Single-Atom Co─O4 Sites Embedded in a Defective-Rich Porous Carbon Layer for Efficient H2O2 Electrosynthesis.

The production of hydrogen peroxide (H2O2) via the two-electron electrochemical oxygen reduction reaction (2e- ORR) is an essential alteration in the current anthraquinone-based method. Herein, a single-atom Co─O4 electrocatalyst is embedded in a defective and porous graphene-like carbon layer (Co─O4@PC). The Co─O4@PC electrocatalyst shows promising potential in H2O2 electrosynthesis via 2e- ORR, providing a high H2O2 selectivity of 98.8% at 0.6 V and a low onset potential of 0.73 V for generating H2O2. In situ surface-sensitive attenuated total reflection Fourier transform infrared spectra and density functional theory calculations reveal that the electronic and geometric modification of Co─O4 induced by defective carbon sites result in decreased d-band center of Co atoms, providing the optimum adsorption energies of OOH* intermediate. The H-cell and flow cell assembled using Co─O4@PC as the cathode present long-term stability and high efficiency for H2O2 production. Particularly, a high H2O2 production rate of 0.25 mol g-1 cat h-1 at 0.6 V can be obtained by the flow cell. The in situ-generated H2O2 can promote the degradation of rhodamine B and sterilize Staphylococcus aureus via the Fenton process. This work can pave the way for the efficient production of H2O2 by using Co─O4 single atom electrocatalyst and unveil the electrocatalytic mechanism.

Cu x O@DNA sphere-based electrochemical bioassay for sensitive detection of Pb2.

The paper describes a one-step synthetic method to chemically reduce cupric sulfate by ascorbic acid in the presence of DNA strands to directly produce Cu x O@DNA spheres. The DNA strands act as template to assist the preparation of Cu x O, and also are capable of specifically binding  Pb(II) ions. The Cu x O@DNA spheres possess high specific surface area and strong bioaffinity. They can be directly employed as platform for detecting Pb2+ sensitively. Electrochemical impedance spectroscopy data showed that the assay exhibits high sensitivity and a wide linear analytical range that extends from 0.1 to 100 nM, and the detection limit is 6.8 pM at a signal-to-noise ratio of 3. The assay is selective, acceptably reproducible, stable, and well feasible for the detection of Pb2+ in blood serum. Graphical abstract Schematic presentation of the preparation of DNA-templated Cu x O spheres (Cu x O@DNA) for use in electrochemical detection of Pb2+. The assay exhibits detection limit of 6.8 pM, high selectivity, acceptable reproducibility, stability, and good applicability for Pb2+ detection.

Understanding electron structure of covalent triazine framework embraced with gold nanoparticles for nitrogen reduction to ammonia.

Regulating the electron structure and precise loading sites of metal-active sites within the highly conjugated and porous covalent-triazine frameworks (CTFs) is essential to promoting the nitrogen reduction reaction (NRR) performance for electrocatalytic ammonia (NH3) synthesis under ambient conditions. Herein, experimental method and density functional theory (DFT) calculations were conducted to deeply probe the effect on NRR of the modulation of modulating the electron structure and the loading site of gold nanoparticles (Au NPs) in a two-dimensional (2D) CTF. 2D CTF synthesized using melem and hexaketocyclohexane octahydrate as building blocks (denoted as M-HCO-CTF) served as a robust scaffold for loading Au NPs to form an M-HCO-CTF@AuNP hybrid. DFT results uncovered that well-defined Au sites with tunable local structure were the active site for driving the NRR, which can significantly suppress the conversion of H+ into *H adsorption and enhance the nitrogen (N2) adsorption/activation. The overlapped Au (3d) and *N2 (2p) orbitals lowered the free energy of the rate-determining step to form *NNH, thereby accelerating the NRR. The M-HCO-CTF@AuNPs electrocatalyst exhibited a large NH3 yield rate of 66.3 µg h-1 mg-1cat. and a high Faraday efficiency of 31.4 % at - 0.2 V versus reversible hydrogen electrode in 0.1 M HCl, superior to most reported CTF-based ones. This work can provide deep insights into the modulation of the electron structure of metal atoms within a porous organic framework for artificial NH3 synthesis through NRR.

