Recent Advances in MOF-Based Materials for Biosensing Applications

Abstract

Metal-organic frameworks (MOFs) or coordination polymers have gained enormous interest in recent years due to their extraordinary properties, including their high surface area, tunable pore size, and ability to form nanocomposites with various functional materials. MOF materials possess redox-active properties that are beneficial for electrochemical sensing applications. Furthermore, the tunable pore size and high surface area improve the adsorption or immobilization of enzymes, which can enhance the sensitivity and selectivity for specific analytes. Additionally, MOF-derived metal sulfides, phosphides, and nitrides demonstrate superior electrical conductivity and structural stability, ideal for electrochemical sensing. Moreover, the functionalization of MOFs further increases sensitivity by enhancing electrode-analyte interactions. The inclusion of carbon materials within MOFs enhances their electrical conductivity and reduces background current through optimized loading, preventing agglomeration and ensuring uniform distribution. Noble metals immobilized on MOFs offer improved stability and catalytic performance, providing larger surface areas and uniform nanoparticle dispersion. This review focuses on recent developments in MOF-based biosensors specifically for glucose, dopamine, H₂O₂, ascorbic acid, and uric acid sensing.

Keywords: MOF-derived carbon composites; MOF-derived metal oxides; MOF–noble metal composite; biosensing; metal–organic frameworks; phosphides; sulfides.

Figure 4

(a) Illustration of the 3D CuO NWs@Co₃O₄ fabrication process and its role in glucose oxidation catalysis [52]. (b) Representation of the synthesis process for NiCo₂O₄ hollow nanocages (HNCs) and Co₃O₄ [57].

Figure 5

(a) Schematic showing the bioelectrode fabrication process and its application in the impedimetric detection of E. coli [64]. (b) Fabrication process of Nafion/PANI/ZIF-8 nanocomposites [67].

Figure 8

Phosphorization of MOF into (a) CQDs/MoP nanohybrid [91]. (b) Synthesis of Ni₂P/graphene [92]. (c) Synthesis of CoP_x@NCNTs’ polyhedrons [97].

Figure 11

(a) Differential pulse voltammetry (DPV) response of the MIPs/CuCo₂O₄@carbon/3D−KSC integrated electrode in 0.1 M PBS (pH = 7.0) with various DA concentrations [127]. (b) Histogram showing the current response proportions of the MIPs/CuCo₂O₄@carbon/3D-KSC electrode and CuCo₂O₄@carbon/3D−KSC electrode in 0.1 M PBS (pH = 7.0) with 0.5 mM DA and potential interfering substances [127]. (c) Fabrication of Ag-ZIF-67 nanopinna-modified GCE and its application in the detection of AP and DA [129].

Figure 13

(a) Diagrammatic illustration of the Pd nanocubes@CdIF−8 catalyst fabrication approach for the extremely effective electrocatalytic detection of H₂O₂ [144]. (b) Illustration of the surface functionalization of carbon cloth with Al−CPP−Co MOF [146]. (c) Amperometric curves of Al−TCPP−Co/CC recorded at various working potentials [146]. (d) Current response over time for Al−TCPP−Co/CC during interference analysis in the presence of ethanol, glycerin, glucose, sucrose, and saccharin [146]. (e) Schematic diagram of Au nanoflowers (NFs) and Fe₃O₄@ZIF−8-MoS₂ nanocomposite-modified GCE for the electrochemical detection of H₂O₂ derived from living cells under pharmacological stimulation [148]. (f) Amperometric responses of Au NFs/Fe₃O₄@ZIF−8-MoS₂/GCE to the addition of 400 μM ascorbic acid (AA), both with and without H9C2 cells, as well as in the presence of H9C2 cells without AA (cell count: 2 × 10⁶) [148]. (g) Transmission electron microscopy (TEM) images of Co₃O₄/NCNTs [149]. (h) Amperometric response of the Co₃O₄/NCNT electrode at −0.2 V following the sequential introduction of 0.2 mmol L⁻¹ hydrogen peroxide (H₂O₂), fructose (FRU), glucose (Glu), chloride (Cl⁻), and sulfate (SO₄²⁻) into 0.1 mol L⁻¹ phosphate-buffered saline (PBS) at pH 7.0 [149].

Figure 1

(a) Procedure for the synthesis of porous carbon from zinc-based MOF [18]. (b) SEM image of porous carbon derived from isoreticular metal–organic framework-8 (IRMOF-8) [25].

Figure 2

(a) Synthesis process of the Ni-MOF@CNTs heterogeneous composites [29]. (b) Fabrication of sandwich-like GS@ZIF-67 hybrids [31]. (c) Incorporation of GQD into PCN-222 via direct impregnation [32]. (d) Preparation of MWCNTs/ZIF-67-modified electrode [36].

Figure 3

(a) Description of the typical synthesis approach of ZIF-67/Pt, ZIF-67/Pt, CN@Co/Pt, and CN@Co/Pt/Co nanocomposites [46]. (b) Representation of the assembly process of the modified GCE with GOx-rGO/Pt NPs@Zn-MOF-74 [47].

Figure 6

Schematic representation of the synthesis of SS-MOFNSs and SS-BNNSs [73].

Figure 7

ZIF-67-derived CoS_x polyhedrons and CoS_x@CdS composites [79].

Figure 9

(a) Formation of NiCo₂O₄ hollow nanocages (HNCs) and Co₃O₄, as well as the catalytic mechanism for glucose oxidation [57]. (b) (i) Illustration of vertically oriented CuO nanosheets over Cu foam. (ii) Interference analysis conducted on the CuO/Cu electrode by introducing acetaminophen, ascorbic acid (AA), dopamine (DA), uric acid (UA), sucrose, fructose, L-cysteine, and folic acid into 0.1 M NaOH at 0.54 V [106]. (c) (i) Diagram of the synthesis of rattle-type Au@NiCo LDH hollow core–shell nanostructures. (ii) Amperometric response curves of Au@NiCo LDH/GCE upon the incremental addition of glucose concentrations ranging from 0.005 to 12 mM in 1.0 M NaOH at a potential of 0.5 V [109].

Figure 10

Fabrication of Cu1Co2-MOF/NF and glucose detection on the electrode [111].

Figure 12

(a) Synthesis of La-BTC/CNT by the hydrothermal route; (b) the molecular structure of La-BTC; and (c) the schematic route of the La-BTC/CNT-modified electrode for sensing dopamine [132].

Figure 14

MOF-derived 3D porous octahedral structure of copper sulfide (CuS)/carbon composites (CuS@C-c) for electrochemical detection of ascorbic acid [162].

Figure 15

(a) Detection of uric acid (UA) using Cu₂O/Cu@C core–shell nanowires on GCE electrode. (b) Determination of selectivity of developed UA biosensors. (c) Assessment of stability of fabricated UA biosensors after one month of storage [167].