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.

A Co-Reactive Immunosensor Based on Ti3C2Tx MXene@TiO2-MoS2 Hybrids Promoting luminol@Au@Ni-Co NCs Electrochemiluminescence for CYFRA 21-1 Detection.

The construction of assays is capable of accurately detecting cytokeratin-19 (CYFRA 21-1), which is critical for the rapid diagnosis of nonsmall cell lung cancer. In this work, a novel electrochemiluminescence (ECL) immunosensor based on the co-reaction promotion of luminol@Au@Ni-Co nanocages (NCs) as ECL probe by Ti3C2Tx MXene@TiO2-MoS2 hybrids as co-reaction accelerator was proposed to detect CYFRA 21-1. Ni-Co NCs, as a derivative of Prussian blue analogs, can be loaded with large quantities of Au NPs, luminol, and CYFRA 21-1 secondary antibodies due to their high specific surface area. To further improve the sensitivity of the developed ECL immunosensor, Ti3C2Tx MXene@TiO2-MoS2 hybrids were prepared by in situ growth of TiO2 nanosheets on highly conductive Ti3C2Tx MXene, and MoS2 was homogeneously grown on Ti3C2Tx MXene@TiO2 surfaces by the hydrothermal method. Ti3C2Tx MXene@TiO2-MoS2 hybrids possess excellent catalytic performance on the electro-redox of H2O2 generating more O2·- and obtaining optimal ECL intensity of the luminol/H2O2 system. Under the appropriate experimental conditions, the quantitative detection range of CYFRA 21-1 was from 0.1 pg mL-1 to 100 ng mL-1, and the limit of detection (LOD) was 0.046 pg mL-1. The present sensor has a lower LOD with a wider linear range, which provides a new analytical assay for the early diagnosis of small-cell-type lung cancer labels.

Cathodic electrochemiluminescence of L012 and its application in antioxidant detection.

Cathodic electrochemiluminescence (ECL) of a luminol (or its analogues)-dissolved oxygen (O2) system is an ideal alternative to ECL of the traditional luminol-hydrogen peroxide (H2O2) system, which can efficiently avoid the self-decomposition of H2O2 at room temperature. However, the mechanism for the generation of cathodic ECL by the luminol (or its analogues)-O2 system is still ambiguous. Herein, we report the study of cathodic ECL generation by the L012-O2 system at a glassy carbon electrode (GCE). The types of reactive oxygen species (ROS) involved generated during ECL reactions were verified. A possible reaction mechanism for the system was proposed and the rate constants of related reactions were estimated. Furthermore, several intermediates of L012 involved in the proposed pathways were validated by electrochemistry-coupled mass spectrometry. Finally, the cathodic ECL system was successfully used for measuring the antioxidant capacity of commercial juice with Trolox as a standard.

Photocatalytic Aptamer Chemiluminescent System for a Homogeneous, Reliable, Label-Free, Generic Assay of Small Molecules.

Chemiluminescence is a powerful analytical technique with many advantages, while aptamers are well-known as good molecular recognition units. However, many aptamer-based chemiluminescence assays employed interface sensing, which often needed several immobilization, separation, and washing steps. To minimize the risks of contamination and false-positive, we for the first time proposed a photocatalytic aptamer chemiluminescent system for a homogeneous, label-free, generic assay of small molecules. After binding to a DNA aptamer, thioflavin T has a unique photocatalytic oxidase activity to activate the system's luminol chemiluminescence. Then, the specific binding between the aptamer and target molecules will compete with the above process. Therefore, we can realize the efficient assay of different analytes including estradiol and adenosine. Such a homogeneous chemiluminescent system allowed a direct assay of small molecules with limits of detection in a nM level. Several control tests were carried out to avoid possible false-positive results, which were originated from the interactions between analytes and sensing interfaces previously. This homogeneous chemiluminescent system provides a useful strategy to reliably assay various analytes in the pharmacy or biology field.

Ti3C2 MXene-based nanozyme as coreaction accelerator for enhancing electrochemiluminescence of glucose biosensing.

