Synthesis of Polyoxometalate Microtubes with Hierarchical Structure and the Adsorption of Doxorubicin†

doi:10.7503/cjcu20140563

Abstract

Abstract:

Saturated Keggin-type SiW₁₂ microtubes have been synthesized from the trivacant SiW₉ by a simple template-free method. The microtubes were characterized by Fourier transform infrared(FTIR) spectroscopy, powder X-ray diffraction(PXRD) and thermogravimetric analysis(TGA). The hierarchical structure was exa-mined by optical micrograph and field emission enviromental scanning electron microscope(ESEM). To apply the hierarchical structure, doxorubicin(DOX) was adsorbed in the as-prepared SiW₁₂ microtubes, and DOX-loaded microtubes were obtained, which showed red luminescence of doxorubicin under violet light excitation.

Key words: Polyoxometalate, Hierarchical structure, Microtube, Keggin structure, Doxorubicin

CLC Number:

O611.4
O647

TrendMD:

WEI Yi, PENG Jun, YU Xia, DING Yanhong, LU Haiyang, REN Zixing, XU Min, LI Guangzhe. Synthesis of Polyoxometalate Microtubes with Hierarchical Structure and the Adsorption of Doxorubicin^†[J]. Chem. J. Chinese Universities, 2014, 35(11): 2291.

Figures/Tables 11

Fig.1 Optical micrograph of the SiW12 microtubes

Fig.2 ESEM images with low(A) and high(B) magnification of an individual SiW12 microtube

Fig.3 FTIR spectra of the SiW12 microtubes(a) and the SiW9 precursor(b)

Fig.4 Cyclic voltammograms of the SiW12 microtubes in H2SO4 solution(pH=1) with variable scan rates Scan rates from inner to outer/(mV·s-1): 50, 100, 150, 200, 250, 300.

Fig.5 Thermogravimetric curve of the SiW12 microtubes

Scheme 1 Reaction mechanism postulated for the formation of SiW12 microtubes

Fig.6 Representative nitrogen adsorption/desorption isotherms —■— Adsorption of untreated SiW12 microtubes; —□— desorption of untreated SiW12 microtubes; —▲— adsorption of dehydrated SiW12 microtubes at 100 ℃; —△— desorption of dehydrated SiW12 microtubes at 100 ℃. The inset is BJH pore-size distributions of untreated SiW12 microtubes(■) and dehydrated SiW12 microtubes at 100 ℃(▲).

Scheme 2 Schematic diagram of proposed growth mechanism of SiW12 microtubes (A) Hexagonal prism nanorods are formed on a rough glass substrate; (B) adjacent nanorods grow and array to form tubular structures;(C) ESEM image of a piece of SiW12 microtube wall.

Fig.7 PXRD patterns of the SiW12 microtubes(a) and the DOX@SiW12 microtubes(b)

Fig.8 Fluorescence microscopy images of an individual DOX@SiW12 microtube irradiated under visible light(A), violet light(B) and green light(C)

Fig.9 Solid-state fluorescence emission spectra obtained from the powder samples of DOX@SiW12 microtubes at room temperature, corresponding to the light sources of violet and green light, respectively (A) λex=380 nm; (B) λex=550 nm.

