应用化学 ›› 2022, Vol. 39 ›› Issue (9): 1382-1390.DOI: 10.19894/j.issn.1000-0518.210369
杨振华, 孙宣森, 张月霞, 曹宇娟, 张琪琦, 郭峤志, 范小鹏, 李忠平, 董川()
收稿日期:
2021-07-27
接受日期:
2022-02-23
出版日期:
2022-09-01
发布日期:
2022-09-08
通讯作者:
董川
基金资助:
Zhen-Hua YANG, Xuan-Sen SUN, Yue-Xia ZHANG, Yu-Juan CAO, Qi-Qi ZHANG, Qiao-Zhi GUO, Xiao-Peng FAN, Zhong-Ping LI, Chuan DONG()
Received:
2021-07-27
Accepted:
2022-02-23
Published:
2022-09-01
Online:
2022-09-08
Contact:
Chuan DONG
About author:
dc@sxu.edu.cnSupported by:
摘要:
以柠檬酸和谷胱甘肽为原材料,通过热解法一步合成一种氮硫共掺杂蓝色荧光碳点(N,S-CDs)。使用透射电子显微镜(TEM)、紫外-可见吸收光谱、荧光光谱、X射线光电子能谱等技术对制备的碳点进行形貌及光学性质表征。结果表明,该碳点的激发波长和发射波长分别为366和440 nm,荧光产率为0.46,平均粒径为(2.55 ± 0.75) nm。土霉素可有效猝灭该碳点的蓝色荧光,且具有良好的选择性。将该碳点用于牛奶中土霉素的检测时,在0.77~18.40 μg/mL的范围内,(F0-F)/F0与土霉素浓度有良好的线性关系,回归方程为y=0.02282x+0.02913,检出限为0.09 μg/mL。该检测方法具有简单易操作的优点。
中图分类号:
杨振华, 孙宣森, 张月霞, 曹宇娟, 张琪琦, 郭峤志, 范小鹏, 李忠平, 董川. 氮硫共掺杂碳点的制备及其对牛奶中土霉素的检测[J]. 应用化学, 2022, 39(9): 1382-1390.
Zhen-Hua YANG, Xuan-Sen SUN, Yue-Xia ZHANG, Yu-Juan CAO, Qi-Qi ZHANG, Qiao-Zhi GUO, Xiao-Peng FAN, Zhong-Ping LI, Chuan DONG. Preparation of Nitrogen Sulfur Co⁃doped Carbon Dots with Nitrogen Sulfur and the Application for Detection of Oxytetracycline in Milk[J]. Chinese Journal of Applied Chemistry, 2022, 39(9): 1382-1390.
图1 不同GSH用量(A)、加热时间(B)和加热温度(C)对N,S-CDs荧光强度的影响,*P < 0.05
Fig.1 Effects of different GSH dosage (A), heating time (B) and heating temperature (C) on fluorescence intensity of N,S-CDs, *P < 0.05
图3 (A)N,S-CDs的紫外-可见吸收、荧光激发和发射光谱曲线; (B)不同激发波长下N,S-CDs的荧光发射光谱
Fig.3 (A) UV-Vis absorption, fluorescence excitation, and excitation spectra of N,S-CDs aqueous solution;(B) PL spectra of N,S-CDs aqueous solution at different excitation wavelengths
图5 (A)N,S-CDs的XPS全谱图; (B)C1s XPS图; (C)N1s XPS图; (D)O1s XPS图; (E)S2p XPS图
Fig.5 (A) XPS full spectrum of N,S-CDs; (B) C1s XPS; (C) N1s XPS; (D) O1s XPS; (E) S2p XPS
图8 (A)不同抗生素对N,S-CDs荧光强度的影响;(B)不同反应时间对土霉素荧光强度的影响
Fig.8 (A) Effect of different antibiotics on fluorescence intensity of N,S-CDs; (B) Effect of different reaction time on fluorescence intensity of oxytetracycline
图9 (A)加入不同浓度OTC后N,S-CDs的荧光发射光谱; (B)(F0-F)/F0随OTC浓度变化曲线
Fig.9 (A) Fluorescence emission spectra of N,S-CDs with different concentrations of OTC (c(OTC)/(μmol·L-1): 0, 1.67, 3.34, 5.01, 6.68, 8.35, 10.02, 11.69, 13.36, 15.03, 16.7, 18.37, 20.04, 21.71, 23.38, 25.05, 26.72, 28.39, 30.06, 31.73, 33.4, 35.07, 36.74, 38.41 and 40.08); (B)Plot of(F0-F)/F0 against OTC concentration
样品 Sample | 加入量 Added ρ/(μg·mL-1) | 测定量 Detected ρ/(μg·mL-1) | 回收率 Recovery R/% | 相对标准偏差 RSD St/% |
---|---|---|---|---|
1 | 3.07 | 3.15 | 102.60 | 4.32 |
2 | 4.60 | 4.52 | 98.30 | 3.81 |
3 | 6.13 | 6.00 | 97.90 | 3.42 |
表1 加标回收法测定牛奶中土霉素
Table 1 Determination of oxytetracycline (OTC) in milk by the standard recovery method
样品 Sample | 加入量 Added ρ/(μg·mL-1) | 测定量 Detected ρ/(μg·mL-1) | 回收率 Recovery R/% | 相对标准偏差 RSD St/% |
---|---|---|---|---|
1 | 3.07 | 3.15 | 102.60 | 4.32 |
