Terrestrial algae: pioneer organisms of carbonate rock solutional weathering in South China karst.

The formation of soil in karst ecosystem has always been a scientific problem of great concern to human beings. Algae can grow on the exposed and non-nutrition carbonate surface, inducing and accelerating weathering of rock substrates, thus promoting soil formation. Yet the actual contribution of algae to solutional weathering intensity remains unclear. In this study, we performed weathering simulation experiment on two algae species (Klebsormidium dissectum (F.Gay) H.Ettl & G.Gärtner and Chlorella vulgaris Beijerinck), which were screened from carbonated rock surfaces from a typical karst region in South China. The results showed: (1) both algae have solutional weathering effect on carbonate rock, (2) there is no difference of solutional intensity observed, yet the solutional modes are different, suggesting different ecological adaptative strategies, (3) algae on carbonate rocks have higher carbonic anhydrase activity (CAA) and secrete more extracellular polysaccharide (EPS), accelerating rock weathering. (4) The absolute dissolution amount of carbonate rock with algae participation is 3 times of that of without algae. These results indicate the significant impact of terrestrial algae on carbonate rock solutional weathering and provides quantitative evidence that terrestrial algae are pioneer species. It also contributes to our further understanding of soil formation in karst ecosystems in South China.

Distribution, sources and main controlling factors of nitrate in a typical intensive agricultural region, northwestern China: Vertical profile perspectives.

Nitrate (NO3-) pollution of groundwater is a global concern in agricultural areas. To gain a comprehensive understanding of the sources and destiny of nitrate in soil and groundwater within intensive agricultural areas, this study employed a combination of chemical indicators, dual isotopes of nitrate (δ15N-NO3- and δ18O-NO3-), random forest model, and Bayesian stable isotope mixing model (MixSIAR). These approaches were utilized to examine the spatial distribution of NO3- in soil profiles and groundwater, identify key variables influencing groundwater nitrate concentration, and quantify the sources contribution at various depths of the vadose zone and groundwater with different nitrate concentrations. The results showed that the nitrate accumulation in the cropland and kiwifruit orchard at depths of 0-400 cm increased, leading to subsequent leaching of nitrate into deeper vadose zones and ultimately groundwater. The mean concentration of nitrate in groundwater was 91.89 mg/L, and 52.94% of the samples exceeded the recommended grade III value (88.57 mg/L) according to national standards. The results of the random forest model suggested that the main variables affecting the nitrate concentration in groundwater were well depth (16.6%), dissolved oxygen (11.6%), and soil nitrate (10.4%). The MixSIAR results revealed that nitrate sources vary at different soil depths, which was caused by the biogeochemical process of nitrate. In addition, the highest contribution of nitrate in groundwater, both with high and low concentrations, was found to be soil nitrogen (SN), accounting for 56.0% and 63.0%, respectively, followed by chemical fertilizer (CF) and manure and sewage (M&S). Through the identification of NO3- pollution sources, this study can take targeted measures to ensure the safety of groundwater in intensive agricultural areas.

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.

Aptamer recognition-promoted hybridization chain reaction for amplified label-free and enzyme-free fluorescence analysis of pesticide.

Development of high-performance fluorescence sensors for pesticide is highly urgent but remains a grand challenge. It is due to that most of known fluorescence sensors detect pesticides based on enzyme-inhibited strategy, which requires high-price cholinesterase, suffers from serious interference of reductive materials, and can't difference pesticides with each other; the known aptamer-based fluorescence ones entail tool enzymes or nanomaterials to transducer/amplify the signal and demand signalers to be tagged in nucleic acid, which are expensive and intricate. Herein, we develop a novel aptamer-based fluorescence system for label-free, enzyme-free and highly sensitive detection of pesticide (profenofos) based on target-initiated hybridization chain reaction (HCR)-assisted signal amplification and specific intercalation of N-methylmesoporphyrin IX (NMM) in G-quadruplex DNA. Hairpin probe ON1 recognizes profenofos to generate profenofos@ON1 complex, which switches the HCR to yield multiple G-quadruplex DNA, consequently making large numbers of NMM be locked. In comparison with profenofos absence, a sharply improved fluorescence signal was recorded and it was dependent on profenofos dose. Hence, label-free, enzyme-free and highly sensitive detection of profenofos is achieved with limit of detection of 0.085 nM, which compared favorably with or superior to those of known fluorescence methods. Furthermore, the present method was applied to determine the profenofos residue in rice with agreeable result, and will provide more valuable information for guaranteeing the pesticide-related food safety.

Dual-template hydrophilic imprinted resin as an adsorbent for highly selective simultaneous extraction and determination of multiple trace plant growth regulators in red wine samples.

In recent years, numerous plant growth regulators have been found in foods and have a toxicity to human health, so its simultaneous multiple monitoring is urgently. For the first time, a rapid, accurate, and high-selective method was established to extract and determine multiple plant growth regulators simultaneously in red wines using a new dual-template hydrophilic molecularly imprinted resin (DHMIR) as an adsorbent of pipette tip solid-phase extraction coupled with HPLC. The as-prepared DHMIR combined the advantages of the hydrophilicity of hydrophilic resin and multi-imprinted recognition of dual-template molecular imprinting, overcoming the poor imprinted recognition ability of traditional imprinting materials in water and low extraction efficiency to multiple targets. Under the optimized conditions, the proposed method exhibited high sensitivity (2.29-3.94 ng mL-1) and recoveries (80.9-109.0 %) using only 15 mg DHMIR. This study provides an effective strategy for rapid, accurate, low-cost, and high-selective determination of the multiple analytes in food samples.

