核-壳结构分子印迹材料用于定向脱苦的研究

doi:10.11949/0438-1157.20200210

摘要/Abstract

摘要：

以SiO₂为支撑材料、甲基丙烯酸（MAA）为功能单体、偶氮二异丁腈（AIBN）为引发剂、乙二醇二甲基丙烯酸酯（EGDMA）为交联剂，制备了可选择性吸附柠檬汁中苦味物质的表面分子印迹聚合物（SMIPs）材料。利用透射电镜和红外吸收光谱等手段对SMIPs进行表征，随后进行吸附能力和选择性研究。结果表明，SMIPs具有核-壳结构，且有着良好的吸附性能（27.72 mg/g）和快速吸附能力（60 min），吸附符合二级动力学模型，吸附过程符合Langmuir单层吸附模型。最后，将SMIPs用于柠檬汁中苦味物质吴茱萸内酯的去除，结果显示SMIPs具有良好的脱苦性能。

关键词: 核-壳材料, 纳米材料, 二氧化硅, 表面分子印迹, 吸附剂, 苦味物质, 脱苦

Abstract:

SiO₂ as the support material, methacrylic acid (MAA) as the functional monomer, azodiisobutyronitrile (AIBN) as the initiator, ethylene glycol dimethacrylate (EGDMA) as the cross-linking agent, a surface molecularly imprinted polymer (SMIPs) material which can selectively absorb bitter substances in lemon juice was prepared. Transmission electron microscopy and infrared absorption spectroscopy were used to characterize the SMIPs, followed by adsorption capacity and selectivity studies. The results showed that SMIPs had core-shell structure, good adsorption performance (27.72 mg/g) and fast adsorption capacity (60 min). The adsorption was in accordance with the second-order kinetic model, and the adsorption process was in accordance with the Langmuir monolith adsorption model. Finally, SMIPs were used to remove the bitter substance evodine in lemon juice, and the result showed that SMIPs had good desiccation ability.

Key words: core-shell material, nanomaterials, silica, surface molecular imprinting, sorbents, bitter substances, take off the bitter

中图分类号:

R 917

蒋壮飞, 何家垣, 马蓉蓉, 李清瑶, 杨莉莉, 谭玲, 张起辉. 核-壳结构分子印迹材料用于定向脱苦的研究[J]. 化工学报, 2020, 71(10): 4704-4710.

Zhuangfei JIANG, Jiayuan HE, Rongrong MA, Qingyao LI, Lili YANG, Ling TAN, Qihui ZHANG. Molecularly imprinted materials with core-shell structure for directed desiccation[J]. CIESC Journal, 2020, 71(10): 4704-4710.

图/表 7

图1 表面分子印迹材料的合成示意图及其脱苦步骤

Fig.1 Schematic representation of the preparation of surface molecularly imprinted materials and the process of debitterization

图2 合成条件的优化

Fig.2 Optimization of synthesis conditions

图3 表面分子印迹材料的表征

Fig.3 Characterization of surface molecularly imprinted materials

图4 材料的吸附性能

Fig.4 Adsorption capacity of materials

表1 一级和二级动力学模型拟合参数

Table 1 Relevant parameters of pseudo-first-order and pseudo-second-order model

Samples

Pseudo-first-order

Pseudo-second-order

Q_e/

(mg/g)

K₁/min^-1

R²

Q_e/

(mg/g)

K₂/

(g/(mg·min))

R²

表2 Langmuir和Freundlich 方程拟合参数

Table 2 Relevant parameters of Langmuir and Freundlich equation

Samples

Langmuir

Freundlich

Q_m/

(mg/g)

K_L/

(L/mg)

R²

K_F/

(mg/g)

R²

图5 表面分子印迹材料对柠檬汁的脱苦过程的液相色谱图a— MIP脱苦后的洗脱液；b— 脱苦后柠檬汁；c—脱苦前柠檬汁；d—吴茱萸内酯标品

Fig.5 Liquid chromatogram of demitoring process of lemon juice by surface molecularly imprinted materials