2 | 4.60 | 4.52 | 98.30 | 3.81 |
3 | 6.13 | 6.00 | 97.90 | 3.42 |
1 | LI L L, GE H W, GUO H Y, et al. Focusing on luminescent graphene quantum dots: current status and future perspectives[J]. Nanoscale, 2013, 5(10): 4015-4039. |
2 | ZHOU X, GAO X, SONG F, et al. A sensing approach for dopa mine determination by boronic acid-functionalized molecularly imprinted graphene quantum dots composite[J]. Appl Surf Sci, 2017, 423(30): 810-816. |
3 | WANG Y, LI X, SONG J, et al. All-inorganic colloidal perovskite quantum dots: a new class of lasing materials with favorable characteristics[J]. Adv Mater, 2015, 47(5): 7101-7108. |
4 | PANDIT S, BANERJEE T, SRIVASTAVA I, et al. Machine learning-assisted array-based biomolecular sensing using surface-functionalized carbon dots[J]. ACS Sens, 2019, 4(10): 2730-2737. |
5 | 颜范勇, 邹宇, 王猛, 等. 荧光碳点的制备及应用[J]. 化学进展, 2014, 26(1): 61-74. |
YAN F Y, ZOU Y, WANG M, et al. Synthesis and application of the fluorescent carbon dots[J]. Prog Chem, 2014, 26(1): 61-74. | |
6 | YU C Y, XUAN T T, CHEN Y W, et a1. Gadolinium-doped carbon dots with high quantum yield as an effective fluorescence and magnetic resonance bimodal imaging probe[J]. J Alloys Compd, 2016, 688: 611-619. |
7 | ZHUO K L, SUN D, XU P P, et a1. Green synthesis of sulfur- and nitrogen-co-doped carbon dots using ionic liquid as a precursor and their application in Hg2+ detection[J]. J Lumin, 2017, 187: 227-234. |
8 | MIAO X, YAN X L, QU D, et a1. Red emissive sulfur, nitrogen codoped carbon dots and their application in ion detection and theraonostics[J]. ACS Appl Mater Interfaces, 2017, 9(22): 18549-18556. |
9 | 温广明, 焦婷, 杜孝艳, 等. 硫氮共掺杂碳量子点的制备及应用[J]. 应用化学, 2021, 38(6): 722-730. |
WEN G M, JIAO T, DU X Y, et al. Preparation and application of sulfur and nitrogen co-doped carbon quantum dots[J]. Chinese J Appl Chem, 2021, 38(6): 722-730. | |
10 | 胡国文, 乔玉玲. 叶酸修饰的碳量子点在体外癌细胞成像中的应用[J]. 应用化学, 2020, 37(9): 1003-1009. |
HU G W, QIAO Y L. Folic acid-carbon dot conjugates for cancer cell targeting[J]. Chinese J Appl Chem, 2020, 37(9): 1003-1009. | |
11 | 徐丽萍, 刘清士, 董芷辰, 等. 基于氮掺杂碳点的荧光增强简便、快速而准确地检测环丙沙星[J]. 应用化学, 2020, 37(7): 830-838. |
XU L P, LIU Q S, DONG Z C, et al. Simple, fast and accurate detection of ciprofloxacin based on fluorescence enhancement of nitrogen-doped carbon dots[J]. Chinese J Appl Chem, 2020, 37(7): 830-838. | |
12 | 陈桂秀, 吴银宝. 兽药土霉素的环境行为研究进展[J]. 动物医学进展, 2011, 32(5): 102-107. |
CHEN G X, WU Y B. Progress on environmental behavior of oxytetracycline[J]. Prog Veter Med, 2011, 32(5): 102-107. | |
13 | 宓捷波, 许迪明, 李淑静, 等. 奶粉中残留兽药的QuEChERS方法应用研究[J]. 食品研究与开发, 2015, 36(2): 121-125. |
FU J B, XU D M, LI S J, et al. Applied research on QuEChERS using to determine veterinary drugs residues in milk powder[J]. Food Res Dev, 2015, 36(2): 121-125. | |
14 | 高广慧, 李阳, 孙晓娟, 等. HPLC法测定牛羊肉中土霉素、四环素、金霉素残留量[J]. 食品研究与开发, 2013, 34(16): 94-96. |
