Interfacial charge transfer in sheet Ni2P-FePx heterojunction to promote the study of electrocatalytic oxygen evolution.

The substantial expense associated with catalysts significantly hampers the progress of electrolytic water-based hydrogen production technology. There is an urgent need to find non-precious metal catalysts that are both cost-effective and highly efficient. Here, the porous Ni2P-FePx nanomaterials were successfully prepared by hydrothermal method, nickel foam as the base, iron nitrate solution as the caustic agent and iron source, and finally phosphating at low temperature. The obtained porous Ni2P-FePx nanosheets showed excellent catalytic activity under alkaline PH = 14, and an overpotential of merely 241 mV was required to achieve a current density of 50 mA cm-2. The morphology of the nanosheet can still be flawlessly presented on the screen after 50 h of working at high current density.

MOF-Enhanced Chiral ECL Recognition System: Dual-Function in Phenylalanine Enantiomer Detection and Coreaction Acceleration.

The accurate discernment and separation of chiral isomers with high precision remain a significant challenge in various industries and biological fields. In this investigation, an electrochemiluminescent (ECL) chiral recognition platform was devised to ascertain the presence of phenylalanine (Phe). Notably, a homochiral [Ni2(l-asp)2(bipy)] (Ni-LAB) was established as a dual-function coreactant accelerator and chiral recognition substrate. Ni-LAB facilitates the reaction between the coreactant (K2S2O8) and the luminescent entity 3,4,9,10-perylenetetracar-boxylic-l-cysteine (PTCA-cys), thereby enhancing the ECL luminescence efficiency and improving the sensitivity of the chiral sensor. The chiral recognition potential of Ni-LAB was assessed to differentiate between Phe chiral isomers, and the underlying mechanism was comprehensively elucidated. This system exhibited remarkable proficiency in detecting Phe enantiomers and precisely differentiating a single Phe enantiomer within a mixture, showcasing exceptional levels of selectivity, stability, and reproducibility. This study paves the way for the development of advanced chiral recognition systems, potentially revolutionizing the field of chiral sensing and discrimination.

Supramolecular Anchored Copper Nanoclusters for a Multipath Electrochemiluminescence Probe.

Copper nanoclusters (Cu NCs) are highly promising nanomaterials in the field of electrochemiluminescence (ECL). Nevertheless, their limited stability and efficiency have impeded their practical applications. Here, we introduced a novel supramolecular anchoring strategy resulting in the creation of exceptionally stable Cu NCs (CET-Cu NCs) with remarkable ECL properties. Specifically, CET-Cu NCs exhibited a relative ECL efficiency (ΦECL) of 62% based on the annihilation ECL efficiency of [Ru(bpy)3]2+ (100%), with tripropylamine employed as a coreactant. Moreover, CET-Cu NCs can generate ECL emission through multiple different paths, which enables them to serve as signal probes in a wider range of testing scenarios, thereby enhancing the reliability and robustness of sensing and analytical systems. To demonstrate the practical utility, CET-Cu NCs were selected as an ECL signal probe for a sensing platform that facilitated ultrasensitive detection of progesterone via oriented immobilization technology and antibody/aptamer sandwich assays. This study surmounted the barriers to the practical application of Cu NCs through the implementation of a supramolecular anchoring strategy, thereby providing enhanced utility of Cu NCs in ECL sensing and analysis.

An amorphous Ni-Fe catalyst for electrocatalytic dehydrogenation of alcohols to value-added chemicals.

As for the hydrogen production process via electrocatalytic water splitting, the green and sustainable electro-oxidation of organic molecules at the anode is thermodynamically more favourable than the oxygen evolution reaction (OER). Here, we proposed for the first time to replace the OER process by the oxidation of N-Boc-4-piperidine methanol (BPM), via a parallel reaction, which finally leads to the green production of N-Boc-4-piperidine carboxaldehyde (BPC). The amorphous NiFeO(OH) nanospheres with rich valence states were adopted as the anode catalyst, with creation of more active sites. The gas chromatography results showed that nearly all the BPM converted to BPC after 15 h reaction. The electrochemical tests showed that the Faraday efficiency (FE) approaches nearly 100% when the charge transfer is approximately equal to the theoretical charge. This work reports a new process for the alcohol oxidation, providing a valuable green organic synthesis process.