A novel PEC and ECL bifunctional aptasensor based on V2CTx MXene-derived MOF embedded with silver nanoparticles for selectively aptasensing miRNA-126.

A novel photoelectrochemical (PEC) and electrochemiluminescence (ECL) bifunctional aptasensor has been established for the detection of miRNA-126 using V2CTx MXene-derived porphyrin-based metal-organic framework embedded with Ag nanoparticles (Ag NPs) (denoted as AgNPs@V-PMOF) as a robust bioplatform. Due to the presence of V nodes in V2CTx MXene nanosheets, V-based MOF was prepared using tetrakis(4-carboxyphenyl)porphyrin as ligand, followed by the incorporation of Ag+ ions to form the AgNPs@V-PMOF Schottky heterojunction. Benefiting from the fast electron transfer of the V2CTx substrate and well-matched band-edge energy level of the photosensitive Ag NPs and V-PMOF, the constructed AgNPs@V-PMOF Schottky heterojunction exhibited the promoted transfer of the photogenerated carriers, showing superior PEC and ECL performances. Moreover, a large number of the complementary DNA strand of miRNA-126 can be immobilized over AgNPs@V-PMOF in view of the combined interaction of π-π stacking, van der Waals force, and Ag-N coordination between AgNPs@V-PMOF. Consequently, the developed AgNPs@V-PMOF-based aptasensor illustrated extremely low detection limits of 0.78 and 0.53 fM within a wide range from 1.0 fM to 1.0 nM of miRNA-126 detected by PEC and ECL techniques, respectively, superior to most reported miRNA aptasensors. Also, the provided bifunctional aptasensor demonstrated high selectivity, good stability, fine reproducibility, and acceptable regenerability, as well as promising potential for the analysis of miRNA-126 from living cancer cells. This work puts forward the development of aptasensors for the early and accurate diagnosis of cancer markers and extends the application of MOF in the biosensing field.

Correction: A novel PEC and ECL bifunctional aptasensor based on V2CTx MXene-derived MOF embedded with silver nanoparticles for selectively aptasensing miRNA-126.

Correction for 'A novel PEC and ECL bifunctional aptasensor based on V2CTx MXene-derived MOF embedded with silver nanoparticles for selectively aptasensing miRNA-126' by Yu Li et al., J. Mater. Chem. B, 2023, https://doi.org/10.1039/d3tb01380d.

Photo-assisted Zn-air battery-driven self-powered aptasensor based on the 2D/2D Schottky heterojunction of cadmium-doped molybdenum disulfide and Ti3C2Tx nanosheets for the sensitive detection of penicillin G.

A novel photocatalyzed Zn-air battery-driven (ZAB)-based aptasensor has been manufactured using the two dimensional (2D)/2D Schottky heterojunction as photocathode and Zn plate as photoanode. It was then employed to sensitively and selectively detect penicillin G (PG) in the complex environment. The 2D/2D Schottky heterojunction was established by the in situ growth of cadmium-doped molybdenum disulfide nanosheets (Cd-MoS2 NSs) around Ti3C2Tx NSs (denoted as Cd-MoS2@Ti3C2Tx) by using phosphomolybdic acid (PMo12) as precursor, thioacetamide as sulfur source, and Cd(NO3)2 as a doping agent through the hydrothermal method. The gained Cd-MoS2@Ti3C2Tx heterojunction possessed contact interface, hierarchical structure, and plenty of sulfur and oxygen vacancies, thus showing the enhanced separation ability of photocarriers and electron transfer. Due to the enhanced UV-vis light adsorption ability, high photoelectric conversion efficiency, and exposed catalytic active sites, the constructed photocatalyzed ZAB displayed a boosted output voltage of 1.43 V under UV-vis light irradiation. The developed ZAB-driven self-powered aptasensor demonstrated an ultralow detection limit of 0.06 fg mL-1 within a PG concentration ranged from 1.0 fg mL-1 to 0.1 ng mL-1, as deduced from the power density-current curves, along with high specificity, good stability and promising reproducibility, as well as excellent regeneration ability and wide applicability. The present work provided an alternative analysis method for the sensitive analysis of antibiotics based on the portable photocatalyzed ZAB-driven self-powered aptasensor.

