High-performance fentanyl molecularly imprinted electrochemical sensing platform designed through molecular simulations.

BACKGROUND: Fentanyl and its derivatives are a type of potent opioid analgesics, with the characteristics of diverse structure, high toxicity, extremely low content, and high fatality rate. Currently, they have become one of the most serious problems in international drug abuse control due to their extensive use in drug production and use. Therefore, the development of a rapid, sensitive, and accurate method for detecting trace fentanyl is of great significance. In this study, in view of its complex structure and trace concentration, a new molecular imprinting electrochemical sensor was developed through molecular simulations followed by experimental validation to detect trace fentanyl. RESULTS: The process consisted of first obtaining the optimal functional monomer and its molar ratio through molecular simulations. The recognition sites of fentanyl-imprinted polymers were predicted to guide the synthesis of imprinted membranes with precision approach to ensure an efficient and accurate reaction process. Reduced graphene oxide (ErGO) was then deposited on glassy carbon electrode surface by electrochemical reduction to yield large numbers of active sites suitable for catalyzing reactions of fentanyl piperidine for promoted efficient electron transfer and amplified sensitivity of the sensor. Accordingly, fentanyl molecularly imprinted film was formed through one-step electropolymerization to yield greatly improved sensing selectivity due to the specific recognition of molecularly imprinted polymer. Under optimal experimental conditions, the fentanyl sensor showed an extended detection range of 3.84 × 10-9 mol L-1-1.72 × 10-6 mol L-1 and a detection limit of 1.28 × 10-9 mol L-1. SIGNIFICANCE: A distinctive feature of this sensor is its molecularly imprinted polymerized membrane, which offers excellent specific recognition, thereby boosting the sensor's selectivity. Throughout the sensor's development process, molecular simulations were employed to steer the synthesis of molecularly imprinted polymers and predict the recognition sites of fentanyl-imprinted polymers. The experimental outcomes proved to align with the simulation data. The final sensor exhibited outstanding selectivity, repeatability, stability, and high sensitivity. The sensor was effectively used to reliably track fentanyl in human serum samples, with acceptable analytical reliability, suggesting its potential for practical applications.

Changeable Active Sites by Pr Doping CuSA-TiO2 Photocatalyst for Excellent Hydrogen Production.

Photocatalytic water splitting for clean hydrogen production has been a very attractive research field for decades. However, the insightful understanding of the actual active sites and their impact on catalytic performance is still ambiguous. Herein, a Pr-doped TiO2-supported Cu single atom (SA) photocatalyst is successfully synthesized (noted as Cu/Pr-TiO2). It is found that Pr dopants passivate the formation of oxygen vacancies, promoting the density of photogenerated electrons on the CuSAs, and optimizing the electronic structure and H* adsorption behavior on the CuSA active sites. The photocatalytic hydrogen evolution rate of the obtained Cu/Pr-TiO2 catalyst reaches 32.88 mmol g-1 h-1, 2.3 times higher than the Cu/TiO2. Innovatively, the excellent catalytic activity and performance is attributed to the active sites change from O atoms to CuSAs after Pr doping is found. This work provides new insight for understanding the accurate roles of single atoms in photocatalytic water splitting.

Porphyrin-based covalent organic framework as oxidase mimic for highly sensitive colorimetric detection of pesticides.

A covalent organic framework-based strategy was designed for label-free colorimetric detection of pesticides. Covalent organic framework-based nanoenzyme with excellent oxidase-like catalytic activity was synthesized. Unlike other artificial enzymes, porphyrin-based covalent organic framework (p-COF) as the oxidase mimic showed highly catalytic chromogenic activity and good affinity toward TMB without the presence of H2O2, which can be used as substitute for peroxidase mimics and H2O2 system in the colorimetric reaction. Based on the fact that the pesticide-aptamer complex can inhibit the oxidase activity of p-COF and reduced the absorbance at 650 nm in UV-Vis spectrum, a label-free and facile colorimetric detection of pesticides was designed and fabricated. Under the optimized conditions, the COF-based colorimetric probe for pesticide detection displayed high sensitivity and selectivity. Taking fipronil for example the limit of detection was 2.7 ng/mL and the linear range was 5 -500,000 ng/mL. The strategy was successfully applied to the detection of pesticides with good recovery , which was in accordance with that of HPLC-MS/MS. The COF-based colorimetric detection was free of complicated modification H2O2, which guaranteed the accuracy and reliability of measurements. The COF-based sensing strategy is a potential candidate for the sensitive detection of pesticides of interests.