References 26

[1]	Iijima S., Nature, 1991, 354(6348), 56—58
[2]	Tenne R., Margulis L., Genut M., Hodes G., Nature,1992, 360(6403), 444—446
[3]	Xia Y., Yang P. D., Sun Y. G., Wu Y. Y., Mayers B., Gates B., Yin Y. D., Kim F., Yan H. Q., Adv. Mater., 2003, 15(5), 353—389
[4]	Zhang H., Wu F., Han C. B., Shen W., Cui Q., Qiu Z. L., Liu C. W., Gao F., Wang M. T., Chem. J. Chinese Universities,2013, 34(10), 2401—2407
	(张慧, 吴璠, 韩昌报, 沈薇, 崔奇, 邱泽亮, 刘长文, 高锋, 王命泰. 高等学校化学学报,2013, 34(10), 2401—2407)
[5]	He Y. H., Wang S. L., Huang B. Y., Liu C. T., Liaw P. K., Appl. Phys. Lett., 2006, 88(22), 31071—31072
[6]	Qu Y., Zhou W., Ren Z. Y., Pan K., Jiang L., Fu H. G., Chem. J. Chinese Universities,2014, 35(5), 995—999
	(曲阳, 周卫, 任志宇, 潘凯, 姜乐, 付宏刚. 高等学校化学学报,2014, 35(5), 995—999)
[7]	Hoffman W. P., Phan H. T., Wapner P. G., Mat. Res. Innova., 1998, 2(2), 87—96
[8]	Judd D. A., Nettles J. H., Nevins N., Snyder J. P., Liotta D. C., Tang J., Ermolieff J., Schinazi R. F., J. Am. Chem. Soc., 2001, 123(5), 886—897
[9]	Feng C. G., Shang H. R., Chem. Res. Chinese Universities,2012, 28(3), 366—370
[10]	Feng X. J., Li Y. G., Zhang Z. M., Wang E. B., Acta Chim. Sinica,2013, 71(12), 1575—1588
	(冯晓佳, 李阳光, 张志明, 王恩波. 化学学报,2013, 71(12), 1575—1588)
[11]	Li D., Zhang J., Landskron K., Liu T. B., J. Am. Chem. Soc., 2008, 130(13), 4226—4227
[12]	Bu W. F., Li H. L., Sun H., Yin S. Y., Wu L. X., J. Am. Chem. Soc., 2005, 127(22), 8016—8017
[13]	Ritchie C., Cooper G. J., Song Y. F., Streb C., Yin H. B., Parenty A. D., MacLaren D. A., Cronin L., Nat. Chem., 2009, 1(1), 47—52
[14]	Zhang H. Q., Peng J., Shen Y., Yu X., Zhang F., Mei J. L., Li B., Zhang L. M., Chem. Commun., 2012, 48(37), 4462—4464
[15]	Shen Y., Peng J., Pang H. J., Zhang P. P., Chen D., Chen C. Y., Zhang H. Q., Meng C. L., Su Z. M., Chem-Eur. J., 2011, 17(13), 3657—3662
[16]	Yu X., Zhang H. Q., Shi Z. Y., Alimaje K., Shen Y., Peng J., Li B., Zhang L. M., Dyes Pigments,2013, 98(3), 479—485
[17]	Xin Z. F., Peng J., Wang T., Xue B., Kong Y. M., Li L., Wang E. B., Inorg. Chem., 2006, 45(22), 8856—8858
[18]	Ewer M., Ewer S., Nat. Rev. Cardiol., 2010, 7(10), 564—575
[19]	Minotti G., Menna P., Salvatorelli E., Cairo G., Gianni L., Pharmacol. Rev., 2004, 56(2), 185—229
[20]	Yang Q., Lv Q., Chen J., Tian C. X., Fan X. J., Wang R., Wang X. D., Chinese Journal of Bases and Clinics in General Surgery,2013, 20(7), 797—799
	(杨钱, 吕青, 陈洁, 田春祥, 范雪娇, 王荣, 王晓东. 中国普外基础与临床杂志,2013, 20(7), 797—799)
[21]	Li X., Zhao D. L., Bai L. Z., Li F., Zhao H. J., Gao L. F., Journal of Functional Materials,2013, 44(1), 96—102
	(李晓, 赵东林, 白利忠, 李峰, 赵海静, 高龙飞. 功能材料,2013, 44(1), 96—102)
[22]	Herve G., Teze A., Inorg. Chem., 1977, 16(8), 2115—2117
[23]	Rocchiccioli D. C., Fournier M., Franck R., Thouvenot R., Inorg. Chem., 1983, 22(2), 207—216
[24]	Sadakane M., Steckhan E., Chem. Rev., 1998, 98(1), 219—238
[25]	Jeong J. S., Lee J. Y., Cho J. H., Suh H. J., Lee C. J., Chem. Mater., 2005, 17(10), 2752—2756
[26]	Wang S. L., He Y. H., Huang B. Y., Zou J., Liu C., Liaw P. K., Chem. Phys. Lett., 2005, 427(2006), 350—355