生物模板法制备磁性中空微球的方法和应用

doi:10.16085/j.issn.1000-6613.2020-1283

摘要/Abstract

摘要：

磁性中空微球在功能性吸附、酶固定化载体、物质的分离纯化、活性物质和药物的封装与控释、靶向给药、污染防治、食品和材料学等领域有突出的应用价值。文章综述了利用生物模板法制备磁性中空微球的制备原理和最新研究成果，并主要分析了软模板法和自模板法两种制备工艺。软模板法工艺主要通过吸附-高温炭化法除去生物模板材料获得固定外形的磁性中空微球。自模板法制备磁性中空微球可依据生物材料自身成分经水热碳化反应或在惰性气体氛围保护下的高温炭化反应生成具有特殊官能团结构的中空碳微球，并将磁性物质溶入或吸附到中空微球中，具体分为水热碳化法和浸渍-高温炭化法；也可将制备好的磁性物质吸附于经过特殊处理过的生物模板材料表面，如吸附-共沉淀法和高温炭化-共沉淀法。总之，生物模板法制备磁性中空微球条件较为温和、无污染，生物模板材料对人体无毒，特别适合于食品、医药等行业的应用，具有很好的生产应用前景。

关键词: 生物模板, 磁性中空微球, 高温炭化, 水热, 生物质, 复合材料

Abstract:

Magnetic hollow microsphere has the prominent application in functional adsorption, immobilized carriers of enzyme, separation and purification of substances, encapsulation and controlled release of active substance and medicine, targeted drug delivery, contaminant prevention, food and material science. The article summarizes the preparation principle of magnetic hollow microsphere by bio-template method and research achievement, and mainly analyzes the two preparation technologies, soft template method and self-template method. Soft-template technologies adopt adsorption-calcination method for obtaining stable shapes of the microsphere when removing template materials. Self-template technologies adopt the methods of hydrothermal carbonization or calcination under the protection of inert gas to create special groups on the surface of hollow microsphere and hollow spherical structure which cause the magnetic substances to be adsorbed on and enter into the microspheres, and they can be classified as hydrothermal carbonization method and dipping-calcination method. Besides, the adsorption of magnetic substances on the surface of pretreated bio-template is another way, such as adsorption-coprecipitation and calcination-coprecipitation. In conclusion, the conditions of preparing magnetic hollow microsphere by bio-template are gentle and non-contaminant, and moreover, bio-template materials are nontoxic, so it will have the wide application in food processing and pharmaceutical industry.

Key words: bio-template, magnetic hollow microsphere, calcination, hydrothermal, biomass, composites

中图分类号:

黄冠华, 刘序彦, 房晨曦, 顾庆峰, 雷浩. 生物模板法制备磁性中空微球的方法和应用[J]. 化工进展, 2021, 40(5): 2613-2623.

HUANG Guanhua, LIU Xuyan, FANG Chenxi, GU Qingfeng, LEI Hao. Methods and application of magnetic hollow microsphere prepared from bio-template[J]. Chemical Industry and Engineering Progress, 2021, 40(5): 2613-2623.

