分子印迹在线固相萃取分离奥克托今合成反应中间体
吴思宇等
摘 要 采用分子印迹在线固相萃取和液相色谱质谱联用技术建立了奥克托今合成反应中间体1，3，5，7四乙酰基1，3，5，7四氮杂环辛烷（TAT）与1，3，5三乙酰基1，3，5三氮杂环己烷（TRAT）的分离鉴定方法。固相萃取填料采用TAT分子印迹聚合物，液相色谱分离检测采用亲水色谱柱。首先以乙腈为固相萃取柱上样溶剂，流速为0.1 mL/min， 然后以乙酸乙酯淋洗萃取柱，用甲醇洗脱，并以甲醇为流动相对洗脱溶液进行液相色谱分离，与质谱仪联用鉴定各分离组分。在上述条件下，TAT回收率在79%～93%，4 结 论
以MAA为单体、TRIM为交联剂、乙腈为溶剂合成的TAT印迹聚合物作为固相萃取填料，HPLC分离检测采用HILIC色谱柱， 实现了在线固相萃取液相色谱质谱联用技术对TAT和TRAT混合溶液的分离检测。相比离线固相萃取实验，本方法耗时短，整个实验在30 min内即可完成，溶剂消耗量少。实验采用印迹聚合物作为固相萃取填料，使用加标回收方法测得样品的加标回收率为79%～93%，分离效果良好，表明本方法可有效用于TAT与TRAT的快速分离。
References
1 Akifumi K， Tadahiro K， Takeshi N. Chem. Commun.， 2014， 50（76）： 11101-11103
2 Deniz T； Nilay B， Emin C M. Artif. Cells Nanomed Biotechnol.， 2014， 42（5）： 316-322
3 LI Li， HU ShuGuo， HE XiWen，LI WenYou，CHEN LangXing，ZHANG YuKui. Chem. J. Chinese Universities， 2006， 27（4）： 608-611
李 礼， 胡树国， 何锡文， 李文友， 陈朗星， 张玉奎. 高等学校化学学报， 2006， 27（4）： 608-611
4 Zhong S A， Kong Y Y， Zhou L. J. Chromatogr. B ， 2014， 945： 39-45
5 ZHANG GaoKui， WANG XuFeng， ZHANG GuiJun， WANG LiQi， YANG JianWen， HE LiMin. Chinese J. Anal.Chem.， 2013， 41（9）： 1401-1405
张高奎， 杨建文， 王宗楠， 卞 愧， 杨海翠， 贺利民. 分析化学， 2013， 41（9）： 1401-1405
6 Zhang C B， Li Z Z. Food Sci.， 2014， 35（9）： 323-328
7 Li J W， Xia L J， Su Y H. J. Biol. Chem.， 2012， 287（17）： 13713-13721
8 Yarman A， Scheller F W. Angew. Chem. Int. Edit.， 2013， 52（44）： 11521-11525
9 Mashaalah Z， Petra F， Monika M. Talanta， 2014， 129： 132-138
10 Scorrano S， Mergola L， Del Sole R， Lazzoi M R， Vasapollo G. J. Appl. Polym. Sci.， 2014， 131（19）： 40819
11 Mazumder A， Kumar A， Dubey D K. J. Chromatogr. A， 2013， 1284： 88-99
12 Kubo T， Kuroda K， Tominaga Y. J. Pharmaceut. Biomed.， 2014， 89：111-117
13 Willenberg I， von Elsner L， Steinberg P， Schebb N H. Food Chem.， 2014， 166： 537-543
14 Bourdat Daudin J， Nelieu S， Deschamps M， Leang S， Bernet N， Daudin J， Nelieu S. J. Chromatogr. A， 2014， 1349： 11-23
15 Cooper P W. Explosives Engineering. Weinheim： WileyVCH， 1996： 27-50
16 LI Xin， CHEN XueGuo， KONG Liang， ZOU HanFa. Chinese Bulletin of Life Science， 2003， 15（2）： 95-100
厉 欣， 陈学国， 孔 亮， 邹汉法. 生命科学， 2003， 15（2）： 95-100
17 Opiteck G J， Jorgenson J W. Anal. Chem ， 1997， 69： 2283
18 Howa J D， Lott M J， Chesson L A. Forensic. Sci. Int.， 2014， 240： 80-87
19 RodriguezMozaz S， Lopez de Alda M J， Barceló D. J. Chromatogr. A， 2007， 1152（1）： 97-115
20 HE ZhiYong， LUO Jun. Chinese Journal of Energetic Materials， 2012， 20（4）： 427-431
何志勇， 罗 军. 含能材料， 2012， 20（4）： 427-431
Separation of Cyclotetramethylenetetranitramine Synthetic
Intermediates by Online Molecular Imprinted Solid
Phase Extraction and Liquid Chromatography
WU SiYu， XUE Min*， WANG Jian， MENG ZiHui*
（School of Chemical Engineering and Environment， Beijing Institute of Technology， Beijing 100081， China）
