PDF(1186 KB)
PDF(1186 KB)
PDF(1186 KB)
纳米金增强SPR铅离子检测器构建
Characterization of AuNP-enhanced SPR biosensor for Pb2+ detection
为满足采用简便方法检测痕量铅离子（Pb2+）的需求，构建了新型的超灵敏、高特异性表面等离子体共振（SPR）生物传感器，用于水中Pb2+检测.以硫醇化GR-5脱氧核酶（DNAzyme）为Pb2+特异性识别探针，并自组装到芯片金膜表面，底物官能化的纳米金（S-AuNPs）用于信号增强，并与DNAzyme杂交形成传感薄膜.AuNPs不仅增加了质量变化，其局部表面等离子体共振（LSPR）与芯片表面传播SPR的耦合作用也可产生信号放大的效果.在Pb2+离子存在下，DNAzyme催化底物裂解，导致AuNPs的去除并引起SPR信号显著变化.通过X射线光电子能谱和扫描电镜对芯片表面的表征分析验证了传感薄膜构建过程和检测原理.Pb2+检测实验结果表明，1 μmol/L DNAzyme修饰的传感器检测效果最好，检测限为80pmol/L，并在100nmol/L范围内与Pb2+浓度的对数呈线性关系（R2=0.992）.该传感器对10倍浓度的其他金属离子无明显响应，说明其具有良好的Pb2+特异性；检测自来水和地下水中Pb2+的结果与ICP-MS方法有良好的一致性.研究建立的Pb2+检测方法具有高灵敏度和特异性，且操作简便，具有现场检测的应用前景.
In order to cope with the challenge of simple methods for Pb2+ detection, a novel ultra-sensitive, highly specific surface plasmon resonance (SPR) biosensor was developed. Thiolated GR-5DNAzyme was used for specific recognition of Pb2+ and immobilized on the SPR sensor surface. Substrate functionalized gold nanoparticles (S-AuNPs) were used for signal enhancement and hybridized with DNAzyme for the formation of the Pb2+ sensing layer. The enhancement of SPR signal was induced by the mass of AuNPs and the coupling effect between their local surface plasmon resonance (LSPR) and the SPR propagated on the chip surface. In the presence of Pb2+ ions, the substrate cleavage was catalyzed by DNAzyme, resulting in the removal of AuNPs and the significant weakening of SPR signal. The sensor surface was characterized and analyzed using X-ray photoelectron spectrometer and field emission scanning electron microscope, and the detection mechanism was verified. The biosensor incorporating 1 μmol/L DNAzyme showed the best Pb2+ detection performance. Its detection limit was 80pmol/L, and the SPR angle shift demonstrated a linear relationship with the logarithm of Pb2+ concentration in the range of 10~100nmol/L. It also showed good specificity against highly concentrated other metal ions. These results of Pb2+ detection in tap water and ground water showed good consistency with the ICP-MS measurements. This Pb2+ detection method features high sensitivity and specificity, and may have application prospects for onsite detection due to its simplicity.
Pb2+ / 表面等离子体共振 / 纳米金 / 生物传感器 / 脱氧核酶
AuNPs / biosensor / DNAzyme / Pb2+ / surface plasmon resonance
[1] 韩志轩,王学求,迟清华,等.珠江三角洲冲积平原土壤重金属元素含量和来源解析[J]. 中国环境科学, 2018,38(9):3455-3463. Han Z X, Wang X Q, Chi Q H, et al. Occurrence and source identification of heavy metals in the alluvial soils of Pearl River Delta region, south China[J]. China Environmental Sciencece, 2018,38(9):3455-3463.
[2] Carolin C F, Kumar P S, Saravanan A, et al. Efficient techniques for the removal of toxic heavy metals from aquatic environment:A review[J]. Journal of Environmental Chemical Engineering, 2017,5(3):2782-2799.
[3] 董兆敏,吴世闽,胡建英.中国部分地区铅暴露儿童健康风险评价[J]. 中国环境科学, 2011,31(11):1910-1916. Dong Z, Wu S, Hu J. Health risk assessment for children due to lead exposure in some region of China[J]. China Environmental Science, 2011,31(11):1910-1916.
[4] Moens L, Desmaele T, Dams R, et al. Sensitive, simultaneous determination of organomercury, lead, and tin compounds with headspace solid phase microextraction capillary gas chromatography combined with inductively coupled plasma mass spectrometry[J]. Analytical Chemistry, 1997,69(8):1604-1611.
