In this work, a Pt nanoparticles-functionalized Co-based metal organic frameworks (PtNPs@Co(II)MOFs@PtNPs) was synthesized and applied in electrochemical aptasensor for thrombin (TB) detection. ...First, the Co(II)MOFs@PtNPs were prepared via the mixed solvothermal method, which consists of inner Pt nanoparticles (PtNPs) encapsulated by aminofunctionalized Co(II)MOFs materials. Following that, additional PtNPs were adsorbed on the surface of Co(II)MOFs@PtNPs, resulting in the formation of PtNPs@Co(II)MOFs@PtNPs nanocomposite. The PtNPs@Co(II)MOFs@PtNPs nanocomposites with a large surface area were implimented as nanocarriers to immobilize a mass of TBA II for the formation of the TBA II bioconjugates that could be captured onto the electrode surface by sandwich-type format. Moreover, the PtNPs@Co(II)MOFs@PtNPs nanocomposites could directly use as redox tags for charge-generating and electron-transporting with the electron transfer from Co(II) to Co(III). Furthermore, in the presence of H2O2, the PtNPs@Co(II)MOF@PtNPs could effectively catalyze H2O2 oxidation with improvement electron transfer of redox probe, resulting in electrochemical signal amplification. Based on the above superior advantages, TB was determined in the concentration range from 0.1pM to 50nM with a detection limit of 0.33fM. Furthermore, the excellent sensitivity and selectivity can be easily established for quantitative analysis of other analytes.
A novel electrochemical aptasensor has been developed using Pt nanoparticles-functionalized Co-based metal organic frameworks (PtNPs@Co-MOFs@PtNPs) as redox probe and signal enhancer for sensitive thrombin (TB) detection. Display omitted
•PtNPs@Co(II)MOFs@PtNPs could act as electroactive materials, redox probe and signal enhancer.•PtNPs modified on the suface of MOFs and encapsulated in the MOFs exhibit high catalytic activity.•PtNPs@Co(II)MOFs@PtNPs with large surface area were used as nanocarriers.
Herein, giant DNA networks were assembled from two kinds of functionalized tetrahedral DNA nanostructures (f-TDNs) for sensitive detection and intracellular imaging of apurinic/apyrimidinic ...endonuclease 1 (APE1) as well as gene therapy in tumor cells. Impressively, the reaction rate of the catalytic hairpin assembly (CHA) reaction on f-TDNs was much faster than that of the conventional free CHA reaction owing to the high local concentration of hairpins, spatial confinement effect and production of giant DNA networks, which significantly enhanced the fluorescence signal to achieve sensitive detection of APE1 with a limit of 3.34 × 10
−8
U μL
−1
. More importantly, the aptamer Sgc8 assembled on f-TDNs could enhance the targeting activity of the DNA structure to tumor cells, allowing it to endocytose into cells without any transfection reagents, which could achieve selective imaging of intracellular APE1 in living cells. Meanwhile, the siRNA carried by f-TDN1 could be accurately released to promote tumor cell apoptosis in the presence of endogenous target APE1, realizing effective and precise tumor therapy. Benefiting from the high specificity and sensitivity, the developed DNA nanostructures provide an excellent nanoplatform for precise cancer diagnosis and therapy.
We designed two functionalized tetrahedral DNA nanostructures (f-TDN1 and f-TDN2), which could assemble into giant DNA networks triggered by APE1, achieving sensitive detection and intracellular imaging of APE1 as well as gene therapy.
Electrochemiluminescence (ECL) micro-reactors with enhanced intensity and extreme stability were first established by the assembly of tris(2,2′-bipyridyl) ruthenium(
ii
) (Ru(bpy)
3
2+
) onto ...covalent organic frameworks (COFs), in which a type of imine-linked COF (denoted as COF-LZU1) was employed as a model for ECL micro-reactors. Compared with the dominant ECL system of Ru(bpy)
3
2+
/tri-
n
-propylamine (TPrA) (TPrA as a co-reactant), the intensity of the COF-LZU1 micro-reactor-based electrode was significantly increased nearly 5-fold under the same experimental conditions, which is unprecedented in other Ru(bpy)
3
2+
-based ECL systems. This enhancement can be attributed to the large surface area, delimited space, and stable and hydrophobic porous structure of COF-LZU1, which not only enabled a huge amount of Ru(bpy)
3
2+
to be loaded in/on COF-LZU1, but also enriched a large amount of TPrA from the aqueous solution into its inner hydrophobic cavity due to the lipophilicity of TPrA. More importantly, with its hydrophobic porous nanochannels, COF-LZU1 could act as micro-reactors to provide a delimited reaction micro-environment for the electrochemical oxidation of TPrA and the survival of TPrA&z.rad;, achieving significant confinement-enhanced ECL. To prove this principle, these Ru@COF-LZU1 micro-reactors were developed to prepare an ECL aptasensor for aflatoxin M1 (AFM1) detection with a wide detection range and a low detection limit. Overall, this work is the first report in which ECL micro-reactors are constructed with COFs to enhance the intensity and stability of the Ru(bpy)
3
2+
-based ECL system, and opens a new route to the design of other ECL micro-reactors for bioanalysis applications.
