Search

Metal–organic frameworks (MOFs) are novel inorganic–organic hybridized crystals with a wide range of applications. In the last twenty years, fluorescence sensing based on MOFs has attracted much attention. MOFs can exhibit luminescence from metal nodes, ligands or introduced guests, which provides an excellent fluorescence response in sensing. However, single-signal emitting MOFs are susceptible to interference from concentration, environment, and excitation intensity, resulting in poor accuracy. To overcome the shortcomings, dual-emission MOF-based ratiometric fluorescence sensors have been proposed and rapidly developed. In this review, we first introduce the luminescence mechanisms, synthetic methods, and detection mechanisms of dual-emission MOFs, highlight the strategies for constructing ratiometric fluorescence sensors based on dual-emission MOFs, and classify them into three categories: intrinsic dual-emission and single-emission MOFs with luminescent guests, and non-emission MOFs with other luminescent materials. Then, we summarize the recent advances in dual-emission MOF-based ratiometric fluorescence sensors in various analytical industries. Finally, we discuss the current challenges and prospects for the future development of these sensors. [ABSTRACT FROM AUTHOR]

Zr-metal–organic frameworks (Zr-MOFs) have received increasing interest for their use as the signal marker in the development of sandwich-structured aptasensors for the detection of exosomes. However, Zr4+ ions of the Zr-MOFs can interact with not only the exosomes, but also the aptamers, leading to possible false positives and a large background response. In the present study, we report for the first time aptasensors with Pd nanoparticle (NP)-decorated and hemin-embedded UiO-66 MOFs serving as the signal amplification marker to eliminate false positives and decrease the background response of aptasensors. To construct aptasensors for detection of exosomes, CD63-specific aptamers were tethered onto magnetic Fe3O4 particles coated with polydopamine (PDA) and UiO-66-NH2 using glutaraldehyde crosslinking for capturing the exosomes. To prepare highly catalytic Zr-MOF-based signal markers, UiO-66 MOFs were modified with hemin followed by Pd NPs. The as-prepared Pd-decorated hemin-embedded MOFs showed high catalytic activity towards the chromogenic oxidation reaction of TMB by H2O2. Moreover, the decoration with Pd NPs led to the change of the surface charge state of the catalytic hemin-embedded UiO-66 MOFs from positive to negative, weakening the interaction between the signal marker and the negatively charged aptamers. Therefore, the as-prepared aptasensors showed an improved sensing performance towards exosomes with a linear concentration range from 4.28 × 102 to 4.28 × 105 and a limit of detection (LOD) of 86.2 particles per μL. The as-prepared aptasensors also showed high sensitivity and selectivity to the exosomes from different origins including the HeLa cell line and MCF-7 cell line. [ABSTRACT FROM AUTHOR]

Preeclampsia (PE) seriously affects pregnant women and fetuses' health and causes maternal near-misses. CD81 has been confirmed to be a novel PE biomarker with great potential. Herein, a hypersensitive dichromatic biosensor based on the plasmonic enzyme-linked immunosorbent assay (plasmonic ELISA) is proposed initially for the application of CD81 in early screening for PE. In this work, a novel chromogenic substrate [(HAuCl4)-(N-methylpyrrolidone)-(Na3C6H5O7)] is designed based on the H2O2 dual catalysis reduction pathway of Au ions. The two reduction pathways of Au ions are controlled by H2O2 which ensures that the synthesis and growth of AuNPs are sensitive to H2O2. The amount of H2O2 correlates with the concentration of CD81 and directs the production of different-sized AuNPs in this sensor. Blue solutions are generated when analytes are present. When analytes are absent, solutions turn red. Therefore, due to different absorption peaks in red and blue, bimodal detection can be performed, and then two detection signals can be generated, one on signal at 550 nm and another off signal at 600 nm. This method exhibits a linear response to the logarithmic CD81 concentrations in the range of 0.1–1000 pg mL−1 with detection limits of 86 fg mL−1 and 152 fg mL−1 at two wavelengths. The false positive rate is low due to the nonspecific coloration caused by serum, which produces a more intense color contrast. The results indicate that the proposed dichromatic sensor could be used as a visual sensing platform for the direct detection of CD81 in biological samples and demonstrate its potential in preeclampsia diagnosis. [ABSTRACT FROM AUTHOR]

