碱木质素/聚乙烯亚胺碳点的制备及其对pH敏感性
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摘要
以碱木质素(alkali lignin,AL)、聚乙烯亚胺(polyethylenimine,PEI)为碳源,其中PEI不仅作为碳源还作为表面钝化剂,在H_2O_2氧化下通过一步水热法绿色、高效制备高荧光、寿命长和多氨基化功能碳点(alkali lignin/polyethylenimine carbon dots,AL/PEI-CDs)。探究了碱木质素/PEI质量比、水热温度和水热时间等因素对碳点荧光强度的影响,确定了最佳的反应条件,同时考察了AL/PEI-CDs对pH的敏感性及稳定性。采用紫外分光光度计(ultraviolet spectrophotometer,UV-vis)、荧光分光光度计、原子力显微镜(atomic force microscope,AFM)、高分辨透射显微镜(high resolution transmission electon microscopy, HRTEM)、傅里叶红外光谱仪(Fourier transform infrared spectroscopy,FTIR)和X射线衍射仪(X-ray diffractometer,XRD),对AL/PEI-CDs的光学性质、形貌结构、化学结构和晶体结构等进行了表征分析。结果表明,在碱木质素/PEI质量比为1∶12、水热温度190℃、水热时间12h的条件下,合成的AL/PEI-CDs荧光量子产率为25.53%,荧光寿命为5.06ns,表面含有丰富的氨基和羟基,且粒径均一、水溶性好,有良好的稳定性,在最佳激发波长为ex=313nm下对应的发射峰位为405nm,稀释液在紫外灯下发出明亮的蓝光。本研究制备的碳点在离子监测和细胞代谢过程监测质子传感器中可能具有良好的应用前景。
Alkali lignin(AL) and polyethylenimine(PEI) were used as carbon sources. PEI was used not only as a carbon source but to efficiently prepare the also as a surface passivator. Under the oxidation of H_2 O_2, it was one step hydrothermal green method to efficiently prepare the high fluorescence, long life and polyethylenimine carbon dots(AL/PEI-CDs). The effects of alkali lignin/PEI mass ratio, hydrothermal temperature and hydrothermal time on the fluorescence intensity of carbon dots were studied. The optimal reaction conditions were determined. The sensitivity and stability of AL/PEI-CDs to pH were also investigated. Ultraviolet spectrophotometer(UV-vis), fluorescence spectrophotometer, atomic force microscope(AFM), high resolution transmission electron microscopy(HRTEM), Fourier infrared spectrometer(Fourier), the optical properties, morphology, chemical structure and crystal structure of AL/PEI-CDs were characterized by transform infrared spectroscopy (FTIR) and X-ray diffractometer(XRD). The results showed that the fluorescence quantum yield(QY) of the synthesized AL/PEI-CDs was25.53%, fluorescence under the condition of alkali lignin/PEI mass ratio of 1∶12, hydrothermal temperature of 190℃ and hydrothermal time of 12 h. The life was 5.06 ns, the surface was rich in amino and hydroxyl groups, and the particle size was uniform, water-soluble and good stability. The corresponding emission peak was 405 nm at the optimal excitation wavelength of ex=313 nm. Bright blue light was emitted under the UV lamp. The carbon dots prepared in this study may have good application prospects in ion monitoring and cell metabolic process monitoring proton sensors.
Alkali lignin(AL) and polyethylenimine(PEI) were used as carbon sources. PEI was used not only as a carbon source but to efficiently prepare the also as a surface passivator. Under the oxidation of H_2 O_2, it was one step hydrothermal green method to efficiently prepare the high fluorescence, long life and polyethylenimine carbon dots(AL/PEI-CDs). The effects of alkali lignin/PEI mass ratio, hydrothermal temperature and hydrothermal time on the fluorescence intensity of carbon dots were studied. The optimal reaction conditions were determined. The sensitivity and stability of AL/PEI-CDs to pH were also investigated. Ultraviolet spectrophotometer(UV-vis), fluorescence spectrophotometer, atomic force microscope(AFM), high resolution transmission electron microscopy(HRTEM), Fourier infrared spectrometer(Fourier), the optical properties, morphology, chemical structure and crystal structure of AL/PEI-CDs were characterized by transform infrared spectroscopy (FTIR) and X-ray diffractometer(XRD). The results showed that the fluorescence quantum yield(QY) of the synthesized AL/PEI-CDs was25.53%, fluorescence under the condition of alkali lignin/PEI mass ratio of 1∶12, hydrothermal temperature of 190℃ and hydrothermal time of 12 h. The life was 5.06 ns, the surface was rich in amino and hydroxyl groups, and the particle size was uniform, water-soluble and good stability. The corresponding emission peak was 405 nm at the optimal excitation wavelength of ex=313 nm. Bright blue light was emitted under the UV lamp. The carbon dots prepared in this study may have good application prospects in ion monitoring and cell metabolic process monitoring proton sensors.
引文
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[26] RAI S, SINGH B K, BHARTIYA P, et al. Lignin derived reduced fluorescence carbon dots with theranostic approaches:nano-drugcarrier and bioimaging[J]. Journal of Luminescence, 2017, 190:492-503.
[27] SCHULMAN S G. Molecular luminescence spectroscopy[M]. New York:Wiley, 1985.
[2] PAN D, GUO L, ZHANG J, et al. Cutting sp2clusters in graphene sheets into colloidal graphene quantum dots with strong green fluorescence[J]. Journal of Materials Chemistry, 2012, 22(8):3314-3318.
