Page 43 - 精细化工2019年第8期

第 8 期 王 芳，等: 氧化石墨烯/丙酸氯倍他索分子捕获器的制备及性能 ·1531·

2.3.3 分子捕获器耐用性实验 参考文献：
取 4 片分子捕获器，加入 1.5 mg/L 的丙酸氯倍 [1] Ruan Haolan (阮浩澜), Chen Qi (陈琪), Luo Zhuoya (罗卓雅). The
他索标准溶液 5 mL，按 1.5 节方法反复多次进行固 situation and harm of glucocorticoid abuse in cosmetic masks[J].
Pharmacy Today (今日药学), 2018, 28(10): 717-720.
相萃取实验，计算各次的回收率。以分子捕获器吸 [2] Qian Yefei (钱叶飞), Jia Changping(贾昌平), Lu Hui (鲁辉), et al.
Rapid determination of 38 glucocorticoids illegally added into
附丙酸氯倍他索的回收率来评价其耐用性，用相对
Chinese patent medicines and dietary supplements by UPLC-MS-MS[J].
标准偏差评价该方法的稳定性及精密度，结果见图 9。 Chinese Journal of Experimental Traditional Medical Formulae (中
国实验方剂学杂志), 2016, 22(10): 60-66.
由图 9 可知，在丙酸氯倍他索标准品质量浓度
[3] Capelli A M, Bruno A, Guadix A E, et al. Unbinding pathways from
为 1.5 mg/L、加入量 5 mL 条件下，MC 使用 4 次时， the glucocorticoid receptor shed light on the reduced sensitivity of
glucocorticoid ligands to a naturally occurring, clinically relevant
仍有超过 70%的回收率，到第 5 次时，回收率才逐
mutant receptor[J].Journal of Medicinal Chemistry, 2013, 56(17):
渐变低，但仍有 60%以上的回收率，且 RSD≤0.68%。 7003-7014.
[4] Li Yangjie (李杨杰), Zhao Xianglong (赵祥龙), Cen Liyi (岑立怡),
由于吸附和洗脱过程增多，分子捕获器材料的表面 et al. Rapid screening and detection of glucocorticoids illegally
逐渐耗损，吸附能力逐渐下降。实验结果表明，该 added in cosmetics by Q-TOF method[J]. Flavour Fragrance
Cosmetics(香料香精化妆品), 2018, (1): 58-62.
固相萃取材料可以重复使用 4 次，具有良好的耐用性。 [5] Desmedt B, Rogiers V, Courselle P, et al. Development and
validation of a fast chromatographic method for screening and
quantification of legal and illegal skin whitening agents[J].Journal of
Pharmaceutical & Biomedical Analysis, 2013, 83: 82-88.
[6] Gineys N, Giroud B, Vulliet E. Analytical method for the
determination of trace levels of steroid hormones and corticosteroids
in soil, based on HPLE/SPE/LC-MS/MS[J]. Analytical and Bioanalytical
Chemistry, 2010, 397(6): 2295-2302.
[7] Rodionova O, Pomerantsev A, Houmøller L, et al.Noninvasive
detection of counterfeited ampoules of dexamethasone using NIR
with confirmation by HPLC-DAD-MS and CE-UV methods[J].
Analytical and Bioanalytical Chemistry, 2010, 397(5): 1927-1935.
[8] Du Xiaohui (杜晓辉), Luo Xinpeng (罗新鹏). Rapidly detection
metronidazole, tinidazole, chloramphenicol, dexamethasone acetate
illegally added in acne removal cosmetic[J]. Chinese Journal of
Ethnomedicine and Ethnopharmacy (中外健康文摘), 2014, (6): 9-10.

图 9 分子捕获器耐用实验结果 [9] Bagot R C, Meaney M J. Separation of steroids and the determination
of estradiol content in transdermic patches by microemulsion
Fig. 9 Results of reuse of MC upon clobetasol propionate recovery electrokinetic chromatography[J].Chromatographia, 2011, 73(3):
373-378.
[10] De Baere S, Larsen T R, Devreese M, et al. Use of LC–MS–MS as
3 结论 an alternative to currently available immunoassay methods to
quantitate corticosterone in egg yolk and albumen[J]. Analytical and
Bioanalytical Chemistry, 2015, 407(15): 4351-4362.
（1）本文制备了一种基于氧化石墨烯的丙酸氯 [11] Zhang Jing (张静), Yan Xiaohong (严小红), Lai Junmin (赖俊敏), et
倍他索分子捕获器。此分子捕获器对模板丙酸氯倍 al. Simultaneous detection of 3 other standard glucocorticoids illegally
added in cosmetics by liquid chromatography-tandem mass
他索有较快吸附速率（2 h 达吸附平衡）。通过拟一 spectrometry[J]. Pharmacy Today (今日药学), 2018, 28(11): 733-735.
[12] Fiori J, Andrisano V. LC-MS method for the simultaneous
级动力学速率方程和拟二级动力学速率方程对分子
determination of six glucocorticoids in pharmaceutical formulations
捕获器的吸附动力学数据进行拟合，结果表明，分 and counterfeit cosmetic products[J].Journal of Pharmaceutical &
Biomedical Analysis, 2014, 91(5): 185-192.
子捕获器对丙酸氯倍他索的吸附动力学符合拟二级 [13] Zhang Yukui (张玉奎), Li Yuxing (刘雨星), Chen Langxing (陈朗
动力学速率方程。采用 Langmuir 方程和 Freundlich 星), et al. Preparation and application of core-shell structural carbon
nanotubes-molecularly imprinted composite material for
方程对分子捕获器的等温吸附数据进行拟合，结果 determination of nafcillin in egg samples[J]. Chinese Journal of
表明分子捕获器对丙酸氯倍他索的等温吸附模型符 Analytical Chemistry (分析化学), 2013, 41(2): 161-166.
[14] Eersels K, Lieberzeit P, Wagner P. A review on synthetic receptors for
合 Langmuir 方程，为单分子层吸附。 bio-particle detection created by surface-imprinting techniques-From
principles to applications[J]. Acs Sensors, 2016, 1: 1171-1187.
（2）吸附选择性实验结果显示，分子捕获器对
[15] Sun P, Miao Z, Wang K, et al. Small temperature coefficient of
模板丙酸氯倍他索的吸附能力明显高于其结构类似 resistivity of graphene/graphene oxide hybrid membranes[J]. Acs
Applied Materials & Interfaces, 2016, 5(19): 9563.
物地塞米松、泼尼松、氢化可的松，分子捕获器对 [16] Cao J, Zhang Y, Men C, et al. Programmable writing of graphene
丙酸氯倍他索有特异性吸附。耐用性实验结果显示， oxide/reduced graphene oxide fibers for sensible networks with in
situ welded junctions[J]. Acs Nano, 2014, 8(5): 4325.
分子捕获器可重复使用 4 次，具有良好的耐用性。 [17] Marcano D C, Kosynkin D V, Berlin J M, et al. Improved synthesis
of graphene oxide[J]. ACS Nano, 2010, 4(8): 4806-4814.
加标回收实验结果表明，所建立 MC-SPE-HPLC 检
[18] Krupa A N D, Vimala R. Evaluation of tetraethoxysilane (TEOS)
测化妆品中丙酸氯倍他索的分析方法可为化妆品的 sol-gel coatings, modified with green synthesized zinc oxide
nanoparticles for combating microfouling[J].Materials Science and
安全检测提供一种新型样品前处理材料及检测方法。 Engineering: C, 2016, 61: 728-735.