图/表 14

参考文献 53

1	陈艳华. 磁性微球的制备及其用于免疫层析检测中的研究[D]. 南京: 东南大学, 2016.
	CHEN Yanhua. Study of magnetic microspheres and their use in lateral flow immunoassay[D]. Nanjing: Southeast University, 2016.
2	ZHOU Xuan, YOU Shijie, WANG Xiuheng, et al. Hydrothermal synthesis of magnetic carbon microspheres for effective adsorption of Cd(Ⅱ) in water[J]. Journal of Chemical Technology & Biotechnology, 2014, 89: 1051-1059.
3	王苗苗. 介孔二氧化硅磁性复合微球的制备及漆酶固定化[D]. 北京: 北京工业大学, 2012.
	WANG Miaomiao. Mesoporous silica magnetic composite microspheres: preparation and laccase immobilization[D]. Beijing: BeijingUniversity of Technology, 2012.
4	LORCH M, THOMASSON M J, DIEGO-TABOADA A, et al. MRI contrast agent delivery using spore capsules: controlled release in blood plasma[J]. Chemical Communication, 2009(42): 6442-6444.
5	YANG Zhenfeng, CUI Bin, BU Yumei, et al. Preparation of flower-dewdrops Fe₃O₄/carbon-SiO₂ microsphere for microwave-triggered drug delivery[J]. Journal of Alloys and Compounds, 2019, 775: 826-835.
6	马丽霞, 余兰. 磁性药物载体在抗肿瘤方面的研究进展[J]. 药学研究, 2019, 38(4): 225-228.
	MA Lixia, YU Lan. Reseach progress of magnetic drug carriers in antitumor[J]. Journal of Pharmaceutical Research, 2019, 38(4): 225-228.
7	刘庆祖, 杨慧恺, 刘建恒, 等. 磁性纳米颗粒在肿瘤药物及肿瘤治疗中的研究进展[J]. 解放军医学院学报, 2020, 41(4): 409-412.
	LIU Qingzu, YANG Huikai, LIU Jianheng, et al. Research advances in magnetic nanoparticles for chemotherapy drug-delivery[J]. Academic Journal of Chinese PLA Medical School, 2020, 41(4): 409-412.
8	WANG Guangshuo, ZHAO Dexing, LI Nannan, et al. Drug-loaded poly(ε-caprolactone)/Fe₃O₄ composite microspheres for magnetic resonance imaging and controlled drug delivery[J]. Journal of Magnetism and Magnetic Materials, 2018, 456: 316-323.
9	徐雪. 磁性复合TiO₂中空微球的制备及药物缓释性能研究[D]. 哈尔滨: 哈尔滨工业大学, 2014.
	XU Xue. Study on the preparation of magnetic composite TiO₂ hollow microspheres and application for the drug delivery[D]. Harbin: Harbin Institute of Technology, 2014.
10	王春蕾. 磁性纳米中空材料的制备及载药性能研究[D]. 长春: 吉林大学, 2012.
	WANG Chunlei. Study on the preparation and drug-loading property of magnetic hollow materials[D]. Changchun: Jilin University, 2012.
11	那丽丽. 中空磁性Fe₃O₄/SiO₂@CMCS复合微球的制备及药物缓释和固定化酶应用研究[D]. 西安: 陕西师范大学, 2013.
	NA Lili. Hollow magnetic Fe₃O₄/SiO₂@CMCS preparation of composite microspheres and application of drug sustained release and immobilized enzyme[J]. Xi’an: Shaanxi Normal University, 2013.
12	周田, 袁俊杰, 浦鸿汀, 等. 二氧化硅/MeFe₂O₄中空复合微球的制备、结构及其磁性能[J]. 功能材料, 2010, 41: 1232-1235.
	ZHOU Tian, YUAN Junjie, PU Hongting, et al. Preparation, structure and magnetic properties of silica/MeFe₂O₄ hollow composite spheres[J]. Journal of Functional Materials, 2010, 41: 1232-1235.
13	LU Lu, Li Jia, YU Jing, et al. A hierarchically porous MgFe₂O₄/γ-Fe₂O₃ magnetic microspheres for efficient removals of dye and pharmaceutical from water[J]. Chemical Engineering Journal, 2016, 283: 524-534.
14	NEVEU S, BEE A, ROBINEAU M, et al. Size-selective chemical synthesis of tartrate stabilized cobalt ferrite ionic magnetic fluid[J]. Journal of Colloid and Interface Science, 2002, 255: 293-298.
15	MORNET S, GRASSET F, DUGUET E, et al. Magnetic nanoparticle design for medical diagnosis and therapy[J]. Journal of Materials Chemistry, 2004, 14: 2161-2175.
16	SUN Shouheng, MURRAY C B, WELLER D, et al. Monodisperse FePt nanoparticles and ferromagnetic FePt nanocrystal superlattices[J]. Science, 2000, 287(5460): 1989-1992.
17	SHEVECHENKO E V, TALAPIN D V, ROGACH A L. Charge carrier dynamics in colloidal semiconductors[J]. Journal of the American Chemical Society, 2002, 124: 11480-11485.
18	CHEN Q, RONDINONE A J, CHAKOUMAKOS B C. Synthesis of superparamagnetic MgFe₂O₄ nanoparticles by coprecipitation[J]. Journal of Magnetism and Magnetic Materials, 1999, 194(1/2/3): 1-7.
19	HUANG Guanhua, CHEN Feng, KUANG Yali, et al. Current techniques of growing algae using flue gas from exhaust gas industry: a review[J]. Applied Biochemistry and Biotechnology2016, 178: 1220-1238.
20	BI Lei, PAN Gang. Facile and green fabrication of multiple magnetite nano-cores@porous shell microspheres for delivery vehicles[J]. Journal of Material Chemistry A, 2014, 2: 3715-3718.
21	NI Dezhi, WANG Lei, SUN Yunhui, et al. Amphiphilic hollow carbonaceous microspheres with permeable shells[J]. Angewandte Chemie: International Edition, 2010, 49(25): 4223-4227.
22	GOMEZ J H, HÖFFNER K, BARTON P I. From sugars to biodiesel using microalgae and yeast[J]. Green Chemistry, 2016, 18: 461-475.
23	EBRAHIMINEZHAD A, NAJAFIPOUR S, KOUHPAYEH A, et al. Facile fabrication of uniform hollow silica microspheres using a novel biological template[J]. Colloids and Surfaces B: Biointerfaces, 2014, 118: 249-253.
24	YANG Dapeng, CHEN Shouhui, HUANG Peng, et al. Bacteria-template synthesized silver microspheres with hollow and porous structures as excellent SERS substrate[J]. Green Chemistry, 2010, 12(11): 2038.
25	张昔玉, 葛圣松, 邵谦, 等. 酵母菌模板法制备CeO₂空心微球及其光催化性能[J]. 无机化学学报, 2016, 32(9): 1535-1542.
	ZHANG Xiyu, GE Shengsong, SHAO Qian, et al. Synthesis and photocatalytic activity of CeO₂ hollow microspheres via yeast template route[J]. Chinese Journal of Inorganic Chemistry, 2016, 32(9): 1535-1542.
26	DIEGO-TABOADA A, MAILLET L, BANOUB J H, et al. Protein free microcapsules obtained from plant spores as a model for drug delivery: ibuprofen encapsulation, release and taste masking[J]. Journal of Materials Chemistry B, 2013, 1: 707-713.
27	ZHAO Baoqin, SHAO Qian, HAO Luhan, et al. Yeast-template synthesized Fe-doped cerium oxide hollow microspheres for visible photodegradation of Acid Orange 7[J]. Journal of Colloid and Interface Science, 2018, 511: 39-47.
