Abstract
A sensitive electrochemical strategy for carcinoembryonic antigen 15–3 (CA15-3) detection is reported using CTAB-Co-MOFs@AuPt NPs as signal probes. The electrochemical strategy was designed as follows: First, the graphene aerogel@gold nanoparticles (GA@Au NPs) nanocomposites were employed to modify the sensing surface for promoting electron transfer rate and primary antibody (Ab1) immobilization due to GA possesses a large specific surface area, eminent conductivity, and a 3D network structure. Cobalt metal–organic frameworks (CTAB-Co-MOFs) synthesized were then used as a carrier for AuPt NPs and secondary antibody (Ab2) immobilization (notes: labelled-Ab2). With sandwich immunoreaction, the labelled-Ab2 was captured on the surface of the GA@Au NPs nanocomposites. Finally, differential pulse voltammetry (DPV) was employed to register the electrochemical signal of the immunosensor at the potential of − 0.85 V (vs SCE) in phosphate buffer saline (PBS) containing 2.5 mM H2O2. It was verified that the electrochemical reduction signal from Co3+ to Co2+ was recorded. The AuPt NPs could catalyze the reaction of H2O2 oxidizing Co2+ to Co3+, resulting in the amplification of the electrochemical signal. Under the selected conditions, the immunosensor can detect CA15-3 in the range 10 µU/mL to 250 U/mL with a low detection limit of 1.1 µU/mL. In the designed strategy, the CTAB-Co-MOFs were not only employed as carriers for AuPt NPs, but also acted as signal probes. The CTAB-Co-MOFs were investigated including SEM, TEM, XPS, and XRD. The application ability of the immunosensor was evaluated using serum sample, demonstrating the immunosensor can be applied to clinic serum analysis.
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Sung H, Ferlay J, Siegel RL, Laversanne M, Soerjomataram I, Jemal A, Bray F (2021) Global Cancer Statistics 2020: GLOBOCAN estimates of incidence and mortality worldwide for 36 cancers in 185 countries. CA A Cancer J Clin 71(3):209–249
Xiong X, Zhang Y, Wang YF, Sha HF, Jia NQ (2019) One-step electrochemiluminescence immunoassay for BC biomarker CA 15–3 based on Ru(bpy)62+-coated UiO-66-NH2 metal-organic framework. Sens Actuat B Chem 297:126812
Ribeiro JA, Sales MGF, Pereira CM (2021) Electrochemistry-assisted surface plasmon resonance biosensor for detection of CA 15–3. Anal Chem 93(22):7815–7824
Peng MX, Lin SY, Lin ZB, Zheng DL, Song YB, Lu FS, Chen YW, Gao WH (2022) Rationally constructed ZnCdS-HDCs@In2S3-HNRs double-hollow heterojunction with promoted light capture capability for photoelectrochemical biosensing. Biosens Bioelectron 201:113957
Jiang XY, Wang HJ, Yuan R, Chai YQ (2015) Sensitive electrochemiluminescence detection for CA15-3 based on immobilizing luminol on dendrimer functionalized ZnO nanorods. Biosens Bioelectron 63:33–38
Wu YW, Chen XL, Wang XF, Yang M, Xu FL, Hou CJ, Huo DQ (2021) A fluorescent biosensor based on prismatic hollow Metal-polydopamine frameworks and 6-carboxyfluorescein (FAM)-labeled protein aptamer for CA15-3 detection. Sensors Actuat B-Chem 329:129249
Ambrosi A, Airo F, Merkoci A (2010) Enhanced gold nanoparticle based ELISA for a BC biomarker. Anal Chem 82(3):1151–1156
Ge XY, Feng YG, Cen SY, Wang AJ, Mei LP, Luo XL, Feng JJ (2021) A label-free electrochemical immnunosensor based on signal magnification of oxygen reduction reaction catalyzed by uniform PtCo nanodendrites for highly sensitive detection of carbohydrate antigen 15–3. Anal Chim Acta 1176:338750
Feng YG, He JW, Chen DN, Jiang LY, Wang AJ, Bao N, Feng JJ (2022) 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
Thangapandi K, Arumugam S, Amalesh N, Ajeet K, Saikat K (2021) Bio-nanocomposite based highly sensitive and label-free electrochemical immunosensor for endometriosis diagnosticsapplication. Bioelectrochemistry 139:107740–107749
Jin H, Mo K, Wen F, Li Y (2019) Preparation and pervaporation performance of CAU-10-H MOF membranes. J Membrane Sci 577:129–136
Zhi D, Li T, Li J, Ren H, Meng F (2021) A review of three-dimensional graphene-based aerogels: Synthesis, structure and application for microwave absorption. Compos Part B-Eng 211:108642
Sahoo BB, Kumar N, Panda HS, Panigrahy B, Sahoo NK, Soam A, Mahanto BS, Sahoo PK (2021) Self-assembled 3D graphene-based aerogel with Au nanoparticles as high-performance supercapacitor electrode. J Energy Storage 43:103157
