Green synthesis of superhydrophilic resin/graphene oxide for efficient analysis of multiple pesticide residues in fruits and vegetables.

The escalating use of pesticides on fruits and vegetables has raised concerns about potential health risks. Therefore, we developed a superhydrophilic resin/graphene oxide (SR/GO) with rich adsorption interactions using an eco-friendly synthetic approach. SR/GO demonstrated excellent hydrophilicity, ensuring optimal contact with aqueous sample matrices. The multiple adsorption interactions, including π-π conjugation, hydrogen bonding, and electrostatic adsorption, facilitated multi-pesticide residue co-extraction. The synthesized SR/GO was applied to a miniaturized centrifugation-accelerated pipette-tip extraction method, coupled with high-performance liquid chromatography. The optimized method exhibited low consumption (15.0 mg adsorbent), and high efficiency, with low detection limits (1.4-2.9 ng g-1) and high recoveries (75.3-113.0%). Water-compatible SR/GO, along with a miniaturized extraction process, showcases a potent analytical approach for pesticide residue analysis in fruits and vegetables. The significance of this method lies in its ability to ensure agricultural and food safety by using a low-cost and efficient multi-pesticide residue analytical strategy.

Gemfibrozil-Platinum(IV) Precursors for New Enhanced-Starvation and Chemotherapy In Vitro and In Vivo.

A brand-new enhanced starvation is put forward to trigger sensitized chemotherapy: blocking tumor-relation blood vessel formation and accelerating nutrient degradation and efflux. Following this concept, two cisplatin-like gemfibrozil-derived Pt(IV) prodrugs, GP and GPG, are synthesized. GP and GPG had nanomolar IC50 against A2780 cells and higher selectivity against normal cells than cisplatin. Bioactivity results confirmed that GP and GPG highly accumulated in cells and induced DNA damage, G2-phase arrest, and p53 expression. Besides, they could increase ROS and MDA levels and reduce mitochondrial membrane potential and Bcl-2 expression to promote cell apoptosis. In vivo, GP showed superior antitumor activity in A2780 tumor-bearing mice with no observable tissue damage. Mechanistic studies suggested that highly selective chemotherapy could be due to the new enhanced starvation effect: blocking vasculature formation via inhibiting the CYP2C8/EETs pathway and VEGFR2, NF-κB, and COX-2 expression and cholesterol efflux and degradation acceleration via increasing ABCA1 and PPARα.

Acetylation of the polysaccharide from Houttuynia cordata rhizome and their α-glucosidase inhibition mechanism.

In this study, the polysaccharide (RHCP) extracted from Houttuynia cordata rhizome was acetylated through the acetic anhydride method. The physicochemical properties of RHCP and its acetylated derivatives (Ac-RHCP) were determined by infrared spectra, scanning electron microscopy, and Congo red test. Meanwhile, the α-glucosidase inhibition mechanism of RHCP and Ac-RHCP was analyzed by inhibition kinetics, and circular dichroism and fluorescence spectroscopy. Ac-RHCP resulted in a more porous surface structure and 1.83-fold higher solubility compared with RHCP. At a concentration of 6 mg/mL, the α-glucosidase inhibition rate of Ac-RHCP was 75.40%, while that of RHCP was 44.68%. RHCP and Ac-RHCP inhibited α-glucosidase in a mixed-type manner, reduced the endogenous fluorescence of α-glucosidase, affected the microenvironment of amino acid residues, and changed the conformation of α-glucosidase. The study indicates that Ac-RHCP exhibits a certain level of α-glucosidase inhibition, demonstrating its potential as a functional food for glycemic control.

Miniaturized centrifugation accelerated pipette-tip matrix solid-phase dispersion based on poly(deep eutectic solvents) surface imprinted graphene oxide composite adsorbent for rapid extraction of anti-adipogenesis markers from Solidago decurrens Lour.