28	SUN Qinglei, TANG Mei, HENDRIKSEN P V, et al. Biotemplated fabrication of a 3D hierarchical structure of magnetic ZnFe₂O₄/MgAl-LDH for efficient elimination of dye from water[J]. Journal of Alloys and Compounds, 2020, 829: 154552.
29	毕磊, 潘纲. 微生物自模板法制备多孔中空微球及应用[J]. 科学通报, 2014, 59(25): 2440-2451.
	BI Lei, PAN Gang. Preparation and application of hollow microspheres with porous shell via microorganism self-template method[J]. Chinese Science Bulletin, 2014, 59(25): 2440-2451.
30	孙予罕, 朱春春, 孔令照, 等. 一种基于微藻的磁性生物碳复合材料制备方法: CN105233792A[P]. 2016-01-13.
	SUN Yuhan, ZHU Chunchun, KONG Lingzhao, et al. Magnetic biochar composite material preparation method based on microalgae: CN105233792A[P]. 2016-01-13.
31	王东升, 邹瑜斌, 肖峰, 等. 一种磁性微藻基生物炭的制备方法及其应用: CN109876810A[P]. 2019-06-14.
	WANG Dongsheng, ZOU Yubing, XIAO Feng, et al. Preparation and application of magnetic microalgae based biochar: CN109876810A[P]. 2019-06-14.
32	TAN Hongyi, ZHANG Peng, WANG Lei, et al. Multifunctional amphiphilic carbonaceous microcapsules catalyze water/oil biphasic reactions[J]. Chemical Communication, 2011, 47: 11903-11905.
33	GUAN Zhengrong, LIU Li, HE Lilu, et al. Amphiphilic hollow carbonaceous microspheres for the sorption of phenol from water[J]. Journal of Hazardous Materials, 2011, 196: 270-277.
34	CAI Bin, ZHAO Minggang, MA Ye, et al. Bioinspired formation of 3D hierarchical CoFe₂O₄ porous microspheres for magnetic-controlled drug release[J]. Applied Materials and Interfaces, 2015, 7: 1327-1333.
35	李黎明. 磁性藻的制备及其对刚果红和亚甲基蓝废水吸附脱色效果研究[D]. 秦皇岛: 燕山大学, 2017.
	LI Liming. The preparation of magnetical microalgae and its decolorization of Congo red and methylene blue[D]. Qinhuangdao: Yanshan University, 2017.
36	李晨, 高峰, 赵科全, 等. 一种用于吸附废水中铅的磁性微藻生物吸附剂的制备方法: CN108970588A[P]. 2018-12-11.
	LI Chen, GAO Feng, ZHAO Kequan, et al. Preparation method for magnetic microalgae bio-sorbent for adsorbing lead in wastewater: CN108970588A[P]. 2018-12-11.
37	李晨, 高峰, 杨红丽, 等. 一种复合型磁性微藻生物吸附剂及其吸附废水镉的方法: CN109225163A[P]. 2019-01-18.
	LI Chen, GAO Feng, YANG Hongli, et al. Composite type magnetic microalgae biological absorbent and method there of for absorbing cadmium in wastewater: CN109225163A[P]. 2019-01-18.
38	路晏红, 王彦堂, 周明, 等. 一种微藻基磁性石墨烯和生物炭的制备方法及应用: CN110947369A[P]. 2020-04-03.
	LU Yanhong, WANG Yantang, ZHOU Ming, et al. Preparation method and application of microalgae-based magnetic graphene and biochar: CN110947369A[P]. 2020-04-03.
39	王珏玉. 磁性灵芝孢子微球的合成、催化性能及应用[D]. 哈尔滨: 东北林业大学, 2017.
	WANG Jueyu. Synthesis and catalytic performance of magnetic Ganoderma lucidum spore microspheres and its application[D]. Harbin: Northeast Forestry University, 2017.
40	陶惠箐. 以廉价模板制备磁性ZSM-5中空纤维与微球的研究[D]. 南京: 南京工业大学, 2008.
	TAO Huijing. Preparation of magnetic ZSM-5 hollow fiber and microspheres by cheap template[D]. Nanjing: Nanjing University of Technology, 2008.
41	欧阳兆辉, 伍林, 易德莲. Co、Ce共掺杂TiO₂-SiO₂/NiFe₂O₄磁性介孔微球的光催化性能[J]. 化工环保, 2012, 32(5): 466-470.
	OUYANG Zhaohui, WU Lin, YI Delian. Photocatalytic activity of Co-Ce codoped TiO₂-SiO₂/NiFe₂O₄ magnetic mesoporous microspheres[J]. Environmental Protection of Chemical Industry, 2012, 32(5): 466-470.
42	ZHAO Wenru, CHEN Hangrong, LI Yongsheng, et al. Uniform rattle-type hollow magnetic mesoporous spheres as drug delivery carriers and their sustained-release property[J]. Advanced Functional Materials, 2008, 18(18): 2780-2788.
43	解林艳, 李艳群, 王志宏, 等. 介孔SiO₂/Fe₃O₄中空磁性复合微球的制备与表征[J]. 无机化学学报, 2010, 26(10): 1756-1760.
	XIE Linyan, LI Yanqun, WANG Zhihong, et al. Preparation and characterization of Fe₃O₄/mesoporous SiO₂ hollow microsphere[J]. Chinese Journal of Inorganic Chemistry, 2010, 26(10): 1756-1760.
44	刘潇. 实心及中空型磁性高分子复合微球的制备及其固定化脂肪酶的研究[D]. 兰州: 兰州大学, 2013.
	LIU Xiao. Preparation of solid and hollow magnetic polymer supports and their application for lipase immobilization[D]. Lanzhou: Lanzhou University, 2013.
45	SHCHUKIN D, MOHWALD H. A coat of many functions[J]. Science, 2013, 341(6153): 1458-1459.
46	佟若菲, 张囡, 李维超, 等. 自模板法制备中空介孔硅球及其载药释药性能的研究[J]. 天津医科大学学报, 2017, 23(6): 562-566.
	TONG Ruofei, ZHANG Nan, LI Weichao, et al. Preparation of hollow mesoporous silica nanaparticles by template method and study of drug loading release properties[J]. Journal of Tianjin Medical University, 2017, 23(6): 562-566.
47	ZHOU Han, FAN Tongxiang, ZHANG Di. Biotemplated materials for sustainable energy and environment: current status and challenges[J]. ChemSusChem, 2011, 4: 1344-1387.
48	SCHNEPP Z, YANG Wen, ANTONIETTI M, et al. Biotemplating of metal carbide microstructures: the magnetic leaf[J]. Angewandte Chemie: International Edition, 2010, 49: 6564-6566.
49	LIU Jian, QIAO Shizhan, HU Qiuhong, et al. Magnetic nanocomposites with mesoporous structures: synthesis and applications[J]. Small, 2011, 7: 425-443.
50	YILMAZ E, SEZGIN M, YILMAZ M. Enantioselective hydrolysis of rasemic naproxen methyl ester with sol-gel encapsulated lipase in the presence of sporopollenin[J]. Journal of Molecular Catalysis B: Enzymatic, 2010, 62: 162-168.
51	ZHAO Wenru, GU Jinlou, ZHANG Lingxia, et al. Fabrication of uniform magnetic nanocomposite spheres with a magnetic core/mesoporous silica shell structure[J]. Journal of the American Chemical Society, 2005, 127: 8916-8917.
52	DIEGO-TABOADA A, COUSSON P, RAYNAUD E, et al. Sequestration of edible oil from emulsions using new single and double layered microcapsules from plant spores[J]. Journal of Material Chemistry, 2012, 22: 9767-9773.
53	岳敏, 赵熙宁, 宋亚楠, 等. 蛋白核小球藻超声波破壁方法的优化[J]. 山西农业大学学报(自然科学版), 2018, 38(10): 37-42.
	YUE Min, ZHAO Xining, SONG Yanan, et al. Optimization study on the ultrasonic treatment for cell wall disruption of Chlorella pyrenoidosa[J]. Journal of Shanxi Agricultural University (Natural Science Edition), 2018, 38(10): 37-42.