Chiral Discrimination of Penicillamine Enantiomers: The Role of Aggregation-Caused Quenching in Achieving High Selectivity.

The recognition and separation of chiral isomers are of great importance in both industrial and biological applications. In this study, a chiral recognition system based on electrochemiluminescence was established for the detection of penicillamine (PA) enantiomers. The system utilized a homochiral [Zn2(BDC)(d-lac)] (Zn-BL) platform for the uniform distribution of Ru(bpy)32+ nanoparticles, effectively mitigating aggregation-caused quenching. The chiral recognition ability of Zn-BL was tested to distinguish between PA enantiomers, and the results indicated a substantial increase in the chiral electrochemiluminescence (ECL) signal when l-PA was present, in contrast to d-PA. The mechanism underlying ECL chiral discrimination was investigated using water contact angle measurements, DFT calculations, and electrochemical characterization. The system exhibited high selectivity, stability, and reproducibility for PA enantiomer detection. Furthermore, the proposed method can accurately identify one enantiomer of PA in a mixture. This study provides a reliable and sensitive approach for achieving the highly selective detection of chiral molecules.

Controlled Growth of MoS2 on Dendritic Ferric Oxide to Enhance Electrochemiluminescence of Nitrogen-Doped Carbon Quantum Dots for Sensitive Immunoassay.

The essential expansion of electrochemiluminescence (ECL) technology into clinical detection relies on sensitive and stable signal and maintenance of the activity of the immune molecules during the analysis. This poses a critical challenge for an ECL biosensor as a luminophore in general requires high potential excitation resulting in a strong ECL signal; nevertheless, it has an irreversible effect on the activity of the antigen or antibody. Herein, a novel electrochemiluminescence (ECL) biosensor utilizing nitrogen-doped carbon quantum dots (N-CQDs) as emitters and molybdenum sulfide/ferric oxide (MoS2@Fe2O3) nanocomposites as a coreaction accelerator was developed for detection of neuron-specific enolase (NSE), a biomarker of small cell lung cancer. The doping of nitrogen allows the CQDs to exhibit ECL signals with low excitation potential, with a more viable activity possible for immune molecules. MoS2@Fe2O3 nanocomposites exhibit superior coreaction acceleration characteristics in hydrogen peroxide than any single component of them, and the highly branched dendrite microstructure provides a large number of binding sites for immune molecular, which is an inevitable factor for trace detection. In addition, ion beam sputtering gold particle technology is introduced into the sensor fabrication via an Au-N bond, which will provide sufficient density orientation for capturing the antibody load via the Au-N bonds. With excellent repeatability, stability, and specificity, the as-purposed sensing platform showed differentiated ECL responses of NSE range from 10.00 fg/mL to 500 ng/mL, and the limit of detection (LOD) was calculated of 6.30 fg/mL (S/N = 3). The proposed biosensor is prospective to provide a new avenue for the analysis of NSE or other biomarkers.

Ultrasensitive Electrochemiluminescence Biosensor with Silver Nanoclusters as a Novel Signal Probe and α-Fe2O3-Pt as an Efficient Co-reaction Accelerator for Procalcitonin Immunoassay.

Herein, a high-efficiency biosensor based on ternary electrochemiluminescence (ECL) system was constructed for procalcitonin (PCT) detection. Specifically, silver nanoclusters (Ag NCs) with stable luminescence properties were prepared with small-molecule lipoic acid (LA) as the ligand, and its ECL emission in persulfate (S2O82-) was first reported. Meanwhile, the prepared Ag NCs possessed ligand-to-metal charge-transfer characteristics, thus transferring energy from LA to Ag+ for luminescence. Based on the small particle size, good biocompatibility, and molecular binding ability, Ag NCs-LA was used as an ideal luminescent probe. In addition, α-Fe2O3-Pt was introduced to facilitate the activation of S2O82-, thereby generating more sulfate radicals to react with the free radicals of Ag NCs to enhance ECL emission. The synergistic effect of the variable valence state of transition metals and high catalytic activity of noble metals endows α-Fe2O3-Pt with excellent catalytic ability for S2O82-. Importantly, the sensing mechanism was systematically demonstrated by UV-vis, fluorescence, and ECL analysis, as well as density functional theory calculations. At last, NKFRGKYKC was designed for specific immobilization of antibodies, thus releasing the antigen binding sites to improve the antigen recognition efficiency. Based on this, the developed biosensor showed high sensitivity for PCT detection, with a wide linear range (10 fg/mL-100 ng/mL) and a low detection limit (3.56 fg/mL), which could be extended to clinical detection of multiple biomarkers.

