Preparation of Nitrogen Sulfur Co⁃doped Carbon Dots with Nitrogen Sulfur and the Application for Detection of Oxytetracycline in Milk

doi:10.19894/j.issn.1000-0518.210369

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (9): 1382-1390.DOI: 10.19894/j.issn.1000-0518.210369

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Preparation of Nitrogen Sulfur Co⁃doped Carbon Dots with Nitrogen Sulfur and the Application for Detection of Oxytetracycline in Milk

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()

Institute of Environmental Science，Shanxi University，Taiyuan 030006，China

Received:2021-07-27 Accepted:2022-02-23 Published:2022-09-01 Online:2022-09-08
Contact: Chuan DONG
About author:dc@sxu.edu.cn
Supported by:
the National Natural Science Foundation of China(91843301);the Scholarship Fund of Shanxi Province(2020?002)

Abstract

Abstract:

A nitrogen sulfur co-doped fluorescent carbon dot （N，S-CDs） is synthesized by pyrolysis from citric acid and glutathione as starting materials. The morphology and properties of synthesized N，S-CDs are characterized by transition electron microscopy（TEM）， UV-Vis absorption， fluorescence spectroscopy， and X-ray photoelectron spectroscopy（XPS）. The N，S-CDs has an average particle size of （2.55 ± 0.75） nm， and is also highly fluorescent at about 440 nm with excitation at 360 nm， respectively， and a relative fluorescence quantum yield as 0.46. The presence of oxytetracycline can effectively quench the fluorescence of N，S-CDs with a good selectivity. The N，S-CDs is applied for the detection of oxytetracycline in milk， and the linear relationship is found in the range of 0.77~18.40 μg/mL， with the detection limit as 0.09 μg/mL. And the regression equation is y=0.02282x+0.02913. The preparation is straightforward and the detection of oxytetracycline is also less complicated.

Key words: Pyrolysis of citric acid, Glutathione, Carbon dots, Oxytetracycline

CLC Number:

O657.3

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.

Figures/Tables 11

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

Fig.2 TEM image and its magnification （A） and particle size distribution （B） of N，S-CDs

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

Fig.4 FT-IR spectrum of N，S-CDs

Fig.5 （A） XPS full spectrum of N，S-CDs；（B） C1s XPS；（C） N1s XPS；（D） O1s XPS；（E） S2p XPS

Fig.6 Effect of continuous xenon lamp irradiation on fluorescence intensity of N，S-CDs

Fig.7 Fluorescence intensity of N，S-CDs at different pHs

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

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

Fig.10 Fitting graph of N，S-CDs fluorescence life time

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/%

References 26

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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Preparation of Nitrogen Sulfur Co⁃doped Carbon Dots with Nitrogen Sulfur and the Application for Detection of Oxytetracycline in Milk

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