Silica Nanochannels as Nanoreactors for the Confined Synthesis of Ag NPs to Boost Electrochemical Stripping Chemiluminescence of the Luminol-O2 System for the Sensitive Aptasensor.

Herein, we, for the first time, synthesize silver nanoparticles (Ag NPs) within the nanochannels of amino group-functionalized vertically ordered mesoporous silica films (NH2-VMSF) and investigate their coreaction accelerator role in the luminol-dissolved oxygen (O2) electrochemical stripping chemiluminescence (ESCL) system. The synthesized Ag NPs are capable of electrocatalytic reduction of O2 to superoxide radicals, and meanwhile, sliver ions (Ag+) electrochemically stripped from Ag NPs can promote the amount of luminol anion radicals, generating the boosted ECL intensity of the luminol-dissolved O2 system. This proposed Ag NPs@NH2-VMSF on the indium tin oxide electrode was applied to construct the ESCL aptasensor for quantitative determination of prostate-specific antigen (PSA), yielding a low detection limit [0.19 pg/mL (S/N = 3)] and a broad linear dynamic range (1 pg/mL to 100 ng/mL). Furthermore, good analytical performance of PSA in serum with satisfactory recoveries and low relative standard deviation values is achieved by our developed ESCL aptasensor, rendering it a convenient and sensitive method for PSA determination in clinical applications and further broadening the strategy of ESCL techniques.

Electrochemiluminescence resonance energy transfer detection of HBsAg based on Co doped 3D porous luminol-based conjugates and quencher UiO-66-NH2@Au.

An electrochemiluminescence (ECL) biosensor based on ECL resonance energy transfer (ECL-RET) was designed to sensitively detect hepatitis B virus surface antigen (HBsAg). In this ECL-RET system, luminol was employed as ECL donor, and gold nanoparticles functionalized zirconium organoskeleton (UiO-66-NH2@Au) was prepared and served as ECL acceptor. The UiO-66-NH2@Au possessed an ultraviolet-visible (UV-vis) absorption between 400 nm and 500 nm, and the absorption spectra overlapped with the ECL spectrum of luminol. Furthermore, Graphene oxide-poly(aniline-luminol)-cobalt nanoparticles conjugates (GO-PALu-Co) was prepared to optimize the ECL behavior through the catalysis of Cobalt nanoparticles and served as a stable 3D porous film to load capture probe primary antibody (Ab1). Based on the ECL-RET biosensing method, the UiO-66-NH2@Au-labeled Ab2 and target HBsAg could pair with primary antibody Ab1 to form sandwich-type structure, and the ECL signal of GO-PALu-Co was quenched. Under optimized experimental conditions, the ECL-RET analytical method represented eminent analytical performance for HBsAg detection with a wide linear relationship from 2.2 × 10-13 to 2.2 × 10-5 mg/mL, and a detection limit of 9 × 10-14 mg/mL (S/N = 3), with spiked sample recoveries ranging from 97.27 % to 102.73 %. The constructed sensor has good stability, reproducibility, and specificity. It can be used to detect HBsAg in human serum and has the potential to be used for the sensitive detection of other disease biomarkers.

Study on the methods of visualizing bloodstains after thermal exposure.

To establish the correlation between thermal conditions imposed on bloodstains and visualizing effect of enhancement techniques, infrared photography and four chemical enhancement reagents were used to visualize bloodstains following thermal exposure. A black tile was selected as the substrate to intensify the visualization challenge, with a Cone Calorimeter serving as the standardized heating source to control thermal conditions. Compared with standard photography, infrared photography is proven to be a valuable complement to chemical reagents, showing significant advantages in visualizing bloodstains after thermal exposure. However, it is worth noting that infrared image fell short of standard image when bloodstains displayed raised, embossed morphology or when bloodstains almost disappeared under specific conditions. The enhancement effectiveness was found to be strongly correlated with thermal conditions imposed on bloodstains, and the morphology evolution of bloodstains during heating affected the chemical enhancement effect additionally, especially when the bulge morphology was formed, and it was observed that reagents were more effective after removing the dense shell of the bulge. Among the four selected chemical enhancement reagents, fluorescein performed exceptionally well, maintaining its effectiveness even for bloodstains heated at 641°C for 10 min. TMB demonstrated its visualizing ability for bloodstains heated at 396°C for 5 min and heated at 310°C for 20 min. BLUESTAR® followed afterwards, while luminol performed worst. The correlation between thermal conditions imposed on bloodstains and the corresponding visualizing effectiveness of enhancement techniques provides important references for detecting bloodstains at fire scenes.

