Hexagonal Cobalt Nanosheets for High-Performance Electrocatalytic NO Reduction to NH3.

Electrocatalytic nitric oxide (NO) reduction not only provides an extremely promising strategy for ambient NH3 generation but also alleviates the artificially disrupted N-cycle balance. However, exploring efficient electrocatalysts to enhance the NO electroreduction performance remains a significant challenge. Herein, a hexagonal-close-packed Co nanosheet (hcp-Co) is prepared and exhibits a high NH3 yield of 439.50 µmol cm-2 h-1 and a Faraday efficiency of 72.58%, outperforming the face-centered cubic phase of the Co nanosheet (fcc-Co) and most reported electrocatalysts. Through the combination of density functional theory calculations and NO temperature-programmed desorption experiments, the superior catalytic NO reduction reaction (NORR) activity on the hcp-Co can be attributed to the unique electron structures and proton shuttle effect. A proof-of-concept device of Zn-NO batteries using the hcp-Co as the cathode is assembled and shows a power density of 4.66 mW cm-2, which is superior to the reported performance in the literature so far.

Practical method for improving the accuracy of weakly stressed birefringence detection by circularly polarized instantaneous photoelasticity.

Due to the mismatch between the quarter-wave plate and the wavelength of the light source, the circularly polarized field photoelastic stress analysis method has an impact on the measurement of the phase delay and the stress direction angle. In particular, the measurement of the phase delay is inaccurate for weakly stressed samples with phase delays less than a quarter-wavelength. In this paper, we first give a method for calculating the mismatch value δ, which requires only one air calibration without prior calibration of the parameters of the quarter-wave plate with other equipment. We then introduce δ into the correction process for the phase delay, derive the correction equation, and give a theoretical comparison of the relative error curves. The results show that the correction method can theoretically limit the maximum amount of error. Finally, we have verified the accuracy of the method by measurements of the internal lens stress before and after the correction and by stitching measurements on SiC wafers.

C-Bound or O-Bound Surface: Which One Boosts Electrocatalytic Urea Synthesis?

The electrocatalytic C-N coupling from carbon dioxide and nitrate under ambient conditions is kind of sustainable and promising alternative method for urea synthesis. To date, the influence of catalyst surface properties on molecular adsorption configuration and electrocatalytic urea synthesis activity is unclear. In this work, we proposed that the urea synthesis activity is closely linked with the localized surface charge on bimetallic electrocatalysts, it is found that a negatively charged surface induces C-bound path and boosts urea synthesis. The urea yield rate can reach 13.1 mmol g-1 h-1 on negatively charged Cu97 In3 -C, which is about 13 times that of positively charged Cu30 In70 -C counterpart with O-bound surface. This conclusion also applies to Cu-Bi and Cu-Sn systems. The molecular modification shifts the surface of Cu97 In3 -C to positively charged state, which leads to a sharp decline in urea synthesis performance. We demonstrated that the C-bound surface is more favorable than O-bound one to boost electrocatalytic urea synthesis.

Electrocatalytic Urea Synthesis with 63.5 % Faradaic Efficiency and 100 % N-Selectivity via One-step C-N coupling.

Electrocatalytic urea synthesis via coupling N2 and CO2 provides an effective route to mitigate energy crisis and close carbon footprint. However, the difficulty on breaking N≡N is the main reason that caused low efficiencies for both electrocatalytic NH3 and urea synthesis, which is the bottleneck restricting their industrial applications. Herein, a new mechanism to overcome the inert of the nitrogen molecule was proposed by elongating N≡N instead of breaking N≡N to realize one-step C-N coupling in the process for urea production. We constructed a Zn-Mn diatomic catalyst with axial chloride coordination, Zn-Mn sites display high tolerance to CO poisoning and the Faradaic efficiency can even be increased to 63.5 %, which is the highest value that has ever been reported. More importantly, negligible N≡N bond breakage effectively avoids the generation of ammonia as intermediates, therefore, the N-selectivity in the co-electrocatalytic system reaches100 % for urea synthesis. The previous cognition that electrocatalysts for urea synthesis must possess ammonia synthesis activity has been broken. Isotope-labelled measurements and Operando synchrotron-radiation Fourier transform infrared spectroscopy validate that activation of N-N triple bond and nitrogen fixation activity arise from the one-step C-N coupling process of CO species with adsorbed N2 molecules.