In the present study, a mediator release test (MRT) strategy has been designed for the photoluminescent sensing of glutathione (GSH). On the basis of the redox reaction of GSH and cerium-based nanosheets (Ce(CO3)2 NSs), Ce3+ ions were released to act as a mediator for the photoluminescence emission of the Au–thiolate complexes through an aggregation-induced emission (AIE) process. Remarkably, AIE was also accompanied by high chirality for the in situ synthesis of AuNCs using Ce(CO3)2 NSs as a template and GSH as a releaser for oligomeric Au–thiolate complexes. Multiple characterization techniques, including high-resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM), selected-area electron diffraction (SAED), X-ray powder diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), were employed to check the structure and morphology of the Ce(CO3)2 NSs as well as the successful in situ fabrication of the AuNCs. Using this new MRT strategy, an eco-friendly, selective, biocompatible and label-free AIE probe was established for the sensitive sensing of GSH with a limit of detection (LOD) of 1.02 μM. Moreover, this switch-on luminescent nanoplatform of the conjugate probe of Au–thiolate/Ce-based NSs was successfully applied for the selective and reliable GSH detection in human serum samples. [ABSTRACT FROM AUTHOR]

Endogenous H2O2 generated by a single HeLa cell that was adhered on the PDA-coated PDMS substrates under 25 mM glucose culture conditions was detected using a home-built photoelectric dual detection platform. With PMA as the stimulus, the cell released a small amount of H2O2 and its mitochondrial membrane potential (MMP) decrease was smaller, compared with that on the PDMS substrates. [ABSTRACT FROM AUTHOR]

Chemical and biological/biochemical sensors are capable of generating readout signals that are proportional to the concentration of specific analytes of interest. Signal sensitivity and limit of detection/quantitation can be enhanced through the use of polymers, nanomaterials, and their hybrids. Of particular interest are stimuli-responsive polymers and nanomaterials due to their ability to change their physical and/or chemical characteristics in response to their environment, and/or in the presence of molecular/biomolecular species of interest. Their individual use for sensing applications have many benefits, although this review focuses on the utility of stimuli-responsive polymer and nanomaterial hybrids. We discuss three main topics: stimuli-responsive nanogels, stimuli-responsive network polymers doped with nanomaterials, and nanoparticles modified with stimuli-responsive polymers. [ABSTRACT FROM AUTHOR]

The discrimination of living and dead cells shows great importance in the development of biology, pathology, medicine, and pharmacology research. Herein, we synthesized a simple benzothiazole-based probe, EP, which was characterized via1H NMR (hydrogen nuclear magnetic resonance) spectroscopy, 13C NMR (carbon nuclear magnetic resonance) spectroscopy and HRMS (high-resolution mass spectroscopy). The fluorescence changes in response to esterase were characterized via fluorescence spectroscopy. EP exhibited a 70-fold fluorescence enhancement in the presence of esterase and possessed a very low limit of detection (4.73 × 10−5 U mL−1). EP also showed high selectivity to esterase compared to other biological species. Bright fluorescence appeared in living cells, which was activated by esterase when incubated with EP. In paraformaldehyde or H2O2 pretreated cells, the fluorescence became very weak since esterase became inactive in these cells. In summary, the EP probe can monitor esterase activity both in vitro and in living cells and can be used to evaluate the health status of cells and discriminate living and dead cells effectively. [ABSTRACT FROM AUTHOR]

Capillarity is an extremely common physical–chemical phenomenon related to wettability in nature, which has wide theoretical and practical interest. Herein, we reported a facile sensing device based on capillary force change in a vertical capillary tube. In this height-based capillary sensor (HCS), the inner surface of the capillary tube was modified with a layer of molecules with wetting responsibility based on the well-known simple surface chemistry. With targets in different concentrations, the wettability of the surface modified with responsive molecules would produce different changes. The responsive surfaces would change the capillary force of the vertical capillary tube, and result in different column heights. Like a thermometer, H+ and phenol have been quantified visually based on the height of the liquid inside the capillary tube. [ABSTRACT FROM AUTHOR]

This review highlights the considerable advances in the chemical imaging of human fingermarks that provide more chemical information, including numerous endogenous and exogenous constituents. Despite remarkable development in DNA analysis and recognition, human fingermark analysis remains one of the priority approaches available for obtaining reliable forensic evidence. Additional information about the donor can be obtained from the chemical composition of latent fingermarks in addition to the ridge pattern, such as the age, gender, medical history, and possible drug habits. The analytical approaches reviewed here include spectroscopy, mass spectrometry, immuno-labelling and electrochemical methods. Each method has different capabilities with respect to sensitivity, reproducibility, selectivity, reliability and ultimately applicability, either for use in routine forensic practice or in academic research work. The advantages of spectroscopic techniques, including infrared, Raman and micro-X-ray fluorescence spectroscopy, are the capabilities of a rapid and non-destructive imaging of fingermarks by providing spectral information on chemical composition. In addition, mass spectrometry imaging can provide spatially specific information on fingermark chemical composition. Recently, the use of immuno-labelling in latent fingermark detection has attracted significant attention because it can overcome the sensitivity and selectivity problems experienced with other existing methods. The electrochemical method has also been employed to image latent fingermarks by measuring the electric current changes with the spatial chemical composition from the ridges and valleys at high resolution to provide a third level of detail, which is especially useful for multicoloured background surfaces or for surfaces contaminated with blood or other bodily fluids. [ABSTRACT FROM AUTHOR]

