p-d Orbital Hybridization-Engineered PdSn Nanozymes for a Sensitive Immunoassay.

Nanozymes with peroxidase-like activity have been extensively studied for colorimetric biosensing. However, their catalytic activity and specificity still lag far behind those of natural enzymes, which significantly affects the accuracy and sensitivity of colorimetric biosensing. To address this issue, we design PdSn nanozymes with selectively enhanced peroxidase-like activity, which improves the sensitivity and accuracy of a colorimetric immunoassay. The peroxidase-like activity of PdSn nanozymes is significantly higher than that of Pd nanozymes. Theoretical calculations reveal that the p-d orbital hybridization of Pd and Sn not only results in an upward shift of the d-band center to enhance hydrogen peroxide (H2O2) adsorption but also regulates the O-O bonding strength of H2O2 to achieve selective H2O2 activation. Ultimately, the nanozyme-linked immunosorbent assay has been successfully developed to sensitively and accurately detect the prostate-specific antigen (PSA), achieving a low detection limit of 1.696 pg mL-1. This work demonstrates a promising approach for detecting PSA in a clinical diagnosis.

Bright Luminescence of Free Radical TEMPO Enabled by Electrochemiluminescence Technique.

Radicals can feature theoretically 100% light utilization owing to their nonelectron spin-forbidden transition and represent the most advanced luminescent materials at present. 2,2,6,6-Tetramethyl-1-piperidinyloxy (TEMPO) acts as a typically stable radical with very broad applications. However, their luminescent properties have not been discovered to date. In the present work, we observed the bright electrochemiluminescence (ECL) emission of TEMPO with a higher efficiency (72.3%) via the electrochemistry and coreactant strategies for the first time. Moreover, the radical-based ECL achieved high detection toward boron acid with a lower limit of detection (LOD) of 1.9 nM. This study offers a new approach to generate emissions for some unconventional luminophores and makes a major breakthrough in the field of new luminescent materials as well.

Realizing Ultrasensitive and Accurate Point-of-Care Profiling for ATP with a Triple-Mode Strategy Based on the ATP-Induced Reassembly of a Copper Coordination Polymer Nanoflower.

New strategies for accurate and reliable detection of adenosine triphosphate (ATP) with portable devices are significant for biochemical analysis, while most recently reported approaches cannot satisfy the detection accuracy and independent of large instruments simultaneously, which are unsuitable for fast, simple, and on-site ATP monitoring. Herein, a unique, convenient, and label-free point-of-care sensing strategy based on novel copper coordination polymer nanoflowers (CuCPNFs) was fabricated for multimode (UV-vis, photothermal, and RGB values) onsite ATP determination with high selectivity, sensitivity, and accuracy. The resulting CuCPNFs with a 3D hierarchical structure exhibit the ATP-triggered decomposition behavior because the competitive coordination between ATP and the copper ions of CuCPNFs can result in the formation of ATP-Cu, which reveals preeminent peroxidase mimics activity and can accelerate the oxidation of 3, 3', 5, 5'-tetramethylbenzidine (TMB) to form oxTMB. During this process, the detection system displayed not only color changes but also a strong NIR laser-driven photothermal effect. Thus, the photothermal and color signal variations are easily monitored by a portable thermometer and a smartphone. This multimode point-of-care platform can meet the requirements of onsite, without bulky equipment, accuracy, and reliability all at once, greatly enhancing its application in practice and paving a new way in ATP analysis.

Bioinspired FeN5 Sites with Enhanced Peroxidase-like Activity Enable Colorimetric Sensing of Uranyl Ions in Seawater.

