Honeycomb-like triazine-based conjugated microporous polymers exhibiting simultaneous and ultrasensitive detection of fifteen polycyclic aromatic hydrocarbons using solid-phase microextraction technique.

BACKGROUND: Since the severe hazard to the ecosystem and widespread distribution through biological and man-made ways of polycyclic aromatic hydrocarbons (PAHs), it is very urgent to establish the ultrasensitive analytical method to quantitatively and directly monitor PAHs in real samples. However, because of the complicated environmental matrix and their trace concentration, the pre-concentration process is a necessary step to analyze of these compounds. In this study, solid phase microextraction (SPME) technique was proposed to separate and enrich fifteen trace PAHs from environmental samples. RESULTS: In this work, a honeycomb-like triazine-based conjugated microporous polymers (T-CMPs) were prepared by Yamamoto reaction and firstly used as SPME coating material for the ultrasensitive direct-immersion-SPME of PAHs prior to high performance liquid chromatography-fluorescence detector (HPLC-FLD). The synthesized T-CMPs was characterized using various spectroscopy and electron microscopy techniques. The unique porous network of T-CMPs might deliver abundant adsorption sites for PAHs. Orthogonal experimental design (OED) was used to investigate the influence of four experimental parameters on the enrichment ability. Under optimal situation, a wide linear range (which lasted from 0.003 to 1000 µg L-1) with the coefficients of determination (R2) varying 0.9981 to 0.9993 was obtained. The limits of detection (LODs) for the analytes varied from 0.001 to 1.650 µg L-1, and the limits of quantification (LOQs) were between 0.003 and 4.960 µg L-1. The proposed method was effectively employed to the simultaneous and ultrasensitive detection of fifteen PAHs in industrial wastewaters. The relative recoveries for PAHs analysis varied from 74.6 % to 105 % with the relative standard deviations (RSD) of 0.1 %-7.5 % in real water samples. SIGNIFICANCE: The prepared SPME coating material exhibited a simultaneous, high extraction and adsorption capacity for fifteen PAHs due to its honeycomb-like porous structure, ultra-large specific surface area, strong π-π stacking, and hydrophobic interactions. The present research developed a novel strategy for the construction of SPME fiber coating composites and demonstrated great application potential in the field of sample pretreatment and environmental analytical chemistry.

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.

Yolk-shell MOF-on-MOF hybrid solid-phase microextraction coatings for efficient enrichment and detection of pesticides: Structural regulation cause performance differences.

Metal-organic frameworks (MOFs) based composites with different structure-activity relationships have been widely used in the field of organic pollutant adsorption and extraction. Here, two MOF-on-MOF composites with different structures (yolk-shell and core-shell) from homologous sources were prepared by a simple in-situ growth synthesis method and structural regulation. In order to verify the effect of composite structure on the extraction capacity, the adsorption performance of the yolk-shell structure (YS-NH2-UiO-66@CoZn-ZIF) and the core-shell structured (NH2-UiO-66@CoZn-ZIF) material were compared by using them as coating material of direct immersion solid-phase microextraction (DI-SPME) to enrich six pesticides in five matrices. The results showed that because of the unique hollow hierarchical structure, high specific surface area (930.68 m2 g-1), abundant and open active sites, and synergistic and complementary adsorption forces, YS-NH2-UiO-66@CoZn-ZIF composites had the maximum adsorption amount of 36.01-66.31 mg g-1 under the same experiment condition, which was 6.81%-34.26 % higher than that of NH2-UiO-66@CoZn-ZIF. In addition, the adsorption mechanism of the prepared materials was verified and elaborated through theoretical simulations and material characterization. Under the optimized conditions, the YS-NH2-UiO-66@CoZn-ZIF-coated SPME-HPLC-UV method had a wide linear range (0.241-500 µg L-1), a good linear correlation coefficient (R2 > 0.9988), a low detection limits (0.072-0.567 µg L-1, S/N = 3) and low quantification limits (0.241-1.891 µg L-1, S/N = 10). The relative standard deviations of individual fibers and different batches of fibers were 0.47-6.20 % and 0.22-2.48 %, respectively, and individual fibers could be recycled more than 104 times. This work provided a good synthetic route and comparative ideas for exploring the in-situ growth synthesis of yolk-shell composites with reasonable structure-activity relationships.