制备技术	模板组成	微球组成	制备方法	微球构型	参考文献
软模板法	酵母	Fe 掺杂CeO₂	共沉淀+高温炭化	壳磁型	[27]
	松花粉	MgFe₂O₄/γ-Fe₂O₃	高温炭化+水热碳化	壳磁型	[13]
	松花粉	ZnFe₂O₄/MgAl-LDH	高温炭化+水热碳化	壳磁型	[28]
	油菜花粉	ZSM-5/SiO₂/Fe₃O₄	共沉淀+高温炭化	多磁壳型	[40]
自模板法	微藻	Fe₃O₄+生物炭	高温炭化	壳磁型	[29]
	微藻	Fe₃O₄+生物炭	水热碳化+高温炭化	壳磁型	[30]
	微藻	Fe₃O₄+生物炭	水热碳化	多磁核型	[20]
	蒲公英花粉	CoFeO₄	水热碳化	多磁核型	[34]
	微藻	Fe₃O₄+微藻	吸附	磁壳型	[35]
	微藻	Fe₃O₄+微藻	吸附+共沉淀	磁壳型	[36-37]
	微藻	石墨烯+Fe₃O₄+生物炭+微藻	吸附+共沉淀	磁壳型	[38]
	灵芝孢子	生物炭+ Fe₃O₄	高温炭化+共沉淀	磁壳型	[39]