Computational electrocatalysis beyond conventional hydrogen electrode model: CO2 reduction to C2 species on copper facilitated by dynamically formed solvent halide ions at the solid-liquid interface.

The reduction of CO2 into value-added chemicals and fuels has been actively studied as a promising strategy for mitigating carbon dioxide emissions. However, the dilemma for the experimentalist in choosing an appropriate reaction medium and neglecting the effect of solvent ions when using a simple thermochemical model, normally leads to the disagreement between experimental observations and theoretical calculations. In this work, by considering the effects of both the anion and cation, a more realistic CO2 reduction environment at the solid-liquid interface between copper and solvent ions has been systematically studied by using ab initio molecular dynamics and density functional theory. We revealed that the co-occurrence of alkali ions (K+) and halide ions (F-, Cl-, Br-, and I-) in the electric double layer (EDL) can enhance the adsorption of CO2 by more than 0.45 eV compared to that in pure water, and the calculated energy barrier for CO-CO coupling also decreases 0.32 eV in the presence of I ion on a negatively charged copper electrode. The hydrated ions can modulate the distribution of the charge near the solid-liquid interface, which significantly promotes CO2 reduction and meanwhile impedes the hydrogen evolution reaction. Therefore, our work unveils the significant role of halide ions at the electrode-electrolyte interface for promoting CO2 reduction on copper electrode.

Nonstoichiometric Doping of La0.9FexSn1-xO3 Hollow Microspheres for an Ultrasensitive Formaldehyde Sensor.

Oxygen vacancies play an essential role in gas-sensitive materials, but the intrinsic oxides are poorly controlled and contain low oxygen vacancy concentrations. In this work, we prepared La0.9Fe1-xSnxO3 microspheres with high sensitivity and controllability by a simple hydrothermal method, and then, we demonstrated that it has many oxygen ion defects by X-ray photoelectron spectroscopy and electron paramagnetic resonance characterization. The gas sensor exhibited ultrahigh response, specific recognition of formaldehyde gas, and excellent moisture resistance. By comparing the composites with different doping ratios, it was found that the highest catalytic activity was reached when x = 0.75, and the response value of La0.9Fe0.75Sn0.25O3 hollow microspheres at 200 °C reached 73-10 ppm of formaldehyde, which is 188% higher than that of intrinsic LaFeO3 hollow microspheres. On the one hand, due to the absence of A-site La3+ and the replacement of B-site Fe3+ by Sn4+, a large number of oxygen vacancies are induced on the surface and in the interior of the materials; on the other hand, it is also related to the large specific surface area and gas channels caused by the particular structure.

Dissipation and Dietary Risk Assessment of Prochloraz in Strawberries under Greenhouse Conditions.

Prochloraz and its metabolites in strawberries have not been determined until now. Meanwhile, few reports in the literature have concerned the dissipation behavior and risk assessment of prochloraz and its metabolites in strawberries under greenhouse conditions in Beijing. A method for the determination of prochloraz and its metabolites in strawberries was developed using QuEChERS in combination with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Prochloraz and its metabolites recovered from strawberries were present in concentrations of 73.06% to 116.01%, their RSDs ranged from 1.12% to 9.17%, and their limits of detection ranged from 0.1 to 1 µg kg-1. Then, a study was conducted on the dissipation of prochloraz in strawberries under greenhouse conditions. The dissipation of prochloraz in strawberries followed the first-order kinetic equation, and its half-life was 8.06 days. The health risk associated with prochloraz in strawberries was evaluated using the target hazard quotient (THQ) method and EFSA PRIMo model. The results showed that the THQ values, %ARfD values, and %ADI values were less than 1. These results indicate that no health concerns of prochloraz are associated with the consumption of the studied strawberries. The government can use the results of this study to support the establishment of a maximum residue level for prochloraz in strawberries.

