水热-硝酸氧化合成发蓝光和绿光木质素基碳点的研究

doi:10.3969/j.issn.0253-2417.2022.04.005

摘要/Abstract

摘要：

以木质素和间苯二胺为前体，通过简单的一步水热法合成了蓝色发光碳量子点(B-CQDs)，进一步通过硝酸氧化作用，合成了绿色发光碳量子点(G-CQDs)；通过紫外吸收光谱、荧光光谱、TEM、FT-IR和XPS对两种CQDs的光学性质和结构特征进行表征分析，并测试了G-CQDs的细胞毒性及细胞成像性能。结果表明：硝酸在G-CQDs的合成中起着重要的作用，硝酸的氧化作用使CQDs石墨N含量增加，石墨化程度加深，表面态被钝化，荧光发射波长红移。结构性质分析表明所制备的B-CQDs和G-CQDs主要由C、N、O这3种元素构成，表面都具有—OH、—NH、C—O和—COOH等丰富的亲水基团，在水中是单分散的，平均粒径分别为1.3和2.5 nm。光学性质分析表明B-CQDs和G-CQDs的特征激发波长分别为392和446 nm，对应的发射波长分别为488和514 nm。B-CQDs和G-CQDs分别表现出激发相关的发射行为和激发无关的发射行为。研究发现G-CQDs的可能发射机制属于基于共轭π-域的带隙荧光发射。所合成的G-CQDs具有优异的光致发光、稳定的荧光和低细胞毒性等优点，可以应用于HeLa细胞生物成像。

关键词: 木质素, 绿色碳量子点, 带隙荧光发射, 细胞成像

Abstract:

Blue luminescent carbon quantum dots(B-CQDs) were synthesized by a simple one-step hydrothermal method using lignin and m-phenylenediamine as precursors. Green luminescent carbon quantum dots(G-CQDs) were synthesized by nitric acid oxidation. The optical properties and structures characteristics of these two CQDs were characterized by UV absorption spectroscopy, fluorescence spectroscopy, TEM, FT-IR and XPS. The cytotoxicity and cell imaging properties of G-CQDs were also tested. The results showed that nitric acid played an important role in the synthesis of G-CQDs. The oxidation of nitric acid increased the graphite N content, deepened the graphitization, passivated the surface state, and red-shifted the fluorescence emission wavelength. The results of structural characterization showed that the prepared B-CQDs and G-CQDs were mainly composed of C, N and O elements. All of them had abundant hydrophilic groups such as —OH, —NH, C—O and —COOH on the surface, which were monodisperse in water with the average particle size were 1.3 nm and 2.5 nm, respectively. The results of optical property analysis showed that the excitation wavelengths of B-CQDs and G-CQDs were Ex=392 nm and Ex=446 nm, and the corresponding emission wavelengths were 488 nm and 514 nm, respectively. They exhibited excitation-dependent fluorescence emission behavior and excitation-independent emission behavior, respectively. The results revealed that the possible emission mechanism of G-CQDs belonged to the bandgap fluorescence emissions based on conjugated π-domains. The synthesized G-CQDs with excellent photoluminescence, stable fluorescence and low cytotoxicity could be applied to bioimaging of HeLa cells.

Key words: lignin, green carbon quantum dots, bandgap emission, cell imaging

中图分类号:

TQ35
O613

王颖, 安邦, 徐明聪, 岳金权, 刘守新, 李伟. 水热-硝酸氧化合成发蓝光和绿光木质素基碳点的研究[J]. 林产化学与工业, 2022, 42(4): 33-39.

Ying WANG, Bang AN, Mingcong XU, Jinquan YUE, Shouxin LIU, Wei LI. Synthesis of Blue and Green Lignin-based Luminescent Carbon Dots by Hydrothermal-Nitric Acid Oxidation[J]. Chemistry and Industry of Forest Products, 2022, 42(4): 33-39.

图/表 11

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样品sample	粒径分布particle size distribution/%						平均粒径/nm average particle size
样品sample	1-1.5 nm	1.5-2 nm	2-2.5 nm	2.5-3 nm	3-3.5 nm	3.5-4 nm	平均粒径/nm average particle size
B-CQDs	25	49	23	3	0	0	1.3
G-CQDs	0	4	17	40	23	16	2.5

样品sample	C/%	N/%	O/%	O/C	N/C
B-CQDs	64.84	12.60	22.56	0.35	0.19
G-CQDs	63.50	6.85	29.65	0.46	0.11

样品sample	C1s				N1s			O1s
样品sample	C=C/C—C	C—N	C—O	C=O	吡啶N pyridinic N	吡咯N pyrrolic N	石墨N graphitic N	C=O	C—O
B-CQDs	0.37	0.30	0.24	0.09	0.26	0.46	0.28	0.73	0.27
G-CQDs	0.24	0.30	0.38	0.08	0.20	0.41	0.39	0.30	0.70

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