Overweight and obesity are the causes of many diseases and have become global "epidemics". Research on natural active components with anti-adipogenesis effects in plants has aroused the interest of researchers. One of the most critical problems is establishing sample preparation and analytical techniques for quickly and selectively extracting and determining the active anti-adipogenesis components in complex plant matrices for developing new anti-adipogenic drugs. In this study, a new poly(deep eutectic solvents) surface imprinted graphene oxide composite (PDESs-MIP/GO) with high selectivity for phenolic acids was prepared using deep eutectic solvents as monomers and crosslinkers. A miniaturized centrifugation-accelerated pipette-tip matrix solid-phase dispersion method (CPT-MSPD) with PDESs-MIP/GO as adsorbent, coupled with high-performance liquid chromatography, was further developed for the rapid determination of anti-adipogenesis markers in Solidago decurrens Lour. (SDL). The established method was successfully used to determination anti-adipogenesis markers in SDL from different regions, with the advantages of accuracy (recoveries: 94.4 - 115.9 %, RSDs ≤ 9.8 %), speed (CPT-MSPD time: 11 min), selectivity (imprinting factor: ∼2.0), and economy (2 mg of adsorbent and 1 mL of solvents), which is in line with the current advanced principle of "3S+2A" in analytical chemistry.

Identification of key phenolic compounds for alleviating gouty inflammation in edible chrysanthemums based on spectrum-effect relationship analyses.

Edible chrysanthemum is a common food resource for tea and functional foods with potential benefits for human health. Studies have indicated that chrysanthemum has the potential effect on inflammatory diseases, while the effects on gouty inflammation remain underexplored. The present study aimed to investigate the anti-gout activity and characterize the active ingredients of chrysanthemums by using metabolite profiles, in vitro experiments, and spectrum-effect analysis. Results showed that 'Boju' (BJ), 'Hangbaiju' (HBJ), and 'Huaiju' (HJ) exhibited regulatory effects on monosodium urate (MSU)-induced inflammation. At the dose of 50 µg/mL, the inhibitory rates of IL-1ß secretion were 24.53 %, 14.36 %, and 38.10 %, respectively. A total of 32 phenolic compounds were identified or preliminarily assigned in UPLC-Q/TOF-MS analysis. And seven phenolics related to anti-gout activity were identified by spectrum-effect relationships. According to ADME (absorption, distribution, metabolism, excretion) evaluation and experiments verification, luteolin, acacetin-7-O-glucoside, and apigenin-7-O-glucoside were critical constituents potentially associated with the reduction of inflammation in gout. Additionally, these phenolics might be suitable as quality control indicators. This study clarified the anti-gout properties of different cultivars of chrysanthemums and active compounds, providing a theoretical basis for its scientific utilization in functional foods.

Design of Efficient Oxygen Reduction Reaction Catalysts with Single Transition Metal Atom on N-Doped Graphdiyne.

The revelation of the underlying structure-property relationship of single-atom catalysts (SACs) is a fundamental issue in the oxygen reduction reaction (ORR). Here we present systematic theoretical and experimental investigations of various N-doped graphdiyne (NGDY) supported transition metals (TMs) to shed light on this relationship. Calculation results indicate that the TMs' comprehensive activities follow the order of Pd@NGDY > Ni@NGDY > Co@NGDY > Fe@NGDY, which fits well with our experimental conclusion. Moreover, detailed structure-property relationship (194 in total) analysis suggests that the key-species binding stability (ΔG*OH), the d-orbital center (εd/εd-a) and charge transfer (ΔQTM/ΔQTM-a) of the active metal before/after reactants adsorption and the bond length of TM-O (LTM-O) as descriptors can well reflect the intermediate binding stability or ORR activity on different TM-SACs. Specifically, the change trend of catalytic activity is opposite to that of intermediate binding stability, meaning that too strongly bonded *OOH, *O, and *OH intermediates are unfavorable for ORR.

Progress of Nonmetallic Electrocatalysts for Oxygen Reduction Reactions.

As a key role in hindering the large-scale application of fuel cells, oxygen reduction reaction has always been a hot issue and nodus. Aiming to explore state-of-art electrocatalysts, this paper reviews the latest development of nonmetallic catalysts in oxygen reduction reactions, including single atoms doped with carbon materials such as N, B, P or S and multi-doped carbon materials. Afterward, the remaining challenges and research directions of carbon-based nonmetallic catalysts are prospected.