Tuning electronic structure for enhanced photocatalytic performance: theoretical and experimental investigation of CuM1-xM'xO2 (M, M' = B, Al, Ga, In) solid solutions.

This study introduces robust screening methodology for the efficient design of delafossite CuM1-xM'xO2 solid-solution photocatalysts using band-structure engineering. The investigation not only reveals the formation rules for various CuM1-xM'xO2 solid solutions but also highlights the dependence on both lattice compatibility and thermodynamic stability. Moreover, the study uncovers the nonlinear relationship between composition and band gaps in these solid solutions, with the bowing coefficient determined by the substitution constituents. By optimizing the constituent elements of the conduction band edge and adjusting solubility, the band structure of CuM1-xM'xO2 samples can be fine-tuned to the visible light region. Among the examined photocatalysts, CuAl0.5Ga0.5O2 exhibits the highest H2 evolution rate by striking a balance between visible-light absorption and sufficient reduction potential, showing improvements of 28.8 and 6.9 times those of CuAlO2 and CuGaO2, respectively. Additionally, CuGa0.9In0.1O2 demonstrates enhanced electron migration and surpasses CuGaO2 in H2 evolution due to a reduction in the effective mass of photogenerated electrons. These findings emphasize the pivotal role of theoretical predictions in synthesizing CuM1-xM'xO2 solid solutions and underscore the importance of rational substitution constituents in optimizing light absorption, reduction potentials, and effective mass for efficient hydrogen production.

S-scheme Cu3P/TiO2 heterojunction for outstanding photocatalytic water splitting.

TiO2 photocatalysts are of great interest in the fields of environmental purification, new energy and so on, because of their non-toxicity, high stability, high redox ability and low cost. However, the photogenerated carriers are severely recombined, which limits the application of TiO2 photocatalysts. Herein, S-scheme Cu3P/TiO2 heterojunction composites were successfully synthesized by a simple and efficient microwave hydrothermal method, and the results show that the hydrogen production rate of Cu3P/TiO2 is 5.83 mmol∙g-1∙h-1 under simulated sunlight irradiation, which is 7.3 and 83.3 times higher than that of pure TiO2 and Cu3P, respectively. This excellent performance is derived from the internal electric field (IEF) and energy band bending generated by the S-scheme heterojunction formed between Cu3P and TiO2. The density functional theory (DFT) calculation indicates that the Cu3P possess smaller work function and more negative conduction band (CB) position than that of TiO2, which is very conducive to greatly improve the H+ reduction ability and hydrogen production performance. This work provides a new idea for the reveal of electron transfer paths and active sites in S-scheme heterojunctions and deepens the mechanism understanding.

A promising and highly sensitive electrochemical platform for the detection of fentanyl and alfentanil in human serum.

A novel electrochemical method has been developed, based on a covalent organic framework (COF) and reduced graphene oxide (rGO), to detect fentanyl and alfentanil. COF nanomaterials with chrysanthemum morphology obtained by solvothermal reaction contain rich active sites for electrochemical catalytic reaction, thus improving the detection performance of the designed sensor. Reduced graphene oxide improves the sensor's sensitivity due to enhanced electron transfer. Under optimized experimental conditions, the fabricated electrode presents a linear range of 0.02 to 7.26 µM for alfentanil and 0.1 to 6.54 µM for fentanyl, with detection limits of 6.7 nM and 33 nM, respectively. In addition, the sensor possesses excellent selectivity, outstanding reproducibility, and acceptable stability. The proposed sensor is feasible for the reliable monitoring of fentanyl and alfentanil in human serum samples, with acceptable reliability and high potential in real-world applications. Finally, the electrochemical characteristic fingerprint of fentanyl is investigated by studying the electrochemical behavior of alfentanil and fentanyl on the electrode surface.

Interface Engineering Induced Electron Redistribution at PtNs /NiTe-Ns Interfaces for Promoting pH-Universal and Chloride-Tolerant Hydrogen Evolution Reaction.