Defective porphyrin-based metal-organic framework nanosheets derived from V2CTx MXene as a robust bioplatform for impedimetric aptasensing 17ß-estradiol.

An electrochemical aptasensor was prepared for the efficient, sensitive, and selective detection of 17ß-estradiol. The sensor was based on a defective two-dimensional porphyrin-based metal-organic framework derived from V2CTx MXene. The resulting metal-organic framework nanosheets benefited from the advantages of V2CTx MXene nanosheets and porphyrin-based metal-organic framework, two-dimensional porphyrin-based metal-organic framework nanosheets demonstrated amplified electrochemical response and enhanced aptamer-immobilization ability compared with V2CTx MXene nanosheets. The sensor's detection limit was ultralow at 0.81 fg mL-1 (2.97 fM), and the 17ß-estradiol concentration range was wide, thereby outperforming most reported aptasensors. The high selectivity, superior stability and reproducibility, and excellent regeneration performance of the constructed aptasensor indicated its remarkable potential application for 17ß-estradiol determination in diverse real samples. This aptasensing strategy can be used to analyze other targets by replacing the corresponding aptamer.

Curcumin-regulated constructing of defective zinc-based polymer-metal-organic framework as long-acting antibacterial platform for efficient wound healing.

A dual-modal antibacterial platform has been established for highly efficient wound healing infected by bacteria based on a defective zinc-based metal-organic framework composite, which was synthesized using 1,4-phthalic acid-based polyether polymer (L8) as ligand, curcumin as regulator, and Zn2+ as metal coordinated center (Cur@Zn-MOF). In addition to the integration of the features of polymer-MOF synthesized using L8 (such as high water stability and controllable and long-term release of Zn2+) and Zn-bioMOF prepared using curcumin as ligand (such as feasible release of curcumin and Zn2+ and good biocompatibility), the Cur@Zn-MOF bioplatform also possessed plenty of structure defects. Comparing with Zn-bioMOF and polyZn-MOF synthesized using the sole ligand, the smaller released amount of curcumin (6.08 µg mL-1) and higher release level of Zn2+ ions (5.68 µg mL-1) were simultaneously achieved for the defective Cur@Zn-MOF within a long-term duration (48 h). The synergistic effect afforded Cur@Zn-MOF the high sterilization performance toward Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) even at the low usage of 125 µg mL-1. The in vivo wound healing effect further confirmed the superior treatment ability of Cur@Zn-MOF toward the bacterium-infected wound. Also, the negligible cytotoxicity and low hemolysis of Cur@Zn-MOF greatly promoted the viability of human skin fibroblasts. Accordingly, this work can provide a new dual-modal bioplatform based on the functional MOF via the controllable release of antibacterial drug and metal ions for the efficient wound healing.

A new strategy for the development of efficient impedimetric tobramycin aptasensors with metallo-covalent organic frameworks (MCOFs).

Two bimetallic CoNi-based metallo-covalent organic frameworks (MCOFs) were prepared and explored as the sensitive platforms of impedimetric aptasensors for efficient detection of tobramycin (TOB). The two CoNi-MCOFs were constructed using metallophthalocyanine tetra-amine (MPc-TA, M = Co2+ or Ni2+) and 4,4'-(1,10-phen-anthroline-2,9-diyl) dibenzaldehyde (PTD) as building units and further coordinating to the secondary metal ions (Ni2+ or Co2+) by phenanthroline. Interestingly, the immobilization ability of CoPc-TA-PTD(Ni) to TOB-targeted aptamer is higher than that of NiPc-TA-PTD(Co) due to its stronger binding interactions to aptamer. As a result, the CoPc-TA-PTD(Ni)-based aptasensor shows the superior TOB detection ability, giving a low detection limit of 0.07 fg mL-1 and satisfied sensing performances, such as high selectivity, good reproducibility, and excellent stability. Also, the aptasensor shows the acceptable applicability for detecting TOB in milk or chicken egg. This MCOFs-based sensing strategy could be extensively applied to detect other analytes by anchoring the corresponding probes.

Electrochemical aptasensing strategy based on a multivariate polymertitanium-metal-organic framework for zearalenone analysis.

