Preparation of Silica Nanomaterials Encapsulated with Europium Complex of Eu(DBM)3phen for Fluorescence Detection
摘 要
以十六烷基三甲基溴化铵(CTAB)和一种短链氟碳阴离子表面活性剂(Capstone FS-66)作为双模板,通过四乙氧基硅烷(TEOS)和含氯官能团的硅烷偶联剂制备了含氯官能团的大孔径树枝状介孔二氧化硅纳米球(MSNs);利用EuCl3·6H2O、1,10-邻菲啰啉盐酸盐和二苯甲酰甲烷合成铕的配合物Eu (DBM)3phen,然后以MSNs为基质填充Eu (DBM)3phen。为了更好地将Eu (DBM)3phen嵌入到纳米球孔道内,对所制备的介孔纳米球的孔道表面进行聚乙烯亚胺(PEI)修饰;同时为了解决荧光配合物从孔道泄露的问题,在纳米球表面层层自组装吸附多层聚合物,然后包覆一层二氧化硅膜形成核-壳结构。最后将所制备的荧光纳米球与3-氨丙基三乙氧基硅烷反应,使其表面带有氨基,用来嫁接生物分子如抗体等。通过透射电子显微镜(TEM)、荧光光度计和傅里叶红外光谱仪(FTIR)等多种方法对最终合成的纳米球的结构和性能进行了表征。结果表明:本制备的荧光纳米球粒径约为230 μm、荧光强度约为2 800 a.u,1 543 cm-1处出现了氨基的弯曲振动峰。
Abstract
Large bored, twig-like mesoporous silica nanosphenes (abbrv. MSNs) containing Cl-functional group were prepared through the reaction of tetraethoxysilane and a azotizing reagent, Cl-functional group containing silane, taking CTAB and a short-chained fluorocarbon anionic surfactant (Capstone FS-66) as dual-templates. Fluorescent complex of Eu(DBM)3phen, which was synthesized with EuCl3·6H2O, 1,10-phenanthroline hydrochloride and dibenzoylmenthane, was encased into the matrix MSNs, and the surface of bore channels of the MSNs were modified with polyethyleneimine to give a more effective embedding of Eu(DBM)3phen into the bore channels. Furthermore, multilayer polymers were adsorbed on the surface of the nanospheres layer by layer through self-assembly, and then a layer of silica film was encapsulated onto the surface of the nano-spheres to for core-shell structures. Finally, the fluorescent nanospheres were reacted with 3-aminopropyl-triethoxysilane to have amino groups attached on the surfuce, for conjugating with biomolecules, such as anitbodies. The structure and properties of the final product of the nanospheres prepared was characterized by TEM, fluorescence spectrophotometry, FTIR, showing that the fluorescent nanospheres have bore diameters of about 230 nm, given fluorescence intensity of about 2 800 a.u. and bending vibration peak of amino group was observed at 1 543 cm-1.
中图分类号 O657.3 DOI 10.11973/lhjy-hx202003003
所属栏目 试验与研究
基金项目 上海市科委项目(14440502300);上海理工大学沪江基金(D15011)
收稿日期 2019/4/28
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联系人作者黄明贤(hmx@usst.edu.cn)
备注金权,硕士研究生,主要从事生物分析检测方面的研究
引用该论文: JIN Quan,MA Hongyan,HU Fei,WANG Shige,LIU Lu,HUANG Mingxian. Preparation of Silica Nanomaterials Encapsulated with Europium Complex of Eu(DBM)3phen for Fluorescence Detection[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2020, 56(3): 261~267
金权,马红彦,胡飞,王世革,刘璐,黄明贤. 包覆铕配合物Eu (DBM)3phen的硅胶纳米荧光检测材料的制备[J]. 理化检验-化学分册, 2020, 56(3): 261~267
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【3】BAGSHAW S A, PROUZET E, PINNAVAIA T J. Templating of mesoporous molecular sieves by nonionic polyethylene oxide surfactants[J]. Science, 1995,269(5228):1242-1244.