Nanozymes with peroxidase (POD)-like activity have garnered significant attention due to their exceptional performance in colorimetric assays. However, nanozymes often possess oxidase (OD) and POD-like activity simultaneously, which affects the accuracy and sensitivity of the detection results. To address this issue, inspired by the catalytic pocket of natural POD, a single-atom nanozyme with FeN5 configuration is designed, exhibiting enhanced POD-like activity in comparison with a single-atom nanozyme with FeN4 configuration. The axial N atom in FeN5 highly mimics the amino acid residues in natural POD to optimize the electronic structure of the metal active center Fe, realizing the efficient activation of H2O2. In addition, in the presence of both H2O2 and O2, FeN5 enhances the activation of H2O2, effectively avoiding the interference of dissolved oxygen in colorimetric sensing. As a proof-of-concept application, a colorimetric detection platform for uranyl ions (UO22+) in seawater is successfully constructed, demonstrating satisfactory sensitivity and specificity.

Unveiling the Influence of Sulfur Doping on Photoelectrochemical Performance in BiVO4/FeOOH Heterostructures.

BiVO4 is a promising photoanode for photoelectrochemical (PEC) water splitting but suffers from high charge carrier recombination and sluggish surface water oxidation kinetics that limit its efficiency. In this work, a model of sulfur-incorporated FeOOH cocatalyst-loaded BiVO4 was constructed. The composite photoanode (BiVO4/S-FeOOH) demonstrates an enhanced photocurrent density of 3.58 mA cm-2, which is 3.7 times higher than that of the pristine BiVO4 photoanode. However, the current explanations for the generation of enhanced photocurrent signals through the incorporation of elements and cocatalyst loading remain unclear and require further in-depth research. In this work, the hole transfer kinetics were investigated by using a scanning photoelectrochemical microscope (SPECM). The results suggest that the incorporation of sulfur can effectively improve the charge transfer capacity of FeOOH. Moreover, the oxygen evolution reaction model provides evidence that S-doping can induce a "fast" surface catalytic reaction at the cocatalyst/solution interface. The work not only presents a promising approach for designing a highly efficient photoanode but also offers valuable insights into the role of element doping in the PEC water-splitting system.

Catalase-like Fe Nanoparticles and Single Atoms Catalysts with Boosted Activity and Stability of Oxygen Reduction for Pesticide Detection.

Although oxygen reduction reaction (ORR) as an effective signal amplification strategy has been extensively investigated for the improvement of sensitivity of electrochemical sensors, their activity and stability are still a great challenge. Herein, single-atom Fe (FeSA) and Fe nanoparticles (FeNP) on nitrogen-doped carbon (FeSA/FeNP) catalysts demonstrate a highly active and stable ORR performance, thus achieving the sensitive and stable electrochemical sensing of organophosphorus pesticides (OPs). Experimental investigations indicate that FeNP in FeSA/FeNP can improve the ORR activity by adjusting the electronic structure of FeSA active sites. Besides, owing to the excellent catalase-like activity, FeSA/FeNP can rapidly consume in situ generated H2O2 in the ORR process and avoid the leakage of active sites, thereby improving the stability of ORR. Utilizing the excellent ORR performance of FeSA/FeNP, an electrochemical sensor for OPs is established based on the thiocholine-induced poison of the active sites, demonstrating satisfactory sensitivity and stability. This work provides new insight into the design of high performance ORR catalysts for sensitive and stable electrochemical sensing.

Crystalline-Amorphous Interfaces Engineering of CoO-InOx for Highly Efficient CO2 Electroreduction to CO.

As a fundamental product of CO2 conversion through two-electron transfer, CO is used to produce numerous chemicals and fuels with high efficiency, which has broad application prospects. In this work, it has successfully optimized catalytic activity by fabricating an electrocatalyst featuring crystalline-amorphous CoO-InOx interfaces, thereby significantly expediting CO production. The 1.21%CoO-InOx consists of randomly dispersed CoO crystalline particles among amorphous InOx nanoribbons. In contrast to the same-phase structure, the unique CoO-InOx heterostructure provides plentiful reactive crystalline-amorphous interfacial sites. The Faradaic efficiency of CO (FECO) can reach up to 95.67% with a current density of 61.72 mA cm-2 in a typical H-cell using MeCN containing 0.5 M 1-Butyl-3-methylimidazolium hexafluorophosphate ([Bmim]PF6) as the electrolyte. Comprehensive experiments indicate that CoO-InOx interfaces with optimization of charge transfer enhance the double-layer capacitance and CO2 adsorption capacity. Theoretical calculations further reveal that the regulating of the electronic structure at interfacial sites not only optimizes the Gibbs free energy of *COOH intermediate formation but also inhibits HER, resulting in high selectivity toward CO.

