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基于超级碳点的水致荧光“纳米炸弹”

娄庆 曲松楠

娄庆, 曲松楠. 基于超级碳点的水致荧光“纳米炸弹”[J]. 中国光学, 2015, 8(1): 91-98. doi: 10.3788/CO.20150801.0091
引用本文: 娄庆, 曲松楠. 基于超级碳点的水致荧光“纳米炸弹”[J]. 中国光学, 2015, 8(1): 91-98. doi: 10.3788/CO.20150801.0091
LOU Qing, QU Song-nan. Water triggered luminescent 'nano-bombs' based on supra-carbon-nanodots[J]. Chinese Optics, 2015, 8(1): 91-98. doi: 10.3788/CO.20150801.0091
Citation: LOU Qing, QU Song-nan. Water triggered luminescent "nano-bombs" based on supra-carbon-nanodots[J]. Chinese Optics, 2015, 8(1): 91-98. doi: 10.3788/CO.20150801.0091

基于超级碳点的水致荧光“纳米炸弹”

doi: 10.3788/CO.20150801.0091
基金项目: 国家自然科学基金面上资助项目(No.61274126);国家自然科学基金青年基金资助项目(No.51103144)
详细信息
    通讯作者:

    娄 庆(1986—),男,河南睢县人,博士研究生,2009年、2012年于重庆大学分别获得学士、硕士学位,主要从事量子点发光与器件制作方面的研究。E-mail:468826072@qq.com

    曲松楠(1981—),男,吉林长春人,副研究员,硕士生导师,2004年、2009年于吉林大学分别获得学士、博士学位,主要从事碳基发光材料及应用方面的研究。E-mail:qusn@ciomp.ac.cn

  • 中图分类号: TB383.1;O482.31

Water triggered luminescent "nano-bombs" based on supra-carbon-nanodots

  • 摘要: 介绍了一种发光性质依赖于水接触的新型纳米发光材料——基于超级碳点的发光"纳米炸弹"。在甲苯溶液中, 这种"纳米炸弹"光致发光很弱;当遇见水后, "纳米炸弹"分解为小的碳点, 光致发光显著增强。将"纳米炸弹"与纸复合可应用在喷水荧光打印和汗孔成像。目前, 大部分智能荧光材料存在光稳定性差, 潜在的生物毒性, 制备成本高, 或与传统喷墨打印不兼容等缺点。本文报道的碳基纳米材料没有(或很少有)这些缺点, 并可实际应用在光信息存储, 司法鉴定和医疗检测等领域。
  • 图  1  (a)烷基链修饰前碳点(CD-Rs)和部分烷基链修饰后碳点(CD-Ps)的核磁共振氢谱图。(b)部分烷基链修饰后碳点(CD-Ps)自组装成“超级碳点”(supra-CDs)的过程图

    Figure  1.  (a)1H NMR spectroscopy of CD-Rs and CD-Ps in DMSO-d6. (b)Schematic for formation of supra-CDs from CD-Ps

    图  2  (a)“超级碳点”甲苯溶液和两亲性碳点二甲基亚砜溶液紫外可见吸收谱(黑线)和光致荧光谱(紫线,405 nm光激发)图。内插图:紫外365纳米光激发下“超级碳点”甲苯溶液(左)和两亲性碳点二甲基亚砜溶液(右)照片。(b)405 nm光激发下“超级碳点”甲苯溶液与纸复合物水诱导荧光变化图。(c)“超级碳点”甲苯溶液与纸复合物喷水前后光致发光动态光谱变化图和两亲性碳点二甲基亚砜溶液与纸复合物光致发光动态光谱变化图。(d)405 nm光激发下,两亲性碳点二甲基亚砜溶液玻璃衬底上快速会发干后的共聚焦显微成像图。(e)两亲性碳点二甲基亚砜溶液滴在铜网上透射电镜图。内插图:相应碳点的高分辨透射电镜图。(f,i)硅片基底上“超级碳点”喷水前(f)后(i)原子力显微镜图。高度轮廓图叠加在相应的原子力图片上。(g,h)硅片基底上“超级碳点”喷水前(g)后(h)扫描电镜图。内插图:单个“超级碳点”的透射电镜图

