Stable anode/separator interface enabled by graft modification of polypropylene separator via electron beam irradiation technique toward high-performance sodium metal batteries.

Sodium metal batteries (SMBs) are considered as strong alternatives to lithium-ion batteries (LIBs), due to the inherent merits of sodium metal anodes (SMAs) including low redox potential (-2.71 V vs. SHE), high theoretical capacity (1166 mAh g-1), and abundant resources. However, the uncontrollable Na dendrite growth has significantly impeded the practical deployment of SMBs. Separator modification has emerged as an effective strategy for substantially enhancing the performance of SMAs. Herein, for the first time, we present the successful grafting polyacrylic acid (PAA) onto polypropylene (PP) separators (denoted as PP-g-PAA) using highly efficient electron beam (EB) irradiation to improve the cyclability of SMAs. The polar carboxyl groups of PAA can facilitate the electrolyte wetting and provide ample mechanical strength to resist dendrite penetration. Consequently, the regulation of Na+ ion flux enables uniform Na+ deposition with dendrite-free morphology, facilitated by the favorable anode/separator interface. The PP-g-PAA separator significantly enhances the cyclability of fabricated cells. Notably, the lifespan of Na||Na symmetric cells can be extended up to 5519 h at 1 mA cm-2 and 1 mAh cm-2. The stable design of the anode/separator interface achieved through polyolefin separator modification presented in this study holds promise for the further advancement of next-generation advanced battery systems.

Fabrication of nitrogen-doped carbon dots biomass composite hydrogel for adsorption of Cu (II) in wastewater or soil and DFT simulation for adsorption mechanism.

With the increase of Cu (II) content, its bioaccumulation becomes a potential pollution to the environment. It is necessary to design an economical and efficient material to remove Cu (II) without causing other environmental hazards. A novel material of alginate composite bead (ALG@NCDs) was synthesized by embedding N-doped carbon dots into pure alginate bead for the adsorption of Cu (II) from wastewater and contaminated soil. The initial concentration, the amount of adsorbent, temperature, adsorption time, and pH value were optimized for the adsorption of Cu (II). According to the Langmuir isothermal adsorption model, the maximum adsorption amount of the material to Cu (II) was 152.44 mg/g. The results of selective adsorption showed that ALG@NCDs had higher affinity to Cu (II) than to Pb (II), Co (II), Ni (II), and Zn (II). After five adsorption-desorption experiment, adsorption capacity of the ALG@NCDs was kept 89% of the initial adsorption capacity. Its Cu (II) adsorption mechanism was studied by density functional theory calculations. In addition, the material could effectively adsorb Cu (II) and release the phytonutrient Ca (II) simultaneously when applied to actual wastewater and soil. The fabricated ALG@NCDs would be a promising material for the adsorption of Cu (II) from wastewater or soil.

Rapid sequential detection of Al3+ and glyphosate using an "Off-On-Off" fluorescent probe based on salicylate modified layered double hydroxides.

A fluorescent probe based on salicylate modified layered double hydroxide (LDH-SA) is presented, enabling the swift sequential detection of Al3+, fosetyl-Al and glyphosate in aqueous environment. The probe was synthesized using a simple co-precipitation procedure, and its properties and synthesis conditions were thoroughly characterized and optimized. A unique "off-on-off" fluorescent response was observed when the probe sequentially interacted with Al3+ and glyphosate, and the detection method based on this phenomenon was established. The limits of detection for Al3+ and glyphosate were determined as 0.03 µmol/L and 0.03 mg/L, respectively, with rapid detection periods of one minute and four minutes. The LDH-SA/Al3+ complex requires Al3+ to generate a chelation-gathered fluorescence effect, which is the mechanism by which it quenches LDH-SA. This is possible due to the inhibition of excited-state intramolecular proton transfer and photoinduced electron transfer processes within LDH-SA after incorporating Al3+. Upon interaction with glyphosate, competitive complexation between glyphosate and Al3+ is initiated, which leads to a recovery of the fluorescence spectrum of LDH-SA and demonstrating the "off-on-off" behavior. An "INHIBIT" logic gate system was devised utilizing the response, indicating potential applications in fluorescence-based devices. Such a rapid, sequential detection capacity is impressive. It attests to the utility of LDH-SA as a probe for Al3+ or glyphosate, and suggests promise for applications in pollutant analysis or environmental monitoring applications.