Raspberry-shaped ZIF-8/Au nanozymes with excellent peroxidase-like activity for simple and visual detection of glutathione.

Artificial enzymes with high stability, adjustable catalytic activity, controllable preparation, and good reproducibility have been widely studied. Noble metal nanozymes, particularly gold nanoparticles (Au NPs), exhibit good catalytic activity, but their stability is poor. In this study, zeolitic imidazolate framework-8 (ZIF-8) was used as a carrier for Au NPs, thus improving the utilization efficiency and conservation stability of the nanozymes. A ZIF-8/Au nanocomposite with peroxidase activity and a raspberry-shaped structure was synthesized. In the assay, ZIF-8/Au catalyzed the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) to a blue product oxidized TMB (oxTMB). Glutathione (GSH) selectively inhibited this reaction, with a detection limit of 0.28 µM and linear range of 0.5-60 µM. Using the photo and chromaticity analysis functions, we developed a portable analysis method using a smartphone equipped with a camera module as a detection terminal for a wide range of rapid screening techniques for GSH. Preparation of raspberry-shaped ZIF-8/Au improved the catalytic activity of Au NPs and good results were demonstrated in serum, which suggests their promising application under physiological conditions.

One-step solvent thermal synthesis of 3D networked MOF composites for preparation of an ultrasensitive chemosensor for hydroquinone and catechol.

Pharmaceuticals and personal care products (PPCPs) have a significant impact on the environment and human health, due to their sometimes toxic and carcinogenic characteristics. Therefore, an innovative chemosensor was constructed for ultrasensitive determination of two typical PCCPs (hydroquinone (HQ) and catechol (CC)) in several minutes. The homemade chemosensor (UiO-67@GO/MWCNTs) consisted of MOF(UiO-67), graphene oxide (GO), and multi-walled carbon nanotubes (MWCNTs) composites; it was a networked, structurally sparse, porosity-rich, homogeneous octahedral composite, and had ultra-high electrical conductivity, which provided lots of active adsorption sites, promote charge transfer, and enrich lots of molecules to be measured in a few minutes. The prepared electrochemical sensor showed good long-term stability, applicability, reproducibility, and immunity to interference for the determination of HQ and CC, with a wide linear range of response of 5.0 ~ 940 µM for both HQ and CC, and a low limit of detection with satisfactory recoveries. In addition, a new strategy of using MOF composites as the basis for electrochemical determination of organic small molecules was established, and a new platform was constructed for the quantitative determination of organic small molecules in various environmental samples.

Enhancing the Electrochemiluminescence of Porphyrin via Crystalline Networks of Metal-Organic Frameworks for Sensitive Detection of Cardiac Troponin I.

Porphyrins easily aggregate due to unfavorable π-π accumulation, causing luminescent quenching in the aqueous phase and subsequently reducing luminescent efficiency. It is a feasible way to immobilize porphyrin molecules through metal-organic framework materials (MOFs). In this study, 5,10,15,20-tetrakis (4-carboxyphenyl) porphyrin (TCPP) was introduced into the metal-organic skeleton (PCN-224) as a ligand. The result showed that the electrochemiluminescence (ECL) and photoluminescence (PL) efficiency of the MOF skeleton was 8.2 and 6.5 times higher than TCPP, respectively. Impressively, the periodic distribution of porphyrin molecules in the MOF framework can overcome the bottleneck of porphyrin aggregation, resulting in the organic ligand TCPP participating in the electron transfer reaction. Herein, based on the PCN-224, a sandwich-type ECL immunosensor was constructed for the determination of cardiac troponin I (cTnI). It provided sensitive detection of cTnI in the range of 1 fg/mL to 10 ng/mL with a detection limit of 0.34 fg/mL. This work not only innovatively exploited a disaggregation ECL (DIECL) strategy via the crystalline framework of MOF to enhance the PL and ECL efficiency of porphyrin but also provided a promising ECL platform for the ultrasensitive monitoring of cTnI.

