthalonitrile in DMF. Tetra-[3,5-di-(4 -cyanobenzyloxy)benzyloxy] zinc(II) phthalocyanine (4) was obtained by condensation of 3 in the presence of n-pentanol, acetate zinc(II) and DBU. The corresponding hydrophilic complexes tetra-[3,5-di-(4 -carboxylicbenzyloxy)benzyloxy] zinc phthalocyanine (5) was obtained by hydrolyzation of 4 in NaOH. The structures of above compounds were characterized by elemental analysis, IR, 1H NMR, ESI-MS, MALDI-TOF-MS, and UV/Vis. A polyion complex micelle system 5/m, which was formed via an electronic interaction of anionic dendrimer phthalocyanine 5 and positively poly(L-lysine) segment of poly(ethylene glycol)-poly(L-lysine) block copolymer (PEG-b-PLL). The morphology and photophysical properties of 5/m was investigated by AFM, TEM, UV/Vis and fluorescence spectroscopy methods. The 5/m formed a core-shell-type nanoparticle with diameter ca.100 nm. Electrostatic assembly of 5/m resulted in a red-shif and higher intensity of the Q band, fluorescence intensity and singlet excited life compared with free 5. The time-dependence uptake amount of 5 and 5/m in HUVEC (human umbilical vein endothelial cell) cells showed that the uptake amount of 5/m was significantly increased and reached peak value by ahead of 1 h compared with 5. The in vitro photodynamic therapy efficiency of 5 and 5/m were evaluated by MTT method, and the results indicated that the photodynamic therapy efficacy of 5/m was enhanced when the polymeric nanoparticles was loaded with dendritic phthalocyanine 5.

Key words: poly(aryl benzyl ether)dendritic phthalocyanine, polyion complex micelle, poly(ethylene glycol)-poly(L-lysine), synthesis, characterization