氮硫共掺杂碳量子点对胃液pH值的精确检测

doi:10.7503/cjcu20200133

摘要/Abstract

摘要：

以水杨酸和硫脲为原料, 通过水热法一步合成水溶性好、稳定性强、量子产率高(36.23%)、呈蓝光的氮硫共掺杂碳量子点(N,S-CQDs). 在302 nm波长激发下, N,S-CQDs在发射波长409 nm处的荧光强度与pH值(在2.01~5.11范围内)线性关系良好, 相关系数为0.9931, 可原位、实时检测胃液内pH值在Δ0.01范围内的变化. 可用于胃癌早期诊断和新生儿健康防护. 400 μg/mL N,S-CQDs孵育铜绿微囊藻细胞48 h, 存活率82.8%, 其可作为人体胃细胞荧光探针, 经人体排泄进入水环境, 对淡水浮游生物毒性低, 环境友好.

关键词: 碳量子点, 掺杂, pH值, 胃液, 荧光探针

Abstract:

Nitrogen-sulfur co-doped carbon quantum dots with blue light, good water solubility, strong stability and high quantum yield(36.23%), were synthesized by one-step hydrothermal method, using salicylic acid and thiourea as raw materials. Under the excitation of 302 nm, there is a good linear relationship between the fluorescence intensity and the pH value in the range of 2.01—5.11 at the emission wavelength of 409 nm, and the correlation coefficient is 0.9931. The change of pH value in gastric juice can be detected in situ and in real time. In view of the fact that the pH value of gastric juice is closely related to the diagnosis of gastric cancer and neonatal monitoring, N,S-CQDs are expected to contribute to the early diagnosis of gastric cancer and neonatal health protection. N,S-CQDs have low cytotoxicity and good biocompatibility. When microcystis aeruginosa cells as phytoplankton model are incubated with 400 μg/mL of N,S-CQDs for 48 h, their survival ratesare 82.8%, indicating that N,S-CQDs could be used as a environmental-friendly fluorescent probe for human gastric cells.

Key words: Carbon quantum dots, Doping, pH value, Gastric juice, Fluorescent probe

中图分类号:

O655

TrendMD:

黄加玲,刘凤娇,王婷婷,刘翠娥,郑凤英,王振红,李顺兴. 氮硫共掺杂碳量子点对胃液pH值的精确检测. 高等学校化学学报, 2020, 41(7): 1513.

HUANG Jialing,LIU Fengjiao,WANG Tingting,LIU Cuie,ZHENG Fengying,WANG Zhenhong,LI Shunxing. Nitrogen and Sulfur co-Doped Carbon Quantum Dots for Accurate Detection of pH in Gastric Juice^†. Chem. J. Chinese Universities, 2020, 41(7): 1513.

图/表 11

Fig.1 HRTEM images(A, C), size distribution(B) and XRD pattern(D) of N,S-CQDs

Fig.2 FTIR spectrum of N,S-CQDs

Fig.3 XPS spectra of C1s(A), N1s(B), O1s(C) and S2p(D) of N,S-CQDs

Fig.4 UV-Vis absorption spectrum and fluorescence spectra of N,S-CQDs(A) and fluorescence spectroscopy of N,S-CQDs with different excitation wavelengths(B) Insets in (A) are photos of N,S-CQDs irradiated by natural light(left) and 300 nm UV light(right).

Fig.5 Effects of NaCl concentration(A), irradiation time(B), storage time(C) and cycle number(D) on the fluorescence intensity of N,S-CQDs

Fig.6 Survival rate of Microcystis aeruginosa cells cultured in N,S-CQDs with different concentrations for 0, 24 and 48 h

Fig.7 Effect of different metal ions on the fluorescence intensity of N,S-CQDs a. Blank; b. Na+; c. K+; d. Fe3+; e. Mn2+; f. Cd2+; g. Ca2+; h. Pb2+; i. Zn2+; j. Hg+; k. Co2+; l. Mg2+; m. Ni2+.

Fig.8 Fluorescence emission spectra of N,S-CQDs with different concentrations of Fe(Ⅲ)(A) and the linear relationship between(F0-F)/F0 and Fe(Ⅲ) concentration(B)

Fig.9 Influence of pH value on the fluorescence intensity of N,S-CQDs in gastric juice(A) and the linear relationship between FL intensity at 409 nm and pH value(B) pH: a. 2.01; b. 2.26; c. 2.53; d. 2.76; e. 3.00; f. 3.26; g. 3.53; h. 3.77; i. 3.99; j. 4.20; k. 4.54; l. 5.11.

Fig.10 Zeta potential of N,S-CQDs

Table 1 pH Detection with carbon quantum dot-based fluorescent probes

Carbon quantum dots	Raw material	Linear range	Quantum yield(%)	Sample	Ref.
dCDs	o-Phenylenediamine phosphoric acid	1.5—5.0	10.34	E. coli	[23]
DECDs	o-Phenylenediamine polyethylene glycol oxalic acid	2.2—4.0	4.72(integrating sphere)	pH test papers	[39]
N,S-CDs	Ammoniumpersulfate, glucose, ethylenediamine	3.0—10.0	10.34	HePG2 cells	[22]
N-OGQDs	CA, L-DOPA	4—8	18.0		[40]
S-doped carbon dots	Waste frying oil, sulfuric acid	3.0—9.0	3.66	Helacells	[41]
N,S-CQDs	L-cysteine NH₃·H₂O	5.5—7.0	17.2	Silk fiber	[21]
N,S-QDs	Salicylic acid, thiourea	2.01—5.11	36.23	Human gastric juice	This work

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