Evaluating early apoptosis-related cellular MiRNAs with an ultrasensitive electrochemiluminescence nanoplatform.

It is known that the abnormal expression of specific cellular miRNAs is closely related to cell apoptosis, and so monitoring the level change of these miRNAs can in principle be used to evaluate the process of apoptosis stimulated by drugs. Towards this goal, here we construct an ultrasensitive electrochemiluminescence (ECL) nanoplatform via the target miRNA-triggered immobilization of spherical nucleic acid enzymes (SNAzymes) onto tetrahedral DNA nanostructures on the electrode surface, which catalyzes the luminol-H2O2 reaction to output an ECL signal. This enables the sensitive and specific detection of two apoptosis-related miRNAs, miR-21 and miR-133a, with a detection limit of 33 aM. Furthermore, we employed the developed ECL nanoplatform to monitor the levels of these two miRNAs inside cancer cells stimulated by DOX, showing that the level of miR-21 decreases, while that of miR-133a increases in the early apoptotic cells. This difference highlights the distinct roles of the two target miRNAs, where miR-21 promotes the early apoptosis of cancer cells, whereas miR-133a suppresses it, providing new insight into cell physiological processes.

Luminol-Eu3+-Gd3+-functionalized mesoporous silica for ultrasensitive detection of tetracycline antibiotics and smartphone-assisted sensing analysis.

An organic-inorganic hybrid nanoprobe, namely LML-D-SBA@Eu3+-Gd3+, was constructed, with SBA-15 acting as the carrier material, and luminol and Eu3+ acting as fluorescence channels to achieve ratiometric signals that eliminate external interference (accurate detection). Gd3+ was used as a sensitizer to amplify the red emission of Eu3+ (ultrasensitive detection). In TCs detection, the luminol emission at 428 nm was quenched due to the photoinduced electron transfer mechanism, and the Eu3+ emission at 617 nm was sensitized due to the synergistic energy transfer from TCs and Gd3+ to Eu3+. The fluorescence intensity at 617 and 428 nm showed ratiometric changes as indicated by notable color changes from blue to red. The detection limits for TC and OTC were 0.21 and 0.08 ng/mL, respectively. To realize a facile, rapid, and cost-effective detection, we constructed a portable intelligent sensing platform based on smartphones, and it demonstrated great potential for on-site detection of TCs.

Electrochemiluminescence enhanced by molecular engineering linear π-conjugated polymer: An ingenious ECL emitter for the construction of exosome sensing platform.

Linear π-conjugated polymers (LCPs) with π-electron conjugation system have many remarkable optical characteristics such as fluorescence and electrochemiluminescence (ECL). However, the extremely strong interchain interaction and π-π stacking limit the luminescence efficiency. In this work, 1H-1,2,4-triazole-3,5-diamine was chosen as the polymer monomer and reacted with terephthalaldehyde via simple Schiff base condensation to synthesize LCPs. Subsequently, molecular engineering strategy was adopted to construct zirconium-based LCPs (MLCPs), which not only prevented π-π stacking but also ensured that extended π-coupling was maintained in the LCPs, thus effectively promoting charge transport and achieving strong luminescence. Second, the coreactant polyethyleneimine (PEI) was assembled onto the MLCPs (MLCPs@PEI) to further promote the emission of ECL. To further explore the potential of the obtained MLCPs@PEI as emerging ECL emitter, colorectal cancer exosome was chosen as model biomarker, and an innovative ECL ratiometric system based on MLCPs@PEI and luminol was designed to improve the validity and accuracy of the sensors. This research provides a fresh nanoplatform for exosome detection and broadens the application of LCPs in ECL immunoassay.

