卷烟主流烟气有害挥发性酚类化合物分析方法的改进
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摘要
简单酚类化合物是卷烟主流烟气中的一类重要有害成分,高效液相色谱法因不需要样品预分离和衍生化,具有操作简单,可直接进行样品测定等优点,在酚类化合物的分析中得到了广泛的应用。由于酚类化合物具有较强的荧光性,采用荧光检测器可提高分析灵敏度,所以目前带荧光检测器的高效液相色谱法已成为测定酚类化合物最简便有效的方法。但是,在用这一方法进行酚类化合物的检测时,由于对-甲酚、间-甲酚异构体的光谱严重重叠,常规FLD-HPLC法无法分别定量对-甲酚、间-甲酚。而对-甲酚、间-甲酚的致毒机理及环境行为有所不同,因此人们常需要分别测定间-甲酚和对-甲酚的具体含量。根据以上情况,本研究进行了以下工作来实现对-甲酚、间-甲酚异构体的分别测定:
(1)采用FLD-HPLC法分析卷烟主流烟气中对苯二酚、间苯二酚、邻苯二酚、苯酚、对+间-甲酚、邻甲酚等酚类化合物,重复了前人工作,其测定酚类化合物RSD值为1.03%～4.00%,回收率为92.8%～106.5%,说明该方法分析效果良好,但对-甲酚、间-甲酚无法分离的现象确实存在。
(2)以β-环糊精为流动相添加剂,采用反相高效液相色谱法于C18反相柱上拆分了对-甲酚、间-甲酚异构体,建立了β-环糊精添加剂-高效液相色谱分析卷烟主流烟气中7种主要酚类成分的方法,并与未添加β-环糊精的分析方法进行比较。结果表明:当流动相中添加β-环糊精浓度为5.29×10~(-3) mol/L时,不但可拆分对甲酚和间甲酚异构体,还可同时分离测定卷烟主流烟气中的其它有害酚。该方法测定酚类化合物的RSD值为1.78%～4.33%,回收率在92.9%～102.4%之间。说明以β-环糊精作流动相添加剂的方法,在成功拆分对-甲酚和间-甲酚异构体的同时,仍然保持了良好的重复性和回收率,且操作简单,适用于卷烟样品的有害酚类物质的检测。
(3)将偏最小二乘法(PLS)用于荧光检测-高效液相色谱法,采用荧光检测器扫描对-甲酚、间-甲酚混合物的激发光谱,采用外标定量法对-邻苯二酚、间-苯二酚、对-苯二酚、苯酚和邻-甲酚进行了定量,用PLS法对未能实现液相色谱分离的对-甲酚、间-甲酚进行光谱的建模分析,成功地测定了人工样品中对-甲酚、间-甲酚的含量,对-甲酚、间-甲酚的回收率分别在98.8%～110.4%,92.4%～115.4%之间,从实验结果来看,PLS法在不影响原有液相色谱分离功能的基础上实现了对-甲酚、间-甲酚混合物的快速分析,方法准确可靠,操作简便。
Phenolic compounds are toxic compounds in mainstream cigarette smoke.So far reversed-phase high performance liquid chromatography has been mainly used for the determination of phenols,because it is a fas,efficient and sensitive method which does not need a derivatization step for the routine determination of phenols.Phenols show a natural fluorescence,the use of fluorimetric detection can improve the sensitivity,so the high performance liquid chromatographic(HPLC) with fluorescence detector method for simultaneously determining the phenolic compounds has become the most efficient methord.Since the fluorescence spectrum of m-cresol,p-cresol were seriously overlapped,it does not permit their direct determination without previous separation by conventional FLD-HPLC methodologies.However,as the m-cresol,p-cresol have different toxic mechanics and environmental behavior,the separate determination of the isomers is welcomed.In the present thesis,the following research works were carried out on the investigation:
(1)Repeat other peole's work:hydroquinone,resorcinol,catechol,phenol, m+p-cresol and o-cresol in mainstream cigarette smoke was determined by a high performance liquid chromatographic(HPLC) with fluorescence detector method,with 1.03%～4.00%of RSD and 92.8%～106.5%of recovery.But this methord did not separate m-cresol and p-cresol isomers.
(2) A method using reversed-phase high performance liquid chromatography in whichβ-cyclodextrin(β-CD) was the additive in mobile phase has been developed for the separation of two structural isomers of m-cresol,p-cresol,the simultaneously determining the major 7 phenolic compounds in mainstream cigarette smoke has been developed.The comparison of harmful phenols separation usingβ-cyclodextrin as mobile phase additive and not using has been demonstrated.The results indicated that when the mobile phase consisted of 5.29×10~(-3)β-CD,the complete baseline separation of both the cresol isomers and other harmful phenols were achieved.The RSD was 1.78 %～4.33%of and the recovery was 92.9%～102.4%which indicated the alternative method was easy to control and has been used to determinate phenols in cigarette smoke.
