基于玉米淀粉制备绿色碳量子点及氢离子/氢氧根离子调节荧光开关性能

doi:10.19894/j.issn.1000-0518.200223

摘要/Abstract

摘要： 以玉米淀粉为碳源,在草酸的作用下利用乙醇溶剂热法制备了一种绿色荧光碳量子点(G-CQDs)。通过透射电子显微镜(TEM)、傅里叶红外光谱(FT-IR)、X射线衍射(XRD)、X射线光电子能谱(XPS)和Raman光谱等测试分析了G-CQDs的形貌、组成和结构。结果表明,G-CQDs为粒径为2~5 nm的准球形纳米颗粒,表面含有丰富的C—O、O—H等亲水性基团;且具有类石墨烯结构。荧光测试结果表明,合成的G-CQDs在385 nm的光激发下在~520 nm处呈现明显的荧光发射,且发射强度随着G-CQDs浓度的降低呈现先增大后降低的趋势,其荧光量子产率可达38.5%。此外,G-CQDs的荧光发射强度随着溶液H⁺和OH^-的浓度变化表现出明显不同的淬灭行为,并可用于溶液中H⁺和OH^-的可逆关-开“off-on”型荧光响应探针。

关键词: 碳量子点, 氢离子, 氢氧根离子, 荧光淬灭, 可逆关-开型

Abstract: Green fluorescent carbon quantum dots (G-CQDs) were synthesized from corn starch and oxalic acid via an ethanol solvothermal method. The morphology, composition and structure of G-CQDs were analyzed using transmission electron microscopy (TEM), Fourier transform infrared spectrometer (FT-IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The results show that G-CQDs are quasi-spherical nanoparticles with the particle size of about 2~5 nm and have graphene-like structure with abundant water-soluble groups such as C—O and O—H on the surface. The fluorescence measurement assay results exhibit that the synthesized G-CQDs display strong fluorescence emission at ~520 nm with the excitation wavelength of 385 nm, and the emission intensity increases first and then decreases with the decrease of the concentration of G-CQDs. The fluorescence quantum yield of the synthesized G-CQDs can reach up to 38.5%. Moreover, the fluorescence emission of G-CQDs exhibits various decay behaviors with the varied concentration of H⁺ and OH^-. Therefore, the synthesized G-CQDs can be utilized as the reversible “off-on” switch probe for the detection of H⁺ and OH^-.

Key words: Carbon quantum dots, Hydrogen ion, Hydroxyl ion, Fluorescence quenching, Reversible off-on switch

中图分类号:

O613.7

郝丽娟, 王婷, 董国华, 张文治, 白丽明, 杜海瑶, 郎坤, 李欣. 基于玉米淀粉制备绿色碳量子点及氢离子/氢氧根离子调节荧光开关性能[J]. 应用化学, 2021, 38(2): 202-211.

HAO Li-Juan, WANG Ting, DONG Guo-Hua, ZHANG Wen-Zhi, BAI Li-Ming, DU Hai-Yao, LANG Kun, LI Xin. Preparation of Green Carbon Quantum Dots from Corn Starch and Hydrogen Ion/Hydroxyl Ion Regulated Fluorescent Switch Performance[J]. Chinese Journal of Applied Chemistry, 2021, 38(2): 202-211.