Abstract An online solid phase extraction （SPE） coupled with high performance liquid chromatography （HPLC）mass spectrometry （MS） method was developed for the separation of 1，3，5，7tetraacetyl1，3，5，7tetraazacyclooctane （TAT） and 1，3，5triacetyl1，3，5triazacyclohexane （TRAT） which are the synthetic intermediates of cyclotetramethylenetetranitramine （HMX）. In this experiment， molecularly imprinted polymers with TAT as the template were used as SPE sorbents. PC HILIC column was employed in liquid chromatographic separation. The parameters of SPEHPLC were optimized. Acetonitrile was selected as the loading solution with flow rate of 0.1 mL/min. After flushed by ethyl acetate， the TAT adsorbed on SPE was eluted by methanol， which was also used as the mobile phase in HPLC separation. The mass spectrometry was coupled with HPLC to identify the corresponding peaks. Under the optimized conditions， the linear detection range of this method was 6.0 mg/L to 500.0 mg/L， with the detection limit of 1.8 mg/L （3σ）. The enriching factor was 400 times and TAT recovery was 79%–93% in the standard addition experiment.
Keywords Molecular imprinting technique； Solid phase extraction； High performance liquid chromatographymass spectrometry； Cyclotetramethylenetetranitramine
（Received 31 August 2014； accepted 21 October 2014）
何志勇， 罗 军. 含能材料， 2012， 20（4）： 427-431
Separation of Cyclotetramethylenetetranitramine Synthetic
Intermediates by Online Molecular Imprinted Solid
Phase Extraction and Liquid Chromatography
WU SiYu， XUE Min*， WANG Jian， MENG ZiHui*
（School of Chemical Engineering and Environment， Beijing Institute of Technology， Beijing 100081， China）
Abstract An online solid phase extraction （SPE） coupled with high performance liquid chromatography （HPLC）mass spectrometry （MS） method was developed for the separation of 1，3，5，7tetraacetyl1，3，5，7tetraazacyclooctane （TAT） and 1，3，5triacetyl1，3，5triazacyclohexane （TRAT） which are the synthetic intermediates of cyclotetramethylenetetranitramine （HMX）. In this experiment， molecularly imprinted polymers with TAT as the template were used as SPE sorbents. PC HILIC column was employed in liquid chromatographic separation. The parameters of SPEHPLC were optimized. Acetonitrile was selected as the loading solution with flow rate of 0.1 mL/min. After flushed by ethyl acetate， the TAT adsorbed on SPE was eluted by methanol， which was also used as the mobile phase in HPLC separation. The mass spectrometry was coupled with HPLC to identify the corresponding peaks. Under the optimized conditions， the linear detection range of this method was 6.0 mg/L to 500.0 mg/L， with the detection limit of 1.8 mg/L （3σ）. The enriching factor was 400 times and TAT recovery was 79%–93% in the standard addition experiment.