参考文献 29

1	左安连, 毛海舫, 李琼. 柑橘类果汁脱苦方法研究综述 [J]. 香料香精化妆品, 2008, (3): 33-39.
	Zuo A L, Mao H F, Li Q. A review on the methods of removing bitterness from citrus juice [J]. Fragrance Cosmetics, 2008, (3): 33-39.
2	潘利华, 徐迪, 布文婕. 柑橘类果汁脱苦的研究进展 [J]. 饮料工业, 2006, (2): 6-9.
	Pan L H, Xu D, Bu W J. Research progress of citrus fruit juice anti-bitterness [J]. Beverage Industry, 2006, (2): 6-9.
3	孙明元, 尹燕, 林洪斌, 等. 柠檬汁脱苦工艺条件研究 [J]. 食品科技, 2014, (10): 106-108.
	Sun M Y, Yin Y, Lin H B, et al. Study on the process conditions of removing bitter from lemon juice [J]. Food Science and Technology, 2014, (10): 106-108.
4	Puri M, Kaur A, Singh R S, et al. Immobilized enzyme technology for debittering citrus fruit juices [M]// Busto M D, Ortega N. Food Enzymes: Application of New Technologies. Kerala, India: Transworld Research Network, 2008: 91-104.
5	贺红宇. 三种脱苦方法对柠檬汁脱苦效果的研究 [D]. 成都: 四川农业大学, 2013.
	He H Y. Study on the effects of three methods of removing bitterness from lemon juice [D]. Chengdu: Sichuan Agricultural University, 2013.
6	Leeh S, Kimj G. Effects of debittering on red grapefruit contratr [J]. Food Chem., 2003, 82: 177-1801.
7	Tasselli F, Donato L, Drioli E. Evaluation of molecularly imprinted membranes based on different acrylic copolymers [J]. J. Membrane Sci., 2008, 320: 167-172.
8	Trotta F, Drioli E, Baggiani C. Molecular imprinted polymeric membrane for naringin recognition [J]. J. Membrane Sci., 2002, 201: 77-84.
9	张晨, 刘志伟. 柑橘类果汁的脱苦 [J]. 江苏食品与发酵, 2000, (3): 26-28.
	Zhang C, Liu Z W. Delamination of citrus fruit juices [J]. Jiangsu Food and Fermentation, 2000, (3): 26-28.
10	Busto M D, Cavia-Saiz M, Ortega N, et al. Chapter 20 Enzymatic debittering on antioxidant capacity of grapefruit juice [M]//Processing & Impact on Antioxidants in Beverages. Elsevier Inc., 2014: 195-202.
11	吴雪韦. 朝鲜淫羊藿的化学成分及生物活性研究 [D]. 济南: 山东大学, 2018.
	Wu X W. Study on the chemical composition and biological activity of epimedium from Korea [D]. Jinan: Shandong University, 2018.
12	Cui L, Sun E, Zhang Z H, et al. Metabolite profiles of epimedin B in rats by ultra performance liquid chromatography/quadrupole-time-of-flight mass spectrometry [J]. J. Agri. Food Chem., 2013, 61: 3589-3599.
13	刘永安, 刘欣, 魏法山, 等. 柑橘类果汁脱苦技术研究进展 [J]. 食品安全导刊, 2015, (27): 137-138.
	Liu Y A, Liu X, Wei F S, et al. Research progress of citrus juice desiccation technology [J]. Food Safety Guide, 2015, (27): 137-138.
14	许少丹, 谢婧. 柑橘类果汁脱苦技术研究进展[J]. 饮料工业, 2012, 15(6): 15-19.
	Xu S D, Xie J. Advances in the technology of citrus juice desiccation [J]. Beverage Industry, 2012, 15(6): 15-19.
15	陈秀霞, 张斌. 阳朔金桔脱苦技术的研究现状[J]. 轻工科技, 2015, (11): 1-2.
	Chen X X, Zhang B. Research status of Yangshuo kumquat detaching technology [J]. Light Industry Science and Technology, 2015, (11): 1-2.
16	张夙夙. 袖普酶在柑橘类果汁脱苦中的应用[J]. 安徽农学通报, 2014, (12): 39-44.
	Zhang S S. Application of cuperase in citrus juice desiccating [J]. Journal of Anhui Agriculture, 2014, (12): 39-44.
17	Li X T, Wan J Q, Wang Y, et al. Mechanism of accurate recognition and catalysis of diethyl phthalate (DEP) in wastewater by novel MIL100 molecularly imprinted materials [J]. Applied Catalysis B: Environmental, 2020, 266: 118591.
18	Escobar D, Coelho C, Ruiz M, et al. Molecularly imprinted TiO₂ photocatalysts for degradation of diclofenac in water [J]. Colloid. Surface-A: Physicochemical and Engineering Aspects, 2018, 538: 729-738.
19	Liu Y, Shen T, Hu L, et al. Development of a thermosensitive molecularly imprinted polymer resonance light scattering sensor for rapid and highly selective detection of hepatitis A virus in vitro [J]. Sensor Actuat. B-Chem., 2017, 253: 1188-1193.
20	Yang Q, Li C Y, Li J H, et al. Rational construction of a triple emission molecular imprinting sensor for accurate naked-eye detection of folic acid [J]. Nanoscale, 2020, 12(11): 6529-6536.
21	Dowlatshah S, Saraji M. A silica-based three-dimensional molecularly imprinted coating for the selective solid-phase microextraction of difenoconazole from wheat and fruits samples [J]. Analytica Chimica Acta, 2020, 1098: 37-46.
22	Shi S, Fan D, Xiang H, et al. Effective synthesis of magnetic porous molecularly imprinted polymers for efficient and selective extraction of cinnamic acid from apple juices [J]. Food Chem., 2017, 237: 198-204.
23	Liu M, Li X, Li J, et al. Selective separation and determination of glucocorticoids in cosmetics using dual-template magnetic molecularly imprinted polymers and HPLC[J]. J. Colloid Interface Sci., 2017, 504: 124-133.
24	Zhang Y Z, Qin B, Zhang B, et al. Specific enrichment of caffeic acid from Taraxacum mongolicum Hand.-Mazz. by pH and magnetic dual-responsive molecularly imprinted polymers [J]. Analytica Chimica Acta, 2020, 1096: 193-202.
25	Yin Z Z, Cheng S W, Xu L B, et al. Highly sensitive and selective sensor for sunset yellow based on molecularly imprinted polydopamine-coated multi-walled carbon nanotubes[J]. Biosens. Bioelectron., 2018, 100: 565-570.
26	Leila M, Taghi V M, Moosa E, et al. Design and construction of a carbon paste electrode modified with molecularly imprinted polymer-grafted nanocomposites for the determination of thyroxin in biological samples [J]. Analytical Methods, 2020, 12(3): 333-344.
27	Werner A F, Bohn E. Controlled growth of monodisperse silica spheres in the micron size range[J]. J. Colloid Interf. Sci., 1968, 26: 62-69.
28	吴今人, 耿平, 胡田叶, 等. 柑橘不同部位中柠檬苦素的分布及含量分析[J]. 湖北农业科学, 2015, 54(4): 882-885.
	Wu J R, Geng P, He T Y, et al. Distribution and content of the limonin in different tissues of citrus[J]. Hubei Agriculture Science, 2015, 54(4): 882-885.
29	Peng M, Xiang H, Hu X, et al. Boronate affinity-based surface molecularly imprinted polymers using glucose as fragment template for excellent recognition of glucosides[J]. J. Chromatogr. A, 2016, 1474: 8-13.

