Abstract
A signal-on sandwich-like electrochemical immunosensor was built for determination of cytokeratin 19 fragments 21–1 (CYFRA 21–1) in non-small cell lung cancer (NSCLC) by confining electroactive dye (e.g., methylene blue, MB) as a probe for amplifying signals. Specifically, core–shell gold@rhodium dendritic nanocrystals (Au@Rh DNCs) behaved as a substrate for primary antibody and accelerate interfacial electron transfer. Besides, hollow carbon spheres (HCSs) were subsequently modified with polydopamine (PDA) and PtPd nanoparticles for sequential integration of the secondary antibody and confinement of MB as a label, termed as MB/PtPd/PDA/HCSs for clarity. The built sensors showed a broad linear range (100 fg mL−1 ~ 100 ng mL−1) for detection of CYFRA 21–1 with an ultra-low detection limit (31.72 fg mL−1, S/N = 3), coupled with satisfactory performance in human serum samples. This work can be explored for assays of other proteins and provides some constructive insights for early and accurate diagnosis of NSCLC.
Graphical abstract
Similar content being viewed by others
References
Williamson J (2018) Atezolizumab in patients with metastatic NSCLC. Lancet Respir Med 6:584
Barak V, Goike H, Panaretakis KW, Einarsson R (2004) Clinical utility of cytokeratins as tumor markers. Clin Biochem 37:529–540
Li X, Zhang Y, Hao L, Liu Y, Wang X, Yang H, Kong J (2021) Ultrasensitive label-free detection for lung cancer CYFRA 21–1 DNA based on ring-opening polymerization. Talanta 223:121730
Liu D, Qian Y, Xu R, Zhang Y, Ren X, Ma H, Wei Q (2021) A dual-signal amplification photoelectrochemical immunosensor for ultrasensitive detection of CYFRA 21–1 based on the synergistic effect of SnS2/SnS/Bi2S3 and ZnCdS@NPC-ZnO. Sens Actuators, B 346:130456
Yang L, Jia Y, Wu D, Zhang Y, Ju H, Du Y, Ma H, Wei Q (2019) Synthesis and application of CeO2/SnS2 heterostructures as a highly efficient coreaction accelerator in the luminol-dissolved O2 system for ultrasensitive biomarkers immunoassay. Anal Chem 91:14066–14073
Cohen L, Cui NW, Cai YM, Garden PM, Li X, Weitz DA, Walt DR (2020) Single molecule protein detection with attomolar sensitivity using droplet digital enzyme-linked immunosorbent assay. ACS Nano 14:9491–9501
Lou DD, Fan L, Cui Y, Zhu YF, Gu N, Zhang Y (2018) Fluorescent nanoprobes with oriented modified antibodies to improve lateral flow immunoassay of cardiac troponin I. Anal Chem 90:6502–6508
Jian XX, Xu J, Wang YM, Zhao CX, Gao ZD, Song YY (2021) Deployment of MIL-88B(Fe)/TiO2 nanotube-supported Ti wires as reusable electrochemiluminescence microelectrodes for noninvasive sensing of H2O2 from single cancer cells. Anal Chem 93:11312–11320
Qu L, Yang L, Li Y, Ren X, Wang H, Fan D, Wang X, Wei Q, Ju H (2021) Dual-signaling electrochemical ratiometric method for competitive immunoassay of CYFRA21-1 based on urchin-like Fe3O4@PDA-Ag and Ni3Si2O5(OH)4-Au absorbed methylene blue nanotubes. ACS Appl Mater Interfaces 13:5795–5802
Miao J, Du K, Li X, Xu X, Dong X, Fang J, Cao W, Wei Q (2021) Ratiometric electrochemical immunosensor for the detection of procalcitonin based on the ratios of SiO2-Fc-COOH-Au and UiO-66-TB complexes. Biosens Bioelectron 171:112713