Simultaneous electrochemical recognition of tryptophan and penicillamine enantiomers based on MOF-modified ß-CD.

Chiral recognition is of significant importance in the fields of chemical asymmetric synthesis and biological pharmaceutical research. In this work, an electrochemical chiral sensor with two kinds of chiral sites (chiral cavity for ß-cyclodextrin and chiral skeleton for Ca-sacc/MeOH) by electrooxidation ß-cyclodextrin onto Ca-sacc/MeOH was built. The proposed multichiral ß-CD@Ca-sacc/MeOH/GCE can be used for recognition of tryptophan and penicillamine enantiomers simultaneously with wide linear range, low detection limits value, high repeatability and stability within the available electrochemical window. The strategy for integration multichiral sources is crucial to construct novel chiral platforms for simultaneous recognition of multiple chiral compounds in complicated chiral systems.

Hollow Double-Shell CuCo2O4@Cu2O Heterostructures as a Highly Efficient Coreaction Accelerator for Amplifying NIR Electrochemiluminescence of Gold Nanoclusters in Immunoassay.

The evolution of electrochemiluminescence (ECL) emission amplified by coreaction accelerator in near-infrared (NIR) area has been overwhelmingly anticipated for ultrasensitive detection of disease biomarkers. Herein, the hollow double-shell CuCo2O4@Cu2O (HDS-CuCo2O4@Cu2O) heterostructures were conveniently prepared and utilized as an attractive coreaction accelerator to improve the NIR ECL performance of gold nanoclusters (AuNCs) for the first time. Benefiting from perfect-matched lattice spacing, unique Cu2O nanoparticles (NPs) were formed in situ on the layered-hollow CuCo2O4 nanospheres (NSs) to obtain HDS-CuCo2O4@Cu2O heterostructures. The formed heterojunctions supplied shorter charge transfer distance and better interfacial charge transfer efficiency as well as more effective separation performance. Consequently, HDS-CuCo2O4@Cu2O heterostructures as an admirable electroactive substrate could significantly promote the formation of sufficient coreactant intermediate radicals to react with AuNCs cationic radicals, realizing about 3-folds stronger NIR ECL response than that of individual AuNCs. In addition, the AuNCs templated by l-methionine (l-Met) exhibited NIR ECL emission around 830 nm, which could decrease the photochemical damage to even realize a nondestructive detection with improved susceptibility and circumambient adaptability. Subsequently, a well site-oriented fixation strategy utilizing HWRGWVC heptapeptide as the specific antibody immobilizer was introduced to further preserve the bioactivity of antibody on the HDS-CuCo2O4@Cu2O and AuNCs surface along with enhancing the incubation performance markedly. In view of the progressive sensing mechanism, a NIR immunosensor was obtained for the ultrasensitive analysis of CYFRA21-1, which achieved a broad linear ranging from 2 fg/mL to 50 ng/mL and a low limit of detection (LOD) of 0.67 fg/mL (S/N = 3).

Chromium doping: A new approach to regulate electronic structure of cobalt carbonate hydroxide for oxygen evolution improvement.

Highly efficient catalysts are required to solve the intrinsically sluggish kinetics of oxygen evolution reaction (OER). Herein, chromium doped cobalt carbonate hydroxide nanowire array on Ni foam (Cr-CoCH/NF) has been synthesized for the enhancement of OER activity and stability. Compared with pure CoCH/NF, Cr0.2-CoCH/NF, the optimal doping of Cr, shows a low overpotential of 203 mV at the current density of 10 mA cm-2 and a small Tafel slope of 84 mV dec-1 in 1.0 M NaOH. In addition, there is little deterioration in electrocatalytic performance after 1000-cycle cyclic voltammetry and the high activity can be maintained over 25 h. Density functional theory calculations reveal the Cr doping can regulate the electronic structure of nearby Co active center to achieve great enhancement of OER activity.

