β-环糊精修饰Mn-ZnS量子点荧光探针用于检测血液中对乙酰氨基酚
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摘要
为了能够有效快捷地实现低浓度对乙酰氨基酚的检测,本文利用量子点电子转移荧光猝灭的机理,对量子的的修饰和对乙酰氨基酚的检测方法进行实验研究。首先,将乙二胺-环糊精成功修饰到Mn-ZnS量子点表面,增强其荧光稳定性和水溶性,再利用β-环糊精对对乙酰氨基酚的包合作用,使对乙酰氨基酚进入β-环糊精的空腔内,与量子点表面发生电子转移,进而使荧光猝灭。然后,基于乙二胺-环糊精修饰的ZnS量子点电子转移荧光猝灭的机理,建立了一种检测血液中对乙酰氨基酚含量的荧光光谱分析新方法。实验还考察了反应时间与反应温度对对乙酰氨基酚检测的影响。实验结果表明,在反应时间为35 min、反应温度为40℃的条件下,乙二胺-环糊精修饰ZnS量子点的荧光强度与对乙酰氨基酚的浓度呈良好的负线性关系,对乙酰氨基酚的浓度范围为1～100 ng/L,检出限为0.64 ng/L,RSD(%)为1.69%(n=11),用于血液样品的检测时,加标回收率为91.06%～103.82%。该方法实现了低浓度对乙酰氨基酚含量的检测,且操作快速、简便。
In this study, a direct analysis method of acetaminophen(ACOP) was established by ethanediamine-β-cyclodextrins(EN-β-CDs)-functionalized Mn-ZnS quantum dots(Mn/ZnS-QDs) using an electron transfer quenching mechanism. Actetaminophen is a good electron acceptor, which can enter the cavity of β-CDs, and then the fluorescence quenching form resonance electron transfer between actetaminophen and QDs surface. As indicated in experimental results, the fluorescence intensity reached the maximum under the response time was 35 min and the response temperature was 40 ℃. It was negative linear correlation between the fluorescence intensity and the concentraions of actetaminophen ranges from 1 to 100 ng/L, the detection limit obtained 0.64 ng/L, the relative standard deviation(RSD) was 1.69%(n=11). The method has been successfully applied to the detemination of actetaminophen in blood with the recovery 91.06%-103.82%.
In this study, a direct analysis method of acetaminophen(ACOP) was established by ethanediamine-β-cyclodextrins(EN-β-CDs)-functionalized Mn-ZnS quantum dots(Mn/ZnS-QDs) using an electron transfer quenching mechanism. Actetaminophen is a good electron acceptor, which can enter the cavity of β-CDs, and then the fluorescence quenching form resonance electron transfer between actetaminophen and QDs surface. As indicated in experimental results, the fluorescence intensity reached the maximum under the response time was 35 min and the response temperature was 40 ℃. It was negative linear correlation between the fluorescence intensity and the concentraions of actetaminophen ranges from 1 to 100 ng/L, the detection limit obtained 0.64 ng/L, the relative standard deviation(RSD) was 1.69%(n=11). The method has been successfully applied to the detemination of actetaminophen in blood with the recovery 91.06%-103.82%.
引文
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[2] 贺希,刘鸿凌.炎症小体在对乙酰氨基酚所致肝损伤及急性肝衰竭中的作用 [J].肝脏,2018,23(2):108-110.HE X,LIU H L.The effect of inflammasomes in hepatic injury and acute hepatic failure induced by acetaminophen [J].Chin.Hepatol.,2018,23(2):108-110.(in Chinese)
[3] 郭波,唐秀玲,石磊,等.液相色谱-串联质谱法同时测定对乙酰氨基酚及其相关代谢产物 [J].中国药师,2017,20(4):597-602.GUO B,TANG X L,SHI L,et al..Simultaneous determination of acetaminophen and its related metabolites by LC-MS/MS [J].China Pharm.,2017,20(4):597-602.(in Chinese)
[4] 王书民,樊雪梅.CdS量子点-高锰酸钾-鲁米诺化学发光体系测定对乙酰氨基酚 [J].分析科学学报,2014,30(2):231-234.WANG S M,FAN X M.CdS QDs-KMnO4-luminol chemiluminescence system for determination of acetaminophen [J].J.Anal.Sci.,2014,30(2):231-234.(in Chinese)
[5] 刘益庆,李一,戴铭骏.HPLC-ELSD法测定小儿氨酚烷胺颗粒中对乙酰氨基酚和盐酸金刚烷胺的含量 [J].西北药学杂志,2017,32(2):158-160.LIU Y Q,LI Y,DAI M J.Determination of the content of paracetamol and amantadine hydrochloride in pedi-atric paracetamol and amantadine hydrochloride granules by HPLC-ELSD [J].Northwest Pharm.J.,2017,32(2):158-160.(in Chinese)
[6] BEITOLLAHI H,MOVLAEE K,GANJALI M R,et al..A sensitive graphene and ethyl 2-(4-ferrocenyl-[1,2,3]triazol-l-yl) acetate modified carbon paste electrode for the concurrent determination of isoproterenol,acetaminophen,tryptophan and theophylline in human biological fluids [J].J.Electroanal.Chem.,2017,799:576-582.