Keywords Molecular imprinting technique； Solid phase extraction； High performance liquid chromatographymass spectrometry； Cyclotetramethylenetetranitramine
（Received 31 August 2014； accepted 21 October 2014）
何志勇， 罗 军. 含能材料， 2012， 20（4）： 427-431
Separation of Cyclotetramethylenetetranitramine Synthetic
Intermediates by Online Molecular Imprinted Solid
Phase Extraction and Liquid Chromatography
WU SiYu， XUE Min*， WANG Jian， MENG ZiHui*
（School of Chemical Engineering and Environment， Beijing Institute of Technology， Beijing 100081， China）
Abstract An online solid phase extraction （SPE） coupled with high performance liquid chromatography （HPLC）mass spectrometry （MS） method was developed for the separation of 1，3，5，7tetraacetyl1，3，5，7tetraazacyclooctane （TAT） and 1，3，5triacetyl1，3，5triazacyclohexane （TRAT） which are the synthetic intermediates of cyclotetramethylenetetranitramine （HMX）. In this experiment， molecularly imprinted polymers with TAT as the template were used as SPE sorbents. PC HILIC column was employed in liquid chromatographic separation. The parameters of SPEHPLC were optimized. Acetonitrile was selected as the loading solution with flow rate of 0.1 mL/min. After flushed by ethyl acetate， the TAT adsorbed on SPE was eluted by methanol， which was also used as the mobile phase in HPLC separation. The mass spectrometry was coupled with HPLC to identify the corresponding peaks. Under the optimized conditions， the linear detection range of this method was 6.0 mg/L to 500.0 mg/L， with the detection limit of 1.8 mg/L （3σ）. The enriching factor was 400 times and TAT recovery was 79%–93% in the standard addition experiment.
Keywords Molecular imprinting technique； Solid phase extraction； High performance liquid chromatographymass spectrometry； Cyclotetramethylenetetranitramine
（Received 31 August 2014； accepted 21 October 2014）
摘 要 采用分子印迹在线固相萃取和液相色谱质谱联用技术建立了奥克托今合成反应中间体1，3，5，7四乙酰基1，3，5，7四氮杂环辛烷（TAT）与1，3，5三乙酰基1，3，5三氮杂环己烷（TRAT）的分离鉴定方法。固相萃取填料采用TAT分子印迹聚合物，液相色谱分离检测采用亲水色谱柱。首先以乙腈为固相萃取柱上样溶剂，流速为0.1 mL/min， 然后以乙酸乙酯淋洗萃取柱，用甲醇洗脱，并以甲醇为流动相对洗脱溶液进行液相色谱分离，与质谱仪联用鉴定各分离组分。在上述条件下，TAT回收率在79%～93%，4 结 论
以MAA为单体、TRIM为交联剂、乙腈为溶剂合成的TAT印迹聚合物作为固相萃取填料，HPLC分离检测采用HILIC色谱柱， 实现了在线固相萃取液相色谱质谱联用技术对TAT和TRAT混合溶液的分离检测。相比离线固相萃取实验，本方法耗时短，整个实验在30 min内即可完成，溶剂消耗量少。实验采用印迹聚合物作为固相萃取填料，使用加标回收方法测得样品的加标回收率为79%～93%，分离效果良好，表明本方法可有效用于TAT与TRAT的快速分离。
References
1 Akifumi K， Tadahiro K， Takeshi N. Chem. Commun.， 2014， 50（76）： 11101-11103
2 Deniz T； Nilay B， Emin C M. Artif. Cells Nanomed Biotechnol.， 2014， 42（5）： 316-322
3 LI Li， HU ShuGuo， HE XiWen，LI WenYou，CHEN LangXing，ZHANG YuKui. Chem. J. Chinese Universities， 2006， 27（4）： 608-611
李 礼， 胡树国， 何锡文， 李文友， 陈朗星， 张玉奎. 高等学校化学学报， 2006， 27（4）： 608-611
4 Zhong S A， Kong Y Y， Zhou L. J. Chromatogr. B ， 2014， 945： 39-45