Rapid visual dual-mode detection of Zr(IV) based on L-histidine functionalized gold nanoparticles.

Heavy metal pollution has always been a great threat to human health and safety. Compared with other heavy metals, although zirconium ion (Zr(IV)) is equally harmful, due to the lack of research on Zr(IV) in the biological systems and environment, its detection does not seem to have received the attention it deserves. Herein, a rapid visual dual-mode detection (colorimetric and chrominance method) of Zr(IV) based on L-histidine functionalized gold nanoparticles (HIS-AuNPs) has been reported. AuNPs and HIS-AuNPs before and after adding Zr(IV) were characterized by UV-Vis, TEM, DLS, Zeta potential, EDS and FT-IR, etc. These results showed that L-histidine was successfully modified on the surface of AuNPs by forming a stable Au-N bond, and its modification had little effect on the dispersion degree of AuNPs. After the addition of Zr(IV), interaction of this metal ion with the imidazolyl group on L-histidine can obviously cause the aggregation of HIS-AuNPs within 12 min, and the dispersion state and particle size of HIS-AuNPs can be significantly changed. These two detection modes were established by means of absorbance and color change of solution, and being used in addition and recovery experiments of Zr(IV) in natural water. Under the optimal conditions, these two modes exhibited good linearity within 15-70 and 20-100 µmol L-1, and limit of detection of 2.62 and 6.25 µmol L-1. The proposed method was highly sensitive and selective, which provided a new convenient way to realize the detection of Zr(IV).

Pentanary Oxythiogermanates Ba3MGe3O2S8 (M = Ca, Zn) Featuring [Ge3O2S8]8- Trimers and {[MGe3O2S8]6-}∞ Chains: Structural Chemistry and Physical Properties.

Oxychalcogenides are increasingly attracting wide attention because they contain multiple anions that may combine the advantages of oxides and chalcogenides. In this work, two new pentanary oxythiogermanates, Ba3MGe3O2S8 [M = Ca (1), Zn (2)], were synthesized by a high-temperature solid-state reaction. They crystallize in the orthorhombic space group Pnma, and their structures contain isolated [Ge3O2S8]8- units constructed by one [GeO2S2] and two [GeOS3] tetrahedra that link with M2+ ions to build the {[MGe3O2S8]6-}∞ chain, representing a new type of oxythiogermanate. Notably, a [ZnS5] square pyramid exists in 2. Their structural chemistry and relationship with relevant structures are analyzed. 1 and 2 exhibit wide band gaps of 3.93 and 2.63 eV, birefringences of 0.100 and 0.089 at 2100 nm, respectively, and also obvious photocurrent responses. This work may be extended to a family of AE3MIIMIV3O2Q8 (AE = alkali-earth metal; MII = Ca, Zn, Cd, Hg; MIV = Si, Ge, Sn; Q = S, Se), and further systematic survey on them can be performed to enrich the study of multifunctional oxychalcogenides.

Design of Pentanary Mixed-Chalcogenides Ag2In2SiS6-xSex (x = 1, 2) Based on the Bucket Effect: Local Structural Difference and High-Performance Nonlinear-Optical Properties Realized by Partial Congener Substitution.

Noncentrosymmetric chalcogenides are promising candidates for infrared nonlinear-optical (NLO) crystals, and exploring high-performance ones is a hot topic and challengeable. Herein, the combination of AgQ4, InQ4, and SiQ4 (Q = S, Se) units with different S/Se ratios resulted in the discovery of the tetrahedral chalcogenides Ag2In2SiS4Se2 (1) and Ag2In2SiS5Se (2). They both crystallize in the monoclinic Cc space group with different local structures. Co-occupied S/Se sites only exist in 2, and the arrangement of [In2SiQ3] six-membered rings builds different helical chains and 3D [(In2SiQ6)2-]n polyanionic frameworks in 1 and 2. They show balanced NLO performances, including phase-matchable moderate NLO responses (0.7 and 0.5 × AGS) and enhanced laser-induced damage thresholds (4.5 and 5.1 × AGS). Theoretical calculations reveal that their NLO responses are predominantly contributed by the AgQ4 and InQ4 units.