[7] KIM D,KIM J M,JEON Y,et al..Novel two-step activation of biomass-derived carbon for highly sensitive electrochemical determination of acetaminophen [J].Sens.Actuators B:Chem.,2018,259:50-58.
[8] MENON S,JESNY S,KUMAR K G.A voltammetric sensor for acetaminophen based on electropolymerized- molecularly imprinted poly(o-aminophenol) modified gold electrode [J].Talanta,2018,179:688-675.
[9] ALAM A U,QIN Y H,HOWLADER M M R,et al..Electrochemical sensing of acetaminophen using multi-walled carbon nanotube and β-cyclodextrin [J].Sens.Actuators B:Chem.,2018,254:896-909.
[10] CAO F,DONG Q C,LI C L,et al..Electrochemical sensor for detecting pain reliever/fever reducer drug acetaminophen based on electrospun CeBiOx nanofibers modified screen-printed electrode [J].Sens.Actuators B:Chem.,2018,256:143-150.
[11] 高毓涛,李娜,李亚男.高效液相-示差折光法同时测定复方氨酚烷胺片中对乙酰氨基酚和盐酸金刚烷胺的含量 [J].中国药品标准,2017,18(3):181-185.GAO Y T,LI N,LI Y N.Determination of the contents of paracetamol and amantadine hydrochloride in compound paracetamol and amantadine hydrochloride tablets by HPLC-RID method [J].Drug Stand.China,2017,18(3):181-185.(in Chinese)
[12] 李聪,吴小玲,张彩霞,等.CdTe量子点增敏碱性鲁米诺-高碘酸钾流动注射化学发光法测定对乙酰氨基酚 [J].分析试验室,2014,33(2):129-132.LI C,WU X L,ZHANG C X,et al..CdTe quantum dots enhanced luminol-KIO4 chemiluminescence system for the determination of acetaminophen by flow injection analysis [J].Chin.J.Anal.Lab.,2014,33(2):129-132.(in Chinese)
[13] KONG X Y,WANG Y Y,ZHANG Q Q,et al..Ex-situ decoration of ordered mesoporous carbon with palladium nanoparticles via polyoxometalates and for sensitive detection of acetaminophen in pharmaceutical products [J].J.Colloid Interface Sci.,2017,505:615-621.
[14] MADURAIVEERAN G,RASIK R,SASIDHARAN M,et al..Bimetallic gold-nickel nanoparticles as a sensitive amperometric sensing platform for acetaminophen in human serum [J].J.Electroanal.Chem.,2018,808:259-265.
[15] ARUMUGAM N,KIM J.Synthesis of carbon quantum dots from Broccoli and their ability to detect silver ions [J].Mater.Lett.,2018,219(15):37-40.
[16] ENSAFI A A,NASR-ESFAHANI P,REZAEI B.Simultaneous detection of folic acid and methotrexate by an optical sensor based on molecularly imprinted polymers on dual-color CdTe quantum dots [J].Anal.Chim.Acta,2017,996:64-73.
[17] CADKOVA M,KOVAROVA A,DVORAKOVA V,et al..Electrochemical quantum dots-based magneto-immunoassay for detection of HE4 protein on metal film-modified screen-printed carbon electrodes [J].Talanta,2018,182:111-115.
[18] 郭娜,沈卫阳.量子点在环境污染物检测中的应用研究进展 [J].环境科学与技术,2013,36(6):85-90.GUO N,SHEN W Y.Progress of application of quantum dots in environmental pollutants analysis [J].Environ.Sci.Technol.,2013,36(6):85-90.(in Chinese)
[19] 黄磊,王光辉,于荣,等.甘氨酸-β-环糊精对蒽的增溶、解吸行为研究 [J].土壤,2011,43(2):258-263.HUANG L,WANG G H,YU R,et al..Study on enhanced solubilization and desorption behavior of anthrancene with glycine-β-cyclodextrin [J].Soils,2011,43(2):258-263.(in Chinese)
[20] YANG M,WANG Y,WANG H Y.β-cyclodextrin functionalized CdTe quantum dots for electrochemiluminescent detection of benzo[a]pyrene [J].Electrochim.Acta,2015,169:7-12.