制备技术	模板组成	微球组成	制备方法	微球构型	参考文献
软模板法	酵母	Fe 掺杂CeO₂	共沉淀+高温炭化	壳磁型	[27]
	松花粉	MgFe₂O₄/γ-Fe₂O₃	高温炭化+水热碳化	壳磁型	[13]
	松花粉	ZnFe₂O₄/MgAl-LDH	高温炭化+水热碳化	壳磁型	[28]
	油菜花粉	ZSM-5/SiO₂/Fe₃O₄	共沉淀+高温炭化	多磁壳型	[40]
自模板法	微藻	Fe₃O₄+生物炭	高温炭化	壳磁型	[29]
	微藻	Fe₃O₄+生物炭	水热碳化+高温炭化	壳磁型	[30]
	微藻	Fe₃O₄+生物炭	水热碳化	多磁核型	[20]
	蒲公英花粉	CoFeO₄	水热碳化	多磁核型	[34]
	微藻	Fe₃O₄+微藻	吸附	磁壳型	[35]
	微藻	Fe₃O₄+微藻	吸附+共沉淀	磁壳型	[36-37]
	微藻	石墨烯+Fe₃O₄+生物炭+微藻	吸附+共沉淀	磁壳型	[38]
	灵芝孢子	生物炭+ Fe₃O₄	高温炭化+共沉淀	磁壳型	[39]