Single-Atom Indium Boosts Electrochemical Dopamine Sensing.

A rational design of high-efficiency electrocatalysts and thus achieving sensitive electrochemical sensing remains a great challenge. In this work, single-atom indium anchored on nitrogen-doped carbon (In1-N-C) with an In-N4 configuration is prepared successfully through a high-temperature annealing strategy; the product can serve as an advanced electrocatalyst for sensitive electrochemical sensing of dopamine (DA). Compared with In nanoparticle catalysts, In1-N-C exhibits high catalytic performance for DA oxidation. The theoretical calculation reveals that In1-N-C has high adsorption energy for hydroxy groups and a low energy barrier in the process of DA oxidation compared to In nanoparticles, indicating that In1-N-C with atomically dispersed In-N4 sites possesses enhanced intrinsic activity. An electrochemical sensor for DA detection is established as a concept application with high sensitivity and selectivity. Furthermore, we also verify the feasibility of In1-N-C catalysts for the simultaneous detection of uric acid, ascorbic acid, and DA. This work extends the application prospect of p-block metal single-atom catalysts in electrochemical sensing.

Viscosity-Responsive Electrochemiluminescence of Diphenylbenzofulvene Derivatives.

The development of superior probes is highly desirable and valuable for viscosity measurement. Herein, we designed and reported a series of diphenylbenzofulvene (DPBF)-based organic luminophores according to the molecular regulation strategy. There are two free-rotating phenyl groups attached to the rigid fluorene skeleton in the DPBF, enabling its unique propeller-like noncoplanar chemical structure. Benefiting from this, DPBFs could feature outstanding PL and ECL emissions with intriguing aggregation-induced characteristics. Experimental and theoretical investigations revealed that substituent, spatial structure, and molecular orbital energy profoundly affected their luminescent behaviors. It was disclosed that fluoro-substituted DPBF(F)2 with a smaller LUMO-HOMO band gap demonstrated the strongest ECL emission and was selected as the optimal ECL emitter. Finally, DPBF(F)2 featured a linear response to the viscosity and VC content with lower limits of detection (LOD) of 5.69 µcP and 38.2 nM, respectively. This study represents the first example of the ECL probe toward viscosity and will be of great significance for both ECL application and viscosity measurement.

Single-Site SnOCu Pairs with Interfacial Electron Transfer Effect for Enhanced Electrochemical Catalysis and Sensing.

As advanced electrochemical catalysts, single-atom catalysts have made great progress in the field of catalysis and sensing due to their high atomic utilization efficiency and excellent catalytic performance. Herein, stannum-doped copper oxide (CuOSn1 ) nanosheets with single-site SnOCu pairs as active sites are synthesized as electrocatalysts for biological molecule detection. Compared with CuO-based electrochemical sensors, the CuOSn1 -based electrochemical sensors have improved detection sensitivity with a rapid electrochemical response. Theoretical calculation reveals that the single-site SnOCu pairs induced interfacial electronic transfer effect can strengthen hydroxy adsorption and thus reduce the energy barrier of the biological molecule oxidation process. As a concept application, electrochemical detection of dopamine and uric acid molecules is achieved, exhibiting satisfactory sensitivity and selectivity. This work demonstrates the advantages of single-site SnOCu pairs in electrochemical catalysis and sensing, which provides theoretical guidance for understanding the structure-activity relationship for sensitive electrochemical sensing.

Noncentrosymmetric versus Centrosymmetric: Halogen Induced Variable Coordination Modes of Sn2+ and Structural Transition in Sn3B3O7X (X = Cl and Br).

Two new borate halides, Sn3B3O7X (X = Cl and Br), were successfully synthesized via introducing Sn2+ with lone-pair and halogen into borate. Interestingly, halogen-induced variable coordination modes of Sn2+ and anion frameworks make them crystallize in different space groups, from noncentrosymmetric (Pna21) to centrosymmetric (Pbca). Sn3B3O7Cl possesses an SHG response of about 0.5 times that of KDP, while Sn3B3O7Br exhibits a large birefringence (0.123@1064 nm). The theoretical calculations were performed to elucidate the structure-property relationships.