[3] PAN D, ZHANG J, LI Z, et al. Hydrothermal route for cutting graphene sheets into blue-luminescent graphene quantum dots[J].Advanced Materials, 2010, 22(6):734-738.
[4] SHEN J, ZHU Y, YANG X, et al.One-pot hydrothermal synthesis of graphene quantum dots surface-passivated by polyethylene glycol and their photoelectric conversion under near-infrared light[J]. New Journal of Chemistry, 2011, 36(1):97-101.
[5] WANG X. Microwave assisted one-step green synthesis of cellpermeable multicolor photoluminescent carbon dots without surface passivation reagents[J].Journal of Materials Chemistry, 2011, 21(8):2445-2450.
[6] ZHAI X, ZHANG P, LIU C, et al. Highly luminescent carbon nanodots by microwave-assisted pyrolysis[J]. Chemical Communications, 2012, 48(64):7955-7957.
[7] ZHU H, YANG X. Microwave synthesis of fluorescent carbon nanoparticles with electrochemiluminescence properties[J].Chemical Communications, 2009, 14(34):5118-5120.
[8] JIANG J, HE Y, LI S, et al.Amino acids as the source for producing carbon nanodots:microwave assisted one-step synthesis, intrinsic photoluminescence property and intense chemiluminescence enhancement[J]. Chemical Communications, 2012, 48(77):9634-9636.
[9] YAN X, CUI X, LI L S.Synthesis of large, stable colloidal graphene quantum dots with tunable size[J].Journal of the American Chemical Society, 2010, 132(17):5944-5945.
[10] LI Q, ZHANG S, DAI L, et al. Nitrogen-doped colloidal graphene quantum dots and their size-dependent electrocatalytic activity for the oxygen reduction reaction[J]. Journal of the American Chemical Society, 2012, 134(46):18932-18935.
[11] VINCI J C, COLON L A. Fractionation of carbon-based nanomaterials by anion-exchange HPLC[J]. Analytical Chemistry,2012, 84(2):1178-1183.
[12]罗培辉.碳量子点的化学修饰及功能化研究[D].北京:清华大学, 2013.LUO P H. Chemical modification and functionalization of carbon quantum dots[D].Beijing:Tsinghua University, 2013.
[13] CHEN W, HU C, YANG Y, et al.Rapid synthesis of carbon dots by hydrothermal treatment of lignin[J].Materials, 2016, 9(3):184.
[14] LI Q, OHULCHANSKYY T Y, LIU R, et al.Photoluminescent carbon dots as biocompatible nanoprobes for targeting cancer cells in vitro[J].Journal of Physical Chemistry C, 2010, 114(28):12062-12068.
[15] SUN Y P, ZHOU B, LIN Y, et al. Quantum-sized carbon dots for bright and colorful photoluminescence[J]. Journal of the American Chemical Society, 2006, 128(24):7756-7757.
[16] DONG Y, SHAO J, CHEN C, et al. Blue luminescent graphene quantum dots and graphene oxide prepared by tuning the carbonization degree of citric acid[J]. Carbon, 2012, 50(12):4738-4743.
[17] KIM J, PARK J, KIM H, et al. Transfection and intracellular trafficking properties of carbon dot-gold nanoparticle molecular assembly conjugated with PEI-pDNA[J]. Biomaterials, 2013, 34(29):7168-7180.
[18] LIU C, ZHANG P, ZHAI X, et al.Nano-carrier for gene delivery and bioimaging based on carbon dots with PEI-passivation enhanced fluorescence[J].Biomaterials, 2012, 33(13):3604-3613.
[19] BOURLINOS A B, STASSINOPOULOS A, ANGLOS D, et al.Surface functionalized carbogenic quantum dots[J]. Small, 2008, 4(4):455-458.
[20] SACHDEV A, MATAI I, GOPNATH P. Implications of surface passivation on physicochemical and bioimaging properties of carbon dots[J]. RSC Advances, 2014, 4(40):20915-20921.
[21] LIU H, HE Z, JIANG L P, et al. Microwave-assisted synthesis of wavelength-tunable photoluminescent carbon nanodots and their potential applications[J]. ACS Applied Materials&Interfaces, 2015, 7(8):4913-4920.
[22] ZENG H, LI L, DING Y, et al.Simple and selective determination of6-thioguanine by using polyethylenimine(PEI)functionalized carbon dots[J]. Talanta, 2018, 178:879-885.
[23]木合塔尔·吐尔洪,徐阳,尹学博.碳点的研究进展[J].分析化学,2017, 45(1):139-150.Mhetaer Tuerhong, XU Yang, YIN Xuebo. Review on carbon dots and their applications[J]. Analytical Chemistry, 2017, 45(1):139-150.
[24]吕艳.功能化荧光碳点的制备及其离子分析应用研究[D].黄石:湖北师范学院, 2015.LU Y. Preparation of functionalized fluorescent carbon dots and their application in ion analysis[D]. Huangshi:Hubei Teachers College,2015.
[25]王莉,吕婷,阮枫萍,等.水热法制备的荧光碳量子点[J].发光学报,2014, 35(6):706-709.WANG L, LYU T, YAN F P, et al.Fluorescent carbon quantum dots prepared by hydrothermal method[J]. Chinese Journal of Luminescence,2014, 35(6):706-709.
[26] RAI S, SINGH B K, BHARTIYA P, et al. Lignin derived reduced fluorescence carbon dots with theranostic approaches:nano-drugcarrier and bioimaging[J]. Journal of Luminescence, 2017, 190:492-503.
[27] SCHULMAN S G. Molecular luminescence spectroscopy[M]. New York:Wiley, 1985.
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