Table 1.

Electrochemical biosensing methods involving multifunctional metal-based nanomaterials.

Electrode	Nanomaterial/Role	Biosensing Approach/Format	Detection Technique	Target Analyte	LR/LOD	Sample	Ref.
-Metal nanoparticles (MNPs)-
CILE	CILE modified with AuNT and HRP and coated with nafion/Direct electron transfer of HRP	Enzyme-based	CV	TCA and NaNO2	TCA: 1.0–250 mM/0.33 mM NaNO2: 1.6–66.0 mM/0.53 mM	Facial peel solution	[7]
GCE/AuNPs	Self-assembly of GS-IL/AuNRs through thiolated sol–gel matrix Positively charged GS-IL was used for GOx immobilization GS-IL and Au NRs acted as high electroactive catalyst.	Enzyme-based	Amperometry −0.2 V (H2O2)	Glucose	1–764 μM/0.38 µM	Serum and brain microdialysate	[8]
SPCE	PtNPs-MWCNTs-GOx/Electrode modifier to enzyme immobilization and electrocatalytic	Enzyme-based	Amperometry −0.5 V (H2O2)	Glucose	65.8–260.6 μg mL−1/35.0 μg mL−1	White grapes and glucose tablets	[9]
GCE	Electroactive polymer nanospheres synthesized from polymerization of ferrocenedicarboxylic acid/nanocarriers of Ab2, PtNPs, and hemin/G-quadruplex bioelectrocatalytic complex	Antibody based/Sandwich	DPV	AFP	0.1 pg mL−1–100 ng mL−1/0.086 pg mL−1	Human serum	[11]
GCE	GCE modified with Au@Thi/GO loaded with cAb PtCu@rGO/g-C3N4 conjugated with DAb	Antibody based/Sandwich	Amperometry −0.4 V	PSA	50 fg mL−1–40 ng mL−1/16.6 fg mL−1	Human serum	[14]
SPCE-AuNPs	PEGylated nanoCeO2 conjugated to thiolated-cAb	Antibody based/Direct	CV ([Fe(CN)6]3−/4−)	HER2	1–500 pg mL−1/34.9 pg mL−1	Serum from breast cancer patient	[15]
GCE	Cu2O@CeO2-AuNP/nanocarrier of cAb and electrocatalytic activity reduction of H2O2	Antibody based/Direct	Amperometry −0.4 V	PSA	0.1 pg mL−1–100 ng mL−1/0.03 pg mL−1	Human serum	[17]
GCE-AuNP	Co3O4@CeO2-Au@Pt/nanocarrier of DAb and enzyme-mimetic label	Antibody based/Sandwich	Amperometry −0.2 V	SCCA	100 fg mL−1–80 ng mL−1/33 fg mL−1	Spiked human serum	[18]
GCE	AuBP@Pt/Electrode modifier AuPd-PDA nanozyme/DAb nanocarrier and electrocatalytic activity reduction of H2O2	Antibody based/Sandwich	Amperometry −0.25 V	APOE4	0.05–2000 ng mL−1/15.4 pg mL−1	Commercial goat serum	[19]
SPCE	SPCEs modified with a 3D network PAMAM-AuNPs nanocomposite/to immobilize cAb	Antibody based/Sandwich	Amperometry −0.2 V (H2O2 + HQ)	tau protein	6–5000 pg mL−1/1.7 pg mL−1	Raw plasma and brain tissue from healthy and post mortem diagnosed AD patients	[21]
dSPCE	3D-Au-PAMAM on p-ABA-dSPCE for the immobilization of cAb	Antibody based/Sandwich	Amperometry −0.2 V (H2O2 + HQ)	tau and TDP-43 proteins	Tau: 0.008–5.0 ng mL−1/2.3 pg mL−1 TDP-43: 0.043–15.0 ng mL−1/12.8 pg mL−1	Plasma and brain tissue extracts from healthy and NDD patients	[22]
	Fc-IL-CHO/AuNP-PAMAM-based platform was used to immobilize the cAb	Antibody based/Direct	DPV (Fc)	α-fetoprotein	0.05–30 ng mL−1/0.02 ng mL−1	Human serum samples	[23]
GCE	rGO-TEPA as electrode modifier and Ag@CeO2 nanocomposite as labels	Antibody based/Sandwich	Amperometry −0.4 V (H2O2)	TGSF	0.500–100 pg mL−1/0.2 pg mL−1	Spiked human serum	[25]
GCE	Poly-L-lysine/Electrode modifier DNA-Ag/Pt NCs/peroxidase-mimicking activity	Aptamer based/Sandwich	Amperometry −0.1 V (H2O2 + TMB)	VEGF	6–20 pM/4.6 pM (175 pg mL−1)	Human serum	[27]
