10-DAB分子印迹纳米微球的合成及吸附性能研究

doi:10.3969/j.issn.0253-2417.2022.05.013

摘要/Abstract

摘要：

以10-脱乙酰巴卡亭Ⅲ(10-DAB)为模板，4-乙烯基吡啶(4-VP)为功能单体，制备出对10-DAB具有高选择吸附性的10-DAB分子印迹纳米微球(10-DAB-MINs)，最高吸附量可达37.42 mg/g。通过扫描电子显微镜(SEM)、傅里叶变换红外光谱(FT-IR)仪及热重分析(TG)仪对10-DAB-MINs进行表征，证明该聚合物成功合成。10-DAB-MINs的吸附过程与准二级吸附动力学模型相吻合，R²为0.979 5；10-DAB-MINs的吸附过程符合Langmuir-Freundlich吸附等温线模型，R²为0.982 7；10-DAB-MINs相较不加模板的分子印迹纳米微球(NINs)有较好的重复利用性，重复使用5次吸附量仍达到28.66 mg/g, 具有良好的稳定性。

关键词: 分子印迹技术, 10-脱乙酰巴卡亭Ⅲ, 特异性识别, 纳米微球

Abstract:

Molecular imprinted nanospheres(MINs) with high selective adsorption to 10-deacetyl baccatin Ⅲ(10-DAB) was prepared by 10-DAB as template molecule, and 4-vinylpyridine(4-VP) was used as functional monomer. The maximum adsorption capacity reached to 37.42 mg/g. The polymer was characterized by scanning electron microscope(SEM), Fourier transform infrared spectroscopy(FT-IR) and thermogravimetric(TG) analysis, which indicated that it was successfully synthesized. The adsorption kinetics of 10-DAB-MINs could be well described by the pseudo-second-order model, and R² was 0.979 5. Meanwhile, the adsorption mechanism conformed to the Langmuir-Freundlich model, and R² was 0.982 7. The cyclic adsorption results showed that 10-DAB-MINs had better recycling ability than that of the template free molecular imprinted nanaspheres(NINs). Furthermore, the adsorption capacity of 10-DAB-MINs could still reach 28.66 mg/g after recycling for 5 times, which indicated the good stability.

Key words: molecular imprinting technique, 10-deacetyl bacatin Ⅲ, specificity recognition, nanospheres

中图分类号:

TQ35

王奕洁, 江哲恒, 孙雯佳, 武晓丹, 曹劲松, 付玉杰. 10-DAB分子印迹纳米微球的合成及吸附性能研究[J]. 林产化学与工业, 2022, 42(5): 91-99.

Yijie WANG, Zheheng JIANG, Wenjia SUN, Xiaodan WU, Jingsong CAO, Yujie FU. Preparation and Adsorption Properties of 10-DAB Molecular Imprinted Nanospheres[J]. Chemistry and Industry of Forest Products, 2022, 42(5): 91-99.