Exploring highly efficient hydrogen evolution reaction (HER) electrocatalysts for large-scale water electrolysis in the full potential of hydrogen (pH) range is highly desirable, but it remains a significant challenge. Herein, a simple pathway is proposed to synthesize a hybrid electrocatalyst by decorating small metallic platinum (Pt) nanosheets on a large nickel telluride nanosheet (termed as PtNs /NiTe-Ns). The as-prepared PtNs /NiTe-Ns catalyst only requires overpotentials of 72, 162, and 65 mV to reach a high current density of 200 mA cm-2 in alkaline, neutral and acidic conditions, respectively. Theoretical calculations reveal that the combination of metallic Pt and NiTe-Ns subtly modulates the electronic redistribution at their interface, improves the charge-transfer kinetics, and enhances the performance of Ni active sites. The synergy between the Pt site and activated Ni site near the interface in PtNs /NiTe-Ns promotes the sluggish water-dissociation kinetics and optimizes the subsequent oxyhydrogen/hydrogen intermediates (OH*/H*) adsorption, accelerating the HER process. Additionally, the superhydrophilicity and superaerophobicity of PtNs /NiTe-Ns facilitate the mass transfer process and ensure the rapid desorption of generated bubbles, significantly enhancing overall alkaline water/saline water/seawater electrolysis catalytic activity and stability.

Rational Modulation of Single Atom Coordination Microenvironments in a BCN Monolayer for Multifunctional Electrocatalysis.

Single-atom (SA) catalysts (SACs) have demonstrated outstanding catalytic performances toward plenty of relevant electrochemical reactions. Nevertheless, controlling the coordination microenvironment of catalytically active SAs to further enhance their catalytic oerformences has remained elusive up to now. Herein, a systematic investigation of 20 transition metal atoms that are coordinated with 20 different microenvironments in a boroncarbon-nitride monolayer (BCN) is conducted using high-throughput density functional theory calculations. The experimentally synthesized ternary BCN monolayer contains carbon, nitrogen, and boron atoms in its 2D network, thus providing a lot of new coordination environments than those of the current Cx Ny nanoplatforms. By exploring the structural/electrochemical stability, catalytic activity, selectivity, and electronic properties of 400 (20 × 20) TM-BCN moieties, it is discovered that specific SA coordination environments can achieve superior stability and selectivity for different electrocatalytic reactions. Moreover, a universal descriptor to accelerate the experimental process toward the synthesis of BCN-SACs is reported. These findings not only provide useful guidance for the synthesis of efficient multifunctional BCN-SACs but also will immediately benefit researchers by levering up their understanding of the mechanistic effects of SA coordination microenvironments on electrocatalytic reactions.

Anchored Cu single atoms on porous g-C3N4 for superior photocatalytic H2 evolution from water splitting.

One of the most promising strategies for producing hydrogen is photocatalytic water splitting, in which the photocatalyst is a key component. Among many semiconductor photocatalysts, g-C3N4 has attracted great attention due to its narrow band gap, excellent stability and low cost. However, practical application is limited by its poor intrinsic activity. In this work, a high-performance porous g-C3N4 (PCN) photocatalyst with anchored Cu single atoms (CuSAs) was synthesized by a one-step co-heating approach. The obtained Cu1.5-PCN displays an excellent hydrogen evolution rate (HER) of 2142.4 µmol h-1 g-1 under visible light (=420 nm), which is around 15 and 109 times higher than those of PCN and bulk g-C3N4, respectively. In addition, it also shows good stability during H2 evolution. The results of experimental research and DFT simulations indicate that the single Cu ions formed bonds with the N-ring and these remain stable. Meanwhile, the special electronic structure of the Cu-N charge bridge extends the light absorption band to the visible-light region (380-700 nm). This high-performance and low-cost photocatalyst has great potential in solar energy conversion.

Etching dopant elements to construct active-site-rich Mo2C for the hydrogen evolution reaction.

We propose a strategy to etch dopants to construct Mo2C with more unsaturated coordination of Mo atoms and lattice distortion for enhanced catalytic activity. It is more effective than doping and etching pure Mo2C and provides a novel strategy for the preparation of catalysts with high catalytic activity.

An electrochemical sensor for direct and sensitive detection of ketamine.