Quantitative analysis of CL-20 explosive by smartphone-based chemiluminescence method.

A new smartphone-based chemiluminescence method has been introduced for the quantitative analysis of CL-20 (Hexanitroazaisowuertzitan) explosive. The solvent mixture, oxidizer agent, and concentration of the reactants were optimized using statistical procedures. CL-20 explosive showed a quenching effect on the chemiluminescence intensity of the luminol-NaClO reaction in the solvent mixture of DMSO/H2O. A smartphone was used as a detector to record the light intensity of chemiluminescence reaction as a video file. The recorded video file was converted to an analytical signal as intensity luminescence-time curve by a written code in MATLAB software. Dynamic range and limit of detection of the proposed method were obtained 2.0-240.0 and 1.1 mg⋅L-1, respectively, in optimized concentrations 1.5 × 10-3 mol⋅L-1 luminol and 1.0 × 10-2 mol⋅L-1 NaClO. Precursors TADB, HBIW, and TADNIW in CL-20 explosive synthesis did not show interference in measurement the CL-20 purity. The analysis of CL-20 spiked samples of soil and water indicated the satisfactory ability of the method in the analysis of real samples. The interaction of CL-20 molecules and OCl- ions is due to quench of chemiluminescence reaction of the luminol-NaClO.

Boosting Electrochemiluminescence Performance of a Dual-Active Site Iron Single-Atom Catalyst-Based Luminol-Dissolved Oxygen System via Plasmon-Induced Hot Holes.

Due to the commonly low content of biomarkers in diseases, increasing the sensitivity of electrochemiluminescence (ECL) systems is of great significance for in vitro ECL diagnosis and biodetection. Although dissolved O2 (DO) has recently been considered superior to H2O2 as a coreactant in the most widely used luminol ECL systems owing to its improved stability and less biotoxicity, it still has unsatisfactory ECL performance because of its ultralow reactivity. In this study, an effective plasmonic luminol-DO ECL system has been developed by complexing luminol-capped Ag nanoparticles (AgNPs) with plasma-treated Fe single-atom catalysts (Fe-SACs) embedded in graphitic carbon nitride (g-CN) (pFe-g-CN). Under optimal conditions, the performance of the resulting ECL system could be markedly increased up to 1300-fold compared to the traditional luminol-DO system. Further investigations revealed that duple binding sites of pFe-g-CN and plasmonically induced hot holes that disseminated from AgNPs to g-CN surfaces lead to facilitate significantly the luminous reaction process of the system. The proposed luminol-DO ECL system was further employed for the stable and ultrasensitive detection of prostate-specific antigen in a wide linear range of 1.0 fg/mL to 1 µg/mL, with a pretty low limit of detection of 0.183 fg/mL.

Bifunctional oxidase-peroxidase mimicking Fe-Ce MOF on paper-based analytical devices to intensify luminol chemiluminescence: Application for measuring different sugars with a smartphone readout.

This study presents a potent paper-based analytical device (PAD) for quantifying various sugars using an innovative bi-nanozyme made from a 2-dimensional Fe/Ce metal-organic framework (FeCe-BTC). The MOF showed excellent bifunctional peroxidase-oxidase activities, efficiently catalyzing luminol's chemiluminescence (CL) reaction. As a peroxidase-like nanozyme, FeCe-BTC could facilitate the dissociation of hydrogen peroxide (H2O2) into hydroxyl radicals, which then oxidize luminol. Additionally, it was also discovered that when reacting with H2O2, the MOF turns into a mixed-valence MOF, and acts as an oxidase nanozyme. This activity is caused by the generated Ce4+ ions in the structure of MOF that can directly oxidize luminol. The MOF was directly synthesized on the PAD and cascaded with specific natural enzymes to establish simple, rapid, and selective CL sensors for the measurement of different sugars. A cell phone was also used to record light intensities, which were then correlated to the analyte concentration. The designed PAD showed a wide linear range of 0.1-10 mM for glucose, fructose, and sucrose, with detection limits of 0.03, 0.04, and 0.04 mM, respectively. It showed satisfactory results in food and biological samples with recovery values ranging from 95.8 to 102.4 %, which makes it a promising candidate for point-of-care (POC) testing for food control and medicinal purposes.

