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石墨烯量子点荧光增强及pH响应特性研究

张北龙 李金华 陆冬筱 张可欣 王笑军 马力

张北龙, 李金华, 陆冬筱, 张可欣, 王笑军, 马力. 石墨烯量子点荧光增强及pH响应特性研究[J]. 中国光学(中英文), 2023, 16(3): 523-534. doi: 10.37188/CO.2023-0053
引用本文: 张北龙, 李金华, 陆冬筱, 张可欣, 王笑军, 马力. 石墨烯量子点荧光增强及pH响应特性研究[J]. 中国光学(中英文), 2023, 16(3): 523-534. doi: 10.37188/CO.2023-0053
ZHANG Bei-long, LI Jin-hua, LU Dong-xiao, ZHANG Ke-xin, WANG Xiao-jun, MA Li. Graphene quantum dots fluorescence enhancement and pH response characteristics[J]. Chinese Optics, 2023, 16(3): 523-534. doi: 10.37188/CO.2023-0053
Citation: ZHANG Bei-long, LI Jin-hua, LU Dong-xiao, ZHANG Ke-xin, WANG Xiao-jun, MA Li. Graphene quantum dots fluorescence enhancement and pH response characteristics[J]. Chinese Optics, 2023, 16(3): 523-534. doi: 10.37188/CO.2023-0053

石墨烯量子点荧光增强及pH响应特性研究

基金项目: 国家自然科学基金资助项目(No. 62174015);教育部“111”创新引智项目(No. D17017);吉林省科技厅项目(No. YDZJ202301ZYTS488,No. JJKH20220723KJ)
详细信息
    作者简介:

    张北龙(1993—),男,黑龙江鹤岗人,博士研究生,2015年于长春理工大学光电信息学院获得理学学士学位,主要从事纳米光子学和生物光子学方面的研究。E-mail:2018200016@mails.cust.edu.cn

    李金华(1977—),女,吉林长春人,博士,教授,2006年于中国科学院长春光学精密机械与物理研究所获得博士学位,主要从事纳米技术、光子学技术在生物研究及医学诊断与治疗应用方面的研究工作。E-mail:lijh@cust.edu.cn

    马 力(1957—),女,美籍华人,博士,教授,1993年于美国佐治亚大学获得化学博士学位,主要从事蛋白质大规模提纯工艺、电子自旋共振光谱学等方面的研究。Email:lma@georgiasouthern.edu

  • 中图分类号: O433.4

Graphene quantum dots fluorescence enhancement and pH response characteristics

Funds: Supported by National Natural Science Foundation of China (No. 62174015); the “111” Project of China (No. D17017); the Developing Project of Science and Technology of Jilin Province (No. YDZJ202301ZYTS488, No. JJKH20220723KJ)
More Information
  • 摘要:

    本文详细研究了交联剂1-乙基-3-(3-二甲基氨基丙基)碳二亚胺盐酸盐(EDC)对石墨烯量子点(GQDs)光学性质的影响及原因。采用水热法制备了GQDs,并与EDC反应得到GQDs/EDC复合物,对GQDs和GQDs/EDC的光谱特性进行研究。使用PBS溶液以及人工胃液样品,研究pH对GQDs/EDC荧光影响规律及作用机理。实验结果表明:GQDs表面缺陷被EDC钝化,使得GQDs的荧光在小于1 min内迅速增强,并在5~20 min内保持稳定;相比单独GQDs,GQDs/EDC的荧光强度显著提升约264倍;pH响应实验表明,在pH值为1.75~4.01及4.01~9.28范围内,GQDs/EDC具有荧光和吸收强度线性响应规律。生物兼容性表明,在25~300 µg/mL样品浓度下,人乳腺癌细胞存活率均大于80%;同时,对人工胃液pH具有较高的检测准确性,其相对标准偏差RSD ≤ 1.10%。EDC介导的荧光增强,使GQDs在检测、传感、成像等领域更具优势。同时,GQDs/EDC灵敏的pH响应特性使其在pH值检测应用中具有良好前景。

     

  • 图 1  (a)GQDs的TEM图像;(b)尺寸分布柱状图及(c)与JCPDS 75-1621标准对比的GQDs XRD图谱;(d)GQDs/EDC复合材料TEM图像

    Figure 1.  (a) TEM image of GQDs; (b) histogram of size distribution; (c) XRD pattern of GQDs compared with JCPDS 75-1621 standard; (d) TEM image of GQDs/EDC composites

    图 2  CA和GQDs的FTIR光谱

    Figure 2.  FTIR spectra of CA and GQDs

    图 3  (a)EDC,PBS,GQDs和GQDs/EDC的PL光谱及(b)PL光谱的局部放大图

    Figure 3.  (a) PL spectra of EDC, PBS, GQDs and GQDs/EDC and (b) its local magnification