参考文献

[1] JIANG Q W, JING Y, NI Y Y, et al. Potentiality of carbon quantum dots derived from chitin as a fluorescent sensor for cetection of ClO^-[J]. Microchem J, 2020, 157(9): 105111.
[2] QI H J, TENG M, LIU M, et al. Biomass-derived nitrogen-doped carbon quantum qots: highly selective fluorescent probe for detecting Fe³⁺ ions and tetracyclines[J]. J Colloid Sci, 2019, 539(3): 332-341.
[3] GAO X H, DU C, ZHUANG Z H, et al. Carbon quantum dots-based nanoprobes for metal ions detection[J]. J Mater Chem C, 2016, 4(29): 6927-6945.
[4] LI L L, WU G H, YANG G H, et al. Focusing on luminescent graphene quantum dots: current status and future perspectives[J]. Nanoscale, 2013, 5(10): 4015-4039.
[5] SHEN J H, ZHU Y H, YANG X L, et al. Graphene quantum dots: emergent nanolights for bioimaging, sensors, catalysis and photovoltaic devices[J]. Chem Commun (Camb), 2012, 48(31): 3686-3699.
[6] ZHANG Z P, ZHANG J, CHEN N, et al. Graphene quantum dots: an emerging material for energy-related applications and beyond[J]. Energy Environ Sci, 2012, 5(10): 8869.
[7] 傅鹏, 周丽华, 唐连凤, 等. 碳量子点的制备及其在能源与环境领域应用进展[J]. 应用化学, 2016, 33(7): 742-755.
FU P, ZHOU L H, TANG L F, et al. Progress in preparation of carbon quantum dots and its application in the fields of energy and environment[J]. Chinese J Appl Chem, 2016, 33(7): 742-755.
[8] CHEN Y H, ZHENG M T, XIAO Y, et al. A self-quenching-resistant carbon-dot powder with tunable solid-state fluorescence and construction of dual-fluorescence morphologies for white light-emission[J]. Adv Mater, 2016, 28(2): 312-318.
[9] TU Z Q, HU E Z, WANG B B, et al. Tribological behaviors of Ni-modified citric acid carbon quantum dot particles as a green additive in polyethylene glycol[J]. J Friction, 2019, 8(1): 182-197.
[10] PU Z F, WEN Q L, YANG Y J, et al. Fluorescent carbon quantum dots synthesized using phenylalanine and citric acid for selective detection of Fe³⁺ ions[J]. Spectrochim Acta Part A, 2020, 229(3): 117944.
[11] JIA J B, SUN Y, ZHANG Y J, et al. Facile and efficient fabrication of bandgap tunable carbon quantum dots derived from anthracite and their photoluminescence properties[J]. Front Chem, 2020, 8(2): 123.
[12] WANG Y, WU W T, WU M B, et al. Yellow-visual fluorescent carbon quantum dots from petroleum coke for the efficient detection of Cu²⁺ ions[J]. New Res Carbon Mater, 2015, 30(6): 550-559.
[13] DING H, ZHOU X X, WEI J S, et al. Carbon dots with red/near-infrared emissions and their intrinsic merits for biomedical applications[J]. Carbon, 2020, 167(10): 322-344.
[14] MOHEBBI A, FARAJZADEH M A, MAHMOUDZADEH A, et al. Combination of poly (ε-caprolactone) grafted graphene quantum dots-based dispersive solid phase extraction followed by dispersive liquid-liquid microextraction for extraction of some pesticides from fruit juices prior to their quantification by gas chromatography[J].Microchem J, 2020, 153(3): 104328.
[15] LU M C, DUAN Y X, SONG Y H, et al. Green preparation of versatile nitrogen-doped carbon quantum dots from watermelon juice for cell imaging, detection of Fe³⁺ ions and cysteine, and optical thermometry[J]. J Mol Liq, 2018, 269(11): 766-774.
[16] XIAO P, KE Y, LU J, et al. Photoluminescence immunoassay based on grapefruit peel-extracted carbon quantum dots encapsulated into silica nanospheres for p53 protein[J]. Biochem Eng J, 2018, 139(11): 109-116.
[17] ARUMUGHAM T, ALAGUMUTHU M, AMIMODU R G, et al. A sustainable synthesis of green carbon quantum dot (CQD) from catharanthus roseus (white flowering plant) leaves and investigation of its dual fluorescence responsive behavior in multi-ion detection and biological applications[J]. Sustainable Mater Technol, 2020, 23(4): 138.
[18] ZHAO J, WANG Y N, DONG W W, et al. A robust luminescent Tb(III)-MOF with lewis basic pyridyl sites for the highly sensitive detection of metal ions and small molecules[J]. Inorg Chem, 2016, 55(7): 3265-3271.
[19] ZHANG Y, FU Y Y, ZHU D F, et al. Recent advances in fluorescence sensor for the detection of peroxide explosives[J]. Chinese Chem Lett, 2016, 27(8): 1429-1436.
[20] SHEHAB M, EBRAHIM S, Soliman M. Graphene quantum dots prepared from glucose as optical sensor for glucose[J]. J Lumin, 2017, 184(12): 110-116.