Delamination of the exfoliated multilayer MXenes with electro-catalysts, not only leads to increasing surface area for high electrochemiluminescent (ECL) signal tracer loading but also provides highly sensitive achievements in a coreaction accelerator manner. To this end, herein, we used bromophenol blue (BPB)-delaminated multilayer Ti3C2 MXene as both a coreaction accelerator to promote the electrochemiluminescent (ECL) reaction rate of luminol (LUM) and the co-reactant H2O2 and a substrate for retaining high loading of glucose oxidase (GOx)-conjugated polyethylene imine (PEI) along with luminophore species into more open structure of Ti3C2 MXene for sensitive detection of glucose. In the presence of glucose, in situ generating H2O2 product through a GOx-catalyzed process could produce abundant •OH radicals via the peroxidase-like activity of the BPB@Ti3C2 in the LUM ECL reaction. Moreover, decreasing the distance between the high-content LUM into the BPB@Ti3C2 and the generated •OH, minimizes the decomposition of highly active •OH, providing a superb ECL signal. Last, the proximity of incorporated GOx into the delaminated Ti3C2 MXene near the electrode allows efficient electron transfer between the electrode and enzyme. The integration of such amplifying effects endowed high sensitivity and excellent selectivity for glucose with a low limit of detection of 0.02 µM in the wide range of 0.01 µM-40,000 µM, enabling the feasibility of the glucose analysis in human serum samples. Overall, the enhanced ECL based on the BPB@Ti3C2 opens a new horizon to develop highly sensitive MXene-based ECL toward the field of biosensors.

Shared hairpin structure electrochemiluminescence biosensor based on Au@Ni-Co metal organic frameworks for simultaneous detection of Pb(II) and S.aureus.

The excessive content of lead (Pb(II)) and Staphylococcus aureus (S.aureus) seriously harms the quality of aquatic products. In this paper, a highly sensitive electrochemiluminescence (ECL) biosensor was constructed using the synergistic effect of Au NPs@Nickel-Cobalt-Metal-organic frameworks (Au@Ni-Co-MOFs) and double potential resolution function of urchin-like Au@luminol and Cadmium sulfide quantum dots (CdS QDs) for synchronous detection of Pb(II) and S.aureus in aquatic products. Au@Ni-Co-MOFs as the base material, its cube structure can improve the surface active area and sensitivity of the sensor, providing more catalytic active sites for the two functional probes. Urchin-like Au@luminol binding aptamer DNA2 specifically recognizes Pb(II), CdS QDs binding aptamer DNA3 specifically recognizes S.aureus, which collaboratively catalyzed hydrogen peroxide reduction to produce two electrochemiluminescence signals. The shared hairpin structure DNA1 binds stably to Au@Ni-Co-MOFs via the Au-S bond, and the two functional probes are complementary paired with the DNA1 respectively to ensure the specificity of the aptamer. According to the ECL intensity changes of different potentials signal sources, the synchronous detection of Pb(II) and S.aureus with different concentrations is realized. The sensor realizes the detection of two targets in aquatic products and provides a new strategy for the simultaneous detection of multiple targets.

Novel electrochemiluminescence aptasensor based on AuNPs-ABEI encapsulated TiO2 nanorod for the detection of acetamiprid residues in vegetables.

Gold nanoparticles (AuNPs)@N-(4-aminobutyl)-N-ethylisoluminol (ABEI)@Titanium dioxide nanorods (TiO2NRs) were used as sensing materials to produce a unique encapsulated nanostructure aptasensor for the detection of acetamiprid residues in this work. ABEI, an analog of luminol, was extensively used as an electrochemiluminescence (ECL) reagent. The ECL mechanism of ABEI- hydrogen peroxide (H2O2) system had connections to a number of oxygen-centered free radicals. TiO2NRs improved ECL response with high electron transfer and a specific surface area. AuNPs were easy to biolabel and could catalyze H2O2 to enhance ECL signal. AuNPs were wrapped around TiO2NRs by utilizing the reduction property of ABEI to form wrapped modified nanomaterials. The sulfhydryl-modified aptamer bound to the nanomaterial by forming gold-sulfur (Au-S) bonds. The aptamer selectively bound to its target with the addition of acetamiprid, which caused a considerable decrease in ECL intensity and enabled quantitative detection of acetamiprid. The aptasensor showed good stability, repeatability and specificity with a broad detection range (1×10-2-1×103 nM) and a lower limit of detection (3 pM) for acetamiprid residues in vegetables. Overall, this aptasensor presents a simple and highly sensitive method for ECL detecting acetamiprid, with potential applications in vegetable safety monitoring.