Rapid determination of perfluorinated compounds in pork samples using a molecularly imprinted phenolic resin adsorbent in dispersive solid phase extraction-liquid chromatography tandem mass spectrometry.

Perfluorinated compounds (PFCs) that bioaccumulate enter the food chain through animals-derived foods and ultimately harm human health. However, these compounds are extensively used, and consequently, it is important to focus on the residual PFCs content in various animal-derived foods. In this work, a molecularly imprinted polymer with surface grooves and rapid mass transfer ability was prepared hydrothermally, applied as an adsorbent to a needle filter device, and combined with LC-MS/MS for the rapid extraction and determination of trace PFCs in pork. This method requires simple equipment (syringe filter), small amount of adsorbent (2 mg), and short operation time (6-8 min) and has a low detection limit (0.011-0.08 ng g-1), good recovery (89.3-116.3%), and satisfactory intra-day (≤4.0%) and inter-day (≤8.6%) precision. This study provides a new method for assessing the exposure risk of PFCs in complex samples.

Characterization of a rare mosaic X-ring chromosome in a patient with Turner syndrome.

BACKGROUND: Ring chromosomes can be formed by terminal breaks of two arms of a chromosome and their rejoining, leading to a loss of genetic material. They may also be formed by telomere-telomere fusions with no deletion, resulting in the formation of a complete ring. Mosaic X-ring chromosomes are extremely rare and have highly variable phenotypes. Here, we report a case with a mosaic X-ring chromosome in a patient with Turner syndrome, and we illustrate the unreported complicated mechanism using chromosome analysis and fluorescence in situ hybridization (FISH). CASE PRESENTATION: A 10-year-old girl of short stature presenting Turner syndrome was admitted to our hospital. The patient's clinical characteristics were subsequently documented. Genetic analysis showed a karyotype of mostly 45,X[140]/46,X,r(X)[60]. The X ring chromosome was cytogenetically characterized as 45,X/46,X,r(X)(p22.32q21.1), with a length of approximately 74 Mb. CONCLUSIONS: Taken together, we report a rare case with a mosaic X ring chromosome in Turner syndrome and we believe this case expands our collective knowledge of mosaic structural chromosomal disorders and provides new insight into clinical management and genetic counseling for Turner syndrome.

An integrated solid phase extraction with ionic liquid-thiol-graphene oxide as adsorbent for rapid isolation of fipronil residual in chicken eggs.

A rapid and economic integrated solid-phase extraction (ISPE) method with ionic liquid-thiol-graphene oxide composite (IL-TGO) as a new adsorbent was established for the extraction of fipronil in chicken eggs. In this study, ISPE, a new form of solid-phase extraction, which combined the advantages of pipette-tip solid phase extraction (PT-SPE) and dispersive solid-phase extraction (DSPE), achieving rapid extraction of analyte with only a small amount of adsorbent. The three-dimensional porous IL-TGO was a new ideal adsorbent for fipronil due to the multiple adsorption interactions (π-π interaction, hydrophobic interaction and hydrogen bond), large adsorption capacity and fast adsorption rate. For this ISPE procedure, the analyte was adsorbed by IL-TGO through the pipette tip mode and then eluted through dispersive mode. Under the optimized condition, the proposed method performed following merits: good linearity (r = 0.9999), precision (RSD ≤ 6.3%), high recoveries (83.7% to 97.7%), rapid extraction (16 min), low consumption of adsorbent (3.00 mg of IL-TGO). The excellent recyclability of the ISPE device and the reusability of IL-TGO were observed and high recovery of fipronil (> 90%) was obtained after fifteen cycles. This work might provide promising strategy for the sensitive extraction and analysis of trace levels of fipronil from egg products.

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.

One pot green synthesis of m-aminophenol-urea-glyoxal resin as pipette tip solid-phase extraction adsorbent for simultaneous determination of four plant hormones in watermelon juice.

Plant hormones (PHs) are a type of pesticide that can potentially affect human health. Therefore, their quantitative detection is particularly important. In this study, a green and economic method for the simultaneous extraction and determination of four PHs, namely thidiazuron, forchlorfenuron, 1-naphthylacetic acid, and 2-naphthoxyacetic acid, in watermelon juice was developed by using m-aminophenol-urea-glyoxal resin as the adsorbent for pipette tip solid phase extraction (PT-SPE) coupled with liquid chromatography. The resin was synthesized via a simple (one pot hydrothermal synthesis) and green (ethanol as the solvent and glyoxal as crosslinking agent) process. The synthesized resin possesses multiple functional groups (hydroxyl, amino, and imino, among others), high adsorption capacity, larger specific surface area than the urea-glyoxal resin and m-aminophenol-glyoxal resin, and can be regenerated easily. The PT-SPE device is simple, cheap, and easy to obtain, and the adsorbent dosage is only 5.0 mg. The proposed method has a wide linear detection range, high recovery, good precision, and high sensitivity, and satisfies the measurement requirements for detecting trace levels of PHs in fruits and vegetables.

Imidazolium ionic-liquid-modified phenolic resin for solid-phase extraction of thidiazuron and forchlorfenuron from cucumbers.

