METAL-ORGANIC FRAMEWORK STRUCTURES IN MODERN RESEARCH: MEDICINE, DIAGNOSTICS, ECOLOGY

Biomedical Chemistry: Research and Methods 2025, 8(3), e00270

Yu.V. Tumanov¹, P.P. Gladyshev², A.A. Sergeev¹, A.V. Zaykovskaya¹

¹Federal budgetary institution of science “State Research Center for Virology and Biotechnology “Vector” of Rospotrebnadzor, Koltsovo, Novosibirsk Region, 630559, Russia, e-mail: tumanov@vector.nsc.ru
¹State University Dubna, University Str. 19, Dubna, Moscow region, 141980, Russia

Keywords:biosensors; MOC synthesis; MOC/COF hybrid structures; metal-organic frameworks; nucleic acids; bioimaging; fluorescence detection; fluorescence quencher

DOI:10.18097/BMCRM00270

The whole version of this paper is available in Russian.

The review describe modern technological developments of means of detection of viruses and toxins by using new nanomaterials based on frame structures. Synthesis and functionalization of metal-organic compounds of a frame structure (MOCs) and covalent organic frameworks (COF) are considered as well as the latest achievements in biomedical felds, including the delivery of drugs, nucleic acids, proteins and dyes for cancer therapy, bioimaging, antimicrobial drugs, biosensors and biocatalysis. Special attention is paid to new trends and promising areas in the development of biomedical materials based on MOC/COF. Data on the application of new biotechnological products based on simeconductor nanocrystals (quantum dots, QD) and their composites as part of MOCs in solving the problems of modern disease diagnostics that play a strategic role in the development of nanotechnology, biotechnology and nanomedicine are presented. Issues related to the recognition of biomolecules using hybrid MOC/COF structures are discussed. The use of QD nanocomposites with other carbon-based, grapheme-based or MOC-based nanomaterials resulted in the development of new systems for bioimaging, drug delivery, optogenetics and theranostics. Undoubtedly, the rapidly accumulating data on the behavior of QD/MOC in analytical systems in vitro will increase knowledge for the advancement of QD nanotechnology in research in vivo and clinical application.

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Figure 1. Representative MOF types (adapted from [20]). Schematic illustrations of metal centers (secondary building units), organic linkers, unit cells, and frameworks of IRMOF-1 (a), ZIF-8 (b), MIL-101(Cr) (c), PCN-222(Fe) (d), and UiO-66 (e).

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Figure 2. The anatomy of quantum dots (adapted from [82]). (A) QDs contain a semiconducting core-shell. The surface can be coated with hydrophilic, hydrophobic, and amphiphilic ligands (common coating molecules are shown) which can be further linked with proteins, drugs, antibodies, and other compounds. (B) The emission spectra of QDs can be tuned by adjusting the size. (C) Fluorescence lifetimes of QD in comparison with other flurophores.

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Figure 3. Structures of different 2D materials (adapted from [27, 91]).

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Figure 4. The general form of electrolyte and back gated structures of FETs, which have been used for the sensing elements in Chem/BioFET: This nanomaterial-based structure has been widely used for cell, DNA, enzymatic reaction and chemical sensing; A - sensor structure; B - the most frequent nanomaterials used as sensing element and main conductive channel [103] (CC BY-SA 4.0). C - Schematic of a biosensor based on MXene FETs (adapted from [104]).

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Figure 5. The topology and growth of the COFs (adapted from [137]).

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Figure 6. Timeline of various dynamic linkages for COF formation [134] (CC BY-SA 4.0).

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Figure 7. Crystal structure of PFC-1. A - View of the structure and the connection of adjacent building blocks. B - Hydrogen-bond length and angle. C - The stacking of 2D layers. D - Face-to-face π–π interactions. e) One-dimensional (1D) channels. f) Representation of the porous framework (adapted from [198]).

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Figure 8. Overview of functionalization pathways for RF-NPs. Internal and external surface modification as well as guest incorporation for various intrinsic and extrinsic properties enabling diverse applications [203] (CC BY-SA 4.0).

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Figure 9. MOF/COF Hybrid Materials with Multiple Components [203] (CC BY-SA 4.0).

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Figure 10. COF-on-MOF OPECT-based DNA sensors. a) Gate functionalization process where COF-on-MOF and target DNA trigger GWS growth. b) Schematic of the COF-on-MOF OPECT. c) IDS-step responses of the system to various concentrations of HTLV-II DNA, representing the disparity in values between the currents before and after illumination, and d) the corresponding calibration curve [212] (CC BY-SA 4.0).