An electrochemical aptasensing strategy was developed with a novel bioplatform based on a multivariate titanium metal-organic framework, i.e. MTV polyMOF(Ti), to detect zearalenone (ZEN). MTV polyMOF(Ti) was prepared by using mixed linkers of polyether polymer (pbdc-xa or L8, pbdc = poly(1,4-benzenedicarboxylate) and 1,4-benzenedicarboxylic acid (H2bdc or L0) as well as tetrabutyl titanate as nodes (MTV polyMOF(Ti)-L8,0). Compared with Ti-MOFs synthesized by using the single ligand of L8 or L0, MTV polyMOF(Ti)-L8,0 shows more porous structure assembled with multilayered nanosheets. In light of the improved electrochemical activity and strong bioaffinity to the aptamer, the aptasensor based on MTV polyMOF(Ti)-L8,0 shows excellent performance for detecting ZEN with the ultralow detection limit at fg mL-1 level in the linear range of 10 fg mL-1 to 10 ng mL-1, along with good selectivity, reproducibility, stability, regenerability, and applicability.

Semiconducting CuxNi3-x(hexahydroxytriphenylene)2 framework for electrochemical aptasensing of C6 glioma cells and epidermal growth factor receptor.

A 2D CuNi metal-organic framework (MOF) named CuxNi3-x(HHTP)2 was synthesized with 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) as the linker and was used as a sensitive scaffold to adsorb aptamer strands for the electrochemical detection of living C6 glioma cells and one of their biomarkers, epidermal growth factor receptor (EGFR). Different from conventional MOFs, the CuxNi3-x(HHTP)2 MOF comprises long-range delocalized electrons, a graphene-analog nanostructure, multiple metal states (Cu0/Cu+/Cu2+ and Ni2+/Ni3+), and abundant oxygen vacancies. With these features, the CuxNi3-x(HHTP)2 MOF anchored a large amount of C6 cell-targeted aptamer strands via coordination among metal centers, oligonucleotides, π-π stacking, and van der Waals force. The CuxNi3-x(HHTP)2-based cytosensor showed a low limit of detection (LOD) of 21 cells mL-1 toward C6 glioma cells within a wide range from 50 cells mL-1 to 1 × 105 cells mL-1. Moreover, the proposed aptasensor displayed high selectivity, good stability, acceptable reproducibility, and a low LOD of 0.72 fg mL-1 for detecting EGFR with the concentration ranging from 1 fg mL-1 to 1 ng mL-1. The aptasensor based on the CuxNi3-x(HHTP)2 MOF exhibited superior sensing performance over those based on its monometallic analogues such as Cu3(HHTP)2 MOF and Ni3(HHTP)2 MOF. Hence, this sensing strategy based on a bimetallic semiconducting MOF shows great potential for cancer diagnosis.

Quantification of EGFR and EGFR-overexpressed cancer cells based on carbon dots@bimetallic CuCo Prussian blue analogue.

A new bimetallic CuCo Prussian blue analogue (CuCo PBA) loaded with carbon dots (CDs) was prepared (represented by CD@CuCoPBA) and developed as a scaffold for anchoring the epidermal growth factor receptor (EGFR) aptamer to detect EGFR and living EGFR-overexpressed cancer cells. The basic characterizations revealed CuCo PBA exhibited nanocube shape and still remained its nanostructure and physical/chemical properties after coupling with large amounts of CDs. As compared with the pristine CuCo PBA, the CD@CuCoPBA displayed good electrochemical activity, strong binding interaction toward aptamer, and high stability of aptamer-EGFR G-quadruplex in aqueous solution. As such, the results of electrochemical impedance spectroscopy measurements indicated that the CD@CuCoPBA-based aptasensor displayed an ultra-low detection limit toward EGFR (0.42 fg mL-1) and living EGFR-overexpressed MCF-7 cancer cells (80 cell per mL), as well as high selectivity, good reproducibility, high stability, repeatability, and acceptable applicability. Consequently, the constructed CD@CuCoPBA-based aptasensor can be extended to be a promising universal method for early diagnosis of cancers.

Tailoring the dimensionality of carbon nanostructures as highly electrochemical supports for detection of carcinoembryonic antigens.