Polysubstitution Induced Centrosymmetric-to-Noncentrosymmetric Structural Transformation and Nonlinear-Optical Behavior: The Case of Na0.45Ag0.55Ga3Se5.

Obtaining compounds with large nonlinear-optical (NLO) coefficients and wide band gaps is challenging due to their competitive requirements for chemical bonds. Herein, the first member with mixed cations on the A site in the A-M3-Q5 or A-Ag-M6-Q10 (A = alkali metal; M = Ga, In; Q = S, Se, Te) family, viz. Na0.45Ag0.55Ga3Se5 (NAGSe), was obtained by a solid-state reaction. Its structure features [GaSe4] tetrahedra built three-dimensional {[Ga3Se5]-}∞ network, with Na and Na/Ag cations located at the octahedral cavities. Noncentrosymmetric (R32) NAGSe can also be transformed from centrosymmetric RbGa3S5 (P21/c) via multiple-site cosubstitution. NAGSe exhibits the highest NLO response (1.9 × AGS) in the A-Ag-M-Q family. Crystal structure analysis and theoretical calculations suggest that the NLO response is mainly contributed by the regularly arranged [GaSe4] units. This work enriches the exploration of the undeveloped A-M3-Q5 or A-Ag-M6-Q10 family as potential infrared NLO materials.

Construction of a three-mode sensor based on gold nanoparticles and carbon quantum dots as probes for the detection of thiosemicarbazone.

In this study, ginkgo leaves were used as a carbon source to synthesize carbon quantum dots (CQDs) with uniform particle size, high fluorescence (FL) intensity and strong stability, using a hydrothermal method. FL could be quenched by the FL resonance energy transfer effect between CQDs and gold nanoparticles (AuNPs), an important FL quenching agent. The electrostatic attraction between thiosemicarbazone (TSC) and citrate on the surface of AuNPs and the formation of a stable Au-S bond between TSC and AuNPs led to the aggregation of AuNPs and thus weakened the quenching effect on CQDs and partly recovered the FL. A sensor in FL mode for the detection of TSC was constructed based on the above-mentioned FL "off" and "on" phenomena. The results showed a good linear correlation in the concentration range 0-1.75 µM, and the limit of detection was as low as 0.05 µM. In addition, the aggregation of AuNPs caused by TSC also led to a change in the absorbance curve and color of the solution; colorimetric and chrominance detection modes were also constructed using these two types of changes, with sensitive responses ranging 0-2.25 µM and 0-1.60 µM and the limits of detection of 0.03 µM and 0.08 µM, respectively. More importantly, these three detection modes obtained satisfactory recovery rates in the detection of the TSC content in river water, liquor and wheat samples, and the detection results were mutually verified (95.18% to 104.96%).

Chlorinated paraffins in takeout food and its packaging in Beijing, China and dietary exposure risk.

Chlorinated paraffins (CPs) are hazardous to humans, and dietary intake acts as the primary pathway for human exposure to CPs. Takeout food is popular worldwide, but the presence of CPs in takeout food and its packaging is unclear. In this study, the concentrations and distributions of short- and median-chain CPs (SCCPs and MCCPs, respectively) were measured in 97 samples of four categories of takeout food and 33 samples of three types of takeout packaging. The SCCP and MCCP median concentrations for the takeout food samples were 248 and 339, 77.2 and 98.2, 118 and 258, 42.9 and 64.4 ng/g wet weight in meat, starch, half meat/half starch, and vegetables, respectively. Takeout food contained higher concentrations of SCCPs than MCCPs. The dominant SCCP and MCCP congener groups in takeout food were C10Cl6-7 and C14Cl7-8, respectively. The CP concentrations in takeout food were lower than those in packaging. The SCCP and MCCP median concentrations, respectively, in packaging were 9750 and 245 ng/g in polypropylene, 2830 and 135 ng/g in paper, and 2060 and 119 ng/g in aluminum foil. The concentrations of SCCPs and MCCPs were comparable in aluminum foil, whereas the concentrations of SCCPs were higher than those of MCCPs in polypropylene and paper. Correlations between CP concentrations in the takeout food and packaging indicated that CPs in packaging were potentially an important source of CPs in the takeout food. A dietary exposure risk assessment showed the takeout food posed a low risk for human exposure to CPs; however, high-frequency consumption may pose a health risk. This study clarified the current contamination situation in takeout food in Beijing, China. The resulting data could be used to prevent human exposure to CPs through dietary intake and to facilitate the market's control over the quality of takeout food.