Oxygen Vacancy-Mediated Selective C-N Coupling toward Electrocatalytic Urea Synthesis.

The electrocatalytic C-N coupling for one-step urea synthesis under ambient conditions serves as the promising alternative to the traditional urea synthetic protocol. However, the hydrogenation of intermediate species hinders the efficient urea synthesis. Herein, the oxygen vacancy-enriched CeO2 was demonstrated as the efficient electrocatalyst with the stabilization of the crucial intermediate of *NO via inserting into vacant sites, which is conducive to the subsequent C-N coupling process rather than protonation, whereas the poor selectivity of C-N coupling with protonation was observed on the vacancy-deficient catalyst. The oxygen vacancy-mediated selective C-N coupling was distinguished and validated by the in situ sum frequency generation spectroscopy. The introduction of oxygen vacancies tailors the common catalyst carrier into an efficient electrocatalyst with a high urea yield rate of 943.6 mg h-1 g-1, superior than that of partial noble-metal-based electrocatalysts. This work provides novel insights into the catalyst design and developments of coupling systems.

Three-dimensional stitching of stereo-deflectometry based on marker points.

As a non-contact and three-dimensional (3D) mirror surface measurement method, stereo-deflectometry has been developing rapidly in recent years. For solving the problem of the measurement of large surface inclination with traditional stereo-deflectometry, 3D stitching of stereo-deflectometry based on marker points is proposed. In this method, the 3D points in the subregions under different perspectives were measured. Meanwhile, the 3D coordinates of the marker points on the sample table, which were calculated by binocular stereo vision, were used for coarse stitching, and the ICP algorithm was used for fine stitching. In order to verify the 3D stitching algorithm, we built a measurement system for the freeform surface of an ultra-short lens with a diameter of about 100 mm and a steepness of 52.6°. The spherical fitting error of the reflective bowl after stitching is within 60 mm. The experimental results verify the feasibility of the method, leading to potential mass application of stereo-deflectometry in 3D measurement of complex optical surfaces with a large aperture and high steepness.

Distribution of Diatoms in the Navigable Sections of Beijing-Hangzhou Grand Canal.

OBJECTIVES: To establish a diatom database by analyzing the quatity, species distribution and differences of diatom in water samples of the whole navigable sections of the Beijing-Hangzhou Grand Canal, to provide a reference for the inference of the drowning site. METHODS: Water samples were collected at 22 sites in the navigable sections of the Beijing-Hangzhou Grand Canal (Jining section to Yangzhou Section), and the diatoms at each site were qualitatively and quantitatively analyzed by using graphite digestion-scanning electron microscopy. RESULTS: Sampling site T (Laohuaijiang River Line, Gaoyou City, Yangzhou City, Jiangsu Province) had the highest number of diatoms, while sampling site O (Siyang County, Suqian City, Jiangsu Province) had the lowest number of diatoms, with a large gap of 68 times. At sampling site Q (Jiangpu District, Huaian city, Jiangsu Province), there were 19 species of diatoms. The sampling site O had the least diatoms, with 7 species. There were no significant differences in species evenness and species diversity at each sampling site (P>0.05). Some sampling sites have characterized diatoms, such as Caloneis at station A (Taibai Lake, Weishan County, Shandong Province), Rhoicosphenia at station B (Nanyang Town, Weishan County, Shandong Province), Amphora at station I (Taierzhuang District, Zaozhuang City, Shandong Province) and Epithemia at station J (Pizhou 310 national highway, Xuzhou City, Jiangsu Province). CONCLUSIONS: The species richness of diatoms gradually increased from north to south. Diatom species richness and species diversity might be higher in areas with complex environments and large population flow. Climate type has a certain influence on the distribution of diatoms.