Facile Encapsulation of Iridium(III) Complexes in Apoferritin Nanocages as Promising Electrochemiluminescence Nanodots for Immunoassays.

A class of water-soluble electrochemiluminescence (ECL) nanodots were prepared by encapsulating ECL-active iridium complexes into biocompatible horse spleen apoferritin (apoHSF) nanocages for immunoassays. The preparation feasibility was achieved based on the pH-induced disassembly/reassembly nature originated from apoHSF. Two iridium nanodots (1 and 2) with high ECL efficiency were separately prepared by directing the self-assembly of two water-insoluble luminescent complexes, Ir(ppy)3 (ppy = 2-phenylpyridine) and Ir(ppy)2(acac) (ppy = 2-phenylpyridine and acac = acetylacetonate), in the apoHSF cavity. Using tri-n-propylamine (TPrA) as a coreactant, the electrochemistry and "oxidative-reductive" ECL mechanisms for nanodots 1 and 2 were investigated, respectively. After demonstrating the spectroscopic property and relative ECL efficiency, the ECL emission of nanodots 1 and 2 quenched by TPrA• radicals at high potential was further studied and circumvented by optimizing the potential range and TPrA concentration for generating strong and stable ECL emission in aqueous media. The well-inherited biological functions of apoHSF in nanodots allow the convenient external modification of an antibody to act as a signal probe, thus a versatile ECL immunoassay paradigm was established. Acceptable results from this assay enabled the rapid and accurate detection of biomarkers in real samples. The unprecedented use of apoHSF is feasible and applicable for water-insoluble iridium complexes to fabricate a wide variety of biocompatible ECL nanodots for potential bioanalysis.

Dual-signal electrochemiluminescence immunosensor for Neuron-specific enolase detection based on "dual-potential" emitter Ru(bpy)32+ functionalized zinc-based metal-organic frameworks.

Neuron-specific enolase (NSE) is the preferred marker for monitoring small cell lung cancer and neuroblastoma. We devised a dual-signal ratiometric electrochemiluminescence (ECL) sensing strategy for sensitive detection of NSE. In this work, Ru (bpy)32+ functionalized zinc-based metal-organic framework (Ru-MOF-5) nanoflowers (NFs) with plentiful carboxyl groups provide an excellent biocompatible sensing platform for the construction of immunosensor. Importantly, Ru-MOF-5 NFs possess stable and efficient "dual-potential" ECL emission of cathode (-1.5 V) and anode (1.5 V) in the existence of co-reactant K2S2O8. Simultaneously, the cathode ECL emitter ZnO-AgNPs are employed as the secondary antibody marker, whose participation amplify the cathode ECL signal as well attenuate the anode ECL emission of Ru-MOF-5 NFs. By monitoring the ECL dual-signal of -1.5 V and 1.5 V and calculating their ratios, a ratiometric strategy of quantified readout proportional is implemented for the proposed immunosensor to precise analyze NSE. Based on optimization conditions, the ECL immunosensor displays the wide linear range of 0.0001 ng/mL to 200 ng/mL and the minimum detection limit is 0.041 pg/mL. The "dual-potential" ratiometric ECL immunosensor effectively reduces system error or background signal by self-calibration from both emissions and improves detection reliability. The dual-signal ratiometric strategy with satisfactory reproducibility and stability provides further development possibilities for other biomolecular detection and analysis.

Split-Type Electrochemical Immunoassay System Triggering Ascorbic Acid-Mediated Signal Magnification Based on a Controlled-Release Strategy.

This research put forward a novel split-type electrochemical (EC) immunosensor which integrated the controlled-release strategy with EC detection for application in the field of biosensing. Concretely, ascorbic acid (AA) was packaged in a cadmium sulfide (CdS)-capped spherical mesoporous bioactive glass (SBG) nanocarrier (SBGCdS) on account of encapsulation technology. To reduce the complexity of the bioanalysis, the detection antibody-labeled SBGCdS-AA bioconjugate was applied in a 96-well microplate for the immunoreaction process, which is independent of the EC determination procedure. Thus, the immune interference and steric hindrance caused by the accumulation of nanomaterials on the electrode could be minimized. Subsequently, AA was released efficiently via the destruction effect of dithiothreitol on the disulfide bond. In addition, for the as-prepared FcAI/l-Cys/gold nanoparticles (GNPs)/porous BiVO4 (p-BVO)/ITO EC sensing platform in the detection solution, the synergetic catalysis of Fc and GNPs/p-BVO toward the oxidation of the released AA could be realized, which triggered AA-mediated significant signal magnification throughout this study. In particular, p-BVO with an ordered nanoarray structure could accelerate the electron transfer to assist in sensitivity improvement of this system. This novel biosensor was capable of assaying the neuron-specific enolase (NSE) biomarker sensitively, from which a linear range of 0.001-100 ng/mL was derived along with a low detection limit of 1.08 pg/mL. An innovative way could be paved in the bioanalysis of NSE and other biomarkers.