[5] 王文才,唐春燕,张恒军,等.不确定背景值下浅水湖泊沉积物重金属生态风险评价[J]. 中国环境科学, 2019,39(9):3982-3988. Wang W, Tang C, Zhang H, et al. Potential ecological risk assessment of heavy metals in sediment with uncertain background impact in a shallow lake[J]. China Environmental Science, 2019,39(9):3982-3988.
[6] Ghaedi M, Fathi M R, Marahel F, et al. Simultaneous preconcentration and determination of copper, nickel, cobalt and lead ions content by flame atomic absorption spectrometry[J]. Fresenius Environmental Bulletin, 2005,14:1158-1163.
[7] Ni Z, Chen Z, Cheng J, et al. Simultaneous determination of arsenic and lead in vegetable oil by atomic fluorescence spectrometry after vortex-assisted extraction[J]. Analytical Letters, 2017,50(13):2129-2138.
[8] Daniya W M E M, Saleviter S, Fen Y W. Development of surface plasmon resonance spectroscopy for metal ion detection[J]. Sensors and Materials, 2018,30(9):2023-2038.
[9] Hinman S S, Mckeating K S, Cheng Q. Surface plasmon resonance:material and interface design for universal accessibility[J]. Analytical Chemistry, 2018,90(1):19-39.
[10] Fen Y W, Yunus W M M, Talib Z A. Real-time monitoring of lead ion interaction on gold/chitosan surface using surface plasmon resonance spectroscopy[J]. Indian Journal of Physics, 2012,86(7):619-623.
[11] Alwahib A A A, Kamil Y M, Abu Bakar M H, et al. Reduced graphene oxide/maghemite nanocomposite for detection of lead ions in water using surface plasmon resonance[J]. IEEE Photonics Journal, 2018,10(6):4801310.
[12] Abdi M M, Abdullah L C, Sadrolhosseini A R, et al. Surface plasmon resonance sensing detection of mercury and lead ions based on conducting polymer composite[J]. Plos One, 2011,6:245-789.
[13] Zhou Y, Tang L, Zeng G, et al. Current progress in biosensors for heavy metal ions based on DNAzymes/DNA molecules functionalized nanostructures:A review[J]. Sensors and Actuators B-Chemical, 2016,223:280-294.
[14] Wang J, Zhang Z, Gao X, et al. A single fluorophore ratiometric nanosensor based on dual-emission DNA-templated silver nanoclusters for ultrasensitive and selective Pb2+ detection[J]. Sensors and Actuators B-Chemical, 2019,282:712-718.
[15] Huang Z, Chen J, Luo Z, et al. Label-free and enzyme-free colorimetric detection of Pb2+ based on RNA cleavage and annealing-accelerated hybridization chain reaction[J]. Analytical Chemistry, 2019,91(7):4806-4813.
[16] Wu J, Wei S, Lu Y, et al. Ultrasensitive DNAzyme-based electrochemical biosensor for Pb2+ based on FcHT-mediated biocatalytic amplification[J]. International Journal of Electrochemical Science, 2018,13(10):9630-9641.
[17] Liang G, Man Y, Li A, et al. DNAzyme-based biosensor for detection of lead ion:A review[J]. Microchemical Journal, 2017,131:145-153.
[18] Mock J J, Hill R T, Degiron A, et al. Distance-dependent plasmon resonant coupling between a gold nanoparticle and gold film[J]. Nano Letters, 2008,8(8):2245-2252.
[19] Mustafa D E, Yang T, Xuan Z, et al. Surface Plasmon Coupling Effect of Gold Nanoparticles with Different Shape and Size on Conventional Surface Plasmon Resonance Signal[J]. Plasmonics, 2010,5(3):221-231.
[20] Saprigin A V, Thomas C W, Dulcey C S, et al. Spectroscopic quantification of covalently immobilized oligonucleotides[J]. Surface and Interface Analysis, 2005,37(1):24-32.
[21] Petrovykh D Y, Kimura-Suda H, Whitman L J, et al. Quantitative analysis and characterization of DNA immobilized on gold[J]. Journal of the American Chemical Society, 2003,125(17):5219-5226.
[22] Demers L M, Mirkin C A, Mucic R C, et al. A fluorescence-based method for determining the surface coverage and hybridization efficiency of thiol-capped oligonucleotides bound to gold thin films and nanoparticles[J]. Analytical Chemistry, 2000,72(22):5535-5541.