Transforming Electrocatalytic Biomass Upgrading and Hydrogen Production from Electricity Input to Electricity Output.

Integrating biomass upgrading and hydrogen production in an electrocatalytic system is attractive both environmentally and in terms of sustainability. Conventional electrolyser systems coupling anodic biosubstrate electrooxidation with hydrogen evolution reaction usually require electricity input. Herein, we describe the development of an electrocatalytic system for simultaneous biomass upgrading, hydrogen production, and electricity generation. In contrast to conventional furfural electrooxidation, the employed low-potential furfural oxidation enabled the hydrogen atom of the aldehyde group to be released as gaseous hydrogen at the anode at a low potential of approximately 0 VRHE (vs. RHE). The integrated electrocatalytic system could generate electricity of about 2 kWh per cubic meter of hydrogen produced. This study may provide a transformative technology to convert electrocatalytic biomass upgrading and hydrogen production from a process requiring electricity input into a process to generate electricity.

Experimental analysis of a wavefront coding system with a phase plate in different surfaces.

The application of an integrated phase plate can greatly simplify an optical system structure due to the defocus insensitivity and aberration inhibition of the wavefront coding imaging technology. In addition, the development of free-form surface technology promotes the application of integrated phase plates. In order to view the imaging characteristics of the integrated wavefront coding system, we built two kinds of wavefront coding systems with the phase plate integrated in different surfaces of the optical system. Simulation results show that phase plates with the same parameters but in different surfaces can realize consistent results. For further observation, two separated phase plates with the same parameters are processed, and, correspondingly, experiments of microscopic objective imaging are carried out. Experimental results confirm that the phase plate can be successfully applied to increase the design flexibility of wavefront coding, leading to a potential mass application solution.

A composite prepared from MnO2 nanosheets and a deep eutectic solvent as an oxidase mimic for the colorimetric determination of DNA.

A composite was fabricated from deep eutectic solvent and MnO2 nanosheets (DES/MnO2) and is shown to be a viable oxidase mimic. The property, morphology and composition of DES/MnO2 was characterized. DES/MnO2 displays oxidase-like activity and can oxidize 3,3',5,5'-tetramethylbenzidine (TMB) to form a blue product (oxTMB) with an absorption maximum at 652 nm. Due to the presence of the DES, the polyanionic and negatively charged DNA is easily adsorbed on the surface of the composite by hydrogen bonding and electrostatic interactions. This leads to the inhibition of the oxidase-mimicking activity of DES/MnO2. This finding was used to design a colorimetric method for the determination of DNA. The assay work in the 10-100 µg mL-1 DNA concentration range and has a detection limit of 0.37 µg mL-1. The inhibiting mechanism was further studied by zeta potential measurements, dynamic light scattering and transmission electron microscopy. The selectivity study shows the DES/MnO2-TMB system to be highly selective for DNA when compared with many proteins, carbohydrates, salts and amino acid. RNA, on the other hand, interferes. The real sample analysis result illustrates that the new method can be used for the detection of DNA in bovine whole blood. Graphical abstractA novel oxidase mimic based on deep eutectic solvent-functionalized MnO2 nanosheets was synthesized, which can directly catalyze oxidation of 3,3',5,5'-tetramethylbenzidine (TMB, colorless) to oxTMB (blue). A sensitive and convenient colorimetric strategy for visual detection of DNA was established through DES/MnO2-TMB sensing system.

A composite consisting of a deep eutectic solvent and dispersed magnetic metal-organic framework (type UiO-66-NH2) for solid-phase extraction of RNA.