Electrode coating with polydopamine (PDA) is fast becoming a popular surface modification technique. In this study we report the investigation of the use of PDA as electrode coatings with Prussian blue (PB) as an electrode material model. The PB layer was galvanostatically deposited at an Au electrode, followed by PDA coating with the assistance of ammonium persulfate as an oxidant. The thickness of PDA coatings was measured to be ∼60 nm. Electrochemical characterization of the PDA-coated PB electrode revealed that the PDA coatings could stabilize the PB at neutral pH and allow the permeation of hydrogen peroxide (H2O2). Moreover, the PDA coatings were found to effectively exclude the common interfering compounds such as cysteine, ascorbic acid and uric acid, and exhibit selective electrocatalysis towards the electroreduction of H2O2. Accordingly, the PDA-coated PB electrode was applied for determination of H2O2 released from live cells. [ABSTRACT FROM AUTHOR]

The measurement of sulfide, especially hydrogen sulfide, has held the attention of the analytical community due to its unique physiological and pathophysiological roles in biological systems. Electrochemical detection offers a rapid, highly sensitive, affordable, simple, and real-time technique to measure hydrogen sulfide concentration, which has been a well-documented and reliable method. This review details up-to-date research on the electrochemical detection of hydrogen sulfide (ion selective electrodes, polarographic hydrogen sulfide sensors, etc.) in biological samples for potential therapeutic use. [ABSTRACT FROM AUTHOR]

An efficient catalyst based on artificial bionic peroxidase was synthesized for electrocatalysis. A poly(ethyleneimine)/Au nanoparticle composite (PEI-AuNP) was prepared and it was then linked to hemin via a coupling reaction between carboxyl groups in hemin and amino groups in PEI without the activation of a carboxyl group by carbodiimide. Fourier transform infrared (FTIR) spectroscopy verified the formation of amido bonds within the structure. The presence of AuNPs contributed greatly in establishing the amido bonds within the composite. Transmission electron microscopy (TEM) and UV-visible spectroscopy were also used to characterize the PEI-AuNP–hemin catalyst. PEI-AuNP–hemin exhibited intrinsic peroxidase-like catalytic activities. The PEI-AuNP–hemin deposited on a glass carbon electrode had strong sensing for H2O2 with a well-defined linear relationship between the amperometric response and H2O2 concentration in the range from 1 μM to 0.25 mM. The detection limit was 0.247 nM with a high sensitivity of 0.347 mA mM−1 cm−2. The peroxidase-like catalytic activity of PEI-AuNP–hemin is discussed in relation to its microstructure. The study suggests that PEI-AuNP–hemin may have promising application prospects in biocatalysis and bioelectronics. [ABSTRACT FROM AUTHOR]

Poly(thymine) (polyT) and double-stranded DNA (dsDNA) can act as efficient templates for the formation of copper nanoparticles (CuNPs) at a low concentration of CuSO4, and the formed CuNPs emit excellent fluorescence. In this work, we demonstrated a new and facile strategy for the highly sensitive and selective detection of DNA on streptavidin-functionalized magnetic beads (SA-MB) using DNA-templated CuNPs as the fluorescent probe. Target DNA (tDNA) was hybridized with the capture DNA that was immobilized on the surface of SA-MB. Surface initiated enzymatic polymerization (SIEP) was employed as the signal amplification method to generate the polyT at the 3′ end of tDNA for the formation of CuNPs. The incorporation of polyT by SIEP resulted in ∼35.7 fold signal amplification compared to the dsDNA after hybridization without SIEP. A dose–response curve for detection of DNA was obtained, with a linear dynamic range of 0.1 nM to 10 nM. We showed that this method has a low pM limit of detection (LOD 98.2 pM) and it is also very sensitive to the mismatch type in a specific DNA sequence. In addition, it avoids rigorously controlled temperature, complex synthesis of the fluorescent probe and prelabeling of DNA strands and eliminates the use of sophisticated experimental techniques and equipment. Armed with these intriguing properties, the proposed system could provide an efficient tool for early diagnosis and risk assessment of malignancy. [ABSTRACT FROM AUTHOR]