Boosting Photon Emission from the Chemiluminescence of Luminol Based on Host-Guest Recognition for the Determination of Dopamine.

Modulating the photon emission of the luminophore for boosting chemiluminescence (CL) response is very crucial for the construction of highly sensitive sensors via the introduction of functionalized materials. Herein, the integration of the emitter and coreactant accelerator into one entity is realized by simply assembling cucurbit[7]uril (CB[7]) on the surface of gold nanoparticles (AuNPs) through simple assembly via a Au-O bond. The loaded CB[7] on the AuNPs improves their catalytic capacity for the generation of hydroxyl radicals(•OH). Moreover, the host-guest recognition interaction between luminol and CB[7] enables the capture of luminol on AuNPs efficiently. Also, the intramolecular electron-transfer reaction between the luminol and •OH enables the CL response more effectively in the entity, which greatly boosts photon emission ca 100 folds compared with the individual luminol/H2O2. The host-guest recognition between luminol and CB[7] is revealed by Fourier transform infrared spectroscopy, electrochemical, and thermogravimetric characterization. Moreover, the proposed CL system is successfully used for the sensitive and selective determination of dopamine (DA) based on a synergistic quenching mechanism including the competition quenching and radical-scavenging effect from DA. The present amplified strategy by integrating recognized and amplified elements within one entity simplifies the sensing process and holds great potential for sensitive analysis based on the self-enhanced strategies.

Proximity-Enhanced Electrochemiluminescence Sensing Platform for Effective Capturing of Exosomes and Probing Internal MicroRNAs Involved in Cancer Cell Apoptosis.

Exosomal microRNAs (miRNAs) play critical regulatory roles in many cellular processes, and so how to probe them has attracted increasing interest. Here we propose an aptamer-functionalized dimeric framework nucleic acid (FNA) nanoplatform for effective capture of exosomes and directly probing internal miRNAs with electrochemiluminescence (ECL) detection, not requiring RNA extraction in conventional counterparts. A CD63 protein-binding aptamer is tethered to one of the FNA structures, allowing exosomes to be immobilized there and release internal miRNAs after lysis. The target miRNA induces the formation of a Y-shaped junction on another FNA structure in a close proximity state, which benefits the loading of covalently hemin-modified spherical nucleic acid enzymes for enhanced ECL readout in the luminol-H2O2 system. In this facile way, the ultrasensitive detection of exosomal miR-21 from cancer cells is accomplished and then used for cell apoptosis analysis, indicating that the oncogene miR-21 negatively participates in the regulation of the apoptotic process; namely, downregulating the miR-21 level is unbeneficial for cancer cell growth.

Preparation of Co dual atomic site catalysts loaded on defect-engineered MOFs material with superb chemiluminescent enhancement effect for sensitive detection of bacteria.