Inhibition effect of p-d orbital hybridized PtSn nanozymes for colorimetric sensor array of antioxidants.

Rational design of peroxidase (POD)-like nanozymes with high activity and specificity still faces a great challenge. Besides, the investigations of nanozymes inhibitors commonly focus on inhibition efficiency, the interaction between nanozymes-involved catalytic reactions and inhibitors is rarely reported. In this work, we design a p-block metal Sn-doped Pt (p-d/PtSn) nanozymes with the selective enhancement of POD-like activity. The p-d orbital hybridization interaction between Pt and Sn can effectively optimize the electronic structure of PtSn nanozymes and thus selectively enhance POD-like activity. In addition, the antioxidants as nanozymes inhibitors can effectively inhibit the POD-like activity of p-d/PtSn nanozymes, which results in the fact that antioxidants absorbed on the p-d/PtSn surface can hinder the adsorption of hydrogen peroxide. The inhibition type (glutathione as a model molecule) is reversible mixed-inhibition with inhibition constants (Ki' and Ki) of 0.21 mM and 0.03 mM. Finally, based on the varying inhibition levels of antioxidant molecules, a colorimetric sensor array is constructed to distinguish and simultaneously detect five antioxidants. This work is expected to design highly active and specific nanozymes through p-d orbital hybrid engineering, and also provides insights into the interaction between nanozymes and inhibitors.

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.

Ultra-thin FeCoNi-LDH hollow nanoflower as solid-phase microextraction coating for targeted capture of six pesticides by electrostatic adsorption.

Pesticides are common pollutants that cause detriment to the ecological environmental safety and health of human due to their toxicity, volatility and bioaccumulation. In this work, an ultra-thin polymetallic layered double hydroxide (FeCoNi-LDH) with hollow nanoflower structure composite was synthesized using ZIF-67 as a self-sacrificial template, which was used as solid-phase microextraction (SPME) coating for the targeted capture pesticides, which could be combined with high-performance liquid chromatography (HPLC) to sensitive inspection pesticides in real water samples. Orthogonal experimental design (OAD) was applied to ensure the best SPME condition. Additionally, the adsorption properties were evaluated by chemical thermodynamics and kinetics. Under the optimized conditions, high adsorption capacity was obtained (117.0-21.5 mg g-1). A wide linear range (0.020-1000.0 µg L-1), low detection limit (0.008-0.172 µg L-1) and excellent reproducibility were obtained under the established method. This research provided a new strategy for designing hollow materials with multiple cations for the adsorption of anion or organic pollutants.

Artemisinin: a novel chiral electrochemiluminescence luminophore-assisted enantiospecific recognition and mechanism identification.

Exploring novel electrochemiluminescence (ECL) molecules with high efficiency and good stability in aqueous solutions is crucial for achieving highly sensitive detection of analytes. However, developing chiral luminophores with efficient ECL performance is still a challenge. Herein, we first uncover that artemisinin (ART), a well-known chiral antimalarial drug, features a strong ECL emission at 726 nm with the assistance of a co-reactant potassium persulfate (K2S2O8), and an ECL efficiency of 195.3%, compared to that of standard Ru(bpy)3Cl2/K2S2O8. Mechanistic studies indicate that the strong ECL signal of ART is generated when the excited state formed by the reduction of ART peroxide bonds and combination with persulfate returns to the ground state. Significantly, we found that the ECL sensor based on chiral ART could efficiently identify and detect chiral cysteine (Cys) through ECL signals, with a lower limit of detection of 3.7 nM for l-Cys. Density functional theory calculations and scanning electrochemical microscopy technology further confirm that the disparity in the ECL signals is attributed to the different affinity between chiral ART and d/l-Cys, resulting in distinct electron transfer rates. The study demonstrates a new role of ART in ECL investigation and for the first time, achieves the development of ART for the enantioselective recognition and sensitive detection of chiral substances. This will be of vital significance for ECL and chirality research.