A universal and straightforward electrochemical biosensing strategy for the detection and identification of sequence-specific DNA via click chemistry-mediated labeling of hairpin DNA probes (hairpins) with ethynylferrocene was reported. In the target-unbound form, the immobilized hairpins were kept in the folded stem–loop configuration with their azido terminals held in close proximity of the electrode surface, making them difficult to be labeled with ethynylferrocene due to the remarkable steric hindrance of the densely packed hairpins. Upon hybridization, they were unfolded and underwent a large conformational change, thus enabling the azido terminals to become available for its subsequent conjugation with ethynylferrocene via the Cu(i)-catalyzed azide–alkyne cycloaddition (CuAAC). After that, the quantitatively labeled ethynylferrocene could be exploited as the electroactive probes to monitor the DNA hybridization. As the unfolded hairpins were labeled in a stoichiometric ratio of 1 : 1, the electrochemical measurement based on differential pulse voltammetry enabled a reliable quantification of sequence-specific DNA. Under optimal conditions, the strategy could detect target single-stranded DNA (ssDNA) down to 0.296 pM with a good linear response over the range from 1 pM to 1 nM, and had excellent specificity in the genotyping of single-nucleotide polymorphisms. Furthermore, it also exhibited good detection reliability in serum samples and required no complicated protocols. More importantly, the simplicity of this strategy together with its compatibility with microfluidic chips makes it show great potential in clinical applications, where simple procedures are generally preferred. [ABSTRACT FROM AUTHOR]

Correction for 'In situ synthesis of chiral AuNCs with aggregation-induced emission using glutathione and ceria precursor nanosheets for glutathione biosensing' by Mohamed Ibrahim Halawa et al., Analyst, 2022, https://doi.org/10.1039/d2an00939k. [ABSTRACT FROM AUTHOR]

In this study we report the improved stability of Prussian blue (PB) films in neutral and alkaline solutions via an electrochemical post-treatment procedure. In this procedure, PB films synthesized via the electroless deposition method at glassy carbon electrodes were continuously cycled for 300 cycles (∼12 h) between the potential limits of +0.6 and −0.1 V (vs. Ag/AgCl) at a scan rate of 10 mV s−1 in 2.0 M KCl solution of pH 3. It was found that after such electrochemical post-treatment the PB films exhibit dramatically improved stability in neutral and alkaline solutions. Control experiments confirmed that the longer potential cycling time and the higher KCl concentration are indispensable. In addition, interestingly, it was found that after the successive potential cycling treatments the shape of PB nanoparticles evolves from a sphere into a cube as well as a small amount of a rectangle, indicating the electrochemically induced shape evolution of nanocrystals. The electrochemical post-treatment procedure proposed here could be useful for the development of PB-based devices with improved stability, for instance, biosensors, biofuel cells, etc. [ABSTRACT FROM AUTHOR]

Acute myocardial infarction (AMI) accounts for a significant proportion of global fatalities, and early detection is crucial for improving patient outcomes. However, current diagnostic methods often struggle to detect AMI in its early stages. Herein, we present an electrochemical sensor utilizing a fractal gold (FracAu) electrode and hybridization chain reaction (HCR) amplification technology to detect AMI-specific microRNAs (miRNAs). When the target sequence was added, the HCR was triggered, leading to the formation of a long-nicked DNA double helix that efficiently captured a larger quantity of positively charged RuHex molecules, resulting in significant electrochemical signal amplification. More importantly, to avoid false positive signals, exonuclease I (Exo I) was introduced to selectively cleave single-stranded DNA (ssDNA) probes. These ssDNA probes, underwent random hydrolysis from hpDNA probes, could hybridize with helper DNA1 in the absence of the target, initiating the HCR process and producing a false positive signal. The inclusion of Exo I effectively avoided false positive signals and reduced background noise. Under optimized conditions, the fabricated sensor exhibited significant sensitivity and selectivity, showing a broad linear detection range from 10 pM to 10 nM and a low limit of 0.9 fM. The fabricated electrochemical sensor also successfully detected AMI-specific miRNA in real serum samples, underscoring its diagnostic promise. By providing a reliable tool for early detection, the innovative sensor holds significant potential in combating global cardiovascular disease-related mortality rates.

A highly sensitive method for the rapid flow injection amperometric detection of hydrogen peroxide is reported, which is based on the excellent catalytic activity of carbon nanofiber coated simply on an electrode towards the reduction of H2O2 and has high throughput and interesting potential for the development of rapid and highly sensitive biosensors.