Fabrication of a Novel CNT-COO-/Ag3PO4@AgIO4Composite with Enhanced Photocatalytic Activity under Natural Sunlight.

In this study, a carboxylated carbon nanotube-grafted Ag3PO4@AgIO4 (CNT-COO-/Ag3PO4@AgIO4) composite was synthesized through an in situ electrostatic deposition method. The synthesized composite was characterized by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance spectroscopy (DRS), and energy-dispersive X-ray spectroscopy (EDS). The electron transfer ability of the synthesized composite was studied using electrochemical impedance spectroscopy (EIS). The CNT-COO-/Ag3PO4@AgIO4 composite exhibited higher activity than CNT/Ag3PO4@AgIO4, Ag3PO4@AgIO4, and bare Ag3PO4. The material characterization and the detailed study of the various parameters thataffect the photocatalytic reaction revealed that the enhanced catalytic activity is related to the good interfacial interaction between CNT-COO and Ag3PO4. The energy band structure analysis is further considered as a reason for multi-electron reaction enhancement. The results and discussion in this study provide important information for the use of the functionalized CNT-COOH in the field of photocatalysis. Moreover, providinga new way to functionalize CNT viadifferent functional groups may lead to further development in the field of photocatalysis. This work could provide a new way to use natural sunlight to facilitate the practical application of photocatalysts toenvironmental issues.

Precise Modulation of Intramolecular Aggregation-induced Electrochemiluminescence by Tetraphenylethylene-based Supramolecular Architectures.

The precisely modulated synthesis of programmable light-emitting materials remains a challenge. To address this challenge, we construct four tetraphenylethylene-based supramolecular architectures (SA, SB, SC, and SD), revealing that they exhibit higher electrochemiluminescence (ECL) intensities and efficiencies than the tetraphenylethylene monomer and can be classified as highly efficient and precisely modulated intramolecular aggregation-induced electrochemiluminescence (PI-AIECL) systems. The best-performing system (SD) shows a high ECL cathodic efficiency exceeding that of the benchmark tris(2,2'-bipyridyl)ruthenium(II) chloride in aqueous solution by nearly six-fold. The electrochemical characterization of these architectures in an organic solvent provides deeper mechanistic insights, revealing that SD features the lowest electrochemical band gap. Density functional theory calculations indicate that the band gap of the guest ligand in the SD structure is the smallest and most closely matched to that of the host scaffold. Finally, the SD system is used to realize ECL-based cysteine detection (detection limit=14.4 nM) in real samples. Thus, this study not only provides a precisely modulated supramolecular strategy allowing chromophores to be controllably regulated on a molecular scale, but also inspires the programmable synthesis of high-performance aggregation-induced electrochemiluminescence emitters.

Hexavalent Chromium as a Smart Switch for Peroxidase-like Activity Regulation via the Surface Electronic Redistribution of Silver Nanoparticles Anchored on Carbon Spheres.

Although some ions, due to their unique chemical properties, can regulate the enzyme-like activity of nanomaterials, it is still a huge challenge to explore the mechanism of regulation. Herein, we found that Cr6+ (CrO42-) as a smart switch can significantly increase the peroxidase-like (POD-like) activity of silver nanoparticles (Ag NPs), which were anchored efficiently on carbon spheres (Cal-CS/PEG/Ag) using amino-modified poly(ethylene glycol) (PEG) as a bridge. Density functional theory (DFT) calculations demonstrated that the addition of Cr6+ can not only adjust the surface electronic redistribution of Ag atoms but also improve the geometric structure of the adsorbed intermediate, which resulted in the optimization of free energy and change of bond lengths in the catalytic reaction process, increasing the POD-like activity of Cal-CS/PEG/Ag. Based on the Cr6+-increased POD-like activity of Cal-CS/PEG/Ag, we successfully constructed a visual sensor of Cr6+ along with quantitative analysis by the UV spectrum. The sensor has good selectivity for other 29 interfering ions and molecules with a detection limit of 79 nM. In this work, the detailed mechanism of the Cr6+-increased POD-like activity of Ag NPs was studied and a new possibility for the rational design of ion visual sensors using nanomaterials was proposed.