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Figure 11. Formation of MOF-COF and COF–MOF core-shell composites [220] (CC BY-SA 4.0).

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Figure 12. Schematic representation of various approaches deployed for the preparation of QDs@MOF [229] (CC BY-SA 4.0).

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Figure 13. Four common strategies for loading drugs into nMOFs. A - noncovalent encapsulation, B - conjugation to the linkers, C - use of therapeutics as linkers, D - attachment to the SBUs (adapted from [288]).

Table 1. Transistors for DNA/RNA sensing [137] (CC BY-SA 4.0).

Analyte	Gate	Channel material	Electrolyte	Detection limit	Detection range	Ref.
DNA	AuNPs/CdS QDs	PEDOT:PSS	PBS	1 fM	1 fM–1 pM	134
DNA	AAO-Au	PEDOT:PBS	PBS	0.1 nM	0.5 nM–12.5 nM	11
DNA	Au	PEDOT:PSS	PBS	10 pM	-	140
DNA	Au/AuNPs	PEDOT:PSS	PBS	0.575 fM	0.1 pM–1 nM	12
RNA	6-mercapto-1-hexanol (MCH)/probe/AuNPs/Au	PEDOT:PSS	PBS	2 pM	5 pM–20 nM	125
DNA	Carbon/PDA/Probe	PEDOT:PSS	PBS	0.1 pM	1 pM–10 nM	141
DNA	Au/probe	Graphene	PBS	1 fM	1 fM–5 μM	136
RNA	CdS QDs/TiO₂ nanotubes	PEDOT:PSS	PBS	1 pM	1 pM–10 μM	142
DNA	ssDNA/CQDs/Au	Polymethyl methacrylate (PMMA)/graphene	PBS	1 aM	1 aM–0.1 nM	137
RNA	Au/DNA/miRNA	PEDOT:PSS	PBS	10 pM	10 pM–1 μM	13
RNA	Au/ssDNA	Graphene	PBS	10⁻²⁰ M	10⁻²⁰ M–10⁻¹² M	138
RNA	AuNPs/fluorine-doped tin oxide (FTO)/MCH	PEDOT:PSS	PBS	5.5 fM	-	143
DNA	COF-on-MOF	PEDOT:PSS	PBS	0.003 fM	0.01 fM–1 pM	146
Electrochemical sensors used to detect disease biomarkers
HIV-1 DNA	Cu−MOF@CuPc−TA−COF	DNA hybridization	Electrochemical signal	0,18 fM	1 fM–1 nM	[156]
Acute myocarditis	miR-721	MOF@Au@G-triplex/hemin nanozyme	CA	0.25 fM	0.5 фM–1 нM	[157]
Hepatitis C	HCV gene	S-BN QDs	ECL	0.17 pМ/L	5 pМ/L - 1 nМ/L	[158]
Rheumatoid arthritis	IL-6	AuNPs/graphene	CA	0.42 pg/ml	0.97–250 pg/ml	[159]
Hepatitis B	HBV-DNA	BN-CDs	ECL	18.08 aM	100 aM–1 pM	[160]
HIV	DNA	Ni-MOF/AuNPs/CNTs	DPV	0.13 nM	10 nM–1 μM	[161]
Sepsis	C-reactive protein (CRP)	AuNPs@C-ZIF₆₇	DPV	0.44 pg/ml	10 pg/ml–10 µg/ml	[162]
Neurodegenerative diseases	Dopamine	Ti₃C₂T_xMXene	ECL	100 nM	100 nM ~ 50 мM	[163]
Covid-2	SARS-CoV-2 antigen	MOF nanohybrids < 5 min	Electrochemi cal biosensor chip	6.68 fg/ml (in buffer), 6.20 fg/ml (in serum)	10–10⁷fg/ml	[164]
Breast cancer	CA15-3	GCE/MIL-156 MOF@COF@Au	DPV	2.6 nU/мл	30–100 nU/ml	[165]
Omicron	crRNA	AuE-MXene-AuNPs	SWV	1 fM	1 nM–10 fM	[166]
AIDS	HIV DNA	3D CdSe QDs-DNA/SnO₂ nanolowers	ECL/PEC	1.38 fM	0.5 μM–5 fM	[167]
Ovarian cancer	CA 125	MOF-808/CNTs	ЕС	0.5 pg/ml	0.001~0.1 and 0.1~30 ng/ml	[168]
Hepatitis B	HBV DNA	Al-MOF	–	62.1 aM	100 aM-10 pM	[169]
Ovarian cancer	CA125	Ce-MOF/TPN-COF/CNT, UiO66@MB	ЕС	0, 088 ng/ml	0,0001-100 U/ml−1	[170]
Ovarian cancer	CA125	MXene/MIL-101(Fe)-NH2	ЕС	6,0 ng/ml	0,2−1000 IU/ml−1	[113]