Hemin as a Molecular Probe for Nitric Oxide Detection in Physiological Solutions: Experimental and Theoretical Assessment.

Given its pivotal role in modulating various pathological processes, precise measurement of nitric oxide (●NO) levels in physiological solutions is imperative. The key techniques include the ozone-based chemiluminescence (CL) reactions, amperometric ●NO sensing, and Griess assay, each with its advantages and drawbacks. In this study, a hemin/H2O2/luminol CL reaction was employed for accurately detecting ●NO in diverse solutions. We investigated how the luminescence kinetics was influenced by ●NO from two donors, nitrite and peroxynitrite, while also assessing the impact of culture medium components and reactive species quenchers. Furthermore, we experimentally and theoretically explored the mechanism of hemin oxidation responsible for the initiation of light generation. Although both hemin and ●NO enhanced the H2O2/luminol-based luminescence reactions with distinct kinetics, hemin's interference with ●NO/peroxynitrite- modulated their individual effects. Leveraging the propagated signal due to hemin, the ●NO levels in solution were estimated, observing parallel changes to those detected via amperometric detection in response to varying concentrations of the ●NO-donor. The examined reactions aid in comprehending the mechanism of ●NO/hemin/H2O2/luminol interactions and how these can be used for detecting ●NO in solution with minimal sample size demands. Moreover, the selectivity across different solutions can be improved by incorporating certain quenchers for reactive species into the reaction.

In vitro assessment of thyroid peroxidase inhibition by chemical exposure: comparison of cell models and detection methods.

Disruption of the thyroid hormone (TH) system is connected with diverse adverse health outcomes in wildlife and humans. It is crucial to develop and validate suitable in vitro assays capable of measuring the disruption of the thyroid hormone (TH) system. These assays are also essential to comply with the 3R principles, aiming to replace the ex vivo tests often utilised in the chemical assessment. We compared the two commonly used assays applicable for high throughput screening [Luminol and Amplex UltraRed (AUR)] for the assessment of inhibition of thyroid peroxidase (TPO, a crucial enzyme in TH synthesis) using several cell lines and 21 compounds from different use categories. As the investigated cell lines derived from human and rat thyroid showed low or undetectable TPO expression, we developed a series of novel cell lines overexpressing human TPO protein. The HEK-TPOA7 model was prioritised for further research based on the high and stable TPO gene and protein expression. Notably, the Luminol assay detected significant peroxidase activity and signal inhibition even in Nthy-ori 3-1 and HEK293T cell lines without TPO expression, revealing its lack of specificity. Conversely, the AUR assay was specific to TPO activity. Nevertheless, despite the different specificity, both assays identified similar peroxidation inhibitors. Over half of the tested chemicals with diverse structures and from different use groups caused TPO inhibition, including some widespread environmental contaminants suggesting a potential impact of environmental chemicals on TH synthesis. Furthermore, in silico SeqAPASS analysis confirmed the high similarity of human TPO across mammals and other vertebrate classes, suggesting the applicability of HEK-TPOA7 model findings to other vertebrates.

A simple chemiluminescent method for the quantification of exosomes based on horseradish peroxidase adsorbed on two-dimensional nanomaterials.