    图 4  不同激发波长下(a)GQDs和(c)GQDs/EDC的荧光光谱,以及不同探测波长下(b)GQDs及(d)GQDs/EDC的激发光谱

    Figure 4.  Fluorescence spectra of (a) GQDs and (c) GQDs/EDC at different excitation wavelengths, and excitation spectra of (b) GQDs and (d) GQDs/EDC at different detection wavelengths

    图 5  (a)EDC,GQDs,GQDs/EDC的吸收光谱,以及460 nm探测波长下GQDs/EDC的激发光谱。(b)GQDs的吸收光谱及其460 nm探测波长下的激发光谱。(c)GQDs和(d)GQDs/EDC在不同探测波长下的瞬态PL衰减曲线。各样品最终体积定容至2 mL,EDC含量为50 µL,15.28 mg/mL

    Figure 5.  (a) Absorption spectra of EDC, GQDs, GQDs/EDC, and excitation spectrum of GQDs/EDC at 460 nm detection wavelength. (b) Absorption spectrum of GQDs and excitation spectrum at 460 nm detection wavelength. Transient PL decay curves of (c) GQDs and (d) GQDs/EDC at different detection wavelengths. The final volume of each sample was 2 mL and EDC content is 50 µL, 15.28 mg/mL

    图 6  (a)GQDs分别与浓度为0~1700 µL的EDC混合反应后的荧光光谱以及(b) 荧光积分强度随EDC含量的变化趋势图。(c)pH值分别为7.2和2.3条件下,荧光积分强度随GQDs与EDC反应时间的变化关系

    Figure 6.  (a) Fluorescence spectra of GQDs/EDC with different EDC contents (0−1700 µL), and (b) the trend of fluorescence integrated intensity with EDC content. (c) The integrated PL intensity varies with the reaction time of GQDs/ EDC with the pH value of 7.2 and 2.3, respectively

    图 7  不同pH环境下的GQDs/EDC混合反应10 min后测得的(a)荧光光谱(λex=360 nm)和(c)吸收光谱。以及去基线后(b)荧光积分强度和(d)吸收积分强度随pH值的变化曲线。以及不同pH环境下GQDs/EDC的(e)明场和365 nm光源激发下的(f)暗场实物图

    Figure 7.  (a) Fluorescence spectra (λex=360 nm) and (c) absorption spectra of EDC and GQDs at different pH values after 10 min mixed reaction. (b) Integrated fluorescence and (d) absorption intensity as a function of pH value, after removing the baseline. (e) Bright-field and (f) dark-field images of GQDs/EDC under different pH environments with excitation by a 365 nm light source

    图 8  (a)不同EDC含量及(b)不同pH值条件时GQDs/EDC的瞬态荧光衰减曲线

    Figure 8.  (a) Transient fluorescence attenuation curves of GQDs/ EDCs under different EDC contents and (b) different pH conditions

    图 9  (a)选择性测试,GQDs/EDC对H+和其他常用离子 (5 mM)的荧光强度响应,其中Blank组为仅有PBS(pH 7.2)溶液(b)细胞与不同浓度GQDs/EDC共培养24 h后,MTT法测得的MCF-7细胞存活率

    Figure 9.  (a) Selective tests, the fluorescence intensity response of GQDs/EDC to H+ and other commonly used ions (5 mM), the Blank group was only PBS (pH 7.2) solution. (b) The survival rate of MCF-7 cells was determined by MTT method after 24 h co-culture with different concentrations of GQDs/ EDC

    表  1  不同方法的量子点荧光法测定pH值比较结果

    Table  1.   Comparison of pH values of quantum dots by different fluorometric determination methods

    SensorsMediumLinear rangeRef
    N,S co-doped carbon QDsIntracellular5.5~7.0[28]
    Carbon dotsIntracellular6.1~7.8[29]
    Carbon dotsIntracellulat6.03~8.91[30]
    N-doped GQDsAqueous solution1.25~13.56[31]
    CMC/GODsHydrogels filmNot given[32]
    GQDsIntracellularNot given[33]
    CuInS2/ZnS ODsAqueous solution5.7~8[34]
    GODsAqueous solution1.76~4.01
    4.01~9.28
    This work
    下载: 导出CSV

    表  2  胃液pH值的测定

    Table  2.   Determination of pH value of gastric juices

    Gastric juice samplepH valueRSD (%)b
    Glass electrodeaProposed methoda
    11.81±0.011.83±0.020.92
    22.13±0.022.18±0.010.60
    32.46±0.012.39±0.031.10
    a平均值±标准差(n=3);b相对标准偏差
    下载: 导出CSV
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  • 收稿日期:  2023-03-28
  • 修回日期:  2023-04-07
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