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用于抗结核药物异烟肼检测的碳点/二氧化锰纳米探针的构建
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作者单位
王新旭,樊柄君,闫晓辉,王宁 1. 山西医科大学 第一临床医学院山西 太原 030001 2. 山西医科大学 法医学院山西 太原 030001 3. 山西医科大学 基础医学院山西 太原 030001 
基金项目:山西省自然科学基金项目(201901D111210);山西省高等学校大学生创新创业训练计划项目(2020181);山西医科大学博士启动基金项目(03201514)
中文摘要:采用微波法快速合成了一种生物相容性好、稳定性高的荧光碳点(CDs),并将该碳点与二氧化锰纳米片(MnO2)混合形成纳米荧光探针用于抗结核药物异烟肼(INH)的检测。采用透射电子显微镜(TEM)、X射线光电子能谱(XPS)、X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、紫外可见光谱(UV-Vis)和荧光光谱等手段对碳点和二氧化锰纳米片的形貌、成分、表面基团进行了表征。实验发现,MnO2纳米片通过荧光共振能量转移(FRET)猝灭CDs的荧光,而加入的INH可与MnO2纳米片发生氧化还原反应使后者降解,进而使CDs的荧光得以恢复,基于此构建了一种定量检测INH的纳米荧光探针。该探针对INH表现出良好的灵敏度和选择性,对INH检测的线性范围为0.5 ~ 60 μmol/L,检出限为0.02 μmol/L,并成功地应用于血样、尿样以及片剂中INH的测定,回收率分别为94.8% ~ 116%,99.0% ~ 105%和96.8% ~ 102%,相对标准偏差均小于5%,结果令人满意。该探针为INH的检测提供了新的思路,在生物样品检测方面具有广阔的应用前景。
中文关键词:碳点/二氧化锰纳米探针  异烟肼  荧光共振能量转移  抗结核药物
 
Construction of a Carbon Dot/MnO2 Nanoprobe for Detection of Anti-tuberculosis Drug Isoniazid
Abstract:Isoniazid(INH) is an indispensable drug in the treatment of tuberculosis at this stage.The determination of INH content is of great significance in drug quality control and drug safety.In this paper,carbon dots(CDs) were synthesized rapidly by a microwave method using citric acid as the carbon source and thiourea as the nitrogen source.The carbon dots emit blue fluorescence under UV light,which have the advantage of biocompatibility and high stability.The carbon dots were mixed with manganese dioxide nanosheets(MnO2) to form a fluorescent nanoprobe for the sensitive detection of INH.The morphology,composition and surface groups of the carbon dots and manganese dioxide nanosheets were characterized by transmission electron microscopy(TEM),X ray photon spectroscopy(XPS),X ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR),ultraviolet-visible spectroscopy(UV-Vis) and fluorescence spectroscopy,respectively.TEM results indicated that the carbon dots were nearly spherical with particle sizes of 2.0-3.0 nm,while the manganese dioxide nanosheets had a typical two-dimensional flake morphology.Fourier transmission infrared spectroscopy revealed that there were hydroxyl,amino,and carboxyl groups on the surface of carbon dots.The fluorescence spectrum of carbon dots demonstrated a maximum emission at 445 nm with an excitation wavelength of 360 nm.Meanwhile,manganese dioxide nanosheets had a wide absorption band of 250-600 nm,which had a large overlap with the fluorescence emission spectra of carbon dots.The fluorescence of carbon dots was quenched by fluorescence resonance energy transfer(FRET) between carbon dots and manganese dioxide nanosheets.After the addition of trace INH,the redox reaction between INH and manganese dioxide nanosheets occurred,which degraded manganese dioxide nanosheets and restored the fluorescence of carbon dots.This allowed the development of a nanoprobe for the quantitative detection of INH,which showed good sensitivity and selectivity for INH.The fluorescence intensity of carbon dots at 360 nm excitation under different pH of PBS solution,different concentration of sodium chloride solution and UV irradiation was studied.The experimental results showed that carbon dots had good stability.After optimization of the experimental conditions, the linear range of the nanoprobe for INH detection in pH 7.4 PBS buffer solution was 0.5-60 μmol/L,with a detection limit of 0.02 μmol/L.Selectivity and interference experiments presented that the nanoprobe was highly selective for INH.Moreover,common metal ions, amino acids,and sugars did not interfere with INH detection.The CDs/MnO2 probe was used for the determination of INH in normal human blood,urine samples,and tablets.The recoveries of blood samples,urine samples and tablets were 94.8%-116%,99.0%-105% and 96.8%-102%,respectively.Relative standard deviations(RSDs) were less than 5% for all samples.It is highly sensitive,selective,simple to prepare,economical,and environmentally friendly.The probe provides a new idea for the detection of INH and has a promising application prospect in the detection of biological samples.
Key Words:CDs/MnO2 nanoprobe  isoniazid(INH)  fluorescence resonance energy transfer(FRET)  anti-tuberculosis drug
引用本文:王新旭,樊柄君,闫晓辉,王宁.用于抗结核药物异烟肼检测的碳点/二氧化锰纳米探针的构建[J].分析测试学报,2022,41(7):1058-1065.
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