The electrochemiluminescence (ECL) micro-reactors with enhanced intensity and extreme stability were firstly established, unravelling the mechanism of ECL micro-reactors using COF-LZU1 assembled Ru(bpy)
3
2+
as a case study.
In this article, we used the TiO₂-graphene-Pt-Pd hybrid nanocomposites (TGPHs) as an enhanced element of the integrated sensing platform for increasing the surface area as well as improving the ...electronic transmission rate. Subsequently, Au nanoparticles (AuNPS) and cholesterol oxidase (ChOx) were successively self-assembled to TGPHs with high load amount and superior biological activity. The morphology of TGPHs and stepwise fabrication processes were characterized with cyclic voltammetry (CV), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Based on the efficiently catalytic ability of TGPHs and AuNPS, the fabricated biosensor exhibited wide linear ranges of responses to cholesterol in the concentration ranges of 5.0×10⁻⁸-5.9×10⁻⁴ M, the limit of detection was 0.017 μM (S/N=3). The response time was less than 7 s and the Michaelis-Menten constant (K(m)(app)) was found as 0.21 mM. The fabricated biosensor was further tested using real food samples egg, meat, margarine and fish oil, showing that the biosensor has the potential to be used as a facile cholesterol detection tool in food and supplement quality control.
The poly(9,9-dioctylfuorenyl-2,7-diyl)-alt-co-(1,4-benzo-{2,1′,3}-thiadiazole) (PFBT) was carboxyl-functionalized to prepare polymer dots (C-PFBT Pdots), which served as a self-ECL emitter for ...producing an extraordinary ECL signal without any exogenous coreactants. The C-PFBT Pdots–modified electrode captured the substrate DNA and further hybridized with a ferrocene (Fc)-labeled DNA. The ECL emission of C-PFBT Pdots was quenched by Fc (a signal off state). After the DNAzyme was added, the DNAzyme-substrate hybrids were formed through hybridizing between DNAzyme and substrate and the Fc-labeled DNA was released. In the presence of target Pb
2+
, the DNAzyme-substrate hybrids could be specifically recognized and cleaved to release the DNAzyme and Pb
2+
. Ultimately, the released DNAzyme would further hybridize with the substrate for producing the DNAzyme-substrate hybrids and then were cleaved by the released Pb
2+
. As a result, the DNA walking machine was generated and the substantial Fc was away from C-PFBT Pdots to obtain a signal on state. Such a strategy achieved a sensitive detection of Pb
2+
and the detection limit was as low as 0.17 pM. Moreover, making this ECL biosensor for an intracellular Pb
2+
detecting, a convincing performance was achieved. The self-ECL emitter C-PFBT Pdots combining with the quencher Fc provided a new strategy and platform for constructing a coreactant-free ECL assay.
The abnormal variation of the mucin 1 (MUC1) protein level is associated with the development of multiple cancers, and the monitoring of trace MUC1 can be useful for early disease diagnosis. Here, on ...the basis of the synchronization of DNA-fueled sequence recycling and dual rolling circle amplification (RCA), the establishment of a non-label and highly sensitive fluorescent aptamer-based detection strategy for the MUC1 protein biomarker is described. The target MUC1 binds the aptamer hairpin probe and causes its structure switching to release an ssDNA tail to trigger the recycling of the complex via two toehold-mediated strand displacement reactions under assistance of a fuel DNA. Such a recycling amplification leads to the formation of a partial dsDNA duplex with two primers at both ends, which cooperatively bind the circular DNA ring template to start the dual RCA to produce many G-quadruplex sequences. The protoporphyrin IX dye further associates with the G-quadruplex structures to show a dramatically elevated fluorescent signal for sensitively detecting MUC1 with a low detection limit of 0.5 pM. The established aptamer-based detecting strategy is also highly selective and can realize assay of MUC1 in diluted human serums, highlighting its potential for the detection of different protein biomarkers at low contents.
Electropolymerization of Im on the GCE, the PIm modified electrode was denoted as PIm/GCE. Subsequently, the PIm/GCE was washed with doubly distilled water, and then transferred to 0.1M PBS (pH 4.0) ...for electrochemical oxidation at +1.8V for 250s. The obtained electrode was denoted as PImox/GCE (Fig. A). Then, the deposition of GNPs on PImox/GCE was carried out. The obtained electrode was described as GNPs/PImox/GCE (Fig. B). Display omitted
► The electropolymerization of imidazole (Im) on GCE was first reported. ► The PIm film can be overoxidized to form the overoxidized polyimidazole (PImox). ► PImox allows dispersing of Au and generates additional electrocatalytic sites. ► The overlapping voltammetric response of AA, DA, UA and Trp is well-resolved.