BACKGROUND: Dual atomic site catalysts (DASCs) have aroused extensive interest in analytical chemistry on account of the superb catalytic activity caused by the highly-exposed active centers and synergistic effect of adjacent active centers. The reported protocols for preparing DASCs usually involve harsh conditions such as acid/base etching and high-temperature calcination, leading to unfavorable water dispersity and restricted application. It is crucial to develop DASCs with satisfactory water dispersity, improved stability, and mild preparation procedures to facilitate their application as signal probes in analytical chemistry. RESULTS: Formic acid was adopted as a modulator for preparing MOF-808 with abundant defective sites, which was used as the carrier for implanting Co atoms. Co DASCs with a special coordination structure of Co2-O10 and a high loading efficiency of 11.1 wt% were prepared with a mild solvothermal protocol. The resultant Co DASCs can significantly accelerate decay of H2O2 for forming numerous reactive oxygen radicals and boost chemiluminescent (CL) signal. Co DASCs at 1.0 µg mL-1 can enhance the CL signal of luminol-H2O2 system by about 5800 times. Thanks to their satisfactory water dispersity and excellent CL enhancement performance, they were used as ultra-sensitive CL signal probes for monitoring methicillin-resistant Staphylococcus aureus. The method shows a detection range of 102-107 CFU mL-1 and a detection limit of 47 CFU mL-1. Antibiotic susceptibility test was performed with the established CL method to prove its practicality. SIGNIFICANCE: The water dispersible Co DASCs prepared with facile and mild solvothermal protocol exhibit prominent peroxidase-like activity and can promote the production of reactive oxygen radicals for boosting CL signal. Therefore, this study paves an avenue for implanting DASCs in defect-engineered carrier to prepare signal probes suitable for development of ultra-sensitive CL analytical methods.

Surface Oxygen Vacancy-Rich Co3O4 Nanowires as an Effective Catalyst of Luminol-H2O2 Chemiluminescence for Sensitive Immunoassay.

Oxygen vacancy is one intrinsic defect in metal oxide materials. Interestingly, we herein found that the surface oxygen vacancy can significantly enhance the catalytic activity of Co3O4 nanowires in the luminol-H2O2 chemiluminescence (CL) reaction. 0.1 ng/mL Co3O4 nanowires containing 51.3% surface oxygen vacancies possessed ca. 2.5-fold catalytic activity of free Co2+ (the best metal ionic catalyst for the luminol-H2O2 CL reaction). The superior catalytic efficiency is attributed to the enhanced adsorption of H2O2 by surface oxygen vacancies, which in turn accelerates the cleavage of O-O bonds and generates •OH radicals. More importantly, the surface oxygen vacancy-rich Co3O4 nanowires retained about 90% catalytic activity after modification with antibodies. The surface oxygen vacancy-rich Co3O4 nanowires were used to label the secondary antibody, and one sandwich-type CL immunoassay of carcinoembryonic antigen was established. The detection limit was 0.3 ng/mL with a linear range of 1-10 ng/mL. This proof-of-concept work proves that surface oxygen vacancy-rich Co3O4 nanowires are suitable for labeling biomolecules in CL bioanalysis and biosensing.

Nanozyme-Based Biofuel Cell Ingeniously Coupled with Luminol Chemiluminescence System through In Situ Co-Reactant Generation for Dual-Signal Biosensing.

Classical luminol-based chemiluminescence (CL) is the process of emitting light enhanced by the addition of coreactant hydrogen peroxide (H2O2). To address the instability issue of H2O2 decomposition, herein, we proposed a nanozyme-based biofuel cell (BFC) ingeniously coupled with a luminol CL system via in situ generation of H2O2. Specifically, the gold nanoparticle (AuNP) nanozyme with glucose oxidase-like activity can act as the anodic enzyme of BFC to catalyze the oxidation of glucose to produce H2O2 and electrons. In this case, H2O2 as a coreactant enhanced the CL intensity and the cathode of the BFC obtained electrons to generate the open circuit voltage (EOCV) signals. As a result, a dual-signal biosensing platform was successfully constructed. Interestingly, the AuNPs-catalyzed system operates in an alkaline medium, which precisely meets the pH requirement for luminol luminescence. Such a BFC-CL system not only greatly lessens the effect of unstable exogenous H2O2 on the signal stability but also enhances the CL of luminol. Furthermore, both CL and EOCV signals present a positive correlation with the glucose concentration. Therefore, this novel BFC-CL system shows good performance for dual-signal biosensing, which would serve as a valuable guideline for the design and application of BFC-based self-powered or CL biosensors.