Partially- and fully-unzipped nitrogen-doped carbon nanotubes (NCNTs) were prepared by unzipping pristine NCNTs and three carbon nanostructures were applied to support Au nanoparticles (AuNPs) to form nanocomposites (Au/NCNTs, Au/PU-NCNTs, and Au/FU-NCNTs). The electrochemical behavior and the electrocatalytic activities of the nanocomposite-modified electrodes were examined. The oxygen functional groups, doped N content, and AuNP loaded concentrations are dependent on the unzipping-degree and then affect the electrochemical response and electrocatalytic performance of the electrodes. Besides, the three nanocomposites were also used for the immobilization of carcinoembryonic antigen (CEA) aptamer strands and applied for the detection of CEA. The Au/FU-NCNTs possess the optimal electrocatalytic activity and biosensing performance for the biomolecules and CEA, which is attributed to the maximum loaded AuNPs, the largest specific surface areas and the most active sites. The Au/FU-NCNT-based electrochemical aptasensor exhibits high sensitivity with a low detection limit of 6.84 pg mL-1 within a broad linear range of CEA concentration from 0.01 to 10 ng mL-1. All of these results indicate that the Au/FU-NCNTs may be a potential support for construction of aptasensors with high electrochemical effect and can be employed in the fields of biosensing or biomedical diagnosis.

A γ-cyclodextrin-based metal-organic framework embedded with graphene quantum dots and modified with PEGMA via SI-ATRP for anticancer drug delivery and therapy.

The γ-cyclodextrin-based metal-organic framework (γ-CD-MOF) composite was designed and prepared toward targeted anticancer drug delivery and cancer therapy. Large amounts of graphene quantum dots (GQDs) were embedded in the γ-CD-MOF matrix (denoted as GQDs@γ-CD-MOF) to endow the γ-CD-MOF with strong fluorescence, which was then modified by pH responsive poly(ethyleneglycol)dimethacrylate (PEGMA) through surface initiated atom transfer radical polymerization (SI-ATRP) to fabricate the PEGMA@GQDs@γ-CD-MOF composite. Then, the cancer cell-targeted probe was obtained by immobilizing the AS1411 aptamer over it (denoted as AS1411@PEGMA@GQDs@γ-CD-MOF) and it exhibits pH-responsive release function and excellent targeting ability. Large amounts of antitumour drug, doxorubicin hydrochloride (DOX), could be encapsulated within this composite due to the chemical-rich functionality, and the resultant pH-responsive DOX delivery system (denoted as DOX/AS1411@PEGMA@GQDs@γ-CD-MOF) displayed a higher DOX loading of 89.1% with sustained release than the pristine γ-CD-MOF and GQDs@γ-CD-MOF. The targeting specificity investigation revealed that this DOX delivery system was effectively internalized via receptor mediated endocytosis with high selectivity. The in vivo antitumour study with tumour-bearing mice illustrated that the tumour growth can be effectively suppressed and partially ablated with negligible side effects after treatments. Therefore, the proposed AS1411@PEGMA@GQD@γ-CD-MOF composite is promising for effective DOX delivery and tumour growth inhibition both in vitro and in vivo, showing great potential for anticancer therapy.

Bimetallic ZrHf-based metal-organic framework embedded with carbon dots: Ultra-sensitive platform for early diagnosis of HER2 and HER2-overexpressed living cancer cells.

We report here a new bimetallic ZrHf metal-organic framework (ZrHf-MOF) embedded with abundant carbon dots (CDs) (denoted as CDs@ZrHf-MOF), which exhibits strong fluorescence and rich-amino-functionalization. The CDs@ZrHf-MOF can be applied as the scaffold for anchoring aptamer strands to determine human epidermal growth factor receptor-2 (HER2) and living HER2-overexpressed MCF-7 cells. The basic characterizations reveal that the CDs are embedded within the interior cavities of ZrHf-MOF without varying the nanostructure, leading to good biocompatibility, strong fluorescence, and high electrochemical activity of CDs@ZrHf-MOF. As compared with the pristine ZrHf-MOF, the CDs@ZrHf-MOF-based electrochemical aptasensor displays better sensing performances toward both HER-2 and MCF-7 cells, giving an extremely low detection limit of 19 fg mL-1 (HER2 concentration range: 0.001-10 ng mL-1) and 23 cell mL-1 (cell concentration range: 1 × 102~1 × 105 cell mL-1), with good selectivity, stability, reproducibility, and acceptable applicability. The proposed strategy for developing CDs@ZrHf-MOF-based aptasensor is promising for the early and sensitive detection of cancer markers and living cancer cells.