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.

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.

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.

Highly selective electroreduction of CO2 to CO with ZnO QDs/N-doped porous carbon catalysts.

ZnO quantum dots (QDs) supported on porous nitrogen-doped carbon (ZnOQDs/P-NC) exhibited excellent electrochemical performance for the electroreduction of CO2 to CO with a faradaic efficiency of 95.3% and a current density of 21.6 mA cm-2 at -2.2 V vs. Ag/Ag+.

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.

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.

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.

Ultra-rapid and highly selective colorimetric detection of hydrochloric acid via an aggregation to dispersion change of gold nanoparticles.

A rapid and highly selective naked-eye detection of hydrochloric acid (HCl) in an aqueous medium was established using HCl-triggered redispersion of gold nanoparticle aggregates.

Superhydrophilic Triazine-Based Covalent Organic Frameworks via Post-Modification of FeOOH Clusters for Boosted Photocatalytic Performance.

The triazine-based covalent organic frameworks (tCOF), an intriguing subtype of COFs, are expected as highly promising photocatalysts for various photocatalytic applications owing to their fully conjugated structures and nitrogen-rich skeletons. However, the inherent hydrophobicity and fast recombination of photoexcited electron-hole pairs are two main factors hindering the application of tCOF in practical photocatalytic reactions. Here, a post-synthetic modification strategy to fabricate superhydrophilic tCOF-based photocatalysts is demonstrated by in situ growing FeOOH clusters on TaTz COF (TaTz-FeOOH) for efficient photocatalytic oxidation of various organic pollutants. The strong polar FeOOH endows TaTz-FeOOH with good hydrophilic properties. The well-defined heterogeneous interface between FeOOH and TaTz allows the photoelectrons generated by TaTz to be consumed by Fe (III) to transform into Fe (II), synergistically promoting the separation of holes and the generation of free radicals. Compared with the unmodified TaTz, the optimized TaTz-FeOOH (1%) shows excellent photocatalytic performance, where the photocatalytic degrade rate (k) of rhodamine B is increased by about 12 times, and the degradation rate is maintained at 99% after 5 cycles, thus achieving efficient removal of quinolone antibiotics from water. This study provides a new avenue for the development of COF-based hydrophilic functional materials for a wide range of practical applications.

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.

Immobilizing glucose oxidase on AuCu hydrogels for enhanced electrochromic biosensing.

Development of highly sensitive and accurate biosensors still faces a great challenge. Herein, glucose oxidase (GOx) is efficiently immobilized on the AuCu hydrogels owing to their porous structure and interfacial interaction, demonstrating enhanced catalytic activity, satisfactory stability and recyclability. Besides, by integration of AuCu@GOx and electrochromic material of Prussian blue, a sensitive and stable biosensing platform based on the excellent electrochromic property of Prussian blue and the enhanced enzyme activity of AuCu@GOx is developed, which enables the electrochemical and visual dual-mode detection of glucose. The as-constructed biosensing platform possesses a wide linear range, and good selectivity for glucose detection with a limit of detection of 0.82 µM in visual mode and 0.84 µM in electrochemical mode. This easy-to-operate biosensing platform opens a door for the practical application of the multi-mode strategy for glucose detection.

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.

Selectivity control for CO2 electroreduction to syngas using Fe/CuOx catalysts with high current density.

A novel and tunable synthesis of Fe/CuOx bimetallic catalysts has been achieved via a simple Fe-precipitation and calcination method, which was used for highly efficient CO2 electroreduction to control the wide-ranging CO to H2 ratio by simply changing the ratio of metals. The faradaic efficiency of CO could reach 86.1% with a current density of 49.1 mA cm-2. The ratio of CO/H2 could reach 1.94 to 6.18 and it was discovered that the Fe/CuOx bimetallic catalysts could easily get different ratios of syngas, which can be applied directly in industry.