5 ZHANG GaoKui， WANG XuFeng， ZHANG GuiJun， WANG LiQi， YANG JianWen， HE LiMin. Chinese J. Anal.Chem.， 2013， 41（9）： 1401-1405
张高奎， 杨建文， 王宗楠， 卞 愧， 杨海翠， 贺利民. 分析化学， 2013， 41（9）： 1401-1405
6 Zhang C B， Li Z Z. Food Sci.， 2014， 35（9）： 323-328
7 Li J W， Xia L J， Su Y H. J. Biol. Chem.， 2012， 287（17）： 13713-13721
8 Yarman A， Scheller F W. Angew. Chem. Int. Edit.， 2013， 52（44）： 11521-11525
9 Mashaalah Z， Petra F， Monika M. Talanta， 2014， 129： 132-138
10 Scorrano S， Mergola L， Del Sole R， Lazzoi M R， Vasapollo G. J. Appl. Polym. Sci.， 2014， 131（19）： 40819
11 Mazumder A， Kumar A， Dubey D K. J. Chromatogr. A， 2013， 1284： 88-99
12 Kubo T， Kuroda K， Tominaga Y. J. Pharmaceut. Biomed.， 2014， 89：111-117
13 Willenberg I， von Elsner L， Steinberg P， Schebb N H. Food Chem.， 2014， 166： 537-543
14 Bourdat Daudin J， Nelieu S， Deschamps M， Leang S， Bernet N， Daudin J， Nelieu S. J. Chromatogr. A， 2014， 1349： 11-23
15 Cooper P W. Explosives Engineering. Weinheim： WileyVCH， 1996： 27-50
16 LI Xin， CHEN XueGuo， KONG Liang， ZOU HanFa. Chinese Bulletin of Life Science， 2003， 15（2）： 95-100
厉 欣， 陈学国， 孔 亮， 邹汉法. 生命科学， 2003， 15（2）： 95-100
17 Opiteck G J， Jorgenson J W. Anal. Chem ， 1997， 69： 2283
18 Howa J D， Lott M J， Chesson L A. Forensic. Sci. Int.， 2014， 240： 80-87
19 RodriguezMozaz S， Lopez de Alda M J， Barceló D. J. Chromatogr. A， 2007， 1152（1）： 97-115
20 HE ZhiYong， LUO Jun. Chinese Journal of Energetic Materials， 2012， 20（4）： 427-431
何志勇， 罗 军. 含能材料， 2012， 20（4）： 427-431
Separation of Cyclotetramethylenetetranitramine Synthetic
Intermediates by Online Molecular Imprinted Solid
Phase Extraction and Liquid Chromatography
WU SiYu， XUE Min*， WANG Jian， MENG ZiHui*
（School of Chemical Engineering and Environment， Beijing Institute of Technology， Beijing 100081， China）
Abstract An online solid phase extraction （SPE） coupled with high performance liquid chromatography （HPLC）mass spectrometry （MS） method was developed for the separation of 1，3，5，7tetraacetyl1，3，5，7tetraazacyclooctane （TAT） and 1，3，5triacetyl1，3，5triazacyclohexane （TRAT） which are the synthetic intermediates of cyclotetramethylenetetranitramine （HMX）. In this experiment， molecularly imprinted polymers with TAT as the template were used as SPE sorbents. PC HILIC column was employed in liquid chromatographic separation. The parameters of SPEHPLC were optimized. Acetonitrile was selected as the loading solution with flow rate of 0.1 mL/min. After flushed by ethyl acetate， the TAT adsorbed on SPE was eluted by methanol， which was also used as the mobile phase in HPLC separation. The mass spectrometry was coupled with HPLC to identify the corresponding peaks. Under the optimized conditions， the linear detection range of this method was 6.0 mg/L to 500.0 mg/L， with the detection limit of 1.8 mg/L （3σ）. The enriching factor was 400 times and TAT recovery was 79%–93% in the standard addition experiment.
