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.

Polyelectrolyte modified black phosphorus/titania nanosheet heterojunction enhanced photocatalysis: Synergistic enhancement effect of interface affinity and electron transport channel.

The instability and high electron-hole recombination have limited the application of black phosphorus (BP) as an excellent photocatalyst. To address these challenges, poly dimethyl diallyl ammonium chloride (PDDA), poly (allylamine hydrochloride) (PAH), and polyethyleneimine (PEI) are introduced to the functionalization of BP (F-BP), which can not only enhance its stability, but also boost the carrier transfer. Furthermore, a high-performance heterojunction photocatalyst is fabricated using F-BP and titania nanosheets (TNs) via a layer-by-layer self-assembly approach. The experimental outcomes unequivocally indicate that F-BP exhibits fast charge migration compared to BP. The density functional theory (DFT), in situ Kelvin-probe force microscopy (KPFM) and other advanced characterization techniques collectively unfold that PDDA modified BP can notably boost separation and propagation of charges, along with an enhanced carrier abundance. In summary, this novel strategy of using polyelectrolytes to enhance the electron transfer and the stability of BP permits immense potential in building next-generation BP-based high efficiency photocatalysts.

A statistical study of postmortem heart weight in Chinese adults.

INTRODUCTION: Objective assessment of cardiac hypertrophy in forensic pathology practice is of great significance for forensic pathologists, for whom reference values for normal heart weights are needed. Developed regions such as Europe, the United States, and Japan recalculate the weight of human organs at regular intervals, but in China, there has been no systematic calculation of the weights of human organs since 2006. AIMS: To statistically analyse the heart weight of Chinese adults postmortem and obtain a reference range. MATERIALS AND METHODS: 4170 adult autopsy reports were collected from 12 forensic departments in 10 provinces in China. The causes of death were classified by sex, and heart weight and the heart weight/body height ratio reference values were further calculated according to different body mass index and body heights. Finally, the cutoff value of cardiac hypertrophy in Chinese adults was calculated. RESULTS: In the group of non-cardiovascular disease causes of death, the cardiac weight of the electric death group was higher, while the heart weight of the prolonged bed-rest group was significantly reduced. After the electric death and prolonged bed-rest groups were excluded, heart weight, the heart weight/body height ratio, and cutoff values for cardiac hypertrophy were further classified and analysed according to body mass index. The mean reference values for heart weight in men and women with normal weight status were 325.82 ± 41.60 g and 286.39 ± 44.84 g, and the heart weight/body height ratios were 1.95 ± 0.23 in men and 1.82 ± 0.27, respectively. The cutoff values for cardiac hypertrophy were 387.35 g for men and 346.80 g for women. CONCLUSION: The heart weight reference values of both sexes in this study were significantly higher than those in 2006, which is considered related to the development of China's economy and the improvement of people's living standards. This study also suggests the need for a new round of statistical surveys and updated data on the weight of other organs.

Controlled release of herbicides through glyphosate intercalated layered double hydroxides and enhancement of anti-scouring ability via poly-l-aspartic acid and chitosan modification.

Nanocarrier preparations could effectively improve the utilization rate of pesticides, and reduce pesticide loss. In this study, glyphosate (GLY)-loaded MgAl layered double hydroxide (GLY@LDH) was synthesized via an in-situ method. Subsequently, GLY@LDH composite samples were prepared using a layer-by-layer self-assembly approach and modified with poly-L-aspartic acid (PASP) and chitosan (CS). XRD, FT-IR, SEM, and Zeta potential characterization confirmed that GLY was successfully loaded in the interlayer of LDHs and PASP/CS were successfully encapsulated on the surface of the composite sample. The release effect in different ionic solutions and soils was studied and analyzed. The release behavior conforms to the Ritger-Peppas kinetic model, and the release mechanism was ion exchange, which was further explored by means of XRD, SEM, and molecular simulation. The results of the anti-scouring experiment and contact angle measurement indicated that the layered self-assembly material enhanced the washing resistance of the material. The practical application effect of the sample was verified through a pot experiment. This study provides new insights into the simple preparation of pesticide-controlled release formulations that reduce leaching losses.