Table 2. Electrocatalytic performance of various functional molecules based electrochemical biosensors. Adapted from [15].

Electrode	Analyte	Technique	Linear Range	LOD	Sensitivity	Ref.
Mg-MOF/GNPs/Mb	TCA	CV	1–200 mM	0.33 mM	-	[123]
Mg-MOF/GNPs/Mb	Nitrite	CV	0.8–18 mM	0.26 mM	-	[123]
SPE/MoS₂-Cu-MOF/GNPs/Ab	CA125	DPV	0.5 mU/mL –500 U/mL	0.5 mU	-	[124]
Cu-MOF/GNPs/CHA-HCR	MiR-21	DPV	0.1 fM–100 pM	0.02 fM	-	[125]
GCE/MMOF/GNFs	H₂O₂	CA	5 µM–15 mM; 15–120 mM	0.9 µM	-	[126]
GCE/FA-Zr-MOF	HeLa cells	EIS	1 × 10²–1 ×10⁶ cells/mL	90 cells/mL	-	[127]
GCE/NA-Zr-MOF/dsDNA	MiR-21	DPV	0.02–10 pM	8.2 fM	-	[128]
GCE/NA-Zr-MOF/dsDNA	Let-7a	DPV	0.01–10 pM	3.6 fM	-	[128]
Cr-MOF/PdNPs/c-DNA	HeLa cells	DPV	5 × 10²–1.62 ×10⁷ cells/mL	11.25 cells/mL	-	[129]
Co-MOF/GNPs/MWCNT/Cyt-c	nitrite	DPV	5 nM–1 mM	4.4 nM	-	[131]
ITO/PANI/Cu-MOF/Ab	E. coli	EIS	2–2 × 10⁸ cfu/mL	2 cfu/mL	-	[132]
SPE/TCOF/SOD	Superoxide	CA	10 nM–100 µM	0.5 nM	-	[138]
GCE/COF/ACLE	Carbaryl	EIS	0.48–35 µM	0.16 µM	-	[139]
GCE/Fe₃O₄COF/HRP	HQ	DPV	0.5–300 µM	120 nM	-	[140]
GCE/Fe₃O₄COF/GNPs/DNA	ATP	CV	5 pM–50 µM	1.6 pM	-	[141]
COF/DNA/HRP	exosomes	CA	10⁴– 10⁷ particles/µL	7668 particles/µL	-	[142]

Table 3. The detection performances of carbon nanomaterials-decorated MOF−based electrochemical sensors [251] (CC BY-SA 4.0).