[1]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[2]	刘远超, 关斌, 钟建斌, 徐一帆, 蒋旭浩, 李耑. 单层XSe₂（X=Zr/Hf）的热电输运特性研究[J]. 化工学报, 2023, 74(9): 3968-3978.
[3]	陈美思, 陈威达, 李鑫垚, 李尚予, 吴有庭, 张锋, 张志炳. 硅基离子液体微颗粒强化气体捕集与转化的研究进展[J]. 化工学报, 2023, 74(9): 3628-3639.
[4]	盛冰纯, 于建国, 林森. 铝基锂吸附剂分离高钠型地下卤水锂资源过程研究[J]. 化工学报, 2023, 74(8): 3375-3385.
[5]	陈佳起, 赵万玉, 姚睿充, 侯道林, 董社英. 开心果壳基碳点的合成及其对Q235碳钢的缓蚀行为研究[J]. 化工学报, 2023, 74(8): 3446-3456.
[6]	邢美波, 张中天, 景栋梁, 张洪发. 磁调控水基碳纳米管协同多孔材料强化相变储/释能特性[J]. 化工学报, 2023, 74(7): 3093-3102.
[7]	余娅洁, 李静茹, 周树锋, 李清彪, 詹国武. 基于天然生物模板构建纳米材料及集成催化剂研究进展[J]. 化工学报, 2023, 74(7): 2735-2752.
[8]	葛加丽, 管图祥, 邱新民, 吴健, 沈丽明, 暴宁钟. 垂直多孔碳包覆的FeF₃正极的构筑及储锂性能研究[J]. 化工学报, 2023, 74(7): 3058-3067.
[9]	董茂林, 陈李栋, 黄六莲, 吴伟兵, 戴红旗, 卞辉洋. 酸性助水溶剂制备木质纳米纤维素及功能应用研究进展[J]. 化工学报, 2023, 74(6): 2281-2295.
[10]	杨琴, 秦传鉴, 李明梓, 杨文晶, 赵卫杰, 刘虎. 用于柔性传感的双形状记忆MXene基水凝胶的制备及性能研究[J]. 化工学报, 2023, 74(6): 2699-2707.
[11]	刘远超, 蒋旭浩, 邵钶, 徐一帆, 钟建斌, 李耑. 几何尺寸及缺陷对石墨炔纳米带热输运特性的影响[J]. 化工学报, 2023, 74(6): 2708-2716.
[12]	任金胜, 刘克润, 焦志伟, 刘家祥, 于源. 涡流空气分级机近导叶处团聚体解团机理研究[J]. 化工学报, 2023, 74(4): 1528-1538.
[13]	葛运通, 王玮, 李楷, 肖帆, 于志鹏, 宫敬. 多相分散体系中微油滴与改性二氧化硅表面间作用力的AFM研究[J]. 化工学报, 2023, 74(4): 1651-1659.
[14]	肖川宝, 李林洋, 刘武锋, 钟年丙, 解泉华, 钟登杰, 常海星. 光催化与离子交换吸附耦合有效去除2，4，6-三氯苯酚[J]. 化工学报, 2023, 74(4): 1587-1597.
[15]	潘煜, 王子航, 王佳韵, 王如竹, 张华. 基于可得然-氯化锂复合吸附剂的除湿换热器热湿性能研究[J]. 化工学报, 2023, 74(3): 1352-1359.