Ketamine is an organic drug with weak electrochemical activity, which makes it difficult to directly detect by electrochemical methods. Herein, an electrochemical sensor, with excellent detection sensitivity, is proposed for direct detection of ketamine based on a weakly conductive poly-L-cysteine molecularly imprinted membrane. Poly-L-cysteine molecularly imprinted membrane sensor (poly-L-Cys-KT-MIM/GCE) is obtained using L-cysteine as a functional monomer and ketamine as a template molecule based on electropolymerization. The green and highly active cysteine is selected as a functional monomer during electropolymerization, which cannot only achieve specific recognition but also improve detection sensitivity. Furthermore, the oxidation mechanism and fingerprint of ketamine on the electrode surface are established by analyzing the corresponding oxidation products using high/resolution mass spectrometry, which will help to promote the application of electrochemistry in the rapid detection of drugs. Under optimal conditions, the as-designed sensor demonstrated a linear response to ketamine within the range of 5.0 × 10-7 to 2.0 × 10-5 mol L-1 and a detection limit of 1.6 × 10-7 mol L-1. The proposed method exhibited excellent performance from the viewpoints of selectivity, sensitivity and stability. Notably, the sensor rendered excellent reliability and could be used for the detection of target analytes in hair and urine samples with high recovery rates.

Surface Optics and Color Effects of Liquid Metal Materials.

Liquid metals (LMs) are emerging as new functional materials with rather unique physical or chemical behaviors. They are generally safe and nontoxic, have high boiling points, reflectivities, good thermal and electrical conductivities, flexibility, fluidity, self-healing capability and remain in liquid state at room temperature. However, the further applications of LMs are limited by their single-color physical appearance, such as working in the situations with imposed stringent requirements for color and aesthetics. Recently, the color and fluorescence functionalization of LMs have overcome many conventional technical bottlenecks and opened significant potential for emerging applications in numerous fields owing to their rich colors and unique liquid structure. In this review, the recent developments in the optical properties, color and fluorescence effects of LMs are comprehensively investigated. The synthesis, structures, properties, chromogenic mechanisms, and potential photoelectric applications of colorful LMs are systematically analyzed and compared. The effectiveness and characteristics of colorful LMs induced by coating, mixing, compounding, surface modification, external stimuli are provided, aiming to establish a potential system for the synthesis and practices of colorful LMs. Finally, the challenges and prospects in the field have also been identified and explained to preferably guide further scientific and technical research in the coming time.

A luminescent probe based on terbium-based metal-organic frameworks for organophosphorus pesticides detection.

Terbium-based metal-organic frameworks (Tb-MOF) prepared under mild conditions was utilized to construct a fluorescence probe for determination of organophosphorus pesticides (OPs) coupled with acetylcholinesterase (AChE), acetylcholine chloride (Ach), and choline oxidase (CHO). Since OPs have obvious inhibition on the activity of AChE in the Tb-MOF/ACh/CHO/AChE system, the detection of OPs was accomplished by restoring the fluorescence of Tb-MOF resulting from reduced production of H2O2. By taking chlorpyrifos (CPF) as a pesticide model, the method exhibits high sensitivity in the linear range 0.1-4.0 µg·L-1 with the limit of detection (LOD) of 0.04 µg·L-1 under optimum conditions (λex = 280 nm, λem = 544 nm). The Tb-MOF/ACh/CHO/AChE fluorescence system has high selectivity for CPF. The method was successfully applied to the detection of CPF in tap water and strawberry samples (recovery of 87.36-115.60% for tap water and 95.04-103.20% for strawberry). Free from complicated fabrication operation, the Tb-MOF-based system is rapid, simple, and stable, which provides a reference and new way for the design of OPs fluorescent probes in the future.

Excellent performance supercapacitors with the compounding of Ni(OH)2 and ZIF-67 derived Co-C-N nanosheets as flexible electrode materials.

Owing to the advantages of high theoretical capacity, low cost, and excellent chemical stability, Ni(OH)2 is considered as a potential candidate for electrode materials of supercapacitors. However, its further applications are limited by its adverse surface chemical properties. In this paper, a composite material consisting of ZIF-67 derived Co-C-N nanosheets and Ni(OH)2 was synthesized facilely on carbon cloth in situ, and based on the collective advantages of the various components, excellent electrochemical performance could be achieved when used as a flexible electrode material of supercapacitors. In detail, the as-obtained sample Ni(OH)2/Co-C-N/CC exhibits an ultrahigh specific capacitance of 2100 F g-1 at a current density of 1 A g-1. Moreover, the further assembled asymmetric supercapacitor device exhibits a maximum energy density of 78.6 W h kg-1 at a power density of 749.4 W kg-1. Furthermore, the device also shows outstanding cycling stability with 90.2% capacitance retention after 5000 cycles of charge-discharge. Basically, the remarkable performance can be attributed to the well-developed structure, abundant active sites, complex beneficial components, and their intrinsic properties. Significantly, rational design can broaden the research directions of corresponding electrode materials.