    Figure  2.  (a)UV-vis absorption(black line) and photoluminescence spectra (violet line,excitation at 405 nm) of supra-CDs in toluene(PhMe) and CD-Ps in DMSO. Inset: a photograph of supra-CDs in PhMe(left) and CD-Ps in DMSO(right) under UV (365 nm) illumination. (b)Water induced emission spectral changes of supra-CDs PhMe solution coated paper(excitation at 405 nm). (c)Water induced PL decay dynamic spectral changes of supra-CDs PhMe solution coated paper and PL decay dynamic spectrum of paper directly coated with CD-Ps DMSO solution. (d)Confocal microscopy image of CD-Ps on glass substrate depositing from DMSO solution under 405 nm excitation. (e)TEM image of CD-Ps on a carbon-coated copper grid depositing from DMSO solution. Inset: HRTEM image of a CD-P. (f,i)AFM images of supra-CDs on silicon substrate before (f) and after (i) water-spraying. Superimposed is height profiles along the line marked in the AFM images. (g,h)SEM images of supra-CDs on silicon substrate before (g) and after (h) water-spraying. Inset: TEM image of a supra-CD

    图  3  水诱导“超级碳点”复合纸的荧光增强机制图

    Figure  3.  Schematic for the mechanism of the water induced enhanced luminescence

    图  4  (a,b)在可见光(a)和可见兼紫外光(b)照射下用纯水墨盒和HP-46三色墨盒打印在“超级碳点”复合纸上的照片(标尺=1 cm)。(c)纯水墨盒打印纸“超级碳点”复合纸上紫外辐照照片(标尺=1 cm)。(d)紫外光照射下喷水前后用“超级碳点”甲苯溶液作为墨水书写字母C的照片(标尺=5 mm)。(e)用“超级碳点”甲苯溶液作为墨水书写的水诱导荧光增强和用商用荧光笔书写的字母C的光稳定性测试照片

    Figure  4.  (a,b)Photographs of printed image of supra-CDs coated paper using purely water-filling(3 mL) and HP 46 tricolour cartridges under daylight (a) and under UV and daylight (b)(Scale bar =1 cm). (c)Photographs of printed image of supra-CDs coated paper only using purely water-filling (3ml) cartridges under a UV lamp(Scale bar=1 cm). (d)A handwritten image of “C” on commercially available filter paper with a supra-CDs toluene solution-filled fountain pen before and after water-spraying treatment under UV excitation(Scale bar=5 mm). (e)Photostability of water induced luminescent image of “C” written with supra-CDs toluene solution (left) and luminescent image of “C” written with commercially available highlighter pen(right)(Scale bar=1 mm)

    图  5  (a)“超级碳点”复合纸上用手指按压留下的指纹汗孔荧光照片(标尺=5 mm)。(b)为了得到后续更好的叠加图片,使用Photoshop处理后的(a)图中标示区域放大的荧光照片(标尺=2 mm)。(c)对比度增强荧光亮点叠加在数码指纹图像上的照片(标尺=2 mm)。(d)图是(c)中标示区域的放大图(标尺=0.5 mm)。(e,f)取自同一施主的两张独立的对比度增强荧光亮点指纹汗孔荧光图像。为了对比,使用Photoshop处理成红色(e)和蓝色(f)(标尺=2 mm)。(g)图是(e)和(f)叠加图(标尺=2 mm)。(h)图是(g)标示区域的放大图

    Figure  5.  (a)Photograph of a fingerprint image printed on supra-CD-coated paper(Scale bar=5 mm). (b)Fluorescence microscope images of the magnified fingerprint area marked in (a) using a Photoshop programme for a better subsequently superimposed image(Scale bar=2 mm). (c)Superimposed image of contrast-enhanced luminescent dots on a digital fingertip image(Scale bar=2 mm). (d)Magnified image of the marked area in (c)(Scale bar=0.5 mm). (e,f)Two independently printed contrast-enhanced luminescent microscope fingerprint images deposited by same donor. The red (e) and blue (f)coloured images are intentionally generated using a Photoshop programme for comparison purposes(Scale bar=2 mm). (g)Superimposed images displayed in (e) and (f) (Scale bar=2 mm). (h)Magnified image in the marked area in (g)(Scale bar=0.5 mm)

    表  1  喷水前后“超级碳点”复合纸(2.5 mg/mL)光物理数据

    Table  1.   Photophysical data for supra-CDs (2.5 mg/mL in toluene) coated paper before and after water-spraying treatment

    状态发射峰/nm平均寿命/ns荧光量子效率
    喷水前50010.290.06
    喷水后50012.740.41
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出版历程
  • 收稿日期:  2014-10-21
  • 录用日期:  2014-12-22
  • 刊出日期:  2015-01-25

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