Electrochemiluminescence immunosensor based on the quenching effect of CuO@GO on m-CNNS for cTnI detection.

A sandwich-type electrochemiluminescence (ECL) immunosensor based on the resonance energy transfer (RET) was proposed for ultrasensitive detection of cardiac troponin I (cTnI). The RET behavior could be generated between graphite carbon nitride nanosheets (m-CNNS) as donor and copper oxide@graphene oxide (CuO@GO) as acceptor, achieving the quenching effect of CuO@GO on m-CNNS for cTnI detection. The m-CNNS synthesized by mechanical grinding of the graphite carbon nitride (CN) not only has better dispersion and higher specific surface area, but also has high luminous efficiency and stable chemical properties. Therefore, m-CNNS was used as the matrix material and luminophore. As the acceptor, CuO@GO prepared by in-situ chemical synthesis of CuO NPs onto GO sheets also has a high specific surface area, which could be used as a label of secondary antibody (Ab2). Under optimal conditions, cTnI could be determined within the linear range of 0.1 pg mL-1 to 100 ng mL-1 and had a low detection limit (0.028 pg mL-1, S/N = 3). Meanwhile, the prepared ECL immunosensor possessed great stability, specificity and reproducibility, providing a new method for detecting cTnI and other biomarkers.

A self-powered photoanode-supported photoelectrochemical immunosensor for CYFRA 21-1 detection based on In2O3/In2S3/CdIn2S4 heterojunction.

A self-powered photoanode-supported photoelectrochemical (PEC) immunosensor was designed based on In2O3/In2S3/CdIn2S4 as photoanode and PDA@CNTs as biocathode for the detection of CYFRA 21-1. In this proposal, In2O3/In2S3/CdIn2S4 heterojunction modified indium-tin oxide (ITO) electrode was served as a substitute for platinum (Pt) counter electrode to provide an evident and stable photocurrent signal. The matched band structure of In2O3, In2S3 and CdIn2S4 as well as the unique hollow porous structure of In2O3/In2S3/CdIn2S4 played a pivotal role in accelerating the separation and transfer of photocarrier. Meanwhile, PDA@CNTs with excellent conductivity further enhanced the photocurrent which was provided by photoanode In2O3/In2S3/CdIn2S4 heterojunction. Besides, PDA could effectively capture the antibody (Ab) through Michael addition. Separating photoanode from the sensing biocathode was conducive to improve the anti-interference capability of PEC sensor because the reductive species in biologic media will change PEC properties of the photoanode interface. Under optimal conditions, the PEC immunosensor have realized the detection of CYFRA 21-1 (0.5 pg/mL - 50 ng/mL) and the detection limitation with 0.16 pg/mL. In addition, the proposed self-powered PEC sensor with acceptable selectivity, reproducibility, and stability provide a new horizon for designing PEC immunosensing platform in bioassays.

Ultrasensitive Controlled Release Aptasensor Using Thymine-Hg2+-Thymine Mismatch as a Molecular Switch for Hg2+ Detection.

An ultrasensitive controlled release system electrochemical aptasensor (CRSEA) has been developed for supersensitive determination of mercury ions (Hg2+), using gold nanoparticle-linked specific single-stranded DNA (Au NPs-ssDNA) as a molecular gate and mesoporous silica nanocontainers (MSNs) as containers. MSNs have a rich porous structure, thus entrapping the toluidine blue (TB) molecules inside. It is worth noting that Hg2+ binds to the ssDNA with multiple thymine (T) and induces the ssDNA to form a hairpin structure, which makes the separation of the Au NPs-ssDNA from the MSNs. Eventually, the stored TB molecules were released from MSNs. The electron transfer signals of TB were detected stably by a differential pulse voltammetry (DPV) detection method, which are correlated with the concentration of Hg2+. Therefore, the wide linear range (10 pM-100 µM) and low limit of detection (2.9 pM) were obtained, and the system also displayed an apparent electrochemical signal response in real sample detection and showed a promising possibility in actual monitoring.