Aromaticity-Enhanced pH-Responsive Electrochemiluminescence of Cyclopentadienols.

Due to significantly tackling the problems of aggregation-caused quenching and water insolubility, aggregation-induced emission electrochemiluminescence (AIE-ECL) has emerged as a research highlight in aqueous detection and sensing. Herein, we reported a series of cyclopentadienols featuring excellent AIE-ECL properties on the basis of an enhanced aromaticity strategy. In detail, substituents profoundly determined ECL emission by affecting the characteristic absorption peak intensity ratio in UV-vis spectra and lowest unoccupied molecular orbital (LUMO)-highest occupied molecular orbital (HOMO) energies. It was found that 1,2,3,4,5-pentafluorophenyl cyclopentadienol (PFCD) containing an electron-withdrawing fluorine substituent, the maximum R/B band ratio, and a smaller LUMO-HOMO band gap demonstrated the best ECL performance. Meanwhile, such an AIE-ECL system displayed a wide response range toward pH (4-12) with a good linear relationship. Our research not only enriched polycyclic aromatic hydrocarbon-based AIE-ECL systems but also established an efficient pH sensor in the aqueous phase.

Study on the Electrochemiluminescence of Pentaphenylpyrrole in the Aqueous Phase Based on Structure-Regulated Strategy.

Heterocyclic nitrogen compounds play a vital role in luminescent materials, but most of them face the challenges of aggregation-caused quenching (ACQ) and poor water solubility. In this work, we present the nitrogen heterocyclic pentaphenylpyrrole (PentaPP) with an excellent aggregation-induced electrochemiluminescence (AIE-ECL) performance in the aqueous phase through the comparison of the elegant ECL luminophore 5,10,15,20-tetraphenylporphyrin (TPP). Further studies suggest that such unique AIE-ECL arises from its propeller-like noncoplanar structure and the large conjugation from the phenyl groups on the ring. In addition, the new ECL analysis could feature some advantages of AIE characteristic, water compatibility, and strong signal and finally achieve the ultrasensitive detection toward the explosive 2,4,6-trinitrophenol (TNP) with a lower detection limit (1.1 nM). This study does not only benefit to solve the two key problems mentioned before but also enriches the fundamentals and applications for ECL and pyrrole research.

Synergistic Effect Improves the Response of Active Sites to Target Variations for Picomolar Detection of Silver Ions.

Heavy metal ions seriously threaten human health; even a trace of them can damage the renal, nervous, and immune systems irreversibly. Although established nanozyme-based colorimetric assays have been designed for the rapid detection of heavy metal ions, the general contained surface organic ligands of nanocatalysts and low absorptivity of metal ions on solid substrates might result in a weak effect on active sites and prevent the realization of their full detection potential. Here, we developed a nanozyme-based colorimetric sensor (CPM-Pt) made by pyrolysis of peat moss with preabsorbed traces of Pt ions to ultrasensitively detect Ag+. The calcination removes organic components and produces bare nanozymes that expose rich active sites. The strong protective effect from the porous carbon support enables the embedded Pt nanoparticles (Pt NPs) with a partially stable positive charge after pyrolysis (∼28% Pt2+ species). By the d8-d10 metal-metal interactions between Pt2+ (4f145d8) and Ag+ (4d10), the high proportion of Pt2+ species on the surface of Pt NPs can readily capture/absorb Ag+. Subsequently, Ag+ accepts electrons from the support to form Ag atoms, which rapidly cover the peroxidase-like active sites of bare Pt NPs, weakening the activation of H2O2 to realize the response of Ag+. The colorimetric detection limit of Ag+ reached an unprecedented 1.1 pM, and the corresponding naked-eye color recognition is ultrasensitive to extremely low levels (100 pM).