The development of simple methods for the isolation and quantification of exosomes in biological samples is important. By using the typical two-dimensional (2D) nanomaterials, graphene oxide (GO), the present work first studied the interaction of liposomes with the nanocomposites formed by adsorbing HRP on the GO surface and found the presence of liposomes led to the release of HRP from the GO surface to the solution phase triggering the luminol-H2O2 chemiluminescence (CL) reaction to emit light. Benefiting from the similarity of exosomes to liposomes in both composition and morphology aspects, the GO-HRP nanocomposites with a mass ratio of 120:1 and 160:1 were employed for the quantitative detection of exosomes in 100-fold diluted serum samples. The whole detection process took about 15 min and as low as 3.2 × 102 particles µL-1 of exosomes could be sensitively detected. In addition to GO-HRP nanocomposites, the CL responses of other nanocomposites obtained from adsorbing HRP on other 2D nanomaterials such as layered MoS2 for exosomes were also tested. MoS2-HRP exhibited similar behavior and the LODs for the detection of exosomes were 5.8 × 102 particles µL-1. The proposed assays were a biomarker-independent quantitative method that achieved the quantification of exosomes in serum samples directly without an isolation process.

Fe-single-atom catalysts boosting electrochemiluminescence via bipolar electrode integrated with its peroxidase-like activity for bioanalysis.

Multifunctional single-atom catalysts (SACs) have been extensively investigated as outstanding signal amplifiers in bioanalysis field. Herein, a type of Fe single-atom catalysts with Fe-nitrogen coordination sites in nitrogen-doped carbon (Fe-N/C SACs) was synthesized and demonstrated to possess both catalase and peroxidase-like activity. Utilizing Fe-N/C SACs as dual signal amplifier, an efficient bipolar electrode (BPE)-based electrochemiluminescence (ECL) immunoassay was presented for determination of prostate-specific antigen (PSA). The cathode pole of the BPE-ECL platform modified with Fe-N/C SACs is served as the sensing side and luminol at the anode as signal output side. Fe-N/C SACs could catalyze decomposition of H2O2 via their high catalase-like activity and then increase the Faraday current, which can boost the ECL of luminol due to the electroneutrality in a closed BPE system. Meanwhile, in the presence of the target, glucose oxidase (GOx)-Au NPs-Ab2 was introduced through specific immunoreaction, which catalyzes the formation of H2O2. Subsequently, Fe-N/C SACs with peroxidase-like activity catalyze the reaction of H2O2 and 4-chloro-1-naphthol (4-CN) to generate insoluble precipitates, which hinders electron transfer and then inhibits the ECL at the anode. Thus, dual signal amplification of Fe-N/C SACs was achieved by increasing the initial ECL and inhibiting the ECL in the presence of target. The assay exhibits sensitive detection of PSA linearly from 1.0 pg/mL to 100 ng/mL with a detection limit of 0.62 pg/mL. The work demonstrated a new ECL enhancement strategy of SACs via BPE system and expands the application of SACs in bioanalysis field.

Metal-organic framework-based aptasensor utilizing a novel electrochemiluminescence system for detecting acetamiprid residues in vegetables.

The work was based on N-(4-Aminobutyl)-N-ethylisoluminol (ABEI)-functionalized Fe-MIL-101 and gold nanoparticles (AuNPs) as sensing materials, and an electrochemiluminescence (ECL) aptasensor was constructed for detecting acetamiprid. As a metal-organic framework (MOF) material, Fe-MIL-101, was renowned for its unique three-dimensional network structure and efficient catalytic capability. ABEI, a common ECL reagent, was widely applied. ABEI was introduced into the Fe-MIL-101 structure as a luminescence functionalization reagent to form Fe-MIL-101@ABEI. This approach avoided limitations on the loading capacity of luminescent reagents imposed by modification and encapsulation methods. With character of excellent catalytic activity and ease of bioconjugation, AuNPs offered significant advantages in biosensing. Leveraging the reductive properties of ABEI, AuNPs were reduced around Fe-MIL-101@ABEI, resulting in the modified luminescent functionalized material denoted as Fe-MIL-101@ABEI@AuNPs. An aptamer was employed as a recognition element and was modified accordingly. The aptamer was immobilized on Fe-MIL-101@ABEI@AuNPs through gold-sulfur (Au-S) bonds. After capturing acetamiprid, the aptamer induced a decrease in the ECL signal intensity within the ABEI-hydrogen peroxide (H2O2) system, enabling the quantitative detection of acetamiprid. The aptasensor displayed remarkable stability and repeatability, featured a detection range of 1×10-3-1×102 nM, and had a limit of detection (LOD) of 0.3 pM (S/N=3), which underscored its substantial practical application potential.