Remarkably Enhanced Luminol/H2O2 Chemiluminescence with Excellent Peroxidase-like Activity of FeCoNi-based Metal-Organic Xerogels for the Sensitive Detection of Dopamine.

Metal-organic gels (MOGs) are a category of metal-organic smart soft materials with large specific surface areas, loose porous structures, and open metal active sites. In this work, trimetallic Fe(III)Co(II)Ni(II)-based MOGs (FeCoNi-MOGs) were synthesized at room temperature via a simple and mild one-step procedure. Fe3+, Co2+, and Ni2+ were the three central metal ions in it, while 1,3,5-benzenetricarboxylic acid (H3BTC) served as the ligand. The solvent enclosed in it was then removed by freeze-drying to get the corresponding metal-organic xerogels (MOXs). The as-prepared FeCoNi-MOXs have excellent peroxidase-like activity and can significantly enhance luminol/H2O2 chemiluminescence (CL) by more than 3000 times, which is very effective compared with other reported MOXs. Based on the inhibitory effect of dopamine on the CL of the FeCoNi-MOXs/luminol/H2O2 system, a simple, rapid, sensitive, and selective CL method for dopamine detection was established with a linear range of 5-1000 nM and a limit of detection of 2.9 nM (LOD, S/N = 3). Furthermore, it has been effectively used for the quantitative measurement of dopamine in dopamine injections and human serum samples, with a recovery rate of 99.5-109.1%. This research brings up prospects for the application of MOXs with peroxidase-like activity in CL.

Smartphone-Based Chemiluminescence Glucose Biosensor Employing a Peroxidase-Mimicking, Guanosine-Based Self-Assembled Hydrogel.

Chemiluminescence is widely used for hydrogen peroxide detection, mainly exploiting the highly sensitive peroxidase-luminol-H2O2 system. Hydrogen peroxide plays an important role in several physiological and pathological processes and is produced by oxidases, thus providing a straightforward way to quantify these enzymes and their substrates. Recently, biomolecular self-assembled materials obtained by guanosine and its derivatives and displaying peroxidase enzyme-like catalytic activity have received great interest for hydrogen peroxide biosensing. These soft materials are highly biocompatible and can incorporate foreign substances while preserving a benign environment for biosensing events. In this work, a self-assembled guanosine-derived hydrogel containing a chemiluminescent reagent (luminol) and a catalytic cofactor (hemin) was used as a H2O2-responsive material displaying peroxidase-like activity. Once loaded with glucose oxidase, the hydrogel provided increased enzyme stability and catalytic activity even in alkaline and oxidizing conditions. By exploiting 3D printing technology, a smartphone-based portable chemiluminescence biosensor for glucose was developed. The biosensor allowed the accurate measurement of glucose in serum, including both hypo- and hyperglycemic samples, with a limit of detection of 120 µmol L-1. This approach could be applied for other oxidases, thus enabling the development of bioassays to quantify biomarkers of clinical interest at the point of care.

Co-amplification of luminol-based electrochemiluminescence immunosensors based on multiple enzyme catalysis of bimetallic oxides CoCeOx and NiMnO3 for the detection of CYFRA21-1.

The accelerated energy supply of co-reactants is an extremely effective strategy for achieving highly sensitive electrochemiluminescence analysis, and binary metal oxides would be an excellent tool for this purpose owing to the nano-enzyme acceleration of mixed metal valence states. Herein, an electrochemiluminescent (ECL) immunosensor for monitoring the concentration of cytokeratin 19 fragment antigen 21-1 (CYFRA21-1) was developed based on a co-amplification strategy triggered by two bimetallic oxides, CoCeOx and NiMnO3, with luminol as the luminophore. CoCeOx derived from an MOF exhibits a large specific surface area and excellent loading capacity as a sensing substrate, and the peroxidase properties enable the catalysis of hydrogen peroxide to provide energy supply to the underlying radicals. The dual enzymatic properties of flower-like NiMnO3 were employed as probe carriers for luminol enrichment. The peroxidase properties built on Ni2+/Ni3+ and Mn3+/Mn4+ binary redox pairs resulted in the integration of highly oxidative hydroxyl radicals, and the oxidase properties provided additional superoxide radicals via dissolved oxygen. The practically proven multi-enzyme-catalyzed sandwich-type ECL sensor easily accomplished an accurate immunoassay of CYFRA21-1, harvesting a detection limit of 0.3 pg mL-1 in the linear range of 0.001-150 ng mL-1. In conclusion, this work explores the cyclic catalytic amplification of mixed-valence binary metal oxides with nano-enzyme activity in the field of ECL and develops an effective pathway for ECL immunoassay.