The induction of ferroptosis in posthemorrhagic hydrocephalus.

Posthemorrhagic hydrocephalus (PHH) is a common neurological disease characterized by the disordered secretion of cerebrospinal fluid from the choroid plexus, ventricular dilation, and increased intracranial pressure after hemorrhage. Although these pathological processes are well established, the effective biomarkers for the diagnosis of PHH are still limited, largely because the underlying mechanisms-including cell death in the choroid plexus-are not well defined. Ferroptosis, a newly recognized type of programmed cell death, has been found to play a key role in a variety of pathologic conditions and diseases, including Parkinson's and Alzheimer's diseases. However, whether ferroptosis is induced in PHH is still unknown. In the current study, a rat model of PHH was established to investigate the induction of ferroptosis in PHH. Along with defects in memory and cognition, we observed that rats with experimentally induced PHH also demonstrated lipid peroxidation (a key marker of ferroptosis), as well as a significant increase and a significant decrease in two ferroptosis-specific genes, ACSL4 and SLC7A11, respectively. Thus, ferroptosis may serve as an auxiliary indicator for the diagnosis of PHH.

Phenylboronic acid-functionalized cross-linked chitosan magnetic adsorbents for the magnetic solid-phase extraction of benzoylurea pesticides.

In this study, a 4-formylphenylboronic acid-modified cross-linked chitosan magnetic nanoparticle (FPBA@CCHS@Fe3 O4 ) was fabricated. The synthesized material was utilized as the magnetic solid-phase extraction adsorbent for the enrichment of six benzoylurea pesticides. In addition to B-N coordination, FPBA@CCHS@Fe3 O4 interacts with benzoylureas through hydrogen bonds and π-π stacking interaction on account of rich active groups (amino and hydroxyl) and aromatic rings in structure. Compared to traditional extraction methods, less adsorbent (20 mg) and reduced extraction time (3 min) were achieved. The adsorbent also exhibited good reusability (no less than 10 times). Coupled with a high-performance liquid chromatography-diode array detector, satisfactory recoveries (89.1-103.9%) and an acceptable limit of detection (0.2-0.7 µg/L) were obtained. Under optimized conditions, the established method was successfully applied to the tea infusion samples from six major tea categories with acceptable recoveries ranging from 76.8 to 110%, indicating its application potential for the quantitative detection of pesticides in complex matrices.

Perfluoro octanoic acid-modified magnetic hyperbranched polyamideamine as a sorbent for the extraction of fluorine-containing pesticides from water samples.

Perfluoro octanoic acid was modified on the surface of magnetic hyperbranched polyamideamine by acid amine condensation. The morphology and chemical composition of perfluoro octanoic acid-modified magnetic hyperbranched polyamideamine was characterized by transmission electron microscopy, Fourier transform infrared spectroscopy, zeta potential, particle size analysis, Brunauer-Emmett-Teller measurement, and X-ray photoelectron spectroscopy. Perfluoro octanoic acid-modified magnetic hyperbranched polyamideamine was applied in magnetic solid phase extraction for the separation and enrichment of four fluorine-containing pesticides (indoxacarb, metaflumizone, cyflumetofen, and cyhalothrin). The magnetic solid phase extraction method based on perfluoro octanoic acid-modified magnetic hyperbranched polyamideamine has low method detection limits (0.30-0.49 µg/L), a satisfactory coefficient of determination (0.9995-0.9999), wide linear ranges (2.5-250 µg/L), and good repeatability (intraday: 2.6-4.7%; interday: 1.1-7.9%). The enrichment factors and extraction efficiences varied from 55 to 76 and 69 to 96%, respectively. The sorbent-to-sorbent reproducibility was in the range of 3.2-7.6%, indicating that the synthesis of the sorbent was reliable. For the detection of actual water samples, the relative recoveries were in the range from 80.1 to 114.4% with relative standard deviations less than 9.6%. The calculation results of quantum chemistry calculations showed that after the modification of perfluoro octanoic acid, the interaction between the sorbent and four fluorine-containing pesticides was stronger.