A cactus-shaped magnetic composite was prepared for solid-phase extraction of RNA. It is composed of the metal organic framework UiO-66-NH2 that was modified with Fe3O4 nanoparticles. The composite was then dispersed in a lactic acid-based deep eutectic solvent (DES, Fe3O4-COOH@UiO-66-NH2@DES). The structures of the sorbents were characterized by transmission electron microscopy, scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectrometry, vibrating sample magnetometry and thermogravimetric analysis. The extraction performance of sorbents was optimized and the maximum extraction capacity reached 246 mg·g-1. Extraction is shown to mainly rely on chelation interaction, electrostatic interaction, hydrophobic interaction and hydrogen bonding interaction. The sorbent can selectively extract RNA over DNA, bovine hemoglobin and amino acids. Regeneration studies indicated that the sorbent can be re-used (after regenreation with DES) several times without obvious change of the extraction capacity. The successful extraction of RNA from yeast testified the practical application of the sorbent. Graphical abstractSchematic representation of the fabrication Fe3O4-COOH@UiO-66-NH2@DES, and its application in the magnetic solid phase extraction of RNA.

Preparation of magnetic molecularly imprinted polymers based on a deep eutectic solvent as the functional monomer for specific recognition of lysozyme.

A magnetized molecularly imprinted polymer (MIP) was prepared via a surface-imprinting technique. An allyl-based deep eutectic solvent was chosen as the functional monomer to obtain the polymer for specific recognition of lysozyme. It was deposited on silica-coated magnetite nanoparticles. The structure of the polymer was confirmed by X-ray diffraction, Fourier transform infrared spectrometry, transmission electron microscopy, thermogravimetric analysis and vibrating sample magnetometry. The maximum binding capacity of the imprinted polymer is found to be 108 mg·g-1, which is higher than that of non-imprinted polymer. Compared to reference proteins such as cytochrome C, bovine hemoglobin and bovine serum albumin, the MIP shows favorable selectivity for lysozyme. Besides, the imprinted polymer can be further used to specifically recognize lysozyme from the protein mixture and chicken egg white. Reusability studies demonstrate that the polymer can be recycled four times without significant loss of adsorption capacity. The LOD of the method is 12.8 µg·mL-1. The relative standard deviations (for n = 3) are 1.38% for precision and 2.76% for repeatability. Its facile synthesis, high adsorption performance and excellent selectivity to capture lysozyme make this polymer an attractive candidate to be applied in biomacromolecular purification. Graphical abstract Magnetic molecularly imprinted polymer (MIP) based on deep eutectic solvent as functional monomer was fabricated and applied for the specific recognition of lysozyme. The MIP exhibits high adsorption capacity and excellent selectivity for lysozyme.

Potential of novel antimicrobial peptide P3 from bovine erythrocytes and its analogs to disrupt bacterial membranes in vitro and display activity against drug-resistant bacteria in a mouse model.

With the emergence of many antibiotic-resistant strains worldwide, antimicrobial peptides (AMPs) are being evaluated as promising alternatives to conventional antibiotics. P3, a novel hemoglobin peptide derived from bovine erythrocytes, exhibited modest antimicrobial activity in vitro. We evaluated the antimicrobial activities of P3 and an analog, JH-3, both in vitro and in vivo. The MICs of P3 and JH-3 ranged from 3.125 µg/ml to 50 µg/ml when a wide spectrum of bacteria was tested, including multidrug-resistant strains. P3 killed bacteria within 30 min by disrupting the bacterial cytoplasmic membrane and disturbing the intracellular calcium balance. Circular dichroism (CD) spectrometry showed that P3 assumed an α-helical conformation in bacterial lipid membranes, which was indispensable for antimicrobial activity. Importantly, the 50% lethal dose (LD50) of JH-3 was 180 mg/kg of mouse body weight after intraperitoneal (i.p.) injection, and no death was observed at any dose up to 240 mg/kg body weight following subcutaneous (s.c.) injection. Furthermore, JH-3 significantly decreased the bacterial count and rescued infected mice in a model of mouse bacteremia. In conclusion, P3 and an analog exhibited potent antimicrobial activities and relatively low toxicities in a mouse model, indicating that they may be useful for treating infections caused by drug-resistant bacteria.