Enhanced Chemiluminescence under the Nanoconfinement of Covalent-Organic Frameworks and Its Application in Sensitive Detection of Cancer Biomarkers.

Chemiluminescence (CL) with intensive emission has been pursued for decades. It is still challenging to find a new mechanism to enhance CL. In this work, confinement-enhanced CL was developed for the first time by the coembedding of N-(aminobutyl)-N-(ethylisoluminol) (ABEI) and Co2+ into gold nanoparticle-modified covalent-organic frameworks (COFs). For the consideration of improving the hydrophilicity of COFs and facilitating subsequent biological modification, gold nanoparticles were first reduced on the COF surface (Au-COF) in situ without other reducing reagents. By virtue of the abundant imine bond and π backbones, ABEI and Co2+ were embedded in Au-COF synergistically through π-π stacking and coordination. The confinement of ABEI and Co2+ into Au-COF brought an over 20-fold enhancement of CL intensity compared to that of adding them to a liquid phase, which benefitted from the three aspects of the confinement effect, including the molecular enrichment effect, the physical constraint effect, and the molecular preorganization effect. As proof of concept, a lipid-protein dual-recognition sandwich strategy based on this CL-functionalized COF was developed for the detection of breast cancer cell line-derived extracellular vesicles (EVs) with four orders of magnitude improvement in the detection limit compared to ELISA. The successful distinction of human epidermal growth factor receptor 2 (HER2)-positive patients from HER2-negative patients indicated the great application potential of the proposed bioassay in HER2-positive breast cancer diagnosis. This work proposed a novel enhancement mechanism for CL based on crystalline porous materials, which provides a new perspective for the development of CL-functionalized materials for biosensors and bioassays.

Preparation of oxidized acetylene black by high-temperature calcination for luminol efficient cathodic electrochemiluminescence.

The improvement of electrochemiluminescence (ECL) intensity in luminol, a classic electrochemiluminescent material, remains a controversial topic. In this study, synthesis of acetylene black oxide (ACETO) through simple air annealing was successful in introducing oxygen-containing groups and defects, which can act as active sites for the oxygen reduction reaction (ORR) and exhibit excellent catalytic activity. By introducing the two-electron (2e-) ORR into the cathode ECL system of luminol, integration of ACETO and luminol allows for in situ generation of dissolved oxygen into reactive oxygen species (ROS), thereby enhancing the ECL intensity of luminol. It is worth noting that iron-nitrogen-carbon (FeNC), as a secondary antibody (Ab2) label, can catalyze the decomposition of H2O2, the product of 2e- ORR, into ROS to achieve ECL amplification. Alpha-fetoprotein (AFP), an important tumor marker, was successfully detected with a detection limit of 0.01 pg/mL, indicating that this ECL signal amplification strategy has broad application prospects in biological analysis.

Chiral-Controlled Cyclic Chemiluminescence Reactions for the Analysis of Enantiomer Amino Acids.