[21] WENG C I, CHANG H T, LIN C H, et al. One-step synthesis of biofunctional carbon quantum dots for bacterial labeling[J]. Biosens Bioelectron, 2015, 68(6): 1-6.
[22] SHI Y X, LIU X, WANG M, et al. Synthesis of N-doped carbon quantum dots from bio-waste lignin for selective irons detection and cellular imaging[J]. Int J Biol Macromol, 2019, 128(5): 537-545.
[23] MINTZ K J, ZHOU Y, LEBLANC R M, et al. Recent development of carbon quantum dots regarding their optical properties, photoluminescence mechanism, and core structure[J]. Nanoscale, 2019, 11(11): 4634-4652.
[24] SHAIKH A F, TAMBOLI M S, PATIL R H, et al. Bioinspired carbon quantum dots: an antibiofilm agents[J]. J Nanosci Nanotechnol, 2019, 19(4): 2339-2345.
[25] WU F S, SU H F , ZHU X J, et al. Near-infrared emissive lanthanide hybridized carbon quantum dots for bioimaging applications[J]. J Mater Chem B, 2016, 4(38): 6366-6372.
[26] WU F S, SU H F, WANG K, et al. Facile synthesis of N-rich carbon quantum dots from porphyrins as efficient probes for bioimaging and biosensing in living cells[J]. Int J Nanomed, 2017, 12(10): 7375-7391.
[27] 黄国斌, 骆登峰, 张茂升. 多色高发光效率CsPbX₃(X=Cl,Br,I)钙钛矿量子点的制备及其在发光二极管中的应用[J]. 应用化学, 2019, 36(8): 932-938.
HUANG G B, LUO D F, ZHANG M S. Preparation of CsPbX₃(X=Cl,Br,I) perovskite quantum dots with multicolor and high luminescence efficiency and its application in light emitting diode devices[J]. Chinese J Appl Chem, 2019, 36(8): 932-938.
[28] YUAN F L, WANG Z B, LI X H, et al. Bright multicolor bandgap fluorescent carbon quantum dots for electroluminescent light-emitting diodes[J]. J Adv Mater, 2017, 29(3): 1604436.1-1604436.6.
[29] YU J, XU C X, TIAN Z S, et al. Facilely synthesized N-doped carbon quantum dots with high fluorescent yield for sensing Fe³⁺[J]. New J Chem, 2016, 40(3): 2083-2088.
[30] BHARATHI D, SIDDLINGESHWAR B, KRISHNA R H, et al. Green and cost effective synthesis of fluorescent carbon quantum dots for dopamine detection[J]. J Fluoresc, 2018, 28(2): 573-579.
[31] LIU Y L, ZHOU Q X. Sensitive pH probe developed with water-soluble fluorescent carbon dots from chocolate by one-step hydrothermal method[J]. Int J Environ Anal Chem, 2017, 97(12): 1119-1131.
[32] 马红燕, 王靖原, 张越诚, 等. 以花生碳量子点为探针基于其荧光猝灭-恢复测定多巴胺的研究[J]. 光谱学与光谱分析, 2020, 40(4): 1093-1098.
MA H Y, WANG J Y, ZHANG Y C, et al. Determination of dopamine using peanut carbon quantum dots as probe based on fluorescence quenching recovery[J]. Spectrosc Spectr Anal, 2020, 40(4): 1093-1098.
[33] SHEN J, SHANG S M, CHEN X Y, et al. Facile synthesis of fluorescence carbon dots from sweet potato for Fe³⁺ sensing and cell imaging[J]. Mater Sci Eng C, 2017, 76(7): 856-864.
[34] DU J L, WANG H Y, WANG L, et al. Insight into the effect of functional groups on visible fluorescence emissions of graphene quantum dots[J]. J Mater Chem C, 2016, 4(11): 2235-2242.
[35] LIN L X, ZHANG S W. Creating high yield water soluble luminescent graphene quantum dots via exfoliating and disintegrating carbon nanotubes and graphite flakes[J]. Chem Commun, 2012, 48(82): 10177-10179.
[36] LUCAS B N, JORGE H A, MARIO V V, et al. NADH oxidation onto different carbon-based sensors: effect of structure and surface-oxygenated groups[J]. J Sens, 2018, 2018(3): 1-9.
[37] WANG R, LU K Q, TANG Z R, et al. Recent progress in carbon quantum dots: synthesis, properties and applications in photocatalysis[J]. J Mater Chem A, 2017, 5(8): 3717-3734.
[38] ZHAO H L, QIU F, JIN S B, et al. High work-hardening effect of the pure NiAl intermetallic compound fabricated by the combustion synthesis and hot pressing technique[J]. Mater Lett, 2011, 65(17/18): 2604-2606.
[39] LI C L, ZHANG X X, ZHANG W J, et al. Carbon quantum dots derived from pure solvent tetrahydrofuran as a fluorescent probe to detect pH and silver ion[J]. J Photochem Photobiol A, 2019, 382(9): 111981.
[40] HUANG J X, HE Y L, ZHANG Z B, et al. Synthesis of high-efficient red carbon dots for pH detection[J]. J Lumin, 2019, 215(11): 116640.
[41] ZONG J, YANG X L, TRINCHI A, et al. Carbon dots as fluorescent probes for “off-on” detection of Cu²⁺ and L-cysteine in aqueous solution[J]. Biosens Bioelectron, 2014, 51(1): 330-335.