Rational Design of Novel Promising Infrared Nonlinear Optical Materials: Structural Chemistry and Balanced Performances.

ConspectusSecond-order nonlinear optical (NLO) materials are currently a hot topic in modern solid-state chemistry and optics because they can produce coherent light by frequency conversion. Noncentrosymmetric (NCS) structure is not only the prerequisite for NLO materials but also a challengeable issue because materials tend to be centrosymmetric (CS) in terms of thermodynamical stability. Among NLO materials, an excellent infrared (IR) candidate should simultaneously meet several strict key conditions including a large NLO coefficient, high laser-induced damage threshold (LIDT), phase-matchable (PM) behavior, and so on. Achieving a balance between the large NLO effect and high LIDT is difficult, as they have contradictory requirements for chemical bonds. Considering the urgent need of the high-power IR laser market and the drawbacks of the available ones, exploring new high-performance IR NLO crystals is necessary while challenging. In this Account, we first briefly introduce the status and advancement of IR NLO crystals and emphasize the criteria of an excellent candidate. Then, we will introduce five simple methods developed by us to discover practical NLO candidates through understanding of the chemical composition-structure-NLO performance relationship. (1) A rarely investigated system with simple chemical compositions as new-type NLO crystals, namely, adducts containing S8 molecules, are developed. Combining a chairlike S8 unit with other units through van der Waals forces has successfully obtained several high-performance NLO adducts. (2) The main trend in exploring new NLO crystals is that the chemical composition is more and more diversified and the structure is more and more complex, and expensive and chemically active alkaline and alkaline earth metals are usually introduced as counter cations. In contrast, the research on systems with simple chemical compositions, simple structures, and low costs has been continuously ignored. The binary M2Q3 (M = Ga, In; Q = S, Se) family with rich acentric modifications has been systematically investigated, and they all exhibit strong SHG effects and high LIDTs. (3) We first proposed the concept of inducing CS structures transformed to NCS ones by partial cation substitution to design novel NLO crystals. Considering the huge number of CS structures in the database compared to the number of NCS structures, it is an attractive method to apply CS structures as the parents to obtain potential NLO materials via partial-substitution-induced symmetry breaking. A series of chalcogenides with high NLO performances have been successfully obtained by us in this way. (4) We investigated the first NLO-active rare earth (RE) chalcophosphates and developed this family systematically, and they demonstrate wonderful comprehensive NLO properties. (5) We created a novel mixed-anion system for NLO applications, namely, chalcogenide borates. Usually, mixed-anion compounds can engender a synergistic effect to obtain desired IR NLO properties. Our recent progress on this system suggests that chalcogenide borates are potential candidates for IR NLO applications, although the study is still in its infancy. Finally, we state the current problems of IR NLO materials and give some perspectives for their future development.

KREP2S6 (RE = Sm, Gd, Tb, Dy): A Series of Polar Rare-Earth Thiophosphates with High Laser-Induced Damage Thresholds and Moderate Nonlinear-Optical Responses Synergistically Contributed by Isolated P2S6 Units and {[RE2S15]24-}∞ Layers.

As one of the potential candidates of nonlinear-optical (NLO) materials, rare-earth chalcophosphates have demonstrated promising properties. Here, KREP2S6 (RE = Sm, Gd, Tb, Dy) were synthesized using the facile RE2O3-B-S solid-state method. They crystallize with a monoclinic chiral P21 structure, and their layer structures are built by isolated ethane-like P2S6 dimers and RES8 bicapped trigonal prisms built {[RE2S15]24-}∞ layers. By comparing the structures with related ones, the change of the alkali metal or RE3+ ions can cause structural transformation. Their band gaps are tunable between 2.58 and 3.79 eV, and their powder samples exhibit good NLO properties. Theoretical calculations suggest that the NLO properties are mainly contributed by P2S6 units and {[RE2S15]24-}∞ layers synergistically, in which {[RE2S15]24-}∞ layers and P2S6 units dominate the contribution to the band gap and second-harmonic-generation response, respectively. This work enriches the application of rare-earth chalcophosphates as NLO materials.