Use of 1-octyl-3-methylimidazole hexafluorophosphate modified magnetic hyperbranched polyamideamine as sorbent for the extraction of pyrethroid insecticides from tea infusion.

Magnetic hyperbranched polyamideamine was carboxylated using succinic anhydride and modified further with 1-octyl-3-methylimidazole hexafluorophosphate successively. The morphology and chemical composition of the prepared material was characterized by transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, Brunauer-Emmett-Teller measurement, X-ray photoelectron spectroscopy, etc. 1-Octyl-3-methylimidazole hexafluorophosphate modified magnetic hyperbranched polyamideamine was used as sorbent in the magnetic solid-phase extraction for the separation and enrichment of five pyrethroid insecticides from tea infusion. The magnetic solid-phase extraction method proposed in this article has low method detection limits (0.53-0.71 ng/mL), acceptable coefficient of determination (0.9992-0.9998), wide linear ranges (2.5-500.0 ng/mL), and good repeatability (intraday: 1.2-6.3%; interday: 1.6-5.4%). In the detection of five pyrethroid insecticides in tea infusion, relative recoveries were in the range from 87.7 to 114.7% with satisfactory relative standard deviations (0.2-7.4%). With the aid of quantum chemistry calculations, the interaction energy between the sorbent and five pyrethroid insecticides was calculated, which proved the necessity of the modification of 1-octyl-3-methylimidazole hexafluorophosphate.

Central-collapsed structure of CoFeAl layered double hydroxides and its photocatalytic performance.

Layered double hydroxides (LDHs) has been regarded as one of the most potential photocatalysts for degradation of the pollutants, due to the tunable elements in the laminates, high surface area and exposed active sites. Developing a photocatalyst with a visible light activity and fast charge separation efficiency is a main research focus. In this work, a central-collapsed CoFeAl-LDHs was formed via the selective etching Al3+ in the laminates, which relied on the function of OH- produced by urea hydrolysis. The Central-collapsed structure of CoFeAl-LDHs exhibited enhanced adsorption activity and photocatalytic efficiency. The results show that the pseudo-second-order kinetic model and the Langmuir model are suitable for adsorption behavior. This etching cavity is beneficial to the adsorption of MB and provides a better platform for the direct interaction between MB and CoFeAl-LDHs. The morphology and photoelectrochemical properties of the central-collapsed structure of LDHs were characterized and used to explore the relationship between the etching degree and photocatalytic activity. The photocatalytic properties of all the samples under visible light irradiation were evaluated, and LDH-6 has the best photocatalytic activity. This work provides a novel approach for the fabrication of central-collapsed structure of layered double hydroxides photocatalysts to meet environmental and energy requirements.

Phosphonium-based deep eutectic solvent coupled with vortex-assisted liquid-liquid microextraction for the determination of benzoylurea insecticides in olive oil.

In this study, a novel method using a phosphonium-based deep eutectic solvent coupled with vortex-assisted liquid-liquid microextraction was investigated for the enrichment and separation of five benzoylurea insecticides in olive oil. The experimental factors affecting the extraction efficiency, including the extractant type, deep eutectic solvent volume, extraction time, and extraction mode, were optimized. Under optimal conditions, good linearity was observed for all target analytes, with correlation coefficients (r) ranging from 0.9971 to 0.9998; the limits of detection were in the range of 1.5 to 7.5 µg/L, and the recoveries of analytes using the proposed method ranged between 66.9 and 111.0%. The simple, rapid, and effective method was successfully applied for detecting target analytes in olive oil sample.

Construction of PDDA functionalized black phosphorus nanosheets/BiOI Z-scheme photocatalyst with enhanced visible light photocatalytic activity.