【4】BAE S E, KIM K J, CHOI I H, et al. Preparation of N-doped microporous carbon nanospheres by direct carbonization of as-prepared mesoporous silica nanospheres containing cetylpyridinium bromide template[J]. Carbon, 2016,99:8-16.
【5】HE X, CHEN L, HE G, et al. Cytochrome P450 enzyme-copper phosphate hybrid nano-flowers with superior catalytic performances for selective oxidation of sulfides[J]. Chinese Journal of Chemistry, 2017,35(5):693-698.
【6】ELLIS W C, TRAN C T, DENARDO M A, et al. Design of more powerful iron-TAML peroxidase enzyme mimics[J]. Journal of the American Chemical Society, 2009,131(50):18052-18053.
【7】JIANG Y, LEE C, WANG Q, et al. Monodisperse mesoporous silica nanospheres with radially oriented mesochannels and their size effect on cell uptake[J]. Microporous and Mesoporous Materials, 2013,181:248-253.
【8】GUIDI P, NIGRO M, BERNARDESCHI M, et al. Genotoxicity of amorphous silica particles with different structure and dimension in human and murine cell lines[J]. Mutagenesis, 2013,28(2):171-180.
【9】RAVI S, SELVARAJ M, PARK H, et al. Novel hierarchically dispersed mesoporous silica spheres:effective adsorbents for mercury from wastewater and a thermodynamic study[J]. New Journal of Chemistry, 2014,38(8):3899-3906.
【10】CHEN D, LI Z, WAN Y, et al. Anionic surfactant induced mesophase transformation to synthesize highly ordered large-pore mesoporous silica structures[J]. Journal of Materials Chemistry, 2006,16(16):1511-1519.
【11】HUANG M, LU L, WANG S, et al. Dendritic mesoporous silica nanospheres synthesized by a novel dual-templating micelle system for the preparation of functional nanomaterials[J]. Langmuir, 2016,33(2):519-526.
【12】SCHNIEPP H, SANDOGHDAR V. Spontaneous emission of europium ions embedded in dielectric nanospheres[J]. Physical Review Letters, 2002,89(25):257403-257403.
【13】TAN M, YE Z, WANG G, et al. Preparation and time-resolved fluorometric application of luminescent europium nanoparticles[J]. Chemistry of Materials, 2004,16(12):2494-2498.
【14】DE DOOD M J A, BERKHOUT B, VAN KATS C M, et al. Acid-based synthesis of monodisperse rare-earth-doped colloidal SiO2 spheres[J]. Chemistry of Materials, 2002,14(7):2849-2853.
【15】YAN B, ZHANG H J, WANG S B, et al. Luminescence properties of the ternary rare earth complexes with beta-diketones and 1,10-phenanthroline incorporated in silica matrix by a sol-gel method[J]. Materials Chemistry and Physics, 1997,51(1):92-96.
【16】O'RIORDAN A, O'CONNOR E, MOYNIHAN S, et al. Narrow bandwidth red electroluminescence from solution-processed lanthanide-doped polymer thin films[J]. Thin Solid Films, 2005,491(1):264-269.
【17】SINGH S K, SINGH A K, RAI S B. Efficient dual mode multicolor luminescence in a lanthanide doped hybrid nanostructure:a multifunctional material[J]. Nanotechnology, 2011,22(27):275703-275703.
【18】ZHAO D, QIN W, ZHANG J, et al. Modified spontaneous emission of europium complex nanoclusters embedded in colloidal silica spheres[J]. Chemical Physics Letters, 2005,403(1/3):129-134.
【19】MALBA C, SUDHAKARAN U P, BORSACCHI S, et al. Structural and photophysical properties of rare-earth complexes encapsulated into surface modified mesoporous silica nanoparticles[J]. Dalton Transactions, 2014,43(43):16183-16196.
【20】吴大辉,周仕林,张丽娜,等.Eu(dbm)3phen/SiO2@KH570-NH2核壳结构微球的制备及其性能表征[J].理化检验-化学分册, 2017,53(2):139-145.
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