Rapid extraction of osimertinib and its active metabolite in urine by miniaturized centrifugal spin-column extraction using ionic liquid hybrid hierarchical porous adsorbent.

Osimertinib (OSIM) is widely used as a mainstream drug for the treatment of non-small cell lung cancer (NSCLC). However, the lack of a rapid extraction and detection method for OSIM and its metabolite, AZ-5104, has limited clinical drug metabolism and drug resistance research because the drug is unstable. In this study, a new ionic liquid hybrid hierarchical porous material (IL-HHPM) was synthesized with hierarchical porous structures, including micropores (1.6-2.0 nm), mesopores (2.0-50.0 nm), macropores (50.0-148.7 nm), and multiple functional groups via a one-step hydrothermal method using silanized ionic liquids (IL) as functionalized hybrid monomer. The IL-HHPM has the advantages of a high specific surface area (437.4 ± 4.6 m2 g-1), sizable pore volume (0.74 cm3 g-1), and fast mass transfer, additionally, the IL-HHPM adsorbed OSIM and AZ-5104 via π-π interactions and hydrogen bonding. OSIM and AZ-5104 were rapidly extracted and measured in human urine using rapid and miniaturized centrifugal spin-column extraction (MCSCE), which was based on the IL-HHPM. The optimized factors for the extraction recoveries of OSIM and AZ-5104 were adsorbent dosage (8.0 mg), sample volume (0.5 mL), and operation time (9.0 min), and markedly reduced the adsorbent dosage and operation time. The IL-HHPM-MCSCE-HPLC method displayed good linearity (0.02-5.00 µg mL-1, r ≥ 0.9997), satisfying accuracy (spiked recoveries of 87.7%-100.0%), and good precision (RSDs ≤ 7.0%). The developed method is rapid, sensitive, and reproducible for the simultaneous determination of trace level of OSIM and AZ-5104 in human urine.

Effects and Mechanisms of Resveratrol on the Adhesion of Lactobacillus acidophilus NCFM.

Based on the adhesion and surface properties of Lactobacillus acidophilus NCFM, five common polyphenols in fruits and vegetables, including resveratrol, epicatechin, quercetin, hesperidin, and caffeic acid, were screened, and the reasons for resveratrol promoting adhesion were systematically explained. The results showed that resveratrol could significantly enhance NCFM adhesion to mucin (1.73 fold), followed by epicatechin (1.47 fold), caffeic acid (1.30 fold), and hesperidin (0.99 fold), while quercetin had a certain degree of inhibition (0.84 fold). The effects of these polyphenols on surface hydrophobicity and auto-aggregation of NCFM were consistent with adhesion results. Then, how resveratrol promotes NCFM adhesion was further explored. The results of the proteomic analysis showed that resveratrol changed the surface layer proteins of NCFM, involving 4 up-regulated proteins and 12 down-regulated proteins. In addition, resveratrol promoted the expression of mucin genes and the glycosylation of mucins on the HT-29 cell surface. Our results indicate that resveratrol changes the surface layer proteins of NCFM to modify surface properties and adhere to mucins. Meanwhile, resveratrol promotes expression and glycosylation of mucins in HT-29 cells. Our findings provide theoretical support for an in-depth explanation of the interaction among resveratrol, NCFM, and the HT-29 cells.

Mechanics-based design of lithium-ion batteries: a perspective.

From the overall framework of battery development, the battery structures have not received enough attention compared to the chemical components in batteries. The mechanical-electrochemical coupling behavior is a starting point for investigation on battery structures and the subsequent battery design. This perspective systematically reviews the efforts on the mechanics-based design for lithium-ion batteries (LIBs). Two typical types of mechanics-based LIB designs, namely the design at the preparation stage and that at the cycling stage, have been discussed, respectively. The former systemizes the structure design of multiscale battery components from the particle level to the cell level. The latter focuses on the external mechanics-related control, including external pressures and charge-discharge protocols, of in-service LIBs. Moreover, the general problems currently being faced in the mechanics-based LIB design are summarized, followed by the outlook of possible solutions.

Analysis of anticancer compound, indole-3-carbinol, in broccoli using a new ultrasound-assisted dispersive-filter extraction method based on poly(deep eutectic solvent)-graphene oxide nanocomposite.

