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C60吡咯烷羧酸衍生物的合成及其在水溶液中的聚集行为
  • ISSN号:0567-7351
  • 期刊名称:《化学学报》
  • 时间:0
  • 分类:O635.1[理学—高分子化学;理学—化学]
  • 作者机构:[1]华中科技大学化学系,武汉430074, [2]湖北大学化学化工学院,武汉430062
  • 相关基金:国家自然科学基金(No.20474020)资助项目.
中文摘要:

C60与亚氨基二乙酸甲酯[NH(CH2COOMe)2]的光化学反应制得2,5-双(甲氧羰基)富勒烯吡咯烷(1),产率为52%(基于已反应的C60).C60吡咯烷衍生物1与氯乙酸甲酯(C1CH2COOCH3)的N-烃基化反应,在微波辐射、无溶剂及相转移条件下,得到2,5-双(甲氧羰基)-N-(甲氧羰基)甲基富勒烯吡咯烷(2),产率47%(基于C60吡咯烷衍生物1).C60吡咯烷衍生物1和2用NaH,CH30H水解后,经盐酸酸化得相应的二羧酸衍生物3和三羧酸衍生物4,产率分别为65%和53%(基于C60吡咯烷衍生物1和2)、C60吡咯烷衍生物1~4的结构由^1HNMR,^13CNMR,IR,FAB—MS和元素分析证实.用电导法测定了C60吡咯烷二羧酸3和三羧酸4钠盐的临界聚集浓度(CAC),分别为3.58×10^-4mol/L(3)和3.33×10^-4mol/L(4).这一结果被C60吡咯烷衍生物3和4,在临界聚集浓度(CAC)附近的UV—Vis光谱的特征变化所支持.透射电子显微镜(TEM)和静态光散射(SLS)等方法也被用于检测C60吡咯烷衍生物3和4在临界聚集浓度(CAC)时的聚集行为,结果显示,C60吡咯烷衍生物3在缓冲溶液中(0.001 mol/LNaCO3-NaHCO3),其聚集体粒径的大小(Rg≈21 nm)不同于C60吡咯烷衍生物4(Rg≈23nm).C60吡咯烷二羧酸3钠盐的临界聚集浓度(CAC)比C60吡咯烷三羧酸4钠盐的临界聚集浓度(CAC)大,聚集体粒径大小的不同,表明C60单加成衍生物加成基团中羧基(COOH)数目的多少对其聚集行为的影响.用化学发光法分别检测了C60吡咯烷二羧酸3和C60吡咯烷三羧酸4在缓冲溶液(0.05mol/L NaCO3-NaHCO3)中对邻苯三酚自氧化产生的超氧阴离子(O2^-)的清除活性.C60衍生物3和4对O2^-的清除呈现有明显的剂量效应,但当超过一定浓度时(3:~3.50×10^-4mol/L,4:~3.25×10^-4mol/L),清除效率出现转折,并下降.这一现象与电导率测定时出

英文摘要:

Photochemical reaction of C60 with iminodiacetic methyl ester [NH(CH2COOMe)2] produced 2,5-bis(methoxycarbonyl)fulleropyrrolidine (1) in a 52% yield (based on consumed C60). N-Alkylation of fulleropyrrolidine derivative 1 with methyl chloroacetate (CICHECOOCH3) by phase transfer catalysis without solvent under microwave irradiation afforded 2,5-bis(methoxycarbonyl)-N-(methoxycarbonyl)-methylfulleropyrrolidine (2) in a 47% yield (relative to the methyl derivative 1). Fulleropyrrolidine derivatives 1 and 2 were hydrolyzed with Nail and methanol in toluene, and then acidified with HCI to result in the corresponding fulleropyrrolidine dicarboxylic acid (3) and fulleropyrrolidine tricarboxylic acid (4), respectively, in 65% and 53% yields (relative to fulleropyrrolidine derivatives 1 and 2). Fulleropyrrolidine derivatives 1-4 were structurally characterized by ^1H NMR, ^13C NMR, IR, FAB-MS methods and elementary analysis. Critical aggregation concentrations (CAC) of sodium salts of dicarboxylic acid derivative 3 and tricarboxylic acid derivative 4 were determined by conductivity measurements, which were 3.58×10^-4 mol/L (3) and 3.33 × 10^-4 mol/L (4), respectively. The results were supported by characteristic change of UV-Vis absorption spectra of the derivatives 3 and 4 at the neighborhoods of CAC. The aggregation behavior of 3 and 4 was also examined using static light scattering (SLS) and transmission electron microscopic (TEM) techniques, and the aggregate sizes of derivative 3 (radius Rg-21nm) in a buffer solution (0.001 mol/L Na2CO3-NaHCO3) were found to be different from derivative 4 (radius Rg-21 nm). Critical aggregation concentrations (CAC) of sodium salts of the derivative 3 is bigger than that of sodium salts of derivative 4, and their aggregate sizes were different from each other, indicating that the formation of aggregate is effected by the number of carboxyl connected to fulleropyrrolidine mono-adduct derivatives. Sca

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期刊信息
  • 《化学学报》
  • 北大核心期刊(2014版)
  • 主管单位:中国科学院
  • 主办单位:中国化学会 中国科学院上海有机化学研究所
  • 主编:周其林
  • 地址:上海市零陵路345号
  • 邮编:200032
  • 邮箱:hxxb@sioc.ac.cn
  • 电话:021-54925085
  • 国际标准刊号:ISSN:0567-7351
  • 国内统一刊号:ISSN:31-1320/O6
  • 邮发代号:4-209
  • 获奖情况:
  • 首届国家期刊奖,第二届国家期刊奖提名奖,中国期刊方阵“双高期刊”
  • 国内外数据库收录:
  • 俄罗斯文摘杂志,美国化学文摘(网络版),荷兰文摘与引文数据库,美国科学引文索引(扩展库),日本日本科学技术振兴机构数据库,中国中国科技核心期刊,中国北大核心期刊(2004版),中国北大核心期刊(2008版),中国北大核心期刊(2011版),中国北大核心期刊(2014版),英国英国皇家化学学会文摘,中国北大核心期刊(2000版)
  • 被引量:28694