图/表 13

表1

图1

图2

图3

图4

图5

图6

表2

图7

表3

图8

图9

表4

参考文献 25

1	龚雪元, 杜亚填, 刘姣, 等. 南方红豆杉菌根菌液体纯发酵培养产紫杉醇及10-去乙酰巴卡亭Ⅲ[J]. 林产化学与工业, 2015, 35 (3): 114- 120. doi: 10.3969/j.issn.0253-2417.2015.03.020
	GONG X Y , DU Y T , LIU J , et al. Paclitaxel and 10-DAB produced by liquid fermentation with Taxus chinensis var.mairei mycorrhizal fungus[J]. Chemistry and Industry of Forest Products, 2015, 35 (3): 114- 120. doi: 10.3969/j.issn.0253-2417.2015.03.020
2	姜萍, 赵雅洁, 包信业, 等. 红豆杉枝叶中总生物碱的提取及其抗肿瘤活性研究[J]. 林产化学与工业, 2019, 39 (6): 115- 122.
	JIANG P , ZHAO Y J , BAO X Y , et al. Extraction technology of total alkaloids from Taxus chinensis branches and leaves and their antitumor activities[J]. Chemistry and Industry of Forest Products, 2019, 39 (6): 115- 122.
3	何枭宇, 赵柳婷, 李立威. 四种不同品种红豆杉中10-脱乙酰巴卡亭Ⅲ的含量测定[J]. 荆楚理工学院学报, 2017, 32 (4): 5- 8. doi: 10.3969/j.issn.1008-4657.2017.04.001
	HE X Y , ZHAO L T , LI L W . Determination of 10-deacetylbacatine Ⅲ in four different Taxus chinensis cultivars[J]. Journal of Jingchu University of Technology, 2017, 32 (4): 5- 8. doi: 10.3969/j.issn.1008-4657.2017.04.001
4	杨逢建, 庞海河, 祖元刚, 等. 南方红豆杉生长发育及其紫杉醇含量与环境因子的关系[J]. 植物研究, 2010, 30 (6): 742- 746.
	YANG F J , PANG H H , ZU Y G , et al. Relationships between the growth and taxol content of Taxus chinensis var.mairei and environment factors[J]. Bulletin of Botanical Research,, 2010, 30 (6): 742- 746.
5	张美珍, 应群芳. 南方红豆杉中10-脱乙酰巴卡亭Ⅲ(10-DAB)的测定[J]. 江西中医药, 2009, 40 (5): 68- 69.
	ZHANG M Z , YING Q F . Determination of 10-deacetylbacartin Ⅲ(10-DAB) in Taxus chinensis[J]. Jiangxi Journal of Traditional Chinese Medicine, 2009, 40 (5): 68- 69.
6	黄旭梁, 楼锦芳, 朱巍, 等. 红豆杉中10-DAB Ⅲ的含量测定[J]. 现代中药研究与实践, 2013, 27 (5): 11- 13.
	HUANG X L , LOU J F , ZHU W , et al. Determination of 10-DAB Ⅲ in Taxus chinensis[J]. Research and Practice on Chinese Medicines, 2013, 27 (5): 11- 13.
7	马淑桢, 吴绵斌. 南方红豆杉枝叶中10-脱乙酰巴卡亭Ⅲ的分离与纯化[J]. 中国新药杂志, 2006, 15 (13): 1084- 1086. doi: 10.3321/j.issn:1003-3734.2006.13.015
	MA S Z , WU M B . Extraction and purification of 10-deacetyl bacatine Ⅲ from Taxus mairei[J]. Chinese Journal of New Drugs, 2006, 15 (13): 1084- 1086. doi: 10.3321/j.issn:1003-3734.2006.13.015
8	颜流水, 井晶, 黄智敏, 等. 槲皮素分子印迹聚合物的制备及固相萃取性能研究[J]. 分析试验室, 2006, 22 (5): 97- 100.
	YAN L S , JING J , HUANG Z M , et al. Preparation of quercetin-imprinted polymers and its property as a sorbent for solid phase extraction[J]. Chinese Journal of Analysis Laboratory, 2006, 22 (5): 97- 100.
9	孔繁晟, 严春艳, 庞小雄, 等. 云南红豆杉中10-去乙酰巴卡亭Ⅲ含量的固相萃取-高效液相色谱法测定[J]. 时珍国医国药, 2010, 21 (6): 1426- 1427. doi: 10.3969/j.issn.1008-0805.2010.06.061
	KONG F M , YAN C Y , PANG X X , et al. Determination of 10-deacetylbacartin Ⅲ in Taxus yunnanensis by solid phase extraction and high performance liquid chromatography[J]. Lishizhen Medicine and Materia Medica Research, 2010, 21 (6): 1426- 1427. doi: 10.3969/j.issn.1008-0805.2010.06.061
10	向海艳, 周春山, 钟世安, 等. 白藜芦醇分子印迹聚合物合成及其对中药虎杖提取液活性成分的分离[J]. 应用化学, 2005, 22 (7): 739- 743. doi: 10.3969/j.issn.1000-0518.2005.07.009
	XIANG H Y , ZHOU C S , ZHONG S A , et al. Synthesis of resveratrol imprinted polymer and its application in separation of active ingredent in Polygonum cuspidatum Sieb.et Zucc.extracts[J]. Chinese Journal of Applied Chemistry, 2005, 22 (7): 739- 743. doi: 10.3969/j.issn.1000-0518.2005.07.009
11	王颖, 李楠. 分子印迹技术及其应用[J]. 化工进展, 2010, 29 (12): 2315- 2323.
	WANG Y , LI N . Molecular imprinting technology and its application[J]. Chemical Industry and Engineering Progress, 2010, 29 (12): 2315- 2323.