Directly assembled electrochemical sensor by combining self-supported CoN nanoarray platform grown on carbon cloth with molecularly imprinted polymers for the detection of Tylosin.

Molecularly imprinted polymers (MIPs) based on electrochemical sensors (MIP-EC sensors) have obtained ideal achievements in recent years. However, some challenges are still need to be addressed, such as adjustable preparation, unstable sensing interface and great signal-to-noise ratio. Here, based on the ingenious combination of the MIP and the self-supported CoN nanowire arrays grown on carbon cloth (CoN NWs/CC), a robust MIP-EC sensor was developed, in which the MIP film was uniformly coated on the CoN NWs/CC via a bulk polymerization crosslinking process. Especially, CoN NWs/CC were prepared via in-situ transformation of their oxide precursors and then directly as a candidate of EC electrode. Under the optimal conditions, the MIP-EC sensor can detect Tylosin (TS) in the concentration range from 8.6 × 10-11 to 6.7 × 10-5 mol L-1, and the low detection limit (LOD) is 5.5 × 10-12 mol L-1 (S/N = 3). Furthermore, the MIP-EC sensor showed high selectivity, reproducibility and stability. The practicability of the MIP-EC sensor was tested in the actual samples of surface water and soil with the comparison of the traditional ELISA method. The developed MIP-EC sensor with simple and fabrication process can provide a versatile and reliable method, which has great potential application value for the detection of small hazardous molecules.

MOF-Based Supramolecule Helical Nanomaterials: Toward Highly Enantioselective Electrochemical Recognition of Penicillamine.

For the first time, we report the formation of a chiral MOF-based helical nanomaterial (h-HDGA@ZIF-67) through arranging zeolitic imidazolate framework (ZIF-67) nanocrystals on helical l-glutamic acid terminated bolaamphiphile (h-HDGA) via a facile process at room temperature. The self-assembly leads to the chiral function of the ZIF-67 from an achiral ligand. The h-HDGA@ZIF-67 served as a new type of electrochemical sensing interface for recognizing and quantifying Pen enantiomers that realize significant enantioselectivity, satisfactory stability, and reproducibility. The synergetic effect from ZIF-67 nanocrystals on h-HDGA and stereoselectivity of h-HDGA@ZIF-67 lead to the excellent enantioselectivity. The present strategy showed the first example of a chiral MOF-based supramolecule helical nanomaterial, presenting high enantioselectivity for electrochemical enantiomeric determination.

One-step electrodeposition of the MOF@CCQDs/NiF electrode for chiral recognition of tyrosine isomers.

Electrochemical enantiorecognition of tyrosine (Tyr) isomers using a MOF@CCQDs/NiF electrode prepared by electrodepositing a metal-organic framework (MOF) and chiral carbon quantum dots (CCQDs) on Ni foil is reported. MOF@CCQDs/NiF not only shows highly selective, sensitive and quantitative analysis towards Tyr enantiomers but also presents the ability to determine l-Tyr% in racemic mixtures. This proposed that chiral sensors could be considered for practical applications in the field of Tyr related medical recognition.

Boosting electrocatalytic nitrogen fixation via energy-efficient anodic oxidation of sodium gluconate.

Here, we report an anodic replacement of the water oxidation reaction with more readily oxidizable species to facilitate ambient electrocatalytic nitrogen reduction reaction (NRR). A self-supported catalyst, CuII-MOF on carbon cloth (JUC-1000/CC), acts as a versatile cathode and anode for both NRR and electro-oxidation of sodium gluconate to glucaric acid. Impressively, the two-electrode system requires a potential of only 0.4 V to achieve an NH3 yield rate of 24.7 µg h-1 mgcat-1, an FE of 11.90% and an SA selectivity of 96.96%, and shows strong electrochemical stability. This study reveals that the strategy avoids the sacrifice of the NH3 yield to increase FE, and offers an efficient and simultaneous electrosynthesis of NH3 and SA.