Pd-SnO2/In2O3 with a Unique Structure for the Ultrasensitive Detection of Triethylamine near Room Temperature.

Triethylamine (TEA) is a serious threat to people's health, and it is still a challenge to detect TEA at ppb level near room temperature (RT). Herein, we developed a simple, low-cost, low-temperature, and ultra-sensitive TEA sensor based on Pd-SnO2/In2O3 composites. First, SnO2 nanoparticles were obtained by the pyrolysis of Sn-MOF@SnO2 precursor (MOF: metal organic framework), and Pd-SnO2/In2O3 composites were prepared by further compounding and doping. The results show that the Pd-SnO2/In2O3 sensor is highly sensitive to TEA gas at near RT (at 60 °C, the sensor response to 10 ppm TEA is 12,000, the response/recovery (res/rec) time is 51 s/493 s, and at 30 °C, the response value also reaches 1380, the res/rec time is 66 s/610 s), along with good selectivity, stability, and moisture resistance. Even at 10 °C operating temperature and 75% relative humidity (RH) in a low-temperature and high-humidity environment, it still maintains a high sensitivity of over 1000 to 10 ppm TEA, which shows great application potential in TEA detection. The reason for the enhanced performance of the 0.5%Pd-SnO2/In2O3 sensor can be attributed to a large number of adsorbed oxygens on the unique structure of the material, the good charge transfer ability of the n-n-type heterojunction between SnO2 and In2O3, the chemical sensitization and electronic sensitization of Pd nanoparticles, and the catalytic spillover effect. This work will provide a new approach for preparing sensors with good comprehensive properties, making full use of the advantages of the material structure-activity relationship.

In situ Cu single atoms anchoring on MOF-derived porous TiO2 for the efficient separation of photon-generated carriers and photocatalytic H2 evolution.

Single atom catalysts (SACs) have an extremely high atom utilization and distinctive structures and properties in the field of photocatalysis. However, the premise of conducting scientific research and applications is still the stability and catalytic activity of single atoms on suitable substrates. Metal organic frameworks (MOFs), as one of the most suitable single-atom substrates, have tunable internal structures, unsaturated coordination bonds, and high specific surface areas. In this work, Ti-based MOF, MIL-125, was adopted as the precursor to prepare mesoporous Cu-loaded TiO2. During the synthesis of MIL-125, a Cu source was added, and Cu atoms were fixed by partly replacing Ti atoms in the Ti-O octahedron to coordinate with O atoms, resulting in a good dispersity, good stability and high loading amount. Experimental investigations demonstrated that dispersed Cu single atoms act as reaction centres, besides being able to accelerate the transfer of photoelectrons. Under simulated sunlight, the H2 evolution rate of the optimum Cu-TiO2 sample reaches 17.77 mmol g-1 h-1, nearly 101 times higher than that of the pure mesoporous TiO2. The apparent quantum efficiency (AQE) is 20.15% under 365 nm irradiation. This research opens a new thinking to preparing high stability and high activity single atom photocatalysts.

Highly sensitive triethylamine gas sensor by Pt-loaded p-n heterojunction Co3O4/WO3.

Triethylamine (TEA) exists widely in production and life and is extremely volatile, which seriously endangers human health. It is required to develop high-performance TEA sensors to protect human health. We fabricated Pt-Co3O4/WO3based on our previous work, and the performance was tested against volatile organic compounds. Compared with the previous work, its operating temperature was greatly reduced from 240 °C to 180 °C. The response value of Pt-Co3O4/WO3was increased from 1101 to 1532 for 10 ppm TEA with good selectivity. These results show a significant step toward practical use of the Pt-Co3O4/WO3sensor.