Electrode Material	Analyte	Linear Range	LOD
MIL-101(Cr)@rGO	4-nonylphenol	100 nM~12.5 μM	33 nM
Cu−hemin MOF/CS−rGO	H₂O₂	65 nM~0.41 mM	19 nM
Cu(tpa)−EGR	ACOP and DA	1.0 μM~100 μM and 1.0 μM~50 μM	0.36 and 0.21 μM
Co−MOF/BP−RGO	chlorogenic acid	1.0 nM~391 μM	14 nM
PPy@ZIF-8/GAs	dichlorophenol	10 nM~10 μM	0.1 nM
GA-UiO-66-NH₂	Cd²⁺, Pb²⁺, Cu²⁺, and Hg²⁺	10 nM~1.5 μM, 1.0 nM~2.0 μM, 10 nM~1.6 μM and 1.0 nM~22 μM	9.0, 1.0, 8.0 and 0.9 nM
Ni−MOFs/CNTs	H₂O₂	10 μM~51.6 mM	2.1 μM
UiO-66-NH₂/CNTs	DA and AC	30 nM~2.0 μM	15 and 9.0 nM
Mn−BDC@MWCNT	AA, DA and UA	0.1 μM~1.15 mM, 10 nM~0.5 mM, and 20 nM~1.1 mM	10, 2.0 and 5.0 nM
3D Ni−MOF@CNTs	BPA	1.0 nM~1.0 μM	0.35 nM
MB@MWCNTs/UiO-66-NH₂	doxorubicin	0.1 μM~75 μM	51 nM
Co−MOF@MPC	hydrazine and nitrobenzene	5.0 μM~0.63 mM and 0.5 μM~15 μM	1.75 and 0.21 μM
ZIF67−OMC	HQ and catechol	0.1 μM~100 μM	52 and 36 nM
DUT-9/MC	Baicalein	50 nM~20 μM	15 nM
pFeMOF/OMC	H₂O₂	0.5~70.5 μM	0.45 μM
Cu−MOFs/OMC	hydrazine	0.5 μM~0.711 mM	0.35 μM
Ag−ZIF-8/OMC	xanthine	1.0 μM~0.28 mM	0.167 μM
MOF-808/CNTs	CA 125	0.001~0.1 and 0.1~30 ng/mL	0.5 pg/mL
PDA/ZIF-8@rGO	Glucose	1.2 μM~1.2 mM	0.333 μM
GDH/MG−Tb@MOF−CNTs	Glucose	25 μM~17 mM	8 μM
HRP/ZIF-67(Co)/MWCNT	H2O2	1.86~1050 μM	0.11 μM

Abbreviation: rGO, reduced graphene oxide; MOFs, metal–organic framework; CS, chitosan; tpa, terephthalate; EGR, electrochemically reduced graphene; ACOP, acetaminophen; PPy, polypyrrole; GA, graphene aerogel; CNTs, carbon nanotubes; MWCNT, multiwall carbon nanotubes; MB, methylene blue; MPC, mesoporous carbon; OMC, ordered mesoporous carbon; HQ, hydroquinone.

Table 4. COF–MOF hybrids for extraction and determination of water contaminants (adapted from [335]).

Hybrid materials	Contaminants	Determination methods	Detection limits	Linear ranges
NH₂-MIL-68(In)@COF	SAs	HPLC-VWD	1 ng mL⁻¹	10–2000 ng mL⁻¹
m-NH₂-MIL-68(In)@COF	SAs	MSPE-HPLC	0.1–0.5 ng mL⁻¹	10–2000 ng mL⁻¹
Fe₃O₄@TbBD@ZIF-8	Sedatives	MSPE-HPLC/MS/MS	0.04-0.2 µg k⁻¹ g	0.03-70 µg k⁻¹ g
MOF_L-TpBD	TNP	Fluorescence	3.52 × 10⁻⁶ m	0.01–1 × 10⁻³ m
MOF_L-TpBD	Pb²⁺	SPE	0.32 µg L⁻¹	0.7–12 µg L⁻¹
UiO-66@COF-V	PCAs	d-SPE-LC-MS/MS	0.69-1.79 ng L⁻¹	10–1000 ng L⁻¹
CCF@NH₂-UiO-66@TpBD	BPs	PT-SPE-UPLC	0.16-0.75 ng mL⁻¹	–
Fe₃O₄@NH₂-UiO-66@TbBD-COF	Cu²⁺	MSPE-UV–vis	0.0376 × 10⁻⁶ m	0.05–1.2 × 10⁻⁶ m
UiO@TapbTp	Aspirin	MALDI-TOF MS	0.001 mg L⁻¹	0.05–5 mg L⁻¹
UiO@TapbTp	Ketoprofen	MALDI-TOF MS	0.001 mg L⁻¹	0.01–5 mg L⁻¹
UiO@TapbTp	Naproxen	MALDI-TOF MS	0.010 mg L⁻¹	0.10–5 mg ⁻¹L
Ce-MOF@COF	OTC	Electrochemical sensing	17.4 fg mL⁻¹	0.1–0.5 ng mL⁻¹
Co-MOF@TPN-COF	AMP	Electrochemical sensing	0.217 fg mL⁻¹	1.0 fg mL⁻¹–2.0 ng mL⁻¹
UC-1	F⁻	Fluorescence sensing	–	0-500 × 10⁻⁶ m

FUNDING

The work was carried out within the framework of the state assignment of the Ministry of Science and Higher Education of the Russian Federation “Medical and biological study of boron-containing nanoparticles and bionanoconstructions for diagnostics and boron-neutron capture therapy of superficial malignant tumors” project (No, 1024011000011-7-1.4.2;3.5.2.)

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