(3) a method based on FLD-HPLC by the use of partial least squares(PLS) is proved for the determination of phenolic compounds.Determination of m-cresol and p-cresol has been carried out in mixtures by recording excitation fluorescence spectra, hydroquinone,resorcinol,catechol,phenol and o-cresol by ESTD.The experimental calibration matrix was designed and was successfully used to determine the the m-cresol and p-cresol in artificial samples.The results indicated that the alternative method is fast,reliable and easy control which can be successfully used to determine the phenolic compounds.
(1)采用FLD-HPLC法分析卷烟主流烟气中对苯二酚、间苯二酚、邻苯二酚、苯酚、对+间-甲酚、邻甲酚等酚类化合物,重复了前人工作,其测定酚类化合物RSD值为1.03%～4.00%,回收率为92.8%～106.5%,说明该方法分析效果良好,但对-甲酚、间-甲酚无法分离的现象确实存在。
(2)以β-环糊精为流动相添加剂,采用反相高效液相色谱法于C18反相柱上拆分了对-甲酚、间-甲酚异构体,建立了β-环糊精添加剂-高效液相色谱分析卷烟主流烟气中7种主要酚类成分的方法,并与未添加β-环糊精的分析方法进行比较。结果表明:当流动相中添加β-环糊精浓度为5.29×10~(-3) mol/L时,不但可拆分对甲酚和间甲酚异构体,还可同时分离测定卷烟主流烟气中的其它有害酚。该方法测定酚类化合物的RSD值为1.78%～4.33%,回收率在92.9%～102.4%之间。说明以β-环糊精作流动相添加剂的方法,在成功拆分对-甲酚和间-甲酚异构体的同时,仍然保持了良好的重复性和回收率,且操作简单,适用于卷烟样品的有害酚类物质的检测。
(3)将偏最小二乘法(PLS)用于荧光检测-高效液相色谱法,采用荧光检测器扫描对-甲酚、间-甲酚混合物的激发光谱,采用外标定量法对-邻苯二酚、间-苯二酚、对-苯二酚、苯酚和邻-甲酚进行了定量,用PLS法对未能实现液相色谱分离的对-甲酚、间-甲酚进行光谱的建模分析,成功地测定了人工样品中对-甲酚、间-甲酚的含量,对-甲酚、间-甲酚的回收率分别在98.8%～110.4%,92.4%～115.4%之间,从实验结果来看,PLS法在不影响原有液相色谱分离功能的基础上实现了对-甲酚、间-甲酚混合物的快速分析,方法准确可靠,操作简便。
Phenolic compounds are toxic compounds in mainstream cigarette smoke.So far reversed-phase high performance liquid chromatography has been mainly used for the determination of phenols,because it is a fas,efficient and sensitive method which does not need a derivatization step for the routine determination of phenols.Phenols show a natural fluorescence,the use of fluorimetric detection can improve the sensitivity,so the high performance liquid chromatographic(HPLC) with fluorescence detector method for simultaneously determining the phenolic compounds has become the most efficient methord.Since the fluorescence spectrum of m-cresol,p-cresol were seriously overlapped,it does not permit their direct determination without previous separation by conventional FLD-HPLC methodologies.However,as the m-cresol,p-cresol have different toxic mechanics and environmental behavior,the separate determination of the isomers is welcomed.In the present thesis,the following research works were carried out on the investigation:
(1)Repeat other peole's work:hydroquinone,resorcinol,catechol,phenol, m+p-cresol and o-cresol in mainstream cigarette smoke was determined by a high performance liquid chromatographic(HPLC) with fluorescence detector method,with 1.03%～4.00%of RSD and 92.8%～106.5%of recovery.But this methord did not separate m-cresol and p-cresol isomers.
(2) A method using reversed-phase high performance liquid chromatography in whichβ-cyclodextrin(β-CD) was the additive in mobile phase has been developed for the separation of two structural isomers of m-cresol,p-cresol,the simultaneously determining the major 7 phenolic compounds in mainstream cigarette smoke has been developed.The comparison of harmful phenols separation usingβ-cyclodextrin as mobile phase additive and not using has been demonstrated.The results indicated that when the mobile phase consisted of 5.29×10~(-3)β-CD,the complete baseline separation of both the cresol isomers and other harmful phenols were achieved.The RSD was 1.78 %～4.33%of and the recovery was 92.9%～102.4%which indicated the alternative method was easy to control and has been used to determinate phenols in cigarette smoke.
(3) a method based on FLD-HPLC by the use of partial least squares(PLS) is proved for the determination of phenolic compounds.Determination of m-cresol and p-cresol has been carried out in mixtures by recording excitation fluorescence spectra, hydroquinone,resorcinol,catechol,phenol and o-cresol by ESTD.The experimental calibration matrix was designed and was successfully used to determine the the m-cresol and p-cresol in artificial samples.The results indicated that the alternative method is fast,reliable and easy control which can be successfully used to determine the phenolic compounds.
引文
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