[23] GB5749-2006生活饮用水卫生标准[S]. GB5749-2006 Standards for Drinking Water Quality[S].
[24] World Health Organization, Guidelines for drinking-water quality, 4th edition, incorporating the 1st addendum[S].
[25] Zhao X, Kong R, Zhang X, et al. Graphene-DNAzyme based biosensor for amplified fluorescence "Turn-On" detection of Pb2+ with a high selectivity[J]. Analytical Chemistry, 2011,83(13):5062-5066.
[26] Ravikumar A, Panneerselvam P, Radhakrishnan K, et al. DNAzyme based amplified biosensor on ultrasensitive fluorescence detection of Pb (Ⅱ) Ions from aqueous system[J]. Journal of Fluorescence, 2017,27(6):2101-2109.
[27] Liu J W, Lu Y. A colorimetric lead biosensor using DNAzyme-directed assembly of gold nanoparticles[J]. Journal of the American Chemical Society, 2003,125(22):6642-6643.
[28] Yun W, Cai D, Jiang J, et al. Enzyme-free and label-free ultra-sensitive colorimetric detection of Pb2+ using molecular beacon and DNAzyme based amplification strategy[J]. Biosensors & Bioelectronics, 2016,80:187-193.
[29] Yang X, Xu J, Tang X, et al. A novel electrochemical DNAzyme sensor for the amplified detection of Pb2+ ions[J]. Chemical Communications, 2010,46(18):3107-3109.
[30] Huang J, Zhao L, Lei W, et al. A high-sensitivity electrochemical aptasensor of carcinoembryonic antigen based on graphene quantum dots-ionic liquid-nafion nanomatrix and DNAzyme-assisted signal amplification strategy[J]. Biosensors & Bioelectronics, 2018,99:28-33.
[31] Teh H B, Li H, Li S F Y. Highly sensitive and selective detection of Pb2+ ions using a novel and simple DNAzyme-based quartz crystal microbalance with dissipation biosensor[J]. Analyst, 2014,139(20):5170-5175.
[32] Fu C, Xu W, Wang H, et al. DNAzyme-based plasmonic nanomachine for ultrasensitive selective surface-enhanced raman scattering detection of lead ions via a particle-on-a-film hot spot construction[J]. Analytical Chemistry, 2014,86(23):11494-11497.
[33] Kamaruddin N H, Bakar A A A, Mobarak N N, et al. Binding affinity of a highly sensitive Au/Ag/Au/chitosan-graphene oxide sensor based on direct detection of Pb2+ and Hg2+ ions[J]. Sensors, 2017,17:227-710.
[34] Daniyal W M E M, Fen Y W, Anas N A A, et al. Enhancing the sensitivity of a surface plasmon resonance-based optical sensor for zinc ion detection by the modification of a gold thin film[J]. RSC Advances, 2019,9(71):41729-41736.
[35] Fen Y W, Yunus W M M, Yusof N A. Surface plasmon resonance optical sensor for detection of Pb2+ based on immobilized p-tert-butylcalix
[4]arene-tetrakis in chitosan thin film as an active layer[J]. Sensors and Actuators B-Chemical, 2012,171:287-293.
[36] Kamaruddin N H, Bakar A A A, Yaacob M H, et al. Enhancement of chitosan-graphene oxide SPR sensor with a multi-metallic layers of Au-Ag-Au nanostructure for lead(Ⅱ) ion detection[J]. Applied Surface Science, 2016,361:177-184.
[37] Daniyal W M E M, Fen Y W, Abdullah J, et al. Exploration of surface plasmon resonance for sensing copper ion based on nanocrystalline cellulose-modified thin film[J]. Optics Express, 2018,26(26):34880-34893.
[38] Chen Z, Han K, Zhang Y. Reflective fiber surface plasmon resonance sensor for high-sensitive mercury ion detection[J]. Applied Sciences-Basel, 2019,9:14-807.
[39] Guner H, Ozgur E, Kokturk G, et al. A smartphone based surface plasmon resonance imaging (SPRi) platform for on-site biodetection[J]. Sensors and Actuators B-Chemical, 2017,239:571-577.
国家重点研发计划专项（2018YFC1902903）；深圳市科技计划项目（KJYY20171012103638606,JSGG20170822164024506）
京公网安备 11010802030352号 /
| 〈 |
|
〉 |