GCE	TDNs–aptamer1 as recognition probe Mn3O4-Pd@Pt-aptamer2-HRP as nanozymes and nanoprobe	Aptamer based/Sandwich	DPV (H2O2 + HQ)	HER2	0.1–100.0 ng mL−1/0.08 ng mL−1	Human serum	[29]
AuE	Signal amplification by CHA reaction PtPdNPs/HRP as mimic nanozyme	Aptamer based/Displacement	Amperometry −0.45 V (H2O2 + TMB)	Mucin 1	100 fg mL−1–1 ng mL−1/16 fg mL−1	Human serum	[31]
GCE	MWCNT/Electrode modifier for ssDNA immobilization Ag-DNCs-labeled DNA probe	DNA-based/Direct	Ag+ by DPASV	DNA hybridization	10–300 pM/0.78 pM	-	[32]
GCE	AuNPs/Electrode modifier for immobilization of S-DNA probe MPBA-AgNPs as label	DNA-based/Direct	LSV	miRNA-21	0.1–50 fM/20 aM	Serum	[33]
Gold	MPBA-biotin-AuNPs and Strept-AP as labels	Aptamer-based/Direct	DPV (pAPP)	rHuEPO	0.02–2 pM/8 fM	-	[34]
GCE	SA-PPy/AuNPs/Electrode modifier for hairpin immobilization Signal amplification by CHA reaction and Cu2+/Fe3+ catalytic reaction	Aptamer-based/Displacement	SWV	miRNA	1 fM–1 nM/0.34 fM	Spiked serum	[36]
Au micro-gap electrode	pRhNPs/Electrode modifier and T4 DNA aptamer 3-way junction-Ag+ immobilization	Aptamer-based/Direct	EIS ([Fe(CN)6]3−/4−)	T4	up to 11.41 pM/10.33 pM	Human serum	[37]
GCE	Self-assemble AuNPs superlattice through pPPy for sDNA immobilization/Electrode modifier TB as tracing tag	DNA-based/Direct	DPV	miRNA-21	100 aM–1 nM/78 aM	Human serum	[38]
GCE	poly(FBThF) and Ag-rGO-NH2 nanocomposite/AChE immobilization and catalytic activity	AChE	Amperometry (ATCl)	Malathion trichlorfon	Malathion: 0.099–9.9 μg L−1/0.032 µg mL−1 Trichlorfon: 0.0206–2.06 μg L−1/0.001 μg L−1	Food	[43]
Bare gold	AuNPs functionalized with aptamer/mimetic HRP activity	Nanozyme/target-induced replacement of the aptamer	DPV (H2O2, thi)	kanamycin	0.1–60 nM/0.06 nM	Honey samples	[44]
GE	PtRu nanoparticles/Electrode modifier and for AO and AMO immobilization	Nanozyme-based	Amperometry −0.32 V (H2O2)	Ethanol Methylamine	Ethanol: 25–200 μM Methylamine: 20–600 μM	Red wine	[45]
-	CeO2 NPs/GOx mimicking activity	Nanozyme/TdT induced the aggregation of CeO2	PGM signal	Glucose	up to 100 U mL−1/0.7 U mL−1	Human blood	[46]
-Multifunctional MNPs involving ordered nanostructures-
GCE/AuNP@MWCNTs	bimetallic Cu-TCPP(Fe) nanosheets to immobilize PtNi nanospheres/nanocarriers of detection antibody and electrocatalytic H2O2 reduction	Antibody based/Sandwich	Amperometry (H2O2)	CALP	200 fg mL−1–50 ng mL−1/137 fg mL−1	Healthy human serum	[12]
ITO	In the presence of the target, DNA-walker-induced conformation switch to immobilize Pd/PCN-224/catalysis of NaBH4 oxidation	DNA-based/Direct	LSV (NaBH4)	DNA	100 fM–100 nM/33.6 fM	Human serum	[39]
GCE	rGO-TEPA/AuNPs/Strep/immobilization of thiol-DNA probe hemin-MOFs/PtNPs/signal amplification	DNA-based/Direct	Amperometry (H2O2)	FGFR3 mutation gene	0.1 fM–1 nM/0.033 fM	Serum from patients in different gestation periods	[47]
Bare gold	2D-Zr-MOF/Electrode modifier ad for aptamer immobilization	Apasensor-based/Direct	EIS ([Fe(CN)6]4−/3−)	Mucin 1	0.001–0.5 ng·mL−1/0.12 pg mL−1	Human serum	[48]
