HPLC法研究茚-C_(60)双加成物的纯度及异构体比例

Determination of purity & isomer ratio of indene-C_(60) bisadduct by DAD-HPLC

建立了HPLC法检测茚-C60双加成物(ICBA)纯度及异构体比例。实验条件:色谱柱cosmosil Buckyprep(4.6 mm I.D.×250 mm),检测波长245 nm,流动相为V(四氢呋喃):V(乙腈)=80:20(测纯度)或66:34(测异构体比例),试样用THF溶解。结果表明:ICBA纯度检测在32.3～290.8μg/mL范围内有良好的线性关系(R2=0.9955),定量限为2.4μg/mL,回收率为99.7%～100.2%,RSD为1.8%(n=6);能检测出11个异构体,含量较多的10个异构体比例的RSD小于1.0%(n=6)。分离机理主要是疏水效应和"π-π"作用。从ICBA、茚-C60单加成物(ICMA)、C60的光吸收图谱可以看出,随着茚加成数量的增加,有效光吸收范围变小,故不能为改善溶解性一味增加茚的加成数量。其中异构体7含量较高,且有效吸光范围较宽,与ICMA相似,推测其双茚的夹角较尖锐,较少破坏C60的共轭结构,从而较少破坏其电子亲和能,预估其光电性能较优。

A HPLC method was developed and validated for the determination of purity isomer ratio of indene- C60bisadduct（ ICBA）. Test conditions： cosmosil Buckyprep column（ 4. 6 mm I. D. × 250 mm）,test wavelength was 245 nm,mobile phase were THF / ACN（ V / V） = 80 /20 for ICBA purity,or 67 /33 for isomer ratio,sample was dissolved by THF. The results showed that： the linear detection range for purity was 32. 3 ～290. 8 μg / ml with correlation coefficient（ R2） of 0. 9955,the limit of quantification（ LOQ,S/N =10） was 2. 4μg /ml,recoveries were in the range of 99. 7%- 100. 2%,and the relative standard deviation（ RSD） was 1. 8%（ n =6）; 11 ICBA isomers could be found,the RSDs of ten concentrated isomers were less than 1. 0%（ n =6）.Separation mechanism was mainly hydrophobicity action and function. Seeing from the absorption spectra of ICBA,ICMA and C60,it was found that more indene meant narrower absorption range. The absorption spectra of three most concentrated isomers were investigated,the result showed that the spectrum of 7thisomer was wider than the others,simile to ICMA. It was presumed that the angle containing two indenes was sharper,the conjugate structure of C60was lightly damaged,so that its electronic affinity energy was hardly damaged. It was speculated that the photoelectrical capability of 7thisomer was better.