12	盖青青, 刘秋叶, 何锡文, 等. 分子印迹技术用于蛋白质的识别[J]. 化学进展, 2008, 20 (6): 957- 968.
	GAI Q Q , LIU Q Y , HE X W , et al. Molecular imprinting is used for protein recognition[J]. Progress in Chemistry, 2008, 20 (6): 957- 968.
13	郭秀春, 周文辉. 分子印迹技术研究进展[J]. 化学研究, 2012, 23 (5): 103- 110.
	GUO X C , ZHOU W H . Research progress of molecular imprinting technology[J]. Chemical Research, 2012, 23 (5): 103- 110.
14	何慧清, 叶静敏, 程杏安, 等. 分子印迹聚合物固相萃取花生根茎中白藜芦醇[J]. 仲恺农业工程学院学报, 2020, 33 (3): 1- 7. 1-7, 17
	HE H Q , YE J M , CHENG X A , et al. Molecularly imprinted polymer solid phase extracts resveratrol from peanut rhizome[J]. Journal of Zhongkai University of Agriculture and Engineering, 2020, 33 (3): 1- 7. 1-7, 17
15	楚善明, 苏立强, 于亭亭, 等. 复合模板分子印迹聚合物的制备及对黄酮类化合物的吸附性能研究[J]. 分析科学学报, 2020, 36 (3): 379- 384.
	CHU S M , SU L Q , YU T T , et al. Preparation of molecularly imprinted polymer by composite template and study on its adsorption properties for flavonoids[J]. Journal of Analytical Science, 2020, 36 (3): 379- 384.
16	闫艳, 李宁, 朱旭东, 等. 分子印迹技术应用: 真菌发酵液中紫杉醇的分离富集[J]. 南开大学学报(自然科学版), 2016, 49 (3): 98- 104.
	YAN Y , LI N , ZHU X D , et al. Separation and enrichment of the paclitaxel from fungal fermentation liquid by molecular imprinting technology[J]. Acta Scientiarum Naturalium Universitatis Nankaiensis, 2016, 49 (3): 98- 104.
17	王小刚, 惠俊峰, 雷闫盈. 东北红豆杉枝叶中紫杉醇和10-脱乙酰巴卡亭的分离纯化及检测[J]. 食品与药品, 2006, 8 (12): 35- 37.
	WANG X G , HUI J F , LEI Y Y . Separation, purification and determination of paclitaxel and 10-deacetyl baccatin from Taxus cuspidata leaves[J]. Food and Drug, 2006, 8 (12): 35- 37.
18	PATAER P , MUHAMMAD T , TURAHUN Y , et al. Preparation of a stoichiometric molecularly imprinted polymer for auramine O and application in solid-phase extraction[J]. Journal of Separation Science, 2019, 42 (8): 1634- 1643.
19	段玉清, 张海晖, 徐菲菲, 等. 分子印迹-固相萃取法选择性分离大黄酸的研究[J]. 林产化学与工业, 2009, 29 (5): 35- 40.
	DUAN Y Q , ZHANG H H , XU F F , et al. Selective separation of rhein by moleculari mprinting polymer and solid-phase extraction[J]. Chemistry and Industry of Forest Products, 2009, 29 (5): 35- 40.
20	甄铧. RP-HPLC法测定欧洲红豆杉中10-脱乙酰巴卡亭Ⅲ的含量[J]. 中国药房, 2009, 20 (27): 2125- 2127.
	ZHEN H . Determination of 10-deacetyl-bacratin Ⅲ in Taxus baccata by RP-HPLC[J]. Chinese Pharmacy, 2009, 20 (27): 2125- 2127.
21	胡杰, 蒋剑平, 熊耀康, 等. HPLC、UPLC测定南方红豆杉中10-脱乙酰巴卡亭Ⅲ的含量[J]. 中国中医药科技, 2016, 23 (2): 168- 169. 168-169, 171
	HU J , JIANG J P , XIONG Y K , et al. Determination of 10-deacetylbacartin Ⅲ in Taxus chinensis by HPLC and UPLC[J]. Chinese Journal of Traditional Medicine Science and Technology, 2016, 23 (2): 168- 169. 168-169, 171
22	吴焕领, 魏赛男, 崔淑玲. 吸附等温线的介绍及应用[J]. 染整技术, 2006, 28 (10): 12- 14. 12-14, 27
	WU H L , WEI S N , CUI S L . Introduction and application of adsorption isotherm[J]. Textile Dyeing and Finishing Journal, 2006, 28 (10): 12- 14. 12-14, 27
23	JEPPU G , CLEMENT P . A modified Langmuir-Freundlich isotherm model for simulating pH-dependent adsorption effects[J]. Journal of Contaminant Hydrology, 2012, 129 (130): 46- 53.
24	曾嵘. 壳聚糖/聚乙烯醇共混交联和亲和膜的制备及应用研究[D]. 武汉: 湖北大学, 2018.
	ZENG R. Preparation and application of cross-linked chitosan/polyvinyl alcohol blending and affinity membranes[D]. Wuhan: Hubei University, 2018.
25	CAO J S , SHEN C , WANG X Q , et al. A porous cellulose-based molecular imprinted polymer for specific recognition and enrichment of resveratrol[J]. Carbohydrate Polymers, 2021, 181 (30): 1231- 1242.