制备技术	模板组成	制备方法	微球组成	参考文献
硬模板法
非生物模板	SiO₂	碱液蚀溶	γ-Fe₂O₃/TiO₂	[9]
非生物模板	Fe₃O₄/CaCO₃	酸液蚀溶	Fe₃O₄/PMMA	[10]
软模板法
生物模板	油菜花粉	共沉淀+高温炭化	ZSM-5/SiO₂/Fe₃O₄	[40]
非生物模板	十二烷基磺酸钠，聚乙烯吡咯烷酮	高温炭化	(Co,Ce)-TiO₂-SiO₂/NiFe₂O₄	[41]
	聚苯乙烯	高温煅烧	Fe₃O₄/SiO₂	[11]
	十八烷基三甲氧基硅烷	水热碳化	γ-Fe₂O₃/SiO₂	[42]
硬模板法+软模板法
非生物模板	SiO₂，十八烷基三甲氧基硅烷	碱液蚀溶+高温炭化	Fe₃O₄/SiO₂	[43-45]
自模板法
生物模板	微藻	高温炭化	Fe₃O₄+生物炭	[13]
非生物模板	SiO₂	共沉淀	SiO₂/MeFe₂O₄	[12]

制备技术	模板组成	制备方法	微球组成	参考文献
硬模板法
非生物模板	SiO₂	碱液蚀溶	γ-Fe₂O₃/TiO₂	[9]
非生物模板	Fe₃O₄/CaCO₃	酸液蚀溶	Fe₃O₄/PMMA	[10]
软模板法
生物模板	油菜花粉	共沉淀+高温炭化	ZSM-5/SiO₂/Fe₃O₄	[40]
非生物模板	十二烷基磺酸钠，聚乙烯吡咯烷酮	高温炭化	(Co,Ce)-TiO₂-SiO₂/NiFe₂O₄	[41]
	聚苯乙烯	高温煅烧	Fe₃O₄/SiO₂	[11]
	十八烷基三甲氧基硅烷	水热碳化	γ-Fe₂O₃/SiO₂	[42]
硬模板法+软模板法
非生物模板	SiO₂，十八烷基三甲氧基硅烷	碱液蚀溶+高温炭化	Fe₃O₄/SiO₂	[43-45]
自模板法
生物模板	微藻	高温炭化	Fe₃O₄+生物炭	[13]
非生物模板	SiO₂	共沉淀	SiO₂/MeFe₂O₄	[12]

制备技术	模板来源	生产工艺	模板去除率	产品构型	环境保护	生物兼容性
生物模板法
软模板法	自然界（受限）	简单	高	好控制	好	好
自模板法	自然界（受限）	简单	—	好控制	好	好
非生物模板法	无机和有机材料（不受限）	较复杂	一般	不好控制	差	待评估