Artificial utilization of saline-sodic land promotes carbon stock: The importance of large macroaggregates.

Soil aggregates are essential functional units involved in soil carbon sequestration, particularly in saline-sodic soils prone to severe carbon loss. In the present study, the distribution of aggregate-associated carbon fractions and their influencing factors were investigated after artificial utilization of saline soil in the Songnen Plain, Northeast China. Physicochemical properties, enzymatic activities, and bacterial communities were measured in various hierarchical aggregates among two natural land-use types (saline wasteland and degraded grassland) and three anthropogenic land-use types (artificial forest, upland field, and paddy field). The results indicated that, compared to saline wasteland, anthropogenic land use was witnessed an increase in macroaggregate proportions, and PF in large macroaggregates increased the most, while UF and FL were mainly increased in small macroaggregates. After transforming from natural land to anthropogenic land, the aggregate-associated carbon fractions (total organic carbon, readily soluble organic carbon, dissolved organic carbon, and microbial biomass carbon) increased, especially in small macroaggregates. All enzyme activities increased after artificial utilization, hydrolase (urease, amylase, and invertase), catalase, and ß-glucosidase activities were highest in the small macroaggregates. Bacterial biomass was increased in all three aggregate types compared to natural land. Due to the influence of various factors on soil carbon storage, through partial least squares path modeling revealed that large macroaggregates were conducive to carbon storage. These findings suggested that artificial utilization of saline soil can increase large macroaggregate proportions and the abundance of aggregate-associated carbon, resulting in increased soil carbon stocks, with PF having the greatest carbon sequestration capacity.

Promising adsorbent for dye detoxification: Exploring the potential of chitosan sodium carboxymethylcellulose silk fibroin aerogel.

The main goal of this study is to create a CS-CMC-SF aerogel consisting of chitosan sodium carboxymethylcellulose and silk fibroin. The aerogel is designed to remove types of dyes from water while also being environmentally friendly. This innovative adsorbent has been optimized for extracting both cationic and anionic dyes from solutions. It incorporates chitosan sodium carboxymethylcellulose and silk filament fibers to enhance its strength. Experimental data illustrates that the CS-CMC-SF aerogel possesses remarkable adsorption capabilities - 5461.77 mg/g for Congo Red (CR), 2392.83 mg/g for Malachite Green (MG), and 1262.20 mg/g for Crystal Violet (CV). A kinetic study aligns with the pseudo-second-order kinetic model suggesting predominant chemisorption phenomena occur during adsorption process. Isotherm analysis further identifies multilayered adsorption occurring on irregularly shaped surfaces of the aerogel while thermodynamic assessments validate exothermic and spontaneous characteristics inherent in its absorption mechanism. Several analytical methods such as SEM, FT-IR, XRD, and XPS were employed to examine physicochemical attributes tied to this unique material design conceptually; identifying mechanisms including pore filling, π-π interactions, ion exchange activity, electrostatic connections along with hydrogen bonding inducing overall superior performance output. Furthermore substantial soil biodegradability alongside compostable features associated with our proposed CS-CMC-SF aerogels established it's potential suitability within applications demanding sustainable options thereby validating its underlying ecological credibility.

NaREP2Se6 (RE = Y, Sm, Gd-Dy): Quaternary Rare-Earth Selenophosphates with Unique 3D {[REP2Se6]-}∞ Framework Built by RESe8 and P2Se6 Motifs and Multiple Properties.

Rare-earth (RE) chalcophosphates have been widely studied because of their abundant structures. Here, five new RE selenophosphates, NaREP2Se6 (RE = Y, Sm, Gd-Dy), were synthesized by a facile RE oxide-boron-selenium solid-state route. They crystallize in the triclinic P1̅ space group, featuring three-dimensional (3D) structures constructed by RESe8 and P2Se6 motifs, different from common 2D RE chalcophosphates A-RE-P2-Q6 (A = alkali metal; Q = S, Se) system. Their structural chemistry and relationship with related phases are analyzed. Both the size of A and the coordination geometry of RE have important influences on the system's structures. Their optical band gaps are tunable from 1.79 to 2.50 eV, and they exhibit diverse magnetic behaviors, including Van-Vleck-type paramagnetism, antiferromagnetism, and ferromagnetism. Their photocurrent responses and thermal stabilities are analyzed as well. Calculation results suggest that the RESe8 and P2Se6 units make a great contribution to the optical properties. This work enriches the chemistry and multifunctional properties of RE chalcophosphates.