Indole-3-carbinol (I3C), an important anticancer compound found in broccoli, has attracted considerable attention. The rapid extraction and accurate analysis of I3C in the pharmaceutical industry in broccoli is challenging as I3C is unstable at low pH and high temperature. In this study, a rapid, accurate, and low-cost ultrasound-assisted dispersive-filter extraction (UADFE) technique based on poly(deep eutectic solvent)-graphene oxide (PDES-GO) adsorbent was developed for the isolation and analysis of I3C in broccoli for the first time. PDES-GO with multiple adsorption interactions and a fast mass transfer rate was synthesized to accelerate adsorption and desorption. UADFE was developed by combining dispersive solid-phase extraction (DSPE) and filter solid-phase extraction (FSPE) to realize rapid extraction and separation. Based on the above two strategies, the proposed PDES-GO-UADFE method coupled with high-performance liquid chromatography (HPLC) allowed the rapid (15-16 min), accurate (84.3%-96.4%), and low-cost (adsorbent: 3.00 mg) analysis of I3C in broccoli and was superior to solid-phase extraction, DSPE, and FSPE methods. The proposed method showed remarkable linearity (r=0.9998; range: 0.0840-48.0 µg/g), low limit of quantification (0.0840 µg/g), and high precision (relative standard deviation ≤5.6%). Therefore, the PDES-GO-UADFE-HPLC method shows significant potential in the field of pharmaceutical analysis for the separation and analysis of anti-cancer compounds in complex plant samples.

Enhanced Degradation of Paracetamol by the Fe(III)-Sulfite System under UVA Irradiation.

The Fe(III)-S(IV) system used for advanced oxidation processes (AOPs) at acidic pH has just been proposed and demonstrated valid for very few contaminants in the last several years. In this work, we investigated the effect of ultraviolet A (UVA) radiation on the degradation efficiency of the Fe(III)/S(IV) system at near-neutral pH. Paracetamol (PARA) was selected as a model contaminant. The influencing factors, such as initial pH and Fe(III)/S(IV) molar ratio on chemical kinetics, and the mechanism of PARA degradation are investigated, with an emphasis on the determination of dominant oxidant species. Our results show that irradiation enhances the PARA degradation by accelerating the decrease of pH to acidic levels, and the optimal pH for the degradation of PARA in the Fe(III)/S(IV)/O2 system was around 4.0. At near-neutral pH, more than 60% of PARA was decomposed within 40 min under irradiation, whereas no significant degradation of PARA was observed using Fe(III)/S(IV) at pH 7.0 without irradiation. Mechanism investigation revealed that sulfate radical (SO4•‒) is the main oxidant species generated and responsible for the PARA degradation under these conditions. This finding may have promising implications in developing a new degradation process for dealing with wastewater at near-neutral pH by the Fe(III)/S(IV)/O2 system under UVA irradiation.

Influence of Carboxymethyl Cellulose on the Stability, Rheological Property, and in-vitro Digestion of Soy Protein Isolate (SPI)-Stabilized Rice Bran Oil Emulsion.

In this study, carboxymethyl cellulose (CMC) was added to soybean protein isolate (SPI)-stabilized rice bran oil (RBO) emulsion to improve its physicochemical stability and free fatty acid (FFA) release characteristics. RBO emulsions stabilized by SPI and various contents of CMC were prepared and assessed by measuring zeta potential, particle size, transmission, and microstructure, the rheological properties were analyzed by dynamic shear rheometer. In addition, its chemical stability was characterized by a storage experiment, and the FFA release was explored by a simulated gastrointestinal tract (GIT) model. It showed that the negative charge of the droplets of RBO emulsion was increased with increasing CMC content. The decrease in transmission of SPI-stabilized RBO emulsion with increasing CMC content was due to the droplets not being free to move by the special network interaction and an increase in the viscosity. According to the determination of the reactive substances of lipid hydroperoxide and thiobarbituric acid during 30 days storage at 37°C, the chemical stability of the emulsion added with CMC was enhanced compared with the SPI-stabilized RBO emulsion. In-vitro digestion studies not only evaluated the structural changes of RBO emulsions at different stages, but also found that RBO emulsion with CMC showed a higher level of free fatty acids release in comparison with that without CMC. It indicated that the utilization of CMC can improve the bioavailability of RBO emulsions.