The use of black phosphorus (BP) nanosheets has attracted much attention in the area of photocatalysis owing to the thickness-tunable bandgap and high carrier mobility. In order to improve the stability of BP nanosheets, poly dimethyldiallyl ammonium chloride (PDDA) is used to passivate the BP nanosheets and change its surface properties. The present study concerns the development of a facile electrostatic assembly method for the construction of a Z-scheme system consisting of PDDA-functionalized BP nanosheets and layered BiOI in order to enhance visible light adsorption and promote electron-hole separation. The morphology, structure and photoelectrochemical properties of the composites are thoroughly characterized and the photocatalytic performances of all the samples were assessed under visible light irradiation. The 5-F-BP/BiOI exhibits excellent photocatalytic activity with removal efficiencies of 97.6% and 90.0% for methylene blue (MB) and tetracycline (TC), respectively. Superoxide radicals (·O2-) were found to be the main organic decomposition products according to species trapping experiments. The photocatalyst presents favorable stability after three catalytic cycles. This study provides new insights into the design of highly efficient Z-scheme photocatalysts based on functionalized BP nanosheets in order to meet environmental demands.

Extraction of benzoylurea pesticides from tea and fruit juices using deep eutectic solvents.

In this study, low-density deep eutectic solvent combined with dispersive liquid-liquid microextraction was applied to the extraction of five benzoylurea insecticides (BUs, including diflubenzuron, triflumuron, hexaflumuron, flufenoxuron, and chlorfluazuron) from beverages. Then the extracted and concentrated samples were analyzed and detected using the high-performance liquid chromatography combined with an ultraviolet detector. The DESs were synthesized by [P14,6,6,6]Cl as hydrogen bond acceptor and tetradecyl alcohol as hydrogen bond donor, and then characterized by Fourier transform infrared spectroscopy. In the experiment, the key factors affecting the extraction efficiency were screened by Plackett-Burman design and optimized with the central composite design. The extraction recovery rates were 85.91-95.12%. The limits of detection and correlation coefficients of the method were 0.30-0.60 µg L-1 and 0.9992-0.9997. Finally, the method was applied to determine the BUs in four beverage samples, and satisfactory recoveries, within the range of 76.87-101.19% were achieved. The present method has the potential to be applied to the detection of BUs in aqueous samples.

Study on the adsorption mechanism of benzoylurea insecticides onto modified hyperbranched polysilicon materials.

Several hyperbranched polysilicon (HBPS) materials with different end group modifications were designed and synthesized and the structures were characterized. The modified HBPS polymers were applied to the adsorption of benzoylurea insecticides (BUs). The binding mode and binding energy between the HBPS and BUs were quantified and the results of an adsorption kinetics study and an adsorption thermodynamics experiment were verified by calculation and mutual verification. The adsorption mechanism of BUs onto HBPS was also discussed. The theoretical results show that the most effective way to combine the adsorbent and BUs is via hydrogen bonding when the end group is an amino group. Moreover, the most effective combination when the end group is ß-cyclodextrin is the interaction of the BUs with the interior of the cavity to form a host-guest coating. The theoretical results of other end group-modified HBPS materials were also obtained and verified by adsorption experiments. In this work, an experimental method for obtaining the binding mode by theoretical calculations and then verifying it according to adsorption experiments was established.

Expression and clinical value of PD-L1 which is regulated by BRD4 in tongue squamous cell carcinoma.

The programmed cell death-ligand-1 (PD-L1) and bromodomain protein 4 (BRD4) are frequently overexpressed in cancer and have even been shown to act synergistically. The aim of this study was to determine their potential oncogenic role .in tongue squamous cell carcinoma (TSCC). We detected significantly higher expression levels of both PD-L1 and BRD4 in TSCC tissues compared to normal tissues (P ≤ .05). In addition, the high levels of PD-L1 were significantly associated with increased tumor lymphatic metastasis (P ≤ .05), tumor staging (P ≤ .01), as well as BRD4 expression (P ≤ .05). Genetic and pharmacological inhibition of BRD4 in TSCC cells not only reduced their growth rate but also PD-L1 levels (P ≤ .05), while overexpression of BRD4 upregulated PD-L1. Bioinformatics analysis showed that c-MYC and CDK9 were interactive partners of both BRD4 and PD-L1. While c-MYC clearly modulated the expression of PD-L1, as well as reversed the inhibitory effects of JQ1, no obvious association was observed between CDK9 and PD-L1. We report a novel regulatory axis consisting of BRD4, PD-L1, and c-MYC that likely drives TSCC progression, and is a potential prognostic marker and/or therapeutic target for TSCC.