FeS2 nanosheets-luminol-O2 chemiluminescence method for determination of venlafaxine hydrochloride, imipramine hydrochloride, and cefazolin sodium.

This study introduces a novel chemiluminescence (CL) approach utilizing FeS2 nanosheets (NSs) catalyzed luminol-O2 CL reaction for the measurement of three pharmaceuticals, namely venlafaxine hydrochloride (VFX), imipramine hydrochloride (IPM), and cefazolin sodium (CEF). The CL method involved the phenomenon of quenching induced by the pharmaceuticals in the CL reaction. To achieve the most quenching efficacy of the pharmaceuticals in the CL reaction, the concentrations of reactants comprising luminol, NaOH, and FeS2 NSs were optimized accordingly. The calibration curves demonstrated exceptional linearity within the concentration range spanning from 4.00 × 10-7 to 1.00 × 10-3 mol L-1, 1.00 × 10-7 to 1.00 × 10-4 mol L-1, and 4.00 × 10-6 to 2.00 × 10-4 mol L-1 with detection limits (3σ) of 3.54 × 10-7, 1.08 × 10-8, and 2.63 × 10-6 mol L-1 for VFX, IPM, and CEF, respectively. This study synthesized FeS2 NSs using a facile hydrothermal approach, and then the synthesized FeS2 NSs were subjected to a comprehensive characterization using a range of spectroscopic methods. The proposed CL method was effective in measuring the aforementioned pharmaceuticals in pharmaceutical formulations as well as different water samples. The mechanism of the CL system has been elucidated.

Coreactant-free aggregation-induced electrochemiluminescence system based on the novel zinc-luminol metal-organic gel for ultrasensitive detection of PiRNA-823.

Aggregation-induced electrochemiluminescence (AIECL) technology has aroused widespread interest due to the significant improve in ECL response by solving the problems of aggregation-caused quenching and poor water solubility of the luminophore. However, the existing AIECL emitters still suffer from low ECL efficiency, additional coreactants and complex synthesis steps, which greatly limit their applications. Herein, luminol, as a kind of AIE molecule, was assembled with Zn2+ nodes to obtain a novel microflower-like Zinc-luminol metal-organic gel (Zn-MOG) by one-step method. In the light of the strong affinity of N atoms in luminol ligand to Zn2+, Zn-MOG with vigorous viscosity and stability can be formed immediately after vortex oscillation, overcoming the main difficulties of the complicated synthesis steps and poor film-forming performance encountered in current AIECL materials. Impressively, an AIECL resonance energy transfer (RET) biosensor was constructed using Zn-MOG as a donor and Alexa Fluor 430 as an acceptor in combination with DNA-Fuel-driven target recycling amplification for the ultrasensitive detection of PiRNA-823. The fabricated biosensor exhibited a wide linear relationship in the range of 100 aM to 100 pM and a detection limit as low as 60.0 aM. This work is the first to realize the construction of ECL emitters using the AIE effect of luminol, which provides inspiration for the design of AIECL systems without adding coreactants.

Wireless rotating bipolar electrochemiluminescence for enzymatic detection.

New dynamic, wireless and cost-effective analytical devices are developing rapidly in biochemical analysis. Here, we report on a remotely-controlled rotating electrochemiluminescence (ECL) sensing system for enzymatic detection of a model analyte, glucose, on both polarized sides of an iron wire acting as a bipolar electrode. The iron wire is controlled by double contactless mode, involving remote electric field polarization, and magnetic field-induced rotational motion. The former triggers the interfacial polarization of both extremities of the wire by bipolar electrochemistry, which generates ECL emission of the luminol derivative (L-012) with the enzymatically produced hydrogen peroxide in presence of glucose, at both anodic and cathodic poles, simultaneously. The latter generates a convective flow, leading to an increase in mass transfer and amplifying the corresponding ECL signals. Quantitative glucose detection in human serum samples is achieved. The ECL signals were found to be a linear function of the glucose concentration within the range of 10-1000 µM and with a limit of detection of 10 µM. The dynamic bipolar ECL system simultaneously generates light emissions at both anodic and cathodic poles for glucose detection, which can be further applied to biosensing and imaging in autonomous devices.