Yang ZH, Ren S, Zhuo Y, Yuan R, Chai YQ (2017) Cu/Mn double-doped CeO2 nanocomposites as signal tags and signal amplifiers for sensitive electrochemical detection of procalcitonin. Anal Chem 89:13349–13356
Dong H, Cao L, Tan Z, Liu Q, Zhou J, Zhao P, Wang P, Li Y, Ma W, Dong Y (2020) A signal amplification strategy of CuPtRh CNB-embedded ammoniated Ti3C2 mxene for detecting cardiac troponin i by a sandwich-type electrochemical immunosensor. ACS Appl Bio Mater 3:377–384
Wang XY, Chen Y, Mei LP, Wang AJ, Yuan PX, Feng JJ (2020) Confining signal probe in porous PdPtCoNi@Pt-skin nanopolyhedra to construct a sandwich-type electrochemical immmunosensor for ultrasensitive detection of creatine kinase-MB. Sens Actuators, B 315:128088
Ma E, Wang P, Yang Q, Yu H, Pei F, Li Y, Liu Q, Dong Y (2019) Electrochemical immunosensor based on MoS2 NFs/Au@AgPt YNCs as signal amplification label for sensitive detection of CEA. Biosens Bioelectron 142:111580
Pumera M, Sánchez S, Ichinose I, Tang J (2007) Electrochemical nanobiosensors. Sens Actuators, B 123:1195–1205
Li Y-H, Zhou S, Jian X, Zhang X, Song Y-Y (2021) Asymmetrically coating Pt nanoparticles on magnetic silica nanospheres for target cell capture and therapy. Microchim Acta 188:361
Qu K, Xu J, Xue Y, Guo J, Gao Z, Song Y-Y, Mei Y (2022) Near infrared light-driven photothermal effect on homochiral Au/TiO2 nanotube arrays for enantioselective desorption. Anal Chem 94:588–592
Lim B, Jiang M, Camargo PHC, Cho EC, Tao J, Lu X, Zhu Y, Xia Y (2009) Pd-Pt bimetallic nanodendrites with high activity for oxygen reduction. Science 324:1302–1305
Zheng ZK, Tachikawa T, Majima T (2015) Plasmon-enhanced formic acid dehydrogenation using anisotropic Pd-Au nanorods studied at the single-particle level. J Am Chem Soc 137:948–957
Son SE, Gupta PK, Hur W, Lee HB, Park Y, Park J, Kim SN, Seong GH (2021) Citric acid-functionalized rhodium–platinum nanoparticles as peroxidase mimics for determination of cholesterol. ACS Appl Nano Mater 4:8282–8291
Zhang YP, Gao F, Wang CQ, Shiraishi Y, Du YK (2019) Engineering spiny PtFePd@PtFe/Pt core@multishell nanowires with enhanced performance for alcohol electrooxidation. ACS Appl Mater Interfaces 11:30880–30886
Cai S, Xiao W, Duan H, Liang X, Wang C, Yang R, Li Y (2018) Single-layer Rh nanosheets with ultrahigh peroxidase-like activity for colorimetric biosensing. Nano Res 11:6304–6315
Li F, Ding Y, Xiao X, Yin S, Hu M, Li S, Chen Y (2018) From monometallic Au nanowires to trimetallic AuPtRh nanowires: interface control for the formic acid electrooxidation. J Mater Chem A 6:17164–17170
Cha C, Shin SR, Annabi N, Dokmeci MR, Khademhosseini A (2013) Carbon-based nanomaterials: multifunctional materials for biomedical engineering. ACS Nano 7:2891–2897
Geng HY, Peng Y, Qu LT, Zhang HJ, Wu MH (2020) Structure design and composition engineering of carbon-based nanomaterials for lithium energy storage. Adv Energy Mater 10:1903030
Liu R, Mahurin SM, Li C, Unocic RR, Idrobo JC, Gao H, Pennycook SJ, Dai S (2011) Dopamine as a carbon source: the controlled synthesis of hollow carbon spheres and yolk-structured carbon nanocomposites. Angew Chem Int Ed 50:6799–6802
