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. 2019 Apr 19;9(4):634. doi: 10.3390/nano9040634

Table 1.

Electrochemical affinity biosensors reported over the last five years involving the use of GQDs or CDs.

Electrode Bioassay format Nanomaterial(Role) Target Technique Linear range LOD Assay time Sample Reference
GCE Direct immunosensor AgNPs/thiol-GQDs (electrode modifiers) HCV DPV (riboflavin) 0.05 pg mL−1–60 ng mL−1 3 fg mL−1 30 min + AgNPs (2 h) + Thiol-GQDs (54 h) + CAb/AgNPs/thiol-GQD/GCE (>3 h) Spiked human serum [56]
Au-SPE Direct immunosensor PAMAM/GQDs
(electrode modifiers)
cTnI CV, DPV (Fe(CN)63-) 1.0 10−6–1.0 × 10−3 20 fg mL−1 (CV)
25 fg mL−1 (DPV)
10 min once prepared the Au/GQD/PAMAM/CAb (30 h) Human blood serum [10]
SPCE Direct immunosensor GQDs
(electrode modifiers)
cMyo DPV (Fe3+ group of the cMyo) 0.01–100 ng mL−1 0.01 ng mL−1 10 min once prepared the CAb/GQDs/SPCE (1 h 10 min) Spiked human serum [40]
SPCE Direct immunosensor GQDs grafted with 2-ABA
(electrode modifiers)
Parathion EIS
([Fe(CN)6]3-/4-)
0.01–106 ng L−1 46 pg L−1 5–30 min once prepared the CAb/GQD/SPCE (~3.5 h) [9]
SPCE Direct immunosensor GQDs grafted with 2-ABA
(electrode modifiers)
AXL DPV
([Fe(CN)6]3-/4-)
1.7−1000 pg mL−1 0.5 pg mL−1 90 min once prepared the CAb/GQD/SPCE (~4 h) Human serum [43]
GCE Direct immunosensor PtPd/N-GQDs@Au (electrode modifiers) CEA Amperometry (H2O2) 5 fg mL−1–50 ng mL−1 2 fg mL−1 1 h + CAb/PtPd/N-GQDs@Au/GCE (2 h) + PtPd/N-GQDs@Au (~47 h) Spiked human serum [49]
GCE Sandwich immunosensor Fe3O4@Ag/GQDs
(electrode modifiers) and DAb-AuNPs as labels
CFP-10 DPV (Au3+) 0.005–500 mg mL−1 0.33 ng mL−1 2 h once prepared the CAb/Fe3O4@Ag/GQD/GCE (~13 h) Spiked human urine [57]
SPCE Sandwich immunosensor MWCNTs/GQDs
(nanocarriers of DAb+HRP)
IL-13sRα2 Amperometry (H2O2/HQ) 2.7–100 ng mL−1 0.8 ng mL−1 1 h 45 min + BCAb-Strep/p-ABA/SPCEs (3 h 15 min) + MWCNTs/GQDs-HRP-DAb (~30.5 h) Raw cellular lysates and extracts of paraffin-embedded tissues from CRC patients [47]
SPdCE Sandwich immunosensor MWCNTs/GQDs
(nanocarriers of DAb+HRP)
13sRα2 + CDH-17 Amperometry (H2O2/HQ) 4.92–100 ng mL−1 (IL-13sRα2)
0.11–10 ng mL−1 (CDH-17)
1.44 ng mL−1 (IL-13sRα2) and
0.03 ng mL−1 (CDH-17)
1 h 45 min + BCAb-Strep/p-ABA/SPCEs (3 h 15 min) + MWCNTs/GQDs-HRP-DAb (~30.5 h) Raw cellular lysates and extracts of paraffin-embedded tissues from CRC patients [48]
GCE Sandwich hybridization sensor ZnFe2O4/GQDs (Trace label + nanocarrier of Dp) Target DNA (S2) DPV (H2O2/TH) 10−16–5 × 10−9M 6.2 × 10−17 M 160 min + MCH/S1/Pd/GS/GCE (110 min) ZnFe2O4/GQDs-S3 (11 h) Spiked human serum [45]
Au disk electrode (2-mm φ) Sandwich hybridization sensor GQDs (platform for HRP immobilization) miRNA-155 Chronoamperometry (H2O2/TMB) 1 fM–100 pM 0.14 fM 4 h once prepared the MCH/SHCp/Au (~13 h) Spiked human serum (1/10 diluted) [41]
GCE Direct aptasensing strategy AgNPs/thiol-GQDs (electrode modifiers) TNT DPV (RU) 0.001–0.300 pM 0.33 fM 35 min + AgNPs (2 h) + Thiol-GQDs (54 h) + Ap/AgNPs/thiol-GQD/GCE (>16 h) Spiked soil and water samples [59]
Au-SPE Direct hybridization CDs (electrode modifiers) Target DNAs DPV (safranine) 0.001–20 μM 0.16 nM 1 h + CDs (~3 days) + Cp/CDs/Au-SPEs (~2 days) DNA isolated from peripheral blood leukocytes from cystic fibrosis patients [1]
GCE Direct hybridization GQDs (electrode modifiers) Target HBV-DNA DPV (K3[Fe(CN)6]) 10–500 nM 1 nM 30 min + Cp/GQDs/GCE (12.5 h) + GQDs (50 min) [39]
ITO Direct hybridization CM/GQDs (electrode modifiers) APOe4 DNA DPV (CM) 20–400 pg mL−1 0.48 pg mL−1 — + Cp/CM/GQDs/ITO (>30 min) + GQDs (20 min) 100-fold diluted human blood plasma pre-treated with ammonium sulfate [58]

p-ABA: p-aminobezoic acid; AXL: receptor tyrosine kinase; CAb: capture antibody; CEA: carcinogenic embryonic antigen; CM: curcumin; Cp: capture probe; CRC: colorectal cancer; CV: cyclic voltammetry; DAb: detector antibody; Dp: detector probe; DPV: differential pulse voltammetry; EIS: electrochemical impedance spectroscopy; GCE: glassy carbon electrode; HCV: hepatitis C virus core antigen; HBV: hepatitis B virus; HQ: hydroquinone; ITO: indium-tin oxide; N-GQDs: nitrogen-doped graphene quantum dots; PAMAM: poly(amidoamine); PtPd/N-GQDs@Au: nanocomposites of N-GQDs, PtPd bimetallic nanoparticles and Au nanoparticles; CFP-10: culture filtrate protein; GS: graphene sheet; MCH: mercaptohexanol; RU: rutin; SPCE: screen-printed carbon electrode; SPdCE: screen-printed dual carbon electrode; Strep: streptavidin; TH: thionine; TMB: 3,3′,5,5′-tetramethylbenzidine; TNT: 2,4,6-Trinitrotoluen.