A differential strategy to enhance the anti-interference ability of molecularly imprinted electrochemiluminescence sensor with a semi-logarithmic calibration curve.

The non-specific adsorption behaviors of various interferents on the surface of a molecularly imprinted polymer (MIP) are adverse for the selectivity of an MIP-based sensor, which can be overcome via a differential strategy by using the differential signal between MIP- and non-imprinted polymer (NIP)-based sensors. However, the normal differential mode is not suitable for the MIP-based sensors with non-linear calibration curves. Herein, an improved differential strategy is reported for an MIP-based sensor with a semi-logarithmic calibration curve, demonstrated by an electrochemiluminescence (ECL) sensor for dopamine (DA). Glassy carbon electrode (GCE) was modified by the mixture of g-C3N4, TiO2 nanoparticles (NPs) and carbon nanotubes (CNTs). MIP membrane for DA was fabricated on the surface of g-C3N4/TiO2NPs/CNTs/GCE using chitosan for film-forming, obtained MIP@GCE. To enhance the anti-interference ability of the MIP-based DA sensor, the difference between exponential functions ECL intensities of MIP@GCE and NIP@GCE is used as the analytical signal in the improved differential strategy. The differential signal was increased linearly with increasing DA concentration ranging from 10 pM to 0.10 µM, with the detection limit of 5.6 pM. The interference level of Cu2+ on DA determination in the improved differential mode is only 9.7% of that in the normal MIP mode. The improved differential strategy can be used in other MIP-based sensors with semi-logarithmic calibration curves.

Intrareticular Charge Transfer Triggered Self-Electrochemiluminescence of Zirconium-Based Metal-Organic Framework Nanoparticles for Potential-Resolved Multiplex Immunoassays with Isolated Coreactants.

In this work, a potential-resolved electrochemiluminescence (ECL) multiplex immunoassay (MIA) was developed using zirconium-based metal-organic framework (MOF) nanoparticles with intense self-ECL as an anodic ECL tag and CdTe nanocrystals (NCs) as a cathodic ECL tag. ECL luminophore 5,5'-(anthracene-9,10-diyl)diisophthalic acid (H4ADIP) and coreactant hexamethylenetetramine (HMT) bound to zirconium nodes in the MOF, giving Zr-ADIP-HMT nanoparticles. Benefiting from the intrareticular charge transfer (ICT) between the oxidized ligands of H4ADIP and HMT via hydrogen bonds, the intense self-ECL from Zr-ADIP-HMT was applied to the potential-resolved ECL MIA without an exogenous anodic coreactant, which can eliminate detrimental effects of multiplex coreactants and anodic ECL emission from CdTe NCs. The ICT within Zr-ADIP-HMT nanoparticles could shorten the electron transport path and reduce the complexity of radical intermediate transport. The ECL intensity from Zr-ADIP-HMT was 18.6-fold that from the mixture of H4ADIP and HMT. In potential-resolved ECL MIA, two lung cancer biomarkers, carcinoembryonic antigen and neuron-specific enolase, were adopted as model analytes, with detection limits of 18 and 5.3 fg·mL-1, respectively. The dual-ligand Zr-ADIP-HMT nanoparticles provide a proof of concept using ICT-based self-ECL luminophores for potential-resolved ECL MIAs with isolated coreactants.

Fluorescent nanosensor designing via hybrid of carbon dots and post-imprinted polymers for the detection of ovalbumin.

We reported a facile strategy to assemble a ratiometric nanosensor for the ovalbumin (OVA) fluorescence determination and meanwhile it can be utilized for selective visual identification by naked eyes with fluorescent test papers under 365 nm UV lamp. The nanosensor was prepared through simply mixing blue color carbon dots (CDs) and green color core-shell imprinted polymers. Blue CDs were used directly as the internal reference without participating in the imprinting process and modified molecularly imprinted polymers (MIPs) were synthesized by post-imprinting, using fluorescein isothiocyanate (FITC) as fluorescence enhanced signal. Upon the addition of different concentrations of OVA, the fluorescence intensity of FITC was enhanced, while the fluorescence intensity of CDs was almost unchanged, leading to a detection limit as low as 15.4 nM. Accordingly, the fluorescence color was gradually changed from blue to dark olive green to green with naked eyes observation. Moreover, the ratiometric nanosensor was successfully applied to detect OVA in the human urine samples with satisfactory recoveries attaining of 92.0-104.0% with relative standard deviation (RSD) of 3.3-3.9% and 93.3-101.0% with RSDs of 2.7-3.8% for the spiked chicken egg white samples. This strategy reported here opens a novel pathway for biomacromolecule detection in real applications and can realize the visual observation on fluorescent test papers.

Functional ZnS:Mn(II) quantum dot modified with L-cysteine and 6-mercaptonicotinic acid as a fluorometric probe for copper(II).

Manganese-doped ZnS quantum dots (ZnS:Mn(II) QDs) were synthesized and modified with L-cysteine (L-Cys) and 6-mercaptonicotinic acid (MNA). This prevents the aggregation of the QDs and makes them available for the interaction with Cu(II) ions via Cu(II)-S interaction. As a result, the fluorescence of the QDs is quenched by Cu(II) due to an electron transfer mechanism. The QDs display two emission peaks under 325 nm excitation, one (being red) peaking at 593 nm, the other (blue) at 412 nm. The red fluorescence is strongly quenched, while the blue fluorescence is not affected. An easily distinguishable color change from orange red to purple can be observed in fluorescence as the concentration of Cu(II) is increased. The probe is selective over commonly encountered other ions. The ratio of fluorescence intensities at 593 and 412 nm increases linearly in the 5 to 500 nM Cu(II) concentration range, and the detection limit is 1.2 nM. Graphical abstract Schematic of the preparation of manganese-doped quantum dots functionalized with L-cysteine and 6-mercaptonicotinic acid for selective and sensitive visual detection of copper ions.