A dual amplified gold nanoparticle-based biosensor for ultrasensitive and selective detection of fibrin.

Ultrasensitive, selective, and non-invasive detection of fibrin in human serum is critical for disease diagnosis. So far, the development of high-performance and ultrasensitive biosensors maintains core challenges for biosensing. Herein, we designed a novel ribbon nanoprobe for ultrasensitive detection of fibrin. The probe contains gold nanoparticles (AuNPs) that can not only link with homing peptide Cys-Arg-Glu-Lys-Ala (CREKA) to recognize fibrin but also carry long DNA belts to form G-quadruplex-based DNAzyme, catalyzing the chemiluminescence of luminol-hydrogen peroxide (H2O2) reaction. Combined with the second amplification procedure of rolling circle amplification (RCA), the assay exhibits excellent sensitivity with a detection limit of 0.04 fmol L-1 fibrin based on the 3-sigma. Furthermore, the biosensor shows high specificity on fibrin in samples because the structure of antibody-fibrin-homing peptide was employed to double recognize fibrin. Altogether, the simple and inexpensive approach may present a great potential for reliable detection of biomarkers.

Dual-potential ratiometric electrochemiluminescence based on single emitter and single coreactant for the sensitive detection of carcinoembryonic antigen.

Dual-potential ratiometric electrochemiluminescence (ECL) is in favor of resistance to environmental interference. However, two kinds of emitters or coreactants, and a wide scan potential range (>2 V) are mandatory. This work developed a new dual-potential ratiometric ECL sensor for detection of carcinoembryonic antigen (CEA) using single emitter (luminol) and single coreactant (H2O2) with a mild potential range from -0.1 to 0.6 V. Luminol could produce a strong cathodic ECL (Ec) induced by hydroxyl radicals (HO‧) from the reduction of H2O2, and a relatively weak anodic ECL (Ea). After the ferrocene modified CEA aptamer (Apt-Fc) was attached, Fc could promote Ea by catalyzing the oxidation of H2O2, and reduce Ec by consuming HO‧. With the cycling amplification of the exonuclease I, CEA could substantially reduce the amount of Apt-Fc, resulting in the decrease of Ea and the rise of Ec. So, the ratio of Ec to Ea (Ec/Ea) was used as the detection signal, realizing the sensitive determination of CEA from 0.1 pg mL-1 to 10 ng mL-1 with a LOD of 41.85 fg mL-1 (S/N = 3). The developed sensor demonstrated excellent specificity, stability and reproducibility, with satisfactory results in practical detection.

Controlled-Release Electrochemiluminescence Biosensor with Strong Self-On Effect by a Multiple Signal Amplification Strategy for Trace Detection of Prostate-Specific Antigen.

The enhancement of sensitivity in biological analysis detection can reduce the probability of false positives of the biosensor. In this work, a novel self-on controlled-release electrochemiluminescence (CRE) biosensor was designed by multiple signal amplification and framework-enhanced stability strategies. As a result, the changes of the ECL signal were enhanced before and after the controlled-release process, achieving sensitive detection of prostate-specific antigen (PSA). Specifically, for one thing, Fe3O4@CeO2-NH2 with two paths for enhancing the generation of coreactant radicals was used as the coreaction accelerator to boost ECL performance. For another, due to the framework stability, zeolitic imidazolate framework-8-NH2 (ZIF-8-NH2) was combined with luminol to make the ECL signal more stable. Based on these strategies, the constructed CRE biosensor showed a strong self-on effect in the presence of PSA and high sensitivity in a series of tests. The detection range and limit of detection (LOD) were 5 fg/mL to 10 ng/mL and 2.8 fg/mL (S/N = 3), respectively, providing a feasible approach for clinical detection of PSA.