Didenko VV, Moore VC, Baskin DS, Smalley RE (2005) Visualization of individual single-walled carbon nanotubes by fluorescent polymer wrapping. Nano Lett 5:1563–1567
Wang ZJ, Li MY, Zhang YJ, Yuan JH, Shen YF, Niu L, Ivaska A (2007) Thionine-interlinked multi-walled carbon nanotube/gold nanoparticle composites. Carbon 45:2111–2115
Wang ZX, Zhao HL, Chen KC, Li HY, Lan MB (2021) Sandwich-type electrochemical aptasensor based on hollow mesoporous carbon spheres loaded with porous dendritic Pd@Pt nanoparticles as signal amplifier for ultrasensitive detection of cardiac troponin I. Anal Chim Acta 1188
Fu YC, Li PH, Xie QJ, Xu XH, Lei LH, Chen C, Zou C, Deng WF, Yao SZ (2009) One-pot preparation of polymer-enzyme-metallic nanoparticle composite films for high-performance biosensing of glucose and galactose. Adv Funct Mater 19:1784–1791
Wang AJ, Liao QC, Feng JJ, Yan ZZ, Chen JR (2012) In situ synthesis of polydopamine-Ag hollow microspheres for hydrogen peroxide sensing. Electrochim Acta 61:31–35
Manasa G, Ronald JM, Ashis KS, Ozma JDS, Dhason A (2017) Facile preparation of poly(methylene blue) modified carbon paste electrode for the detection and quantification of catechin. Mater Sci Eng C 73:552–561
Tang Z, He J, Chen J, Niu Y, Zhao Y, Zhang Y, Yu C (2018) A sensitive sandwich-type immunosensor for the detection of galectin-3 based on N-GNRs-Fe-MOFs@AuNPs nanocomposites and a novel AuPt methylene blue nanorod. Biosens Bioelectron 101:253–259
Zhang M, Li G, Zhou Q, Pan D, Zhu M, Xiao R, Zhang Y, Wu G, Wan Y, Shen Y (2018) Boosted electrochemical immunosensing of genetically modified crop markers using nanobody and mesoporous carbon. ACS Sens 3:684–691
Han J, Zhang MF, Chen GJ, Zhang YQ, Wei Q, Zhuo Y, Xie G, Yuan R, Chen SP (2017) Ferrocene covalently confined in porous MOF as signal tag for highly sensitive electrochemical immunoassay of amyloid-β. J Mater Chem B 5:8330–8336
Fan Y, Shi SY, Ma JS, Guo YH (2019) A paper-based electrochemical immunosensor with reduced graphene oxide/thionine/gold nanoparticles nanocomposites modification for the detection of cancer antigen 125. Biosens Bioelectron 135:1–7
Xue Q, Huang H, Zhu JY, Zhao Y, Li FM, Chen P, Chen Y (2020) Au@Rh core-shell nanowires for hydrazine electrooxidation. Appl Catal, B 278:119269
Meng H-L, Lin S-Y, Feng J-J, Zhang L, Wang A-J (2022) Coordination regulated pyrolysis synthesis of ultrafine FeNi/(FeNi)9S8 nanoclusters/nitrogen, sulfur-codoped graphitic carbon nanosheets as efficient bifunctional oxygen electrocatalysts. J Colloid Interface Sci 610:573–582
Han Z, Feng J-J, Yao Y-Q, Wang Z-G, Zhang L, Wang A-J (2021) Mn, N, P-tridoped bamboo-like carbon nanotubes decorated with ultrafine Co2P/FeCo nanoparticles as bifunctional oxygen electrocatalyst for long-term rechargeable Zn-air battery. J Colloid Interface Sci 590:330–340
Wang Z, Zhang H, Liu S, Dai Z, Wang P, Xu Y, Li X, Wang L, Wang H (2020) Engineering bunched RhTe nanochains for efficient methanol oxidation electrocatalysis. Chem Commun 56:13595–13598
Deng K, Ren T, Xu Y, Liu S, Dai Z, Wang Z, Li X, Wang L, Wang H (2020) Transition metal M (M = Co, Ni, and Fe) and boron co-modulation in Rh-based aerogels for highly efficient and pH-universal hydrogen evolution electrocatalysis. J Mater Chem A 8:5595–5600