	Co-MOF nanosheet array on nickel foam/glucose oxidation electrocatalysis	Nanozyme/Direct	Amperometry	Glucose	0.001–3 mM/1.3 nM	Human blood serum and fruit juice	[49]
-Multifunctional nanomaterials involving quantum dots (QDs)-
GCE	Modification with iron magnetic nanoparticles with a core shell MOFs to immobilize the cAb and NiCd-QDs conjugated to DAb as electroactive non-enzymatic probe	Antibody based/Sandwich	DPV	PSA	1 pg mL−1–100 ng mL−1/0.45 pg mL−1	Human serum	[13]
GCE	PbS-QDs conjugated to DAb as a label	Antibody based/Sandwich	stripping of Pb(II) by SWASV	HER2	1–100 ng mL−1/0.28 ng mL−1	Spiked serum samples	[16]
SPCE array	CdSe/ZnS-QDs conjugated with anti-h-IgG as label	Antibody based/Sandwich	DPASV	Anti-tTG IgG	Up to 40 U mL−1/2.2 U mL−1		[20]
GCE	MWCNTs@PDA@AuNPs/Electrode modifier for immobilization of Con A Aptamer-DNA concatamer-QDs/recognizing probes	Aptamer-based/Sandwich	ASV	Cancer cells	1.0 × 102–1.0 × 106 cells mL−1/50 cells mL−1	Model cancer cells	[28]
GCE	Cat@AMQDs/Electrode modifier	Enzyme-based	Amperometry −0.1 V (H2O2)	CA125	50–300 µM/4.4 μM	Ovarian cancer serum	[50]
SPCE	core/shell CdSe@ZnS-QDs-Strep/signal tag	Antibody based/Sandwich	DPASV	HER2-ECD	10–150 ng mL−1/2.1 ng mL−1	spiked human serum samples	[51]
Bare gold	streptavidin-CdQD	DNA-based	SWASV	Telomerase activity	1 to 105 cells	HeLa cells, HEK293T cells and MRC-5 cells	[52]
Bare gold	3-CdTeQD-DNA nanocomposite hybridizes with the cleaved DNA probe on the electrode after DNA probe-mRNA interaction and DSN	DNA-based	DPASV	mRNA of BRCA1	5 aM–5 fM/1.2 aM	Healthy human serum samples	[53]
GCE	AuNP/Electrode modifier for immobilization of two specific harpins PbS@ZIF-8-S1 and CdS@ZIF-8-S2/signaling tag	DNA-based/CHA for signal application	DPASV	Hemophilia A biomarkers: miR-1246 and miR-4521	miR-1246: 0.05 pM–1.0 mM miR-4521: 0.05 pM–1.0 mM	Human serum	[54]
-Two-dimensional (2D) transition metals-
GCE	Ag@Ti3C2Tx nanocomposites as nanocarriers of AChE	Enzyme-based	DPV	Malathion	10−14–10−8 M/3.27 × 10−15 M	Tap water	[10]
GCE	MoS2-AuNPs as electrode modifier and nanoprobe for immobilizing the cAb and HRP-DAb respect.	Antibody based/Sandwich	DPV (H2O2 + o-PD)	CEA	10 fg mL−1–1 ng mL−1/1.2 fg mL−1	Spiked samples	[24]
SPE	MoS2-AuNPs-β-CD as electrode modifier and for immobilizing the MB-aptamer probe	Aptamer-based/Displacement	DPV (Fc-COOH)	OTA	0.1–50 nM/0.06 nM	-	[30]
CPE	PXA film functionalized MoS2 nanosheets/Electrode modifier for DNA immobilization and signal tag	DNA-based/Displacement	EIS	Circulating tumor DNA	1.0 × 10–16–1.0 × 10−10 mol L−1/1.8 × 10–17 mol L−1	PIK3CA gene in peripheral blood of patients with gastric carcinoma	[40]
GCE	AuNPs-MoS2 microcubes/Electrode modifier for biotin-cDNA DNS cleaves duplexes DNA-mRNA and mRNA is released	DNA-based/strep-AP	DPV FcM (redox mediator) TCEP (reducing reagent) and AAP (enzyme substrate)	miRNA-21	0.1 fM–0.1 pM/0.086 fM	Human serum samples breast from cancer patients	[55]
GCE	Av-MBs/Electrode modifier for cAb immobilization AuNP-FMC-WS2 nanocomposite/for DAb immobilization and signal tag	Antibody based/Sandwich	DPV	CA72-4	2–50 U L−1/0.6 U L−1	Human serum	[56]