Loss of longitudinal superiority marks the microarchitecture deterioration of osteoporotic cancellous bones.

Osteoporosis (OP), a skeletal disease making bone mechanically deteriorate and easily fracture, is a global public health issue due to its high prevalence. It has been well recognized that besides bone loss, microarchitecture degradation plays a crucial role in the mechanical deterioration of OP bones, but the specific role of microarchitecture in OP has not been well clarified and quantified from mechanics perspective. Here, we successfully decoupled and identified the specific roles of microarchitecture, bone mass and tissue property in the failure properties of cancellous bones, through µCT-based digital modeling and finite element method simulations on bone samples from healthy and ovariectomy-induced osteoporotic mice. The results show that the microarchitecture of healthy bones exhibits longitudinal superiority in mechanical properties such as the effective stiffness, strength and toughness, which fits them well to bearing loads along their longitudinal direction. OP does not only reduce bone mass but also impair the microarchitecture topology. The former is mainly responsible for the mechanical degradation of bones in magnitude, wherever the latter accounts for the breakdown of their function-favorable anisotropy, the longitudinal superiority. Hence, we identified the microarchitecture-deterioration-induced directional mismatch between material and loading as a hazardous feature of OP and defined a longitudinal superiority index as measurement of the health status of bone microarchitecture. These findings provide useful insights and guidelines for OP diagnosis and treat assessment.

Selective, sensitive, and miniaturized analytical method based on molecularly imprinted graphene oxide composites for the determination of naphthalene-derived plant growth regulators in apples.

This paper reports a selective, sensitive, and miniaturized analytical method based on a molecularly imprinted graphene oxide (MIP-GO) composite as adsorbent for miniaturized tip solid-phase extraction (MTSPE) to determine naphthalene-derived plant growth regulators (PGRs) in apples. The proposed method combines the advantages of MIP-GOs (high selectivity), MTSPE (low consumption), and high-performance liquid chromatography-fluorescence detection (high sensitivity). Under optimized conditions, the method exhibited appreciable linearity (2.00-200 ng/g), low detection limits (0.21-0.53 ng/g), high accuracy (absolute recoveries: 87.6-99.5%), and high precision (relative standard deviations ≤ 3.0%), along with low consumption (0.5 mL sample solution and 2.0 mg adsorbent). In addition, the adsorption performance of the MIP-GO adsorbent did not decrease over ten months, highlighting the long storage and operational lifetime of the adsorbent. The proposed method was employed for the analysis of naphthalene-derived PGR residues in apples and exhibited promising potential for application in food safety analysis.

Efficient enrichment and analysis of atrazine and its degradation products in Chinese Yam using accelerated solvent extraction and pipette tip solid-phase extraction followed by UPLC-DAD.

The Chinese Yam (Dioscorea opposita) is cultivated widely in China. However, there are potential safety risks associated with herbicide residues in Chinese Yam because of its characteristics and unregulated use of pesticides. We developed an efficient sample preparation technique for simultaneous analysis of atrazine and its degradation products in Chinese Yam using accelerated solvent extraction and pipette tip solid-phase extraction followed by UPLC-DAD analysis. Molecularly imprinted polymer (MIP) were used as the adsorbent material. Method performance was evaluated and our results showed the limit of quantification was 1-3 µg/ kg, with recoveries in the range 79.2-103.8%. When compared with other methods, this method provided superior performance in terms of sensitivity, accuracy, and precision. This method is, therefore, expected to be useful in supervised residue analysis.

Deep eutectic solvent functionalized graphene oxide composite adsorbent for miniaturized pipette-tip solid-phase extraction of toluene and xylene exposure biomarkers in urine prior to their determination with HPLC-UV.