NiCo2O4 spinel embedded with carbon nanotubes derived from bimetallic NiCo metal-organic framework for the ultrasensitive detection of human immune deficiency virus-1 gene.

A bimetallic NiCo-based metal-organic framework (NiCo-MOF) was pyrolyzed into a novel composite comprising NiCo2O4 spinel, CoO, and metallic Co/Ni nanoparticles embedded with carbon nanotubes at high temperature 700 °C under N2 atmosphere (represented by NiCo2O4/CoO@CNTs), whereas organic ligands were almost decomposed in H2 atmosphere, leading to absence of carbon nanotubes (denoted by NiCo2O4/CoO). The feasibility of using the composite as efficient bioplatform for immobilizing the probe DNA of human immune deficiency virus-1 (HIV-1) in the electrochemical detection of the HIV-1 DNA was explored. Compared with the pristine NiCo-MOF and NiCo2O4/CoO, the NiCo2O4/CoO@CNTs composite exhibited high electrochemical activity, good biocompatibility, and strong bioaffinity toward the probe DNA. Electrochemical measurements demonstrated that the NiCo2O4/CoO@CNTs-based bioassay displayed superior sensing performances, giving an ultralow detection limit of 16.7 fM toward HIV-1 DNA over the linear range of 0.1 pM to 20 nM; possessing high selectivity even against noncomplementary and two-base mismatch sequences; exhibiting good stability, reproducibility, repeatability and applicability in the application of detecting human serum samples. Thus, the present strategy can broaden the application of MOFs and their derivatives in various fields of biosensing.

Bimetallic cerium and ferric oxides nanoparticles embedded within mesoporous carbon matrix: Electrochemical immunosensor for sensitive detection of carbohydrate antigen 19-9.

A label-free electrochemical immunosensor was successfully developed for sensitively detecting carbohydrate antigen 19-9 (CA19-9) as a cancer marker. To achieve this, a series of bimetallic cerium and ferric oxide nanoparticles embedded within the mesoporous carbon matrix (represented by CeO2/FeOx@mC) was obtained from the bimetallic CeFe-based metal organic framework (CeFe-MOF) by calcination at different high temperatures. The formed CeO2 or FeOx nanoparticles were uniformly distributed within the highly graphitized mesoporous carbon matrix at the calcination temperature of 500 °C (represented by CeO2/FeOx@mC500). However, the obtained nanoparticles were aggregated into large size when calcined at the temperatures of 700 and 900 °C. The CA 19-9 antibody can be anchored to the CeO2/FeOx@mC network through chemical absorption between carboxylic groups of antibody and CeO2 or FeOx by ester-like bridging. The CeO2/FeOx@mC500-based immunosensor displayed superior sensing performance to the pristine CeFe-MOF, CeO2/FeOx@mC700- and CeO2/FeOx@mC900-based ones. Electrochemical impedance spectroscopy results showed that the developed immunosensor exhibited an extremely low detection limit of 10 µU·mL-1 (S/N = 3) within a wide range from 0.1 mU·mL-1 to 10 U·mL-1 toward CA 19-9. It also illustrated excellent specificity, good reproducibility and stability, and acceptable application analysis in the human serum solution which was diluted 100-fold with 0.01 M PBS solution (pH 7.4) and spiked with different amounts of CA19-9. Consequently, the proposed electrochemical immunosensor is capable enough of determining CA 19-9 in clinical diagnostics.

Two-dimensional oriented growth of Zn-MOF-on-Zr-MOF architecture: A highly sensitive and selective platform for detecting cancer markers.