Long-term rice cultivation increases contributions of plant and microbial-derived carbon to soil organic carbon in saline-sodic soils.

Rice cultivation has been demonstrated to have the ability to improve saline-sodic soil. Whether this human activity can influence the accumulation of soil organic carbon (SOC) in saline-sodic soil remains unclear. In this study, the impact of rice cultivation across different planting durations (1, 5, 10, 27 years and abandoned land) on the carbon (C) levels, derived from plant residues and microbial necromass, were assessed. Compared to the control, plant residues and microbial necromass greatly contributed to the carbon accumulation. For the short-term of rice cultivation (1-10 years), the C content originated from both microbial and plant residues gradually accumulated. In the prolonged cultivation phase (27Y), plant residues and microbial necromasses contributed 40.82 % and 21.03 % of the total SOC, respectively. Additionally, rice cultivation significantly reduced the pH by 13.58-22.51 %, electrical conductivity (EC) by 60.06-90.30 %, and exchangeable sodium percentage (ESP) by 60.68-78.39 %. In contrast, total nitrogen (TN), total phosphorus (TP), SOC, particulate organic C, mineral-bound organic C, and microbial biomass all saw statistical increases. The activities of extracellular enzymes in paddy soils, such as peroxidase, phenol oxidase, and leucine aminopeptidase, were significantly reduced, and the decomposition of lignin, phenol, and amino sugars by soil microorganisms was consequently suppressed. The partial least squares path modeling results demonstrated that rice cultivation affected the accumulation of plant and microbial components via the corresponding chemical properties (pH, EC, and ESP), nutrient content (TN, TP, and SOC), enzyme activity (LAP, PER, and POX), microbial biomass, and plant biomass. These findings are crucial for understanding the organic carbon sequestration potential of sodic saline soils.

Three-in-One Tetrahedral Functional Units Constructing Diamondlike Ag2In2SiS3.06Se2.94 with High-Performance Nonlinear-Optical Activity.

Exploration of new functional materials with enhanced performance from known ones is always an attractive strategy. A new infrared (IR) nonlinear-optical (NLO) mixed chalcogenide Ag2In2SiS3.06Se2.94 (1), was obtained through partial congener substitution originated from Ag2In2SiS6 (0). 1 crystallizes in the monoclinic space group Cc, and its three-dimensional (3D) polyanionic network is composed of {[In4Si2Se5(S/Se)11]12-}∞ helical chains sharing S/Se(5) corner atoms with cavities embedded with counterion Ag+ ions. It exhibits a much enhanced NLO response compared to that of 0, reaching 1.1 × AgGaS2. Further theoretical analysis results indicate that the large NLO response can be attributed to the synergistic effect of AgQ4 and InQ4 tetrahedral functional motifs. This work not only reports a new high-performance IR NLO material but also enriches the partial ion substitution strategy to obtain new functional materials.

An 'on-off-on' fluorescent switch based on a luminous covalent organic framework for the rapid and selective detection of glyphosate.

Glyphosate, the most used herbicide in the world, has a residue problem that cannot be ignored. However, glyphosate itself does not have fluorescence emission and lacks the conditions for fluorescence detection. In this work, a rapid and selective fluorescence detection method of glyphosate was designed by an 'on-off-on' fluorescent switch based on a luminous covalent organic framework (L-COF). Only the fixed concentration of Fe3+ as an intermediate could trigger the fluorescent switch and no incubation step was required. The proposed method showed good accuracy with a correlation coefficient of 0.9978. The method's limits of detection and quantitation were 0.88 and 2.93 µmol/L, which were lower than the maximum allowable residue limits in some regulations. Environmental water samples and tomatoes were selected as actual samples to verify the application in a complex matrix. A satisfactory mean recovery from 87% to 106% was gained. Furthermore, Fe3+ could induce fluorescence quenching of L-COF through the photo-induced electron transfer (PET) effect, while the addition of glyphosate could block the PET effect to achieve detection. These results demonstrated the proposed method had abilities to detect glyphosate and broaden the application of L-COF.