A deep eutectic solvent functionalized graphene oxide composite adsorbent (DFG) was synthesized through reversible-addition fragmentation chain-transfer polymerization. The synthesized DFG had multiple adsorption interactions after covalent modification with a deep eutectic solvent (allyltriethylammonium bromide/ethylene glycol). Adsorption isotherms and kinetics studies of DFG indicate that the adsorption of hippuric acid (HA) and methylhippuric acid (MHA) was monolayer chemical adsorption. The comparison of DFG with commercial adsorbents demonstrates that the adsorption ability of DFG was superior. This was due to the multiple adsorption interactions of DFG for the three analytes (mainly π-interaction, hydrogen bonding, electrostatic adsorption, and hydrophobic interaction). The DFG adsorbent was applied to miniaturized pipette-tip solid-phase extraction (MPT-SPE), followed by high-performance liquid chromatography (HPLC) to determine biomarkers in urine for toluene and xylene exposure. The DFG-MPT-SPE-HPLC method required only 2.00 mg of DFG as adsorbent, 0.50 mL of washing solvent, and 0.40 mL of elution solvent to achieve a wide linear range (0.200-200 µg mL-1), high recoveries (90.9-99.1%), and high precision (RSD ≤ 6.3%). The proposed method was applied to determine HA and MHA in urine samples from occupational workers. Graphical abstract Deep eutectic solvent functionalized graphene oxide composite adsorbent for miniaturized pipette-tip solid-phase extraction of toluene and xylene exposure biomarkers in urine prior to their determination with HPLC-UV.

Selective extraction and detection of ß-agonists in swine urine for monitoring illegal use in livestock breeding.

The illegal use of ß-agonists often endangers animal-derived food safety. In this study, a selective detection method for ß-agonists in swine urine was established via the combination of polymeric ionic liquid-molecularly imprinted graphene oxide-miniaturized pipette tip solid-phase extraction and high-performance liquid chromatography. It is worth noting that this method relied mainly on the designed adsorbent, which presented a rich adsorption mechanism, fast mass transfer rate, and high selectivity, and was successfully utilized in the selective extraction of ß-agonists from swine urine samples. The proposed method has low LOD (0.20-0.56 ng/mL), high recovery (94.9-107.9%), and high reusability (4 times, 91.9-108.8%), which indicates its high potential as a selective, sensitive, accurate, and nonfatal method for monitoring the illegal use of ß-agonists in the livestock breeding stage.

[Current situation and consideration of patent protection in classical representative famous prescriptions in China].

Classical Representative Famous Prescription is the valuable cultural heritage of Chinese medicine. In November 2018,the State Council issued the " Intensive Implementation of the National Intellectual Property Strategy in 2018 to Accelerate the Construction of IP Strong Country",explicitly proposing to strengthen the intellectual property protection of Classical Representative Famous Prescription.How about the current situation of intellectual property protection of lassical Representative Famous Prescription in China? We selected Liuwei Dihuang Pills,Shengmai Powder and Guizhi Fuling Pills( three representative drugs on market) from Chinese Pharmacopoeia2015 Volume I issued by Chinese Pharmacopoeia Commission to analyze their patent layout,reflecting its status quo of patent protection as follows: first,in recent years,the number of related patent applications for Classical Representative Famous Prescriptions has declined,which was positively correlated with the drug registration and approval policies in recent years,but the policy dividend has not been reflected in the patent application,which may be related to the long period of pharmaceutical R&D; secondly,the patent applicant in the field of Chinese medicine is mainly based on individuals,but the applicant of Classical Representative Famous Prescription is mainly of enterprises,and in addition,the company applicants have the highest authorization rate; thirdly,the main technologies are to improve preparation method and the dosage form in the research and development of Classical Representative Famous Prescription,but these two types of authorized patents have much difficulty in further application on the market. Therefore,the innovative entities shall look for a new breakthrough in secondary development and utilization of Classical Representative Famous Prescriptions.

Palladium-Catalyzed Coupling of Terminal Alkynes with Benzyl Ammonium Salts.

A highly efficient palladium-catalyzed Sonogashira coupling of benzylic ammonium salts with terminal alkynes is developed. This strategy provides a facile access to a series of internal alkyne derivatives in moderate to excellent yields via C-N bond cleavage and C(sp3)-C(sp) bond formation. The broad substrate scope and high functional group tolerance make this reaction attractive for organic synthesis.