项目 items		吸附量/(mg·g^-1) adsorption capacity	聚合度/% degree of polymerization
功能单体种类 types of functional monomer	MAA	13.46	60.98
	AM	20.21	63.05
	4-VP	27.41	69.74
n_10-DAB∶n_4-VP	1∶6	7.02	55.34
	1∶7	18.54	63.98
	1∶8	8.59	56.17
	1∶9	18.06	63.52
	1∶10	27.41	69.73
n_10-DAB∶n_EGDMA	1∶20	19.49	65.34
	1∶30	27.42	69.69
	1∶40	26.41	66.62
	1∶50	20.07	65.04
聚合温度 polymerization temp.	50 ℃	27.10	69.38
	60 ℃	27.41	69.63
	70 ℃	15.34	60.16

样品 sample	准一级动力学pseudo-first-order			准二级动力学pseudo-second-order
样品 sample	Q_e	K₁	R²	Q_e	K₂	R²
10-DAB-MINs	38.75	0.021 4	0.978 7	45.16	5.44×10^-4	0.979 5
NINs	22.98	0.035 4	0.904 3	25.91	1.80×10^-3	0.821 8

样品 sample	Langmuir			Freundlich			Langmuir-Freundlich
样品 sample	Q_max	K_L	R²	1/n	K_F	R²	Q_max	K_d	R²
10-DAB-MINs	48.93	23.079	0.974 1	0.649 2	500.587	0.967 7	48.90	0.043	0.982 7
NINs	32.13	3.312	0.959 6	0.872 6	162.224	0.958 7	32.10	0.301	0.973 1