Phenylboronic acid-functionalized magnetic metal-organic framework nanoparticles for magnetic solid phase extraction of five benzoylurea insecticides.

This research involves the construction of a phenylboronic acid-functionalized magnetic UiO-66 metal-organic framework (MOF) nanoparticle (CPBA@UiO-66@Fe3O4). Its design is primarily for the magnetic solid phase extraction (MSPE) of benzoylurea insecticides. An organic ligand, 2-amino terephthalic acid (2-ATPA), facilitated the introduction of amino groups while keeping the original crystal structure of UiO-66 intact. The constructed UiO-66 MOF showcases a porous structure and extensive surface area, thereby providing an optimal platform for further functionalization. The employment of 4-carboxylphenylboronic acid as a modifier notably amplified the extraction efficiency for benzoylureas. This improvement was due to the formation of B-N coordination and other secondary interactions. By integrating this with high-performance liquid chromatography (HPLC), we established a quantitative analytical method for benzoylurea insecticides. This method achieved a wide linear range (2.5-500 µg L-1 or 5-500 µg L-1), satisfactory recoveries (83.3-95.1%), and acceptable limits of detection (LODs: 0.3-1.0 µg L-1). The developed method proved successful when applied to six tea infusion samples, representing China's six major tea categories. Semi-fermented and light-fermented tea samples demonstrated relatively higher spiking recoveries.

Numerical Analysis of Fracture Behaviour for Cracked Joints in Corrugated Plate Girders Repaired by Stop-Holes.

The efficient crack eliminated stop-hole measure was proposed to repair and reduce the stress concentration associated fracture risk of the corrugated plate girders by setting it at the critical joint of flange plate with tightened bolts and gaskets under preloading. To investigate the fracture behaviour of these repaired girders, parametric finite element analysis was conducted, focusing on the mechanical feature and stress intensity factor of crack stop-hole in this paper. The numerical model was verified against experimental results first, and then the stress characteristics due to the presence of crack open-hole were analysed. It was found that the moderate-sized open-hole was more effective than the over-sized open-hole in the reduction of stress concentration. For the model with prestressed crack stop-hole through bolt preloading, the stress concentration was nearly 50% with the prestress around open-hole increased to 46 MPa, but such a reduction is inconspicuous for even higher prestress. Relatively high circumferential stress gradients and the crack open angle of oversized crack stop-holes were decreased owing to additional prestress effects from the gasket. Finally, the shift from the original tensile area around the edge of the crack open-hole that was prone to fatigue cracking to a compression-oriented area is beneficial for the reduction of stress intensity factor of the prestressed crack stop-holes. It was also demonstrated that the enlargement of crack open-hole has limited influence on the reduction of stress intensity factor and crack propagation. In contrast, higher bolt prestress was more beneficial in consistently reducing the stress intensity factor of the model with the crack open-hole, even containing long crack.

Investigation on Flexural Fracture Behaviour of Bolted Spherical Joints with Crack Propagation in Screw Threads.

Bolted spherical joints, due to their prominent merits in installation, have been widely used in modern spatial structures. Despite significant research, there is a lack of understanding of their flexural fracture behaviour, which is important for the catastrophe prevention of the whole structure. Given the recent development to fill this knowledge gap, it is the objective of this paper to experimentally investigate the flexural bending capacity of the overall fracture section featured by a heightened neutral axis and fracture behaviour related to variable crack depth in screw threads. Accordingly, two full-scale bolted spherical joints with different bolt diameters were evaluated under three-point bending. The fracture behaviour of bolted spherical joints is first revealed with respect to typical stress distribution and fracture mode. A new theoretical flexural bending capacity expression for the fracture section with a heightened neutral axis is proposed and validated. A numerical model is then developed to estimate the stress amplification and stress intensity factors related to the crack opening (mode-I) fracture for the screw threads of these joints. The model is validated against the theoretical solutions of the thread-tooth-root model. The maximum stress of the screw thread is shown to take place at the same location as the test bolted sphere, while its magnitude can be greatly reduced with an increased thread root radius and flank angle. Finally, different design variants related to threads that have influences on the SIFs are compared, and the moderate steepness of the flank thread has been found to be efficient in reducing the joint fracture. The research findings could thus be beneficial for further improving the fracture resistance of bolted spherical joints.