Santos-Gómez LD, García JR, Montes-Morán MA, Menéndez JA, García-Granda S, Arenillas A (2021) Ultralight-weight graphene aerogels with extremely high electrical conductivity. Small 17(41):2103407
Liu XT, Pang K, Yang H, Guo XZ (2020) Intrinsically microstructured graphene aerogel exhibiting excellent mechanical performance and super-high adsorption capacity. Carbon 161:146–152
Maleki H (2016) Recent advances in aerogels for environmental remediation applications: A review. Chem Eng J 300:98–118
Öner E, Öztürk A, Yurtcan AB (2020) Utilization of the graphene aerogel as PEM fuel cell catalyst support: effect of polypyrrole (PPy) and polydimethylsiloxane (PDMS) addition. Int J Hydrogen Energy 45:34818–34836
Indra A, Song T, Paik U (2018) Metal organic framework derived materials: progress and prospects for the energy conversion and storage. Adv Mater 30:1705146
Li Z, Xi Y, Zhao A, Jiang J, Li B, Yang X, He J, Li F (2021) Cobalt-imidazole metal-organic framework loaded with luminol for paper-based chemiluminescence detection of catechol with use of a smartphone. Anal Bioanal Chem 413(13):3541–3550
Liu SY, Lai C, Liu XG, Li BS, Zhang C, Qin L, Huang DL, Yi H, Zhang MM, Li L, Wang WJ, Zhou XR, Chen L (2020) Metal-organic frameworks and their derivatives as signal amplification elements for electrochemical sensing. Coordin Chem Rev 424:213520
Guan Y, Si PB, Yang T, Wu Y, Yang TH, Hu R (2023) A novel method for detection of ochratoxin A in foods—Co-MOFs based dual signal ratiometric electrochemical aptamer sensor coupled with DNA walker. Food Chem 403:134316
Liu JB, Shang YH, Zhu QY, Zhang XX, Zheng JB (2019) A voltammetric immunoassay for the carcinoembryonic antigen using silver(I)-terephthalate metal-organic frameworks containing gold nanoparticles as a signal probe. Microchim Acta 186:509
Li MY, Zhang TT, Zhang YZ (2023) Ultrasensitive electrochemical sensing platform for miRNA-21 detection based on manganese dioxide-gold nanoparticle nanoconjugates coupled with hybridization chain reaction and horseradish peroxidase signal amplification. Analyst 148(9):2180–2188
Liu JB, Fu SH, Yuan B, Li YL, Deng ZX (2010) Toward a universal “adhesive nanosheet” for the assembly of multiple nanoparticles based on a protein-induced reduction/decoration of graphene oxide. J Am Chem Soc 132(21):7279–7281
Zhu XF, Yuan S, Ju SY, Yang J, Zhao C, Liu H (2019) Water splitting-assisted electrocatalytic oxidation of glucose with a metal-organic framework for wearable nonenzymatic perspiration sensing. Anal Chem 91(16):10764–10771
Zhang TT, Ma Y, Zhang YZ (2023) A simple electrochemical strategy for the detection of the cancer marker CA19-9 by signal amplification using copper organic framework nanocomposite. Analyst 148(23):5905–5914
Zhang LX, Xian JX, Xiang XX, Ouyang H, Wang L, Fu ZF (2022) Surfactant-assisted synthesis of water-stable cobalt-imidazole metal organic frameworks as signal probes for chemiluminescent immunoassay. Sensors Actuat B-Chem 373:132774
Huang Q, Guo Y, Chen D, Zhang L, Li TT, Hu Y, Qian J, Huang S (2021) Rational construction of ultrafine noble metals onto carbon nanoribbons with efficient oxygen reduction in practical alkaline fuel cell. Chem Eng J 424:130336
Oladipo AO, Iku SII, Ntwasa M, Nkambule TTI, Mamba BB, Msagati TAM (2020) Doxorubicin conjugated hydrophilic AuPt bimetallic nanoparticles fabricated from phragmites australis: characterization and cytotoxic activity against human cancer cells. J Drug Deliv Sci Technol 57:101749
Ke H, Zhang X, Huang CS, Jia NQ (2018) Electrochemiluminescence evaluation for carbohydrate antigen 15–3 based on the dual-amplification of ferrocene derivative and Pt/BSA core/shell nanospheres. Biosens Bioelectron 103:62–68
Wang AJ, Zhu XY, Chen Y, Luo XL, Xue YD, Feng JJ (2019) Ultrasensitive label-free electrochemical immunoassay of carbohydrate antigen 15–3 using dendritic Au@Pt nanocrystals/ferrocene-grafted-chitosan for efficient signal amplification. Sens Actuators B, Chem 292:164–170
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This work is supported by the Nature Science Foundation of the Education Department of Anhui Province (No KJ2016A848).
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Zhang, T., Ma, Y., Tian, R. et al. CTAB-Co-MOFs@AuPt NPs as signal probes for the electrochemical detection of carcinoembryonic antigen 15–3. Microchim Acta 191, 176 (2024). https://doi.org/10.1007/s00604-024-06254-y
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DOI: https://doi.org/10.1007/s00604-024-06254-y