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.

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 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).

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.

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%).

Obtaining superior high-density fused-ring energetic materials via the introduction of carbonyl, o-NH2-NO2 and nitroamino groups.

Two carbonyl and o-NH2-NO2-containing energetic materials and their analogues were effectively designed, synthesized and fully characterized with multinuclear NMR, IR and elemental analyses. Their structures were also further confirmed via X-ray diffraction. Among them, compound 7 exhibits good potential for application as a secondary explosive with extremely high density (2.04 g cm-3), good sensitivity (IS > 40 J, FS > 360 N), and excellent calculated detonation performance (Dv = 8943 m s-1, P = 35.0 GPa). Furthermore, a detailed comparative study based on X-ray diffraction, Hirshfeld surfaces and 2D fingerprint plots among compounds 4, 7 and 9 has demonstrated that the density and detonation performance could be effectively improved via introducing a carbonyl group into fused-ring compounds. More importantly, the sensitivity of the resulting energetic materials did not deteriorate. Obviously, this strategy via introducing carbonyl, o-NH2-NO2 and nitroamino groups into fused-ring energetic compounds will help in the design of next-generation high-energy and insensitive fused-ring energetic 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.

Calcium-based polymers for suppression of soil acidification by improving acid-buffering capacity and inhibiting nitrification.

Soil acidification is a major threat to agricultural sustainability in tropical and subtropical regions. Biodegradable and environmentally friendly materials, such as calcium lignosulfonate (CaLS), calcium poly(aspartic acid) (PASP-Ca), and calcium poly γ-glutamic acid (γ-PGA-Ca), are known to effectively ameliorate soil acidity. However, their effectiveness in inhibiting soil acidification has not been studied. This study aimed to evaluate the effect of CaLS, PASP-Ca, and γ-PGA-Ca on the resistance of soil toward acidification as directly and indirectly (i.e., via nitrification) caused by the application of HNO3 and urea, respectively. For comparison, Ca(OH)2 and lignin were used as the inorganic and organic controls, respectively. Among the materials, γ-PGA-Ca drove the substantial improvements in the pH buffering capacity (pHBC) of the soil and exhibited the greatest potential in inhibiting HNO3-induced soil acidification via protonation of carboxyl, complexing with Al3+, and cation exchange processes. Under acidification induced by urea, CaLS was the optimal one in inhibiting acidification and increasing exchangeable acidity during incubation. Furthermore, the sharp reduction in the population sizes of ammonia-oxidizing bacteria (AOB) and ammonia-oxidizing archaea (AOA) confirmed the inhibition of nitrification via CaLS application. Therefore, compared to improving soil pHBC, CaLS may play a more important role in suppressing indirect acidification. Overall, γ-PGA-Ca was superior to PASP-Ca and CaLS in enhancing the soil pHBC and the its resistance to acidification induced by HNO3 addition, whereas CaLS was the best at suppressing urea-driven soil acidification by inhibiting nitrification. In conclusion, these results provide a reference for inhibiting soil re-acidification in intensive agricultural systems.

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.

Stereoselective Photoredox Catalyzed (3+3) Dipolar Cycloaddition of Nitrone with Aryl Cyclopropane.

By resorting to the principle of remote activation, we herein demonstrate the first photoredox catalyzed (3+3) dipolar cycloaddition of nitrones with aryl cyclopropanes. Key to the fidelity of the reaction resides in a facile manner of substrate activation by single-electron transfer (SET) oxidation with photoredox catalysis, and the reaction takes place through a stepwise cascade encompassing a three-electron-type nucleophilic substitution triggered cyclopropane ring-opening and a diastereoselective 6-endo-trig radical cyclization manifold. The reaction proceeds under mild conditions with excellent regio- and stereoselectivity, nicely complementing the well-developed Lewis acid catalyzed cycloaddition of donor-acceptor cyclopropanes. Other merits of the protocol include wide scope of aryl cyclopropanes with diversified substitution patterns and good functional-group compatibility. A mechanism involving an aryl radical cation promoted remote activation mode was also proposed and supported by mechanistic experiments.

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.

The Effect of Terbinafine and Its Ionic Salts on Certain Fungal Plant Pathogens.

Terbinafine, an inhibitor of squalene epoxidase in ergosterol biosynthesis, is chiefly utilized as an antifungal medication with potential uses in pesticide applications. This study explores the fungicidal efficacy of terbinafine against prevalent plant pathogens and confirms its effectiveness. To augment its water solubility, five ionic salts of terbinafine were synthesized by pairing them with organic acids. Among these salts, TIS 5 delivered the most impressive results, amplifying the water solubility of terbinafine by three orders of magnitude and lessening its surface tension to facilitate better dispersion during spraying. The in vivo experiments on cherry tomatoes showed that TIS 5 had a superior therapeutic activity compared to its parent compound and two commonly used broad-spectrum fungicides, pyraclostrobin and carbendazim. The results highlight the potential of terbinafine and its ionic salts, particularly TIS 5, for use as fungicides in agriculture due to their synergistic effects with furan-2-carboxylate.

Construction of multiple modes using gold nanoparticles as probes for the rapid detection of fenpyroximate.

Herein, three patterns for the detection of fenpyroximate based on the response signal of gold nanoparticles are described. The strong interaction between the guanidine group of arginine-modified gold nanoparticles and the ester group of fenpyroximate led to the aggregation of the nanoparticles and to a variation of ultraviolet-visible light spectrum and color of the solution. Sensors were constructed based on the correlation of the concentration of fenpyroximate with the absorbance ratio (A650/A525) and the R value was obtained by extracting the color of the test solution by using a smartphone to take a photo of the solution, which was then analyzed by colorimeter software. The absorbance ratio increased linearly in the range of 0.225-0.375 mg L-1 and the limit of detection was 0.215 mg L-1, while the R value declined linearly in the range of 0.20-0.40 mg L-1 and the limit of detection was 0.21 mg L-1. Further, the gold nanoparticles could cause a fluorescence quenching of fluorescent dyes, such as rhodamine B, and it was found that the fluorescence could be quenched and then restored after aggregation; therefore, a fluorescence method based on fluorescence "off-on" was constructed, and the fluorescence quenching was found to increase linearly in the range of 0.0-1.0 mg L-1 and the limit of detection was 0.013 mg L-1. These three patterns indicated highly selective and sensitive response signals for fenpyroximate, and all were applied to the detection of fenpyroximate in apple juice, pear juice, and environmental water samples, with the results showing that the three methods could be mutually verified, with the recoveries ranging from 94.15% to 110.65%.

Conversion of fungicide cyprodinil to salts with organic acids: preparation, characterization, advantages.

BACKGROUND: As an effective strategy to improve the basic properties of drugs, salt formation was less used in the field of pesticides than the medicine field. It is worth trying to improve the inherent shortcomings of cyprodinil (high Kow values; polymorphism) in this way to enhance its practicality. RESULTS: Eight cyprodinil salts (CYP-Salts) were prepared. The properties of CYP-Salts, including solubility in various solvents, polymorphic behavior, soil absorption, photolysis in aquatic water, in vitro fungicidal activity and curative activity, were assessed. It was observed that compared with those of cyprodinil, CYP-Salts had lower soil adsorption, while also having lower log Kow values and could be more easily photodegraded in water. That is, CYP-Salts have lower impacts on water bodies and aquatic organisms than cyprodinil. Three CYP-Salts showed higher in vitro antifungal activities and curative activity. CYP-Salts have enhanced practicality, as they could avoid possible agglomeration caused by recrystallization. CONCLUSION: Salt forming enhanced the properties of Cyprodinil in many aspects. CYP-Salts may potentially become a better substitute for cyprodinil. This study offers a more economical and effective strategy to prepare better alternatives to existing fungicides. © 2022 Society of Chemical Industry.

Dual-mode detection of fluorine-containing pesticides (bifenthrin, flufenoxuron, diflubenzuron) via ratiometric fluorescence and the Tyndall Effect of fluorescent organic nanoparticles.

The Tyndall Effect assay (TEA) has been applied into colorimetric metal ion detection since 2019. However, the TEA-based sensor for pesticide detection has never been reported till now. Herein, a facile fluorescent organic nanoparticle (FON)-based sensor is firstly developed for fluorine-containing pesticide detection through ratiometric fluorescence assay (FLA) and TEA. For FLA, the intensity of the second-order Tyndall scattering peak (STS590nm) and the fluorescence peak of the FON-based sensor would increase and remain unchanged respectively when adding bifenthrin, flufenoxuron, and diflubenzuron. The detection limits were respectively 9.34, 6.91, and 3.60 µg/kg. For TEA, the increased STS590nm intensity displayed a bright and visible light beam. An economical, simple, and portable device was then constructed to visually monitor the analytes. The sensor was successfully used to detect the analytes in teas through FLA and TEA with the recoveries and RSD ranging from 86.27-100.00 %, and 0.00-5.68 %, respectively.

Analysis of the expression and significance of lymphocyte ratio in different stages and clinical types of COVID-19.

This study aimed to analyze the expression of lymphocyte ratio (LY%) in different stages and clinical staging of COVID-19 and explore the relationship between peripheral blood lymphocyte (PBL) ratio and COVID-19 severity to provide reference for early intervention. For this purpose, a total of 125 patients with COVID-19 admitted to Hebei Provincial People's Hospital from February 1, 2020, to March 1, 2022, were reviewed and divided into moderate, severe, and critical groups by the severity to analyze and compare peripheral lymphocyte ratios of patients with different clinical typing. Results showed that lymphocyte count, lymphocyte percentage, CD3+ T-lymphocyte count, CD4+ T-lymphocyte count, and CD8+ T-lymphocyte count all decreased gradually with increasing severity (F = 27.84, P<0.05; F = 15.28, P<0.05; F = 46.12, P<0.05; F = 34.65, P<0.05); the absolute numbers of CD3+, CD4+ and CD8+ cells in peripheral blood were higher in the recovery phase than in the acute phase (P<0.05). In conclusion, COVID-19 may cause a decrease in the number of lymphocytes, and the decrease in the number of lymphocytes and T-lymphocyte subsets may predict the severity of the disease. The fewer lymphocytes there are, the more likely they are to progress to the severe type and the worse the prognosis.

[Polyamidoamine dendrimer-functionalized silica nanocomposite with polydopamine coating for dispersive micro solid-phase extraction of benzoylurea insecticides in water samples].

Pesticides are used in the agricultural production process to ensure the yield and quality of agricultural products. However, in recent years, environmental pollution issues caused by pesticide residues have sparked widespread concern in society. It is important to develop convenient and efficient approaches to detect and monitor pesticide residues. In this study, targeting benzoylurea insecticides (BUs), polyamidoamine dendrimer-functionalized silica nanocomposite with polydopamine coating (SiO2-PAMAM-PDA) was designed and successfully synthesized. First, monodisperse silica nanoparticles were prepared by the hydrolysis of tetraethyl orthosilicate (TEOS) in mixed solution of ethanol, water and ammonia. The silane coupling agent (3-aminopropyl)triethoxysilane was then employed to introduce amino groups into the silica. Silica with the zeroth generation of polyamidoamine (PAMAM) modification (SiO2-PAMAM-G0) was obtained through Michael addition reaction of methyl acrylate. Ethylenediamine was added to polymerize with methyl acrylate using an amidation reaction to form the first-generation PAMAM (SiO2-PAMAM-G1). Finally, by polymerizing dopamine under alkaline conditions (pH=8.5), the SiO2-PAMAM-G1 was coated with PDA. Thus, the final product named SiO2-PAMAM-PDA was obtained. The composite was characterized using a transmission electron microscope (TEM) and an increase in surface roughness indicated the successful grafting of PDA coating. Dopamine structure contains abundant benzene rings and amino and hydroxyl groups. It could bind with BUs through multiple secondary interactions, such as hydrogen bond and π-π stacking interaction. Therefore, the introduction of PDA could effectively enhance the affinity of the material toward benzoylurea insecticides. The prepared nanocomposites were used as sorbents in a dispersive micro solid-phase extraction approach (D-µ-SPE). The established approach was employed to extract and enrich the BUs in water samples before high-performance liquid chromatography (HPLC) analysis. Diflubenzuron, triflumuron, hexaflumuron, and teflubenzuron were chosen as target analytes. The following was a typical D-µ-SPE procedure. The prepared adsorbents measuring 40 mg were first dispersed in an 8-mL sample solution containing 150 g/L NaCl. The dispersion was assisted by 120-s vortexing to ensure full contact between the SiO2-PAMAM-PDA and the targets. Next, the adsorbents were separated from the liquid phase by 4-min centrifugation (5000 r/min). Thereafter, the adsorbed benzoylureas were eluted using 1 mL acetonitrile as desorption solvent by 120-s vortexing. Separated by centrifugation, the eluate was dried under a mild nitrogen stream. The solid remains were redissolved in 0.1 mL of acetonitrile, filtered by filter membrane (0.22 µm), and then analyzed by HPLC. The experimental conditions in the D-µ-SPE process could have a great impact on the extraction efficiency. Experimental conditions were optimized using a single factor optimization approach to further enhance the extraction recoveries. The optimized conditions included adsorbent amount, extraction time, desorption solvent type, desorption solvent volume, desorption time, and NaCl addition amount. Under the optimal conditions, a linearity range of 10-500 µg/L and limits of detection (LODs, S/N=3) of 1.1-2.1 µg/L were obtained. The extraction recoveries and relative standard deviations (RSDs) of the four BUs were 82.8%-94.1% and 2.1%-8.0%, respectively. The established approach was compared with reported approaches targeting benzoylurea insecticides. It was discovered that this approach consumed less sample, material, organic solvent, and pretreatment time. It provided a more rapid and green choice for the determination of benzoylurea pesticides. To determine the applicability, the proposed approach was applied to analyze the four benzoylurea insecticides in three river water samples. The real water samples were pretreated using the developed approach ahead of instrumental analysis, and no benzoylurea pesticides residue was detected. Next, standard addition experiments were performed under three spiking levels, including 15, 50, and 200 µg/L. The established approach had good accuracy and feasibility with satisfactory recoveries (69.5%-99.4%) and RSDs (0.2%-9.5%).

Simultaneous determination of glyphosate, glufosinate ammonium and their metabolites in maize and soybean by ultra-performance liquid chromatography with tandem mass spectrometry.

Glyphosate and glufosinate ammonium are non-selective, broad spectrum herbicides for controlling grasses in agriculture and forestry. Rapid and sensitive analytical methods for effective monitoring and subsequent risk control of glyphosate and glufosinate ammonium and their metabolites in crops are not available. In this paper, an analytical method for the simultaneous determination of glyphosate, glufosinate ammonium, and their metabolites in maize and soybean by ultra-performance liquid chromatography with tandem mass spectrometry was established. The seven compounds were well separated on an anion exchange analytical column within 10 min, with the mean recoveries of the target compounds ranging from 78.2 to 110.9%. The method showed good linearity (R2 ≥ 0.9819) with a limit of quantification for glyphosate, glufosinate ammonium, and their metabolites of 0.01 mg kg-1 in both maize and soybean. The method simplifies and expedites the sample preparation procedures, overcomes the traditional disadvantages including derivatization, weak retention, and low sensitivity, and has been successfully validated in actual maize and soybean samples.