规模化制备水仙基生物相容抗氧化碳量子点

doi:10.11949/0438-1157.20250131

摘要/Abstract

摘要：

生物质衍生的碳量子点（carbon quantum dots， CDs）具有优异的生物相容性和可再生特性，目前的合成方法具有步骤烦琐、经济性较低的缺点，不利于CDs的规模化生产。通过高温碳化和超声分散分离工艺，简便快速合成水仙基碳量子点（Nar-CDs）。以水仙球茎作为生物质前体材料，其20 L体系产率最高可达16.4%。通过紫外-可见光谱、荧光光谱、透射电子显微镜（TEM）等表征，证实纳米尺度的Nar-CDs成功制备。X射线衍射（XRD）和傅里叶变换红外光谱（FTIR）表明其因带有含氧官能团而具有水溶性，KMnO₄和DPPH法实验的结果显示，Nar-CDs具有较强的还原能力和自由基清除能力。此外，通过细胞毒性测试和溶血试验验证Nar-CDs的优良生物相容性，对人脐静脉内皮细胞（HUVEC）几乎无毒性，并且没有引起明显的溶血作用。这些性能研究证明了Nar-CDs潜在的商业应用价值，为生物基CDs的进一步工业化生产和应用提供理论基础。

关键词: 碳量子点, 合成, 规模化制备, 生物质, 细胞生物学

Abstract:

Biomass-derived carbon quantum dots (CDs) have excellent biocompatibility and renewable properties. The current synthesis methods have the disadvantages of cumbersome steps and low economic efficiency, which is not conducive to the large-scale production of CDs. Herein, using Narcissus bulbs as biomass precursor materials, Narcissus-based carbon dots (Nar-CDs) were synthesized quickly and easily through a high-temperature carbonization and ultrasonic dispersion-separation process. The yield can reach up to 16.4%. The successful synthesis of Nar-CDs was confirmed through various characterization techniques, including UV-visible spectroscopy, fluorescence spectroscopy, TEM, XRD and FTIR. Nar-CDs exhibited bright blue fluorescence when excited at a wavelength of 365 nm. Analysis revealed that the surface of Nar-CDs contained abundant oxygen-functional groups, providing excellent water solubility. The antioxidant properties of Nar-CDs were assessed using KMnO₄ and DPPH methods, showing strong reducing and free radical scavenging abilities. Nar-CDs also exhibited good biocompatibility, almost no toxicity to HUVEC cells, and no obvious hemolysis effect. The above results demonstrate their potential application value.

Key words: carbon quantum dots, synthesis, industrialization-scale synthesis, biomass, cell biology

中图分类号:

O 657.3

宋一博, 杨顺宽, 罗丽芬, 潘发伍, 高媛媛, 李逸鑫, 詹国武. 规模化制备水仙基生物相容抗氧化碳量子点[J]. 化工学报, 2025, 76(10): 5475-5485.

Yibo SONG, Shunkuan YANG, Lifen LUO, Fawu PAN, Yuanyuan GAO, Yixin LI, Guowu ZHAN. Industrialization-scale synthesis of Narcissus-based carbon quantum dots with biocompatibility and antioxidant properties[J]. CIESC Journal, 2025, 76(10): 5475-5485.

图/表 9

图1 Nar-CDs的制备流程

Fig.1 Illustration of the fabrication process of Nar-CDs

图2 Nar-CDs的（a）透射电镜图（插图为相应的HRTEM图像）,（b）粒径分布,（c）X射线衍射谱图,（d）AFM图像和厚度分布和（e）三维AFM图像

Fig.2 (a) TEM image (the inset shows the corresponding HRTEM image), (b) particle size distribution, (c) XRD spectrum, (d) AFM image and thickness distribution of Nar-CDs and (e) 3D AFM image of Nar-CDs

图3 Nar-CDs的光谱图

Fig.3 Spectrum of the Nar-CDs

图4 Nar-CDs的FTIR光谱和XPS谱

Fig.4 FTIR spectra and XPS spectra of Nar-CDs

图5 KMnO4检测Nar-CDs（0~2 mg/ml）抗氧化性能：（a）紫外光谱，（b）KMnO4清除率（插图为反应后的样品图像）；DPPH法检测Nar-CDs（0~2 mg/ml）抗氧化性能：（c）紫外光谱，（d）DPPH清除率（插图为反应后的样品图像）

Fig.5 Detection of antioxidant properties of Nar-CDs (0—2 mg/ml) by KMnO4 and DPPH: (a) UV-Vis absorption spectrum and (b) scavenging activity of KMnO4 (the illustration shows the image of the samples after the reaction); (c) UV-Vis absorption spectrum and (d) scavenging ability of DPPH (the illustration shows the image of the samples after the reaction)

图6 （a）Nar-CDs对HUVEC细胞的细胞毒性；（b）小鼠红细胞经H2O（阳性对照）、PBS（阴性对照）和不同浓度的Nar-CDs溶液在37.0°C下处理2 h后的溶血率（插图为离心后的相应红细胞样品，SD值为标准差）

Fig.6 (a) The cytotoxicity of Nar-CDs on HUVEC cells; (b) the hemolysis rate of mouse red blood cells after being treated at 37.0°C for 2 h with H2O (positive control), PBS (negative control), and different concentrations of Nar-CDs solution (inset shows the corresponding centrifuged red blood cell samples, with SD representing the standard deviation)

图7 （a）Nar-CDs处理后HUVEC细胞的活/死染色激光共聚焦图像；（b）HUVEC细胞孵育Nar-CDs后的激光共聚焦图像

Fig.7 (a) CLSM images of HUVEC cells stained with Calcein-AM and PI; (b) CLSM images of HUVEC cells incubated with Nar-CDs

图8 规模化合成中使用的设备

Fig.8 Equipment used in the enlarged synthesis process

表1 不同生物质碳源制备CDs的产率比较

Table 1 Comparison of yields of CDs prepared from different biomass carbon sources

序号	碳源	合成方法	合成条件	CDs应用	合成产率/%	文献
1	橙汁	水热处理	120℃，2.5 h	生物成像	＜1	[36]
2	鸡蛋	高温热解	250℃，2 h	荧光印刷材料	5.9	[37]
3	壳聚糖	水热处理	180℃，12 h	生物成像	7.8	[38]
4	咖啡	高温煅烧	300℃，2 h	生物成像	12	[39]
5	水仙球茎	高温煅烧	200℃，2 h	抗氧化，细胞成像	16.4	本工作

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