GCE	TiO2–SnS2 nanocomposite/Electrode modifier for GOx immobilization	Enzyme-based	Amperometry −0.45 V	Glucose	0.008–1.13 and 1.13–5.53 mM/1.8 µM	Human serum samples	[57]
GCE	Ti3C2-MXene functionalized with APTES/Electrode modifier for cAb immobilization	Antibody based/Direct	CV ([Ru(NH3)6]3+)	CEA	1.0 × 10−4–2000 ng mL−1/1.8 × 10−5 ng mL−1	Spiked human sera sample	[58]
GCE	MoS2/Ti3C2 nanohybrids and AuNPs/Electrode modifier for probe RNA immobilization	DNA-based/Direct	DPV	miRNA-182	1 fM–0.1/0.43 fM	Serum samples	[59]

AAP: ascorbic acid 2-phosphate; AChE: acetylcholinesterase; AFP: alpha fetal protein; AP: alkaline phosphatase; AMO: methylamine oxidase; AMQDs: antimonene quantum dots; anti-tTG: anti-transglutaminase IgG antibodies; AO: alcohol oxidase; APOE4: apolipoprotein E4; APTES: 3-aminopropyl triethoxysilane; ATCl: acetylthiocholine chloride; AuBP: gold nanobipyramid; AuNRs: gold nanorods; AuNTs: gold nanotriangles; Av: avidin; BRCA1: breast cancer 1 gene mutation; CA72-4: carbohydrate antigen 72-4; cAb: capture antibody; CALP: calprotectin; ASV: anodic stripping voltammetry; Cat: catalase; CD: cyclodextrin; CEA: carcinoembryonic antigen; CHA: catalytic hairpin assembly; CHO: aldehyde groups; CILE: carbon ionic liquid electrode; Con A: concanavalin A; CPE: carbon paste electrode; CV: cyclic voltammetry; DAb: detector antibody; DNC: dendrimer nanocomposite; DPASV: differential pulse anodic stripping voltammetry; DPV: differential pulse voltammetry; dSPCE: dual screen-printed carbon electrode; DSN: double-strand specific nuclease; EIS: electrochemical impedance spectroscopy; FBThF: 4, 7-di (furan-2-yl) benzo thiadiazole; Fc: ferrocene; Fc-COOH: ferrocenecarboxylic acid; FcM: ferrocene methanol; GE: graphite electrode; GO: graphene oxide; GOx: glucose oxidase; GS-IL: ionic liquid modified graphene sheets; HER2: human epidermal growth factor receptor 2; HER2-ECD: extracellular domain of the human epidermal growth factor receptor 2; HRP: horseradish peroxidase; IL: ionic liquid; LOD: detection limit; LR: linear range; ITO: indium tin oxide; MB: methylene blue; MPBA: 4-mercaptophenylboronic acid; MWCNTs: multi-walled carbon nanotubes; NDD: neurodegenerative disorders; PAMAM: G4 polyamidoaminic dendrimers; pAPP: p-aminophenyl phosphate; PCN-224: porphyrinic metal-organic framework; PDA: polydopamine; PGM: personal glucose meter; PPy: polypirrole; pRhNPs: porous rhodium nanoplates; PSA: prostate specific antigen; PtNPs: platinum nanoparticles; PXA: poly-xanthurenic acid; rHuEPO: recombinant human erythropoietin; SA: sodium alginate; SCCA: squamous cell carcinoma antigen; SPCE: screen-printed carbon electrode; SPE: screen-printed electrode; Strep: streptavidin; SWASV: square wave anodic stripping voltammetry; T4: tyroxine; TB: toluidine blue; TCA: trichloroacetic acid; TCEP: tris(carboxyethyl)phosphine; TCPP: tetrakis (4-carboxyphenyl) porphyrin; TDN: tetrahedral DNA nanostructure; TdT: terminal deoxynucleotidyl transferase; TEPA: tetraethylenepentamine; Thi: thionine; TSGF: tumor specific growth factor; VEGF: vascular endothelial growth factor.