GAO G H, LI Y, SUN X J, et al. Determination of oxytetracycline, tetracycline and chlortetracycline residues in beef and mutton by HPLC[J]. Food Res Dev, 2013, 34(16): 94-96. | |
15 | 刘玲. HPLC法测定土霉素片中土霉素的含量[J]. 海峡药学, 2018, 30(10): 77-78. |
LIU L. Determination of oxytetracycline in oxytetracycline tablets by HPLC[J]. Strait Pharm J, 2018, 30(10): 77-78. | |
16 | TARPARN L, MENCARELLI E, NOCCHETTI M, et al. Spectrophotometric analysis of nickel colloid performances as catalysts for hydrogenation of nitro-phenol: influence of the stabilizing agents[J]. Catal Commu, 2016, 74: 28-32. |
17 | DENG H, SU X, WANG H. Simultaneous determination of aflatoxin B1, bisphenol A, and 4-nonylphenol in peanut oils by liquid-liquid extraction combined with solid-phase extraction and ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Food Anal Methods, 2018, 11(5): 1303-1311. |
18 | HIRA S A, NALLAL M, PARK K H. Fabrication of PdAg nanoparticle infused metal-organic framework for electrochemical and solution-chemical reduction and detection of toxic 4-nitrophenol[J]. Sens Actuators B: Chem, 2019, 298: 126861. |
19 | 严拯宇, 赵娜, 刘贞, 等. 生物质碳点的合成及初步用于盐酸土霉素的测定[J]. 无机化学学报, 2014, 30(4): 937-944. |
YAN C Y, ZHAO N, LIU Z, et al. Biomass-based carbon dots: synthesis and application in oxytetracycline hydrochloride determination[J]. Chinese J Inorg Chem, 2014, 30(4): 937-944. | |
20 | KORKMAZ S D, KUPLULU O, CIL G I, et al. Detection of sulfonamide and tetracycline antibiotic residues in Turkish pine honey[J]. Int J Food Prop, 2017, 34(4): 50-55. |
21 | 屈瑞红, 郑国柱. 基于碳量子点荧光猝灭法测定牛奶中的土霉素[J]. 广东化工, 2020, 47(23): 120-121. |
QU R H, ZHENG G Z. Determination of oxytetracycline in milk based on fluorescence quenching of carbon quantum cots[J]. Guangdong Chem Ind, 2020, 47(23): 120-121. | |
22 | 徐铭泽, 廖秀芬, 陶慧林, 等. 基于CdS@ZnS量子点与罗丹明B能量转移荧光猝灭法检测牛奶中土霉素[J]. 分析测试学报, 2013, 32(10): 1217-1221. |
XU M Z, LIAO X F, TAO H L, et al. Study on fluorescence resonance energy transfer between CdS@ZnS QDs and rhodamine B and its application in determination of oxytetracycline in milk[J]. J Instrumental Anal, 2013, 32(10): 1217-1221. | |
23 | WANG Y L, NI P J, JIANG S, et al. Highly sensitive fluorometric determination of oxytetracycline based on carbon dots and Fe3O4 MNPs[J]. Sens Actuators B: Chem 2018, 254: 1118-1124. |
24 | FU Y Z, HUANG L, ZHAO S J, et al. A carbon dot-based fluorometric probe for oxytetracycline detection utilizing a frster resonance energy transfer mechanism[J]. Spectrochim Acta A, 2020, 246: 118947. |
25 | FAN J, QI L, LI Y, et al. A single probe-based sensor array for fingerprinting biothiols in serum and urine via surfactant modulation strategy[J]. Sens Actuators B: Chem, 2019, 301: 127144. |
26 | 孙雪花, 李浩, 杨娇莉, 等. 曲克芦丁对发光碳量子点的荧光猝灭作用[J]. 化学研究与应用, 2018, 30(11): 1857-1860. |
SUN X H, LI H, YANG J L, et al. Fluorescence quenching of luminous carbon quantum dots by troxerutin[J]. Chem Res Appl, 2018, 30(11): 1857-1860. |
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