Keywords Molecular imprinting technique； Solid phase extraction； High performance liquid chromatographymass spectrometry； Cyclotetramethylenetetranitramine
（Received 31 August 2014； accepted 21 October 2014）
何志勇， 罗 军. 含能材料， 2012， 20（4）： 427-431
Separation of Cyclotetramethylenetetranitramine Synthetic
Intermediates by Online Molecular Imprinted Solid
Phase Extraction and Liquid Chromatography
WU SiYu， XUE Min*， WANG Jian， MENG ZiHui*
（School of Chemical Engineering and Environment， Beijing Institute of Technology， Beijing 100081， China）
Abstract An online solid phase extraction （SPE） coupled with high performance liquid chromatography （HPLC）mass spectrometry （MS） method was developed for the separation of 1，3，5，7tetraacetyl1，3，5，7tetraazacyclooctane （TAT） and 1，3，5triacetyl1，3，5triazacyclohexane （TRAT） which are the synthetic intermediates of cyclotetramethylenetetranitramine （HMX）. In this experiment， molecularly imprinted polymers with TAT as the template were used as SPE sorbents. PC HILIC column was employed in liquid chromatographic separation. The parameters of SPEHPLC were optimized. Acetonitrile was selected as the loading solution with flow rate of 0.1 mL/min. After flushed by ethyl acetate， the TAT adsorbed on SPE was eluted by methanol， which was also used as the mobile phase in HPLC separation. The mass spectrometry was coupled with HPLC to identify the corresponding peaks. Under the optimized conditions， the linear detection range of this method was 6.0 mg/L to 500.0 mg/L， with the detection limit of 1.8 mg/L （3σ）. The enriching factor was 400 times and TAT recovery was 79%–93% in the standard addition experiment.
Keywords Molecular imprinting technique； Solid phase extraction； High performance liquid chromatographymass spectrometry； Cyclotetramethylenetetranitramine
（Received 31 August 2014； accepted 21 October 2014）
何志勇， 罗 军. 含能材料， 2012， 20（4）： 427-431
Separation of Cyclotetramethylenetetranitramine Synthetic
Intermediates by Online Molecular Imprinted Solid
Phase Extraction and Liquid Chromatography
WU SiYu， XUE Min*， WANG Jian， MENG ZiHui*
（School of Chemical Engineering and Environment， Beijing Institute of Technology， Beijing 100081， China）
Abstract An online solid phase extraction （SPE） coupled with high performance liquid chromatography （HPLC）mass spectrometry （MS） method was developed for the separation of 1，3，5，7tetraacetyl1，3，5，7tetraazacyclooctane （TAT） and 1，3，5triacetyl1，3，5triazacyclohexane （TRAT） which are the synthetic intermediates of cyclotetramethylenetetranitramine （HMX）. In this experiment， molecularly imprinted polymers with TAT as the template were used as SPE sorbents. PC HILIC column was employed in liquid chromatographic separation. The parameters of SPEHPLC were optimized. Acetonitrile was selected as the loading solution with flow rate of 0.1 mL/min. After flushed by ethyl acetate， the TAT adsorbed on SPE was eluted by methanol， which was also used as the mobile phase in HPLC separation. The mass spectrometry was coupled with HPLC to identify the corresponding peaks. Under the optimized conditions， the linear detection range of this method was 6.0 mg/L to 500.0 mg/L， with the detection limit of 1.8 mg/L （3σ）. The enriching factor was 400 times and TAT recovery was 79%–93% in the standard addition experiment.
Keywords Molecular imprinting technique； Solid phase extraction； High performance liquid chromatographymass spectrometry； Cyclotetramethylenetetranitramine
（Received 31 August 2014； accepted 21 October 2014）
