自组装水热合成碳点-中空氧化硅纳米粒复合材料

doi:10.11944/j.issn.1000-0518.2016.04.160057

摘要/Abstract

摘要：

利用反相微乳液体系制备出粒径均一的中空氧化硅纳米粒(SHN),以此为基础,再利用水热法通过自组装合成了碳点-中空氧化硅纳米粒复合材料(CD-SHN)。采用高分辨透射电子显微镜(HRTEM)和场发射扫描电子显微镜(FESEM)对其结构进行了表征,结果显示SHN尺寸为30~40 nm,壳厚约为10 nm,在此基础上合成出具有和海葵类似结构的CD-SHN,尺寸约为1 μm,并且,在水相中具有良好的分散性。海葵状CD-SHN既具有激发波长依赖的多色荧光发射性能,又具有良好的光稳定性,其最大激发及发射波长分别位于360和435 nm附近,经40 W白炽灯照射60 min,其荧光强度仍可保持97%。该材料的制备过程条件温和,其原材料生物相容性良好,在生物造影方面具有潜在的优势。

关键词: 纳米中空结构, 海葵状, 碳点, 氧化硅, 多色荧光

Abstract:

In this paper, silica hollow nanoparticles(SHNs) with quite uniform particle sizes were prepared by reverse microemulsion system. High resolution transmission electron microscopy(HRTEM) and field emission scanning electron microscopy(FESEM) were used to characterize the structure of SHNs. The carbon dots and silica hollow nanoparticles composite(CD-SHN) was prepared by hydrothermal treatment of self-assembled SHNs in presence of citric acid and ethylene diamine. FESEM images show that the average diameter of sea anemone-like carbon dots-silica nanocomposite is about 1 μm. The size of silica hollow nanosphere is between 30~40 nm, and shell thickness is 10 nm. The CD-SHN demonstrates multicolor fluorescence emission, and high photostability. The maximum excitation and emission wavelengths of CD-SHN are 360 nm and 435 nm, respectively, and 97% of the fluorescence intensity can be retained after being excited for 60 min by a 40 W incandescent lamp. Due to the mild preparation conditions and good biocompatibility of the materials, the composite material has the potential application in biological imaging.

Key words: hollow nanostructure, sea anemone-like, carbon dots, silica, multicolor fluorescence

JATUPAIBOON Nirun, 张德蒙, 王贝贝, 谢红国, 马小军. 自组装水热合成碳点-中空氧化硅纳米粒复合材料[J]. 应用化学, 2016, 33(4): 391-396.

JATUPAIBOON Nirun, ZHANG Demeng, WANG Beibei, XIE Hongguo, MA Xiaojun. Self-assembled Hydrothermal Synthesis of Sea Anemone-like Carbon Dot-Silica Hollow Nanocomposite[J]. Chinese Journal of Applied Chemistry, 2016, 33(4): 391-396.

