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Engineering    2017, Vol. 3 Issue (3) : 402-408     https://doi.org/10.1016/J.ENG.2017.03.014
Research |
荧光碳点的快速宏量制备及多功能应用
王丹1,2,王志勇1,詹求强3,蒲源1(),王洁欣1,Foster Neil R.1,4,戴黎明2()
1. Beijing Advanced Innovation Center for Soft Matter Science and Engineering & State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China
2. Center of Advanced Science and Engineering for Carbon (Case4Carbon), Department of Macromolecular Science and Engineering, Case School of Engineering, Case Western Reserve University, Cleveland, OH 44106, USA
3. SCNU-ZJU Joint Research Center of Photonics, South China Academy of Advanced Optoelectronics, South China Normal University, Guangzhou 510006, China
4. Department of Chemical Engineering, Curtin University, Perth, WA 6845, Australia
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摘要 

荧光纳米材料在化学传感、生物成像及光电器件等领域具有重要应用前景,其合成方法的研究得到广泛关注。我们采用柠檬酸和乙二胺作为原料,在150 ℃、常压的相对温和条件下,通过“一锅法”反应制备了氮掺杂荧光碳点。所得荧光碳点光学带隙为3.4 eV,在单光子或双光子激发下呈现出明亮的荧光,且荧光发射波长稳定(λ = 450 nm)。基于荧光碳点低细胞毒性和长荧光寿命的优势,实现了荧光碳点作为离体肿瘤细胞(HeLa 细胞) 标记和荧光寿命成像探针的应用,获得了高对比度的荧光寿命成像结果。通过将所得荧光碳点与普通油墨混合制备均匀分散的荧光墨水,可用于普通纸张及其他基材( 如柔性塑料薄膜、纺织品、衣服) 的荧光图案化,为固态荧光传感、荧光防伪标记和可穿戴光电子设备应用研究提供了基础。

Abstract

The synthesis of fluorescent nanomaterials has received considerable attention due to the great potential of these materials for a wide range of applications, from chemical sensing through bioimaging to optoelectronics. Herein, we report a facile and scalable approach to prepare fluorescent carbon dots (FCDs) via a one-pot reaction of citric acid with ethylenediamine at 150 °C under ambient air pressure. The resultant FCDs possess an optical bandgap of 3.4 eV and exhibit strong excitation-wavelength-independent blue emission (λEm= 450 nm) under either one- or two-photon excitation. Owing to their low cytotoxicity and long fluorescence lifetime, these FCDs were successfully used as internalized fluorescent probes in human cancer cell lines (HeLa cells) for two-photon excited imaging of cells by fluorescence lifetime imaging microscopy with high-contrast resolution. They were also homogenously mixed with commercial inks and used to draw fluorescent patterns on normal papers and on many other substrates (e.g., certain flexible plastic films, textiles, and clothes). Thus, these nanomaterials are promising for use in solid-state fluorescent sensing, security labeling, and wearable optoelectronics.

Keywords Scalable      Carbon dots      Two-photon      Fluorescence lifetime imaging      Patterning     
通讯作者: 蒲源,戴黎明     E-mail: puyuan@mail.buct.edu.cn;liming.dai@case.edu
最新录用日期:    在线预览日期:    发布日期: 2017-06-30
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Dan Wang
Zhiyong Wang
Qiuqiang Zhan
Yuan Pu
Jie-Xin Wang
Neil R. Foster
Liming Dai
引用本文:   
Dan Wang,Zhiyong Wang,Qiuqiang Zhan, et al. Facile and Scalable Preparation of Fluorescent Carbon Dots for Multifunctional Applications[J]. Engineering, 2017, 3(3): 402-408.
网址:  
http://engineering.org.cn/EN/10.1016/J.ENG.2017.03.014     OR     http://engineering.org.cn/EN/Y2017/V3/I3/402
Fig.1  (a) A schematic process for the formation of FCDs; (b) a photograph of mass FCDs obtained via one-pot synthesis; (c) a typical HRTEM image of the as-synthesized FCDs, where the inset represents the crystal lattice of an individual dot, and the scale bar in the inset is 1 nm; (d) PAGE measurements of the FCDs, where I represents a 12% Tris-glycine gel SDS-PAGE band profile of the Prestained Protein Molecular Weight Marker, II represents an SDS-PAGE of the Protein Molecular Weight Marker, III represents an SDS-PAGE of FCDs under visible light, and IV represents an SDS-PAGE of FCDs under UV illumination (365 nm). SDS: sodium dodecyl sulfate.
Fig.2  Structure and composition characterization of the FCDs. (a) XRD; (b) FTIR; (c) XPS spectrum; (d) TGA results of FCDs in air.
Fig.3  (a) UV-Vis absorption (black curve) and one-photon excited fluorescence (blue curve) spectra for an aqueous solution of FCDs (1 μg·mL-1); the insets are photos of the FCDs solutions with daylight lamp irradiation (left) and UV lamp excitation (right). (b) Excitation-emission map of the FCDs. (c) Two-photon excited fluorescence spectra of the FCDs under excitation of a 750 nm fs laser at various power densities. (d) The proposed mechanism for one and two-photon excitation and for the fluorescence emission, where S0 represents the ground state, S1 represents the lower radiative state, and Si represents a higher electronic or vibronic state. NIR: near-infrared. (e) Quadratic relationship of the fluorescence intensity of the FCDs excited by a 750 nm fs laser at various powers. (f) time-resolved photoluminescence (TRPL) decay curve and line fit for the FCDs excited with a 390 nm picosecond laser and monitored at 450 nm.
Fig.4  Cell viability from MTT assays with different FCD concentrations after 24 h incubation.
Fig.5  (a–c) Bright-field, (d–f) two-photon excited FLIM imaging, and (g–i) recovered lifetime histograms of control cells without FCD treatment (left column), experimental cells incubated with FCDs (middle column), and GQDs (right column), respectively.
Fig.6  Photographs of FCD patterns drawn using FCD ink under (a) daylight and (b) 365 nm UV lamp excitation; the scale bar is 1 cm. (c) Photoluminescence (PL) spectra of the FCDs in the solid state and background fluorescence of the paper.
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