The similarity and complexity of chiral amino acids (AAs) in complex samples remain a significant challenge in their analysis. In this work, the chiral metal-organic framework (MOF)-controlled cyclic chemiluminescence (CCL) reaction is developed and utilized in the analysis of enantiomer AAs. The chiral MOF of d-Co0.75Zn0.25-MOF-74 is designed and prepared by modifying the Co0.75Zn0.25-MOF-74 with d-tartaric acid. The developed chiral bimetallic MOF can not only offer the chiral recognize sites but also act as the catalyst in the cyclic luminol-H2O2 reaction. Moreover, a distinguishable CCL signal can be obtained on enantiomer AAs via the luminol-H2O2 reaction with the control of d-Co0.75Zn0.25-MOF-74. The amplified difference of enantiomer AAs can be quantified by the decay coefficient (k-values) which are calculated from the exponential decay fitting of their obtained CCL signals. According to simulation results, the selective recognition of 19 pairs of AAs is controlled by the pore size of the MOF-74 and their hydrogen-bond interaction with d-tartaric acid on the chiral MOF. Furthermore, the k-values can also be used to estimate the change of chiral AAs in complex samples. Consequently, this chiral MOF-controlled CCL reaction is applied to differentiate enantiomer AAs involved in the quality monitoring of dairy products and auxiliary diagnosis, which provides a new approach for chiral studies and their potential applications.

Highly Stable Fe/Co-TPY-MIL-88(NH2) Metal-Organic Framework (MOF) in Enzymatic Cascade Reactions for Chemiluminescence-Based Detection of Extracellular Vesicles.

Metal-Organic Frameworks (MOFs) can deliver many advantages when acting as enzyme mimics to assist with signal amplification in molecular detection: they have abundant active catalytic sites per unit volume of the material; their structures and elemental compositions are highly tunable, and their high specific surface area and porous property can assist with target separation and enrichment. In the present work, we have demonstrated that, by adding the pore partition agent, 2,4,6-tris(4-pyridyl)pyridine (TPY) during synthesis of the bimetallic Fe/Co-MIL-88(NH2) MOF to block the open metal sites, a highly porous MOF of Fe/Co-TPY-MIL-88(NH2) can be produced. This material also exhibits high stability in basic solutions and biofluids and possesses high peroxidase-mimicking activity, which can be utilized to produce long-lasting chemiluminescence (CL) from luminol and H2O2. Moreover, acting as the peroxidase-mimic, the Fe/Co-TPY-MIL-88(NH2) MOF can form the enzymatic cascade with glucose oxidase (GOx) for biomarker detection. When applied to detect extracellular vesicles (EVs), the MOF material and GOx are brought to the proximity on the EVs through two surface proteins, which triggers the enzyme cascade to produce high CL from glucose and luminol. EVs within the concentration range of 5 × 105 to 4 × 107 particles/mL can be detected with an LOD of 1 × 105 particles/mL, and the method can be used to analyze EV contents in human serum without sample preparation and EV purification. Overall, our work demonstrates that the high versatility and tunability of the MOF structures could bring in significant benefits to biosensing and enable ultrasensitive detection of biomarkers with judicious material designs.

Sensitive Detection of Nitrite and Nitrate in Seawater by 222 nm UV-Irradiated Photochemical Conversion to Peroxynitrite and Ion Chromatography-Luminol Chemiluminescence System.

Sensitive detection methods for nitrite (NO2-) and nitrate (NO3-) ions are essential to understand the nitrogen cycle and for environmental protection and public health. Herein, we report a detection method that combines ion-chromatographic separation of NO2- and NO3-, on-line photochemical conversion of these ions to peroxynitrite (ONOO-) by irradiation with a 222 nm excimer lamp, and chemiluminescence from the reaction between luminol and ONOO-. The detection limits for NO2- and NO3- were 0.01 and 0.03 µM, respectively, with linear ranges of 0.010-2.0 and 0.10-3.0 µM, respectively, at an injection volume of 1 µL. The results obtained by the proposed method for seawater analysis corresponded with those of a reference method (AutoAnalyzer based on the Griess reaction). As luminol chemiluminescence can measure ONOO- at picomolar concentrations, our method is expected to be able to detect NO2- and NO3- at picomolar concentrations owing to the high conversion ratio to ONOO- (>60%), assuming that contamination and background chemiluminescence issues can be resolved. This method has the potential to emerge as an innovative technology for NO2- and NO3- detection in various samples.