分子印跡在線固相萃取分離奧克托今合成反應(yīng)中間體

吳思宇等

摘 要 采用分子印跡在線固相萃取和液相色譜質(zhì)譜聯(lián)用技術(shù)建立了奧克托今合成反應(yīng)中間體1，3，5，7四乙酰基1，3，5，7四氮雜環(huán)辛烷（TAT）與1，3，5三乙酰基1，3，5三氮雜環(huán)己烷（TRAT）的分離鑒定方法。固相萃取填料采用TAT分子印跡聚合物，液相色譜分離檢測采用親水色譜柱。首先以乙腈為固相萃取柱上樣溶劑，流速為0.1 mL/min， 然后以乙酸乙酯淋洗萃取柱，用甲醇洗脫，并以甲醇為流動相對洗脫溶液進行液相色譜分離，與質(zhì)譜儀聯(lián)用鑒定各分離組分。在上述條件下，TAT回收率在79%～93%，4 結(jié) 論

以MAA為單體、TRIM為交聯(lián)劑、乙腈為溶劑合成的TAT印跡聚合物作為固相萃取填料，HPLC分離檢測采用HILIC色譜柱， 實現(xiàn)了在線固相萃取液相色譜質(zhì)譜聯(lián)用技術(shù)對TAT和TRAT混合溶液的分離檢測。相比離線固相萃取實驗，本方法耗時短，整個實驗在30 min內(nèi)即可完成，溶劑消耗量少。實驗采用印跡聚合物作為固相萃取填料，使用加標回收方法測得樣品的加標回收率為79%～93%，分離效果良好，表明本方法可有效用于TAT與TRAT的快速分離。

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何志勇， 羅 軍. 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， 羅 軍. 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， 羅 軍. 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）