Fabricating novel bimetallic metal organic framework (MOF) architectures and exploiting them as aptasensor scaffolds for detecting diverse analytes, especially cancer markers, have aroused widespread research attention. Herein, we report a novel strategy for obtaining ZnZr bimetallic MOFs via the MOF-on-MOF method and exploit them as an aptasensor platform for detecting the cancer marker protein tyrosine kinase-7 (PTK7). Basic characterizations reveal that the chemical structure, crystalline properties, and surface functionality of bimetallic ZnZr-MOFs can be modulated by changing the order of addition of metal precursors and organic ligands. The Zn-MOF-on-Zr-MOF hybrid exhibits a hierarchically decussated foliace, whereas Zr-MOF-on-Zn-MOF demonstrates a multilayered nanosheet structure. The electrochemical results reveal that Zr-MOF facilitates aptamer strand immobilization, whereas the Zn-MOF stabilizes the G-quadruplex formed by aptamer strands and PTK7. The Zn-MOF-on-Zr-MOF-based aptasensor outperforms the Zr-MOF-on-Zn-MOF-based one, providing ultralow detection limits of 0.84 and 0.66 pg mL-1, as obtained by electrochemical impedance spectroscopy and differential pulse voltammetry, respectively, within the PTK7 concentration range of 1.0 pg mL-1 to 1.0 ng mL-1. The proposed Zn-MOF-on-Zr-MOF-based aptasensor exhibits high selectivity in the presence of various interferences, good stability, reproducibility, and acceptability in human serum. The proposed strategy provides a new approach for fabricating ultrasensitive and selective bimetallic MOFs-based aptasensors and contributes to efforts to broaden their applications in early cancer diagnosis.

Covalent organic framework-based electrochemical aptasensors for the ultrasensitive detection of antibiotics.

We designed and synthesized a novel covalent organic framework (COF) by condensation polymerization of 1,3,6,8-tetrakis(4-formylphenyl)pyrene and melamine through imine bonds (represented by Py-M-COF). The basic characterizations revealed that the Py-M-COF not only exhibited an extended π-conjugation framework, a large specific surface area (495.5 m2 g-1), big pore cavities, and nanosheet-like structure but also possessed rich functional groups, such as CË­C, CË­N, CË­O, and NH2. These features endowed the Py-M-COF with high charge carrier mobility, further improving the strong immobilization of DNA aptamer strands via π-π stacking interaction and electrostatic interaction. As such, the Py-M-COF-based electrochemical aptasensors are ultrasensitive in detecting different antibiotics, including enrofloxacin (ENR) and ampicillin (AMP), yielding extremely low detection limits of 6.07 and 0.04 fg mL-1 (S/N = 3) toward ENR and AMP, respectively, along with other excellent sensing performances. This biosensing platform based on Py-M-COF has potential applications for the sensitive detection of antibiotics or other analytes by replacing the corresponding aptamers.

Aptamer-Templated Silver Nanoclusters Embedded in Zirconium Metal-Organic Framework for Bifunctional Electrochemical and SPR Aptasensors toward Carcinoembryonic Antigen.

This study reported a novel biosensor based on the nanocomposite of zirconium metal-organic framework (Zr-MOF, UiO-66) embedded with silver nanoclusters (Ag NCs) using the carcinoembryonic antigen (CEA)-targeted aptamer as template (AgNCs@Apt@UiO-66). The synthesized AgNCs@Apt@UiO-66 nanocomposite not only possesses good biocompatibility, active electrochemical performance, and strong bioaffinity, but also can be dispersed to form two-dimensional nanocomposite with nanoscale thickness. As such, the use of the AgNCs@CEA-aptamer enables AgNC@Apt@UiO-66 with sensitive and selective detection capacity of trace CEA, further concurrently being exploited as scaffold for surface plasmon resonance spectroscopy (SPR) and electrochemical biosensors. The results showed that the proposed electrochemical AgNC@Apt@UiO-66-based aptasensor exhibits high sensitivity with a low detection limit (LOD) of 8.88 and 4.93 pg·mL-1 deduced from electrochemical impedance spectroscopy and differential pulse voltammetry, respectively, within a broad linear range of the CEA concentration (0.01-10 ng·mL-1). Meanwhile, the developed SPR biosensor exhibited a slightly high LOD of 0.3 ng·mL-1 within the CEA concentration of 1.0-250 ng·mL-1. Both the electrochemical and SPR aptasensors displayed high selectivity, good reproducibility, stability, acceptable regenerability, and applicability in real human serum samples. These results proved that the proposed aptamer-targeted Zr-MOF nanocomposite can be utilized in multiple-functionally biosensing, further promoting the potential application of Zr-MOF-related nanomaterials in clinical diagnosis.