Wang HJ, Li YH, Deng K, Li CJ, Xue HR, Wang ZQ, Li XN, Xu Y, Wang L (2019) Trimetallic PtPdNi-truncated octahedral nanocages with a well-defined mesoporous surface for enhanced oxygen reduction electrocatalysis. ACS Appl Mater Interfaces 11:4252–4257
Chen Z, Liu S, Huang J, Huang W, Chen L, Cui Y, Du Y, Fu R (2021) Molecular level design of nitrogen-doped well-defined microporous carbon spheres for selective adsorption and electrocatalysis. ACS Appl Mater Interfaces 13:12025–12032
Chen Y, Ge XY, Cen SY, Wang AJ, Luo XL, Feng JJ (2020) Ultrasensitive dual-signal ratiometric electrochemical aptasensor for neuron-specific enolase based on Au nanoparticles@Pd nanoclusters-poly(bismarck brown Y) and dendritic AuPt nanoassemblies. Sens Actuators, B 311:127931
Feng YG, He JW, Jiang LY, Chen DN, Wang AJ, Feng JJ (2022) Novel sandwich-typed electrochemical immunosensing of C-reactive protein using multiply twinned AuPtRh nanobead chains and nitrogen-rich porous carbon nanospheres decorated with Au nanoparticles. Sens Actuators, B 358:131518
Lin Y, Jia J, Yang R, Chen D, Wang J, Luo F, Guo L, Qiu B, Lin Z (2019) Ratiometric immunosensor for GP73 detection based on the ratios of electrochemiluminescence and electrochemical signal using DNA tetrahedral nanostructure as the carrier of stable reference signal. Anal Chem 91:3717–3724
Chen Y, Mei LP, Feng JJ, Yuan PX, Luo XL, Wang AJ (2019) Simple one-pot aqueous synthesis of 3D superstructured PtCoCuPd alloyed tripods with hierarchical branches for ultrasensitive immunoassay of cardiac troponin I. Biosens Bioelectron 145:111638
Feng YG, Wang XY, Wang ZW, Wang AJ, Mei LP, Luo XL, Feng JJ (2021) A label-free electrochemical immunosensor based on encapsulated signal molecules in mesoporous silica-coated gold nanorods for ultrasensitive assay of procalcitonin. Bioelectrochemistry 140:107753
Wang YG, Wang YL, Wu D, Ma HM, Zhang Y, Fan DW, Pang XH, Du B, Wei Q (2018) Label-free electrochemical immunosensor based on flower-like Ag/MoS2/rGO nanocomposites for ultrasensitive detection of carcinoembryonic antigen. Sens Actuators, B 255:125–132
Chen Z, Liang R, Guo X, Liang J, Deng Q, Li M, An T, Liu T, Wu Y (2017) Simultaneous quantitation of cytokeratin-19 fragment and carcinoembryonic antigen in human serum via quantum dot-doped nanoparticles. Biosens Bioelectron 91:60–65
Kumar S, Sharma JG, Maji S, Malhotra BD (2016) Nanostructured zirconia decorated reduced graphene oxide based efficient biosensing platform for non-invasive oral cancer detection. Biosens Bioelectron 78:497–504
Funding
This research was supported by the National Natural Science Foundation of China (No. 32070397).
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Conflict of interest
The authors declare no competing interests.
Additional information
Publisher's note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Feng, YG., He, JW., Chen, DN. et al. A sandwich-type electrochemical immunosensor for CYFRA 21–1 based on probe-confined in PtPd/polydopamine/hollow carbon spheres coupled with dendritic Au@Rh nanocrystals. Microchim Acta 189, 271 (2022). https://doi.org/10.1007/s00604-022-05372-9
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00604-022-05372-9