参考文献

[1]	Fuji M,Shin T,Watanabe H,et al.Shape-controlled Hollow Silica Nanoparticles Synthesized by an Inorganic Particle Template Method[J]. Adv Powder Technol,2012,23(5):562-565.
[2]	Singh A,Sahoo S K. Magnetic Nanoparticles:A Novel Platform for Cancer Theranostics[J]. Drug Discov Today,2014,19(4):474-481.
[3]	Wang J,Shah Z H,Zhang S,et al.Silica-based Nanocomposites via Reverse Microemulsions: Classifications, Preparations, and Applications[J]. Nanoscale,2014,6(9):4418-4437.
[4]	Chen Y,Chen H,Shi J. In vivo Bio-safety Evaluations and Diagnostic/therapeutic Applications of Chemically Designed Mesoporous Silica Nanoparticles[J]. Adv Mater,2013,25(23):3144-3176.
[5]	Zhou W,Gao P,Shao L,et al.Drug-loaded, Magnetic, Hollow Silica Nanocomposites for Nanomedicine[J]. Nano Med Nanotechnol,2005,1(3):233-237.
[6]	Chen Y,Chen H,Sun Y,et al.Multifunctional Mesoporous Composite Nanocapsules for Highly Efficient MRI-guided High-intensity Focused Ultrasound Cancer Surgery[J]. Angew Chem Int Ed,2011,123(52):12713-12717.
[7]	Yan H,Tan M,Zhang D,et al.Development of Multicolor Carbon Nanoparticles for Cell Imaging[J]. Talanta,2013,108(8): 59-65.
[8]	Tan M,Zhang L,Tang R,et al.Enhanced Photoluminescence and Characterization of Multicolor Carbon Dots Using Plant Soot as a Carbon Source[J]. Talanta,2013,115(17):950-956.
[9]	Wang C,Xu Z,Cheng H,et al.A hydrothermal Route to Water-stable Luminescent Carbon Dots as Nanosensors for pH and Temperature[J]. Carbon,2015,82:87-95.
[10]	Baker S N,Baker G A. Luminescent Carbon Nanodots:Emergent Nanolights[J]. Angew Chem Int Ed,2010,49(38):6726-6744.
[11]	Yang X,Peng L,Zong J,et al.Preparation of Photoluminescent Carbon Dots-embedded Polyelectrolyte Microcapsules[J]. Particuology,2013,11(3):334-339.
[12]	Zhao A,Chen Z,Zhao C,et al.Recent Advances in Bioapplications of C-dots[J]. Carbon,2015,85:309-327.
[13]	Hola K,Zhang Y,Wang Y,et al.Carbon Dots-emerging Light Emitters for Bioimaging, Cancer Therapy and Optoelectronics[J]. Nano Today,2014,9(5):590-603.
[14]	Zheng X T,Ananthanarayanan A,Luo K Q,et al.Glowing Graphene Quantum Dots and Carbon Dots:Properties, Syntheses, and Biological Applications[J]. Small,2015,11(14):1620-1636.
[15]	Fuji M,Takai C, Virtudazo R V R. Development of New Templating Approach for Hollow Nanoparticles and Their Applications[J]. Adv Powder Technol,2014,25(1):91-100.
[16]	Aldaye F A,Palmer A L,Sleiman H F. Assembling Materials with DNA as the Guide[J]. Science,2008,321(5897):1795-1799.
[17]	Park S Y, Lytton-Jean A K R, Lee B, et al. DNA-programmable Nanoparticle Crystallization[J]. Nature,2008,451(7178):553-556.
[18]	Qiu H,Hudson Z M,Winnik M A,et al.Multidimensional Hierarchical Self-assembly of Amphiphilic Cylindrical Block Comicelles[J]. Science,2015,347(6228):1329-1332.
[19]	Jatupaiboon N,Wang Y,Wu H,et al.A facile Microemulsion Template Route for Producing Hollow Silica Nanospheres as Imaging Agents and Drug Nanocarriers[J]. J Mater Chem B,2015,3(16):3130-3133.
[20]	Liu S,Lebedev O I,Mertens M,et al.The Merging of Silica-surfactant Microspheres Under Hydrothermal Conditions[J]. Micropor Mesopor Mater,2008,116(1):141-146.
[21]	Lebedev O I,Turner S,Liu S,et al.New Nano-architectures of Mesoporous Silica Spheres Analyzed by Advanced Electron Microscopy[J]. Nanoscale,2012,4(5):1722-1727.
[22]	Luo P G,Sahu S,Yang S T,et al.Carbon “Quantum” Dots for Optical Bioimaging[J]. J Mater Chem B,2013,1(16):2116-2127.
[23]	Yang S T,Cao L,Luo P G,et al.Carbon Dots for Optical Imaging in vivo[J]. J Am Chem Soc,2009,131(32):11308-11309.
[24]	Wang G,Pan X,Gu L,et al.Fluorescent Carbon Dot(C-dot) Nanoclusters[J]. Nanotechnology,2014,25(37):375601.