A novel electrode was developed through electrodepositing gold nanoparticles (GNPs) on overoxidized-polyimidazole (PImox) film modified glassy carbon electrode (GCE). The combination of GNPs and the PImox film endowed the GNPs/PImox/GCE with good biological compatibility, high selectivity and sensitivity and excellent electrochemical catalytic activities towards ascorbic acid (AA), dopamine (DA), uric acid (UA) and tryptophan (Trp). In the fourfold co-existence system, the peak separations between AA–DA, DA–UA and UA–Trp were large up to 186, 165 and 285mV, respectively. The calibration curves for AA, DA and UA were obtained in the range of 210.0–1010.0μM, 5.0–268.0μM and 6.0–486.0μM with detection limits (S/N=3) of 2.0μM, 0.08μM and 0.5μM, respectively. Two linear calibrations for Trp were obtained over ranges of 3.0–34.0μM and 84.0–464.0μM with detection limit (S/N=3) of 0.7μM. In addition, the modified electrode was applied to detect AA, DA, UA and Trp in samples using standard addition method with satisfactory results.
Clenbuterol (CLB) is harmful to human health when used long term, and it has been listed by the World Anti-Doping Agency (WADA). In this work, a novel zinc-based metal-organic frameworks–reduced ...graphene oxide–CdTe quantum dots (ZnMOF-RGO-CdTe QDs) hybrid was used to construct an electrochemiluminescence (ECL) sensor for detecting CLB. CdTe QDs, loaded by RGO, exhibited an enhanced ECL signal. In addition, the ZnMOFs catalyzed OH
•
generation by coreactant H
2
O
2
, which further strengthened the ECL signal of the CdTe QDs. The integration of ZnMOFs and RGO-CdTe QDs endowed the sensor with high sensitivity for CLB detection. The intensity of the ECL signal increased as the concentration of CLB increased. The linear range of CLB detection was 3.0 × 10
−13
M to 6.0 × 10
−10
M, and the detection limit was estimated to be 1.0 × 10
−13
M. Furthermore, the sensor displayed a good repeatability and stability. The ZnMOF-RGO-CdTe QD hybrids described in this study provide a foundation for the development of new methods of detecting CLB.
Graphical abstract
ᅟ
On the basis of the use of silver nanoclusters (AgNCs) in situ synthesized by cytosine (C)-rich loop DNA templates as signal amplification labels, the development of a label-free and highly sensitive ...method for electrochemical detection of microRNA (miRNA-199a) is described. The target miRNA-199a hybridizes with the partial dsDNA probes to initiate the target-assisted polymerization nicking reaction (TAPNR) amplification to produce massive intermediate sequences, which can be captured on the sensing electrode by the self-assembled DNA secondary probes. These surface-captured intermediate sequences further trigger the hybridization chain reaction (HCR) amplification to form dsDNA polymers with numerous C-rich loop DNA templates on the electrode surface. DNA-templated synthesis of AgNCs can be realized by subsequent incubation of the dsDNA polymer-modified electrode with AgNO3 and sodium borohydride. With this integrated TAPNR and HCR dual amplification strategy, the amount of in situ synthesized AgNCs is dramatically enhanced, leading to substantially amplified current response for highly sensitive detection of miRNA-199a down to 0.64 fM. In addition, the developed method also shows high selectivity toward the target miRNA-199a. Featured with high sensitivity and label-free capability, the proposed sensing scheme can thus offer new opportunities for achieving sensitive, selective, and simple detection of different types of microRNA targets.
DNAzymes exhibit high potential as gene silencing agents for therapeutic applications. Such purposes, however, are significantly challenged by the targeted and successful delivery of unmodified ...DNAzymes into cells with minimal side effects. Here, we set out to formulate and demonstrate a new stimuli-responsive and constrained aptamer/DNAzyme (Apt/Dz) catenane nanostructure for highly specific gene silencing. The rational design of the Apt/Dz catenane nanostructure with the respective integration of the aptamer sequence and the completely closed catenane format enables both the targeted capability and significantly improved nuclease resistance, facilitating the stable and targeted delivery of unmodified Dz into cancer cells. Moreover, the Dz enzymatic activity in the constrained structure can only be conditionally regulated by the specific intracellular mRNA sequences to silence the target gene with highly reduced side effects. Results show that the Apt/Dz catenane nanostructure can effectively inhibit the expression of the target gene and the proliferation of cancer cells with high specificity.
The stimuli-responsive and constrained aptamer/DNAzyme catenane nanostructure enables the targeted delivery of native DNAzymes for highly specific gene silencing.
PDF