吸附质 adsorbate	吸附量adsorption capacity/(mg·g^-1)
吸附质 adsorbate	10-DAB-MINs	NINs
10-DAB	37.08	17.98
巴卡亭Ⅲ Baccatine Ⅲ	17.49	13.11
紫杉醇paclitaxel	20.41	10.22

[1]	李帅, 肖来辉, 王义刚, 陈洁, 李文斌, 聂小安. 水性粘缸剂的制备及表征[J]. 林产化学与工业, 2022, 42(5): 83-90.
[2]	郑昊, 周景辉, 李尧. 生物质基炭气凝胶的制备及其应用于超级电容器[J]. 林产化学与工业, 2022, 42(5): 76-82.
[3]	赵丽红, 柯珣, 吴敏, 王志伟, 钱丽颖, 任俊莉. AKD预絮聚工艺对纸张施胶效果的影响[J]. 林产化学与工业, 2022, 42(5): 69-75.
[4]	何旭华, 石志娇, 彭小伟, 阚欢, 赵平, 刘云. 云南金花茶叶不同极性提取物的抗氧化活性分析[J]. 林产化学与工业, 2022, 42(5): 61-68.
[5]	李耀仓, 邵嘉薇, 马红霞. 松香改性腰果酚漆膜性能的研究[J]. 林产化学与工业, 2022, 42(5): 56-60.
[6]	邹壬萱, 段文贵, 林桂汕, 李宝谕, 崔玉成. 含偕二甲基环丙烷的1, 3, 4-噻二唑-硫脲化合物的合成、抑菌活性及3D-QSAR研究[J]. 林产化学与工业, 2022, 42(5): 45-55.
[7]	罗路, 罗凌聪, 邓剑平, 周亚兰, 范毜仔, 赵伟刚. 杉木树皮基活性炭的制备、表征及其电化学性能研究[J]. 林产化学与工业, 2022, 42(5): 37-44.
[8]	曾磊, 易冯梅, 曹宇, 史伯安, 雷福厚. 漆酚酯键合SiO₂色谱柱分离纯化天麻素及其热力学研究[J]. 林产化学与工业, 2022, 42(5): 30-36.
[9]	傅成龙, 孟霞, 高超, 刘忠明, 王守娟, 孔凡功. 木质素磺酸钠双网络水凝胶的制备及其性能研究[J]. 林产化学与工业, 2022, 42(5): 23-29.
[10]	亓坤, 赵彦芝, 许海棠, 雷福厚, 龙寒, 周菊英. 脱氢枞酸三羟甲基丙烷-丙二酸聚酯的制备及其胶束聚集研究[J]. 林产化学与工业, 2022, 42(5): 15-22.
[11]	姜伟, 辛颖, 巩明月, 王伟众, 王东军, 孙勇. 双金属氧化物 Co₃AlO_x 催化糠醛加氢制备糠醇[J]. 林产化学与工业, 2022, 42(5): 8-14.
[12]	李翠环, 陈胜, 毛健贞, 牟佳慧, 邵自强, 许凤. 电纺纳米纤维基柔性压力传感器的制备及性能研究[J]. 林产化学与工业, 2022, 42(5): 1-7.
[13]	薄采颖, 陈幸良, 周永红, 胡立红. 虫茶营养成分分析及评价[J]. 林产化学与工业, 2022, 42(5): 100-106.
[14]	杨赛瑜, 张亚楠, 李彤, 刘六军, 蒋建新, 段久芳. FeCl₃/聚丙烯酸透明导电木材的制备及性能研究[J]. 林产化学与工业, 2022, 42(5): 107-112.
[15]	李学琴, 刘鹏, 吴幼青, 雷廷宙, 吴诗勇, 黄胜. 生物质气化技术的发展现状及展望[J]. 林产化学与工业, 2022, 42(5): 113-121.