The mechanism and regioselectivity of gold(I) or platinum(II) catalyzed intramolecular hydroarylation to pyrrolopyridinones and pyrroloazepinones.

We report here the theoretical analysis of the mechanism and regioselectivity of gold(I) or platinum(II) catalyzed intramolecular hydroarylation to pyrrolopyridinones and pyrroloazepinones. AuPH3(+) and PtCl2 have been considered to account for some experimental observations. Our calculation results indicate that in the case of cationic gold the nucleophilic attack of the pyrrole on the activated alkyne occurs in an exo-dig fashion generating a six-membered intermediate, which upon deprotonation and protodeauration forms pyrrolopyridinone. When platinum is used, an endo-dig fashion is observed generating a seven-membered intermediate. After deprotonation and protodeplatination pyrroloazepinone is formed. Whether for exo-dig (gold(I)) or endo-dig (platinum(II)) cyclization, a [1,2]-migration would not be needed.

Dual-functional thermal management textiles for dynamic temperature regulation based on ultra-stretchable spiral conductive composite yarn with 500%-strain thermal stability and durability.

Next-generation personal thermal management (PTM) textiles for daily routine environments are attracting extensive attention. However, challenges remain in developing multifunctional PTM textiles that are comfortable to wear, have motion stability and environmental adaptability. Herein, a novel design for fabricating a sandwich-structure PTM textile based on an ultra-stretchable spiral conductive composite yarn (SCCY) with strain-electric stability is proposed. An SCCY composed of carbon nanotubes (CNTs)/polyvinyl pyrrolidone (PVP)/waterborne polyurethane (WPU) and a drawn textured yarn (DTY) is fabricated through a dip-twisting and shaping process. The PVP not only facilitates the interfacial bonding between CNTs and yarn, but also constructs strong hydrogen bond interactions with WPU, resulting in improved structure stability and robust electrical performance. Benefitting from the optimized spiral and composite structure, the SCCY exhibits a fast thermal response (130 °C within 8 s), long-term durability (1500 cycles), and superior thermal stability under large deformation (ΔT/T0 ≈ 8.4%, under 500%). By assembling a stretchable electrothermal fabric based on SCCYs with an elastic fabric and thermochromic layer, temperature visualization and dynamic temperature regulation are integrated into the textile. This multifunctional PTM textile not only features dual thermal regulation modes of radiant cooling and Joule heating, but also maintains flexibility, breathability, and excellent stretchability, which provides broad application prospects in next-generation wearable devices.

Methods for assessing spillover effects between concurrent green initiatives.

This research presents the methods that are used to examine the dynamics and potential spillover effects of various global environmental conservation programs. We specifically show the data and models that we use to analyze the interactions and mutual influences between the U.S.'s Conservation Reserve Program (CRP) and Environmental Quality Incentives Program (EQIP), as well as those between China's Grain-to-Green Program (GTGP) and Forest Ecological Benefit Compensation (FEBC). Additionally, this study illustrates information about global initiatives, their interconnected impacts, and the associated policy strategies for environmental conservation. By utilizing multivariate regression, logistic regression, eigenvector spatial filtering, and scenario modeling, the research aims to understand the collective influence of these initiatives on broader environmental objectives. The findings of this study provide valuable insights for improving conservation policy designs and effectiveness.•Multivariate and logistic regression analyses to dissect global environmental conservation program interactions and mutual influences.•Eigenvector spatial filtering to address spatial autocorrelation and enhance the accuracy of the model results and our interpretations.•Scenario modeling to project potential future outcomes and impacts.

Design of Single-Atom Catalysts for E lectrocatalytic Nitrogen Fixation.

The Electrochemical nitrogen reduction reaction (ENRR) can be used to solve environmental problems as well as energy shortage. However, ENRR still faces the problems of low NH3 yield and low selectivity. The NH3 yield and selectivity in ENRR are affected by multiple factors such as electrolytic cells, electrolytes, and catalysts, etc. Among these catalysts are at the core of ENRR research. Single-atom catalysts (SACs) with intrinsic activity have become an emerging technology for numerous energy regeneration, including ENRR. In particular, regulating the microenvironment of SACs (hydrogen evolution reaction inhibition, carrier engineering, metal-carrier interaction, etc.) can break through the limitation of intrinsic activity of SACs. Therefore, this Review first introduces the basic principles of NRR and outlines the key factors affecting ENRR. Then a comprehensive summary is given of the progress of SACs (precious metals, non-precious metals, non-metallic) and diatomic catalysts (DACs) in ENRR. The impact of SACs microenvironmental regulation on ENRR is highlighted. Finally, further research directions for SACs in ENRR are discussed.

Evaluation of potentially harmful Maillard reaction products in different types of commercial formulae.

Pasteurisation and spray drying are critical steps to ensure the safety and shelf-life of formulae, but these treatments also induce formation of some potentially harmful Maillard reaction products. In this study, the occurrence of potentially harmful Maillard reaction products and proximate compositions in different commercial formulae were analysed. Our results showed that infant formulae had significantly higher concentrations of furosine, Nε-(carboxymethyl)lysine (CML) and Nε-(carboxyethyl)lysine (CEL) than follow-on/toddler formula. Specialty formulae had higher concentrations of glyoxal and CML than other types of formulae. Correlation analysis indicated that concentrations of 5-hydroxymethylfurfural, 3-deoxyglucosone, CML and CEL were closely related to fat contents. These results provided insight into concentrations of potentially harmful Maillard reaction products in different types of formulae and provide a theoretical basis for further optimisation of processing.

Structural changes of rice starch-anthocyanins complexes (V-type) and its impact on gut microbiotas and potential metabolic pathways during in vitro fermentation.

This study explored the differences in the in vitro fermentation properties of rice starch (RS) and rice starch-anthocyanins complexes (RS-A). Structural characterization suggested that RS and RS-A complexes showed a V-type crystalline structure. The degree of order (DO) and degree of double helix (DD) values of RS and RS-A complexes were enhanced after fermentation. Moreover, the RS-A complexes could improve the relative abundance of Bacteroidetes, Ruminococcaceae, and up-regulate gut microbiota diversity to maintain gut homeostasis. Relative abundance of potential metabolic pathways, such as energy metabolism, digestion system, and carbohydrate degradation overexpressed in the presence of RS-A complexes. The results demonstrated that the RS-A complexes had slower fermentation rates contributing to the transport of the formed short-chain fatty acid (SCFA) to the end of the colon and that the crystallinity might be a factor influencing the utilization of the starch matrix by the gut microbiota for SCFA formation.

Discrepancy of Effective Water Diffusivities Determined from Dynamic Vapor Sorption Measurements with Different Relative Humidity Step Sizes: Observations from Cereal Materials.

Water diffusivity, a critical parameter for cereal processing design and quality optimization, is usually concentration-dependent. dynamic vapor sorption (DVS) system provides an approach to establishing the relationship between water concentration and diffusivity. However, the usual relative humidity (RH) jump during practical sorption processes is usually greater than that adopted in DVS measurements. Water vapor sorption kinetics of glutinous rice grains, glutinous rice flour and wheat flour dough films were measured using the DVS system to verify if varying RH step sizes can obtain identical diffusivities within the same range. The effective diffusivities were determined according to Fick's second law. The results revealed that increasing RH step size led to a higher estimated diffusivity, regardless of whether the water concentration gradient or potential chemical gradient was considered a driving force for water diffusion. This finding was further confirmed by a linear RH scanning DVS measurement. The water concentration-dependent diffusivity obtained from a multi-step DVS measurement, according to Fick's second law, will overestimate the required time for practical cereal drying or adsorption. Thus, this paradoxical discrepancy needs a new mass transfer mechanism to be explained.