Insight of soil amelioration process of bauxite residues amended with organic materials from different sources.

It aimed to investigate and evaluate the soil amelioration process of bauxite residues with the amendments of organic materials from different sources. Wheat straw, poultry manure compost, and biosolids were chosen as the added organic materials. A series of essential soil properties were analyzed to evaluate the effects of organic materials on the soil amelioration of bauxite residue. The results indicated that organic amendments could obviously improve the texture of bauxite residues by increasing large aggregates contents, and elevating its organic matter content and fertility level (such as TN and TP). At the same time, organic additions were effective in reducing bauxite residues' salinity as pH, electrical conductivity and sodium content were obviously decreased in all rehabilitated treatments in comparison with control treatment. These improvements created sufficient conditions for a quick recovery of microbial communities in bauxite residues matrix. The maximum microbial biomass C increased to 0.642 g-C·kg-1, and the activities of urease, catalase, and invertase were massively elevated, especially for those after a year of rehabilitation, although alkali-phosphatase was kept a less level compared with other biological parameters. The further principal analysis and cluster analysis indicated that after 1 year of organic amendment, the improved bauxite residues matrix was very close to the reference soil based on the measured soil microbial properties. All the results suggested that organic amendment is an effective way to stimulate the soil amelioration of bauxite residues, and among the three amended organic materials, wheat straw and biosolid were better in improving the abiotic environmental conditions as well as biotic function recovery in soil amelioration of bauxite residue.

Magnetic solid-phase extraction of benzoylurea insecticides in tea samples with Fe3 O4 -hyperbranched polyester magnetic composite as sorbent.

In this work, a method for the analysis of benzoylurea insecticides, including hexaflumuron, flufenoxuron, lufenuron and chlorfluazuron, in tea samples by high-performance liquid chromatography with Fe3 O4 -hyperbranched polyester nanocomposite as the adsorbent for magnetic solid-phase extraction was developed. The magnetic nanocomposite was prepared and characterized by infrared spectroscopy, vibrating sample magnetometry, and scanning electron microscopy. The as-prepared nanocomposite was used as a sorbent for the extraction and preconcentration of pesticide residues in tea samples. The extraction and desorption conditions, including mass ratios of raw materials, amount of sorbent, pH value, extraction time, and desorption time, were investigated. Under the final conditions chosen for the analysis, good linearity was obtained for all the tested compounds, with R2 values of at least 0.9979. The limits of detection were determined in the range of 0.15-0.3 µg/L. The recovery obtained from the analysis of tea samples with various spiked concentrations was between 90.7 and 98.4%, with relative standard deviations (n = 4) lower than 4.1%. Furthermore, the present approach was successfully applied to the quantitative determination of residues of benzoylurea insecticides in real samples.

Enhanced removal of NO3-N from water using Fe-Al modified biochar: behavior and mechanism.

To remove NO3-N from water, coconut shell biochar (CSB) was modified by a solution of FeCl3, a solution of AlCl3 and a mixture solution of FeCl3 and AlCl3 respectively. The obtained modified biochar with the best effect of NO3-N adsorption was screened out to explore the adsorption behavior and mechanism of NO3-N removal by batch experiments and kinetics and thermodynamics and correlated characterization. The results indicated that the mixture solution of FeCl3- and AlCl3- modified CSB (Fe-Al/CSB) showed the best adsorption performance for NO3-N removal. Iron and aluminum elements existed on the surface of Fe-Al/CSB in the form of FeOOH, Fe2O3, Fe2+, and Al2O3 respectively. The adsorption process could reach equilibrium in 20 min. An acidic condition was favorable for NO3-N adsorption. The presence of coexisting anions was not conducive for NO3-N adsorption. The quasi-second-order model and Freundlich model could be well fitted in the adsorption process. The maximum adsorption capacity of Fe-Al/CSB fitted by the Langmuir model could reach 34.20 mg/g. The adsorption of NO3-N by Fe-Al/CSB was an endothermic and spontaneous process. Ligand exchange and chemical redox reaction were the NO3-N adsorption mechanisms which led to NO3-N adsorption by Fe-Al/CSB.

The influence of aging on the comparative terrestrial ecotoxicity potential of copper and zinc in soils.

Metal exposure to terrestrial organism is influenced by the reactivity of the solid-phase metal pool. Aging is one of the important factors that control the reactivity of the solid-phase metal pool in soil. In this study, the selected 13 soils were collected from different locations of China, representing different soil types. The reactivity variation of spiked Cu and Zn with aging was assessed in these 13 soils, and their comparative toxicity potentials (CTPs) were also calculated. The median reactive fractions (freactive) of Cu and Zn with 95% confidence intervals were 1.6 × 10-2 (3.5 × 10-6 to 2.2 × 10-1) and 0.10 (9.1 × 10-4 to 0.44) kgreactive/kgtotal, and the median CTPs for Cu and Zn were 2.09 (8.1 × 10-4 to 2.2 × 104) and 0.85 (8.5 × 10-4 to 7.2 × 102) m3/kg day, respectively. The statistical analysis indicated that aging variability in the CTP of Cu and Zn was mainly associated with the variability in soil organic carbon and pH. These results stress the importance of dealing with aging in the calculation of CTPs for terrestrial ecotoxicity of metals.

Constructing the magnetic bifunctional graphene/titania nanosheet-based composite photocatalysts for enhanced visible-light photodegradation of MB and electrochemical ORR from polluted water.

Photocatalysis is a promising strategy to address the global environmental and energy challenges. However, the studies on the application of the photocatalytically degraded dye-polluted water and the multi-purpose use of one type of catalyst have remained sparse. In this report, we try to demonstrate a concept of multiple and cyclic application of materials and resources in environmentally relevant catalyst reactions. A magnetic composite catalyst prepared from exfoliated titania nanosheets, graphene, the magnetic iron oxide nanoparticles, and a polyelectrolyte enabled such a cyclic application. The composite catalyst decomposed a methylene blue-polluted water under visible light, and then the catalyst was collected and removed from the treated water using a magnet. The photocatalytically treated water was then used to prepare the electrolyte in electrochemical reductive reactions and presented superior electrochemical performance compared with the dye-polluted water. The composite catalyst was once again used as the cathode catalyst in the electrochemical reaction. Each component in the composite catalyst was indispensable in its catalytic activity, but each component played different roles in the photochemical, magnetic recycling, and electrochemical processes. We expect the report inspire the study on the multi-functional catalyst and cyclic use of the catalytically cleaned water, which should contribute for the environmental and energy remedy from a novel perspective.

Anomalous but massive removal of two organic dye pollutants simultaneously.

A one-pot method to remove two organic dye contaminants and alkali simultaneously from alkaline wastewater was developed by forming Zn-Al layered double hydroxide (ZnAl-LDH). Using this process, not only alkali but also methyl orange (MO), an anionic contaminant was totally removed from wastewater. In addition, cationic contaminant, methylene blue (MB) was also removed effectively while maintaining the high removal efficiency of MO. The removal efficiency of MO was almost 100% and the pH of the treated wastewater decreased from 12 to 7.38. The charge-limited removal process, molecular arrangement of the contaminants in LDHs, and the anomalous removal mechanism were analyzed experimentally and through simulation. After MO accumulated in the interlayers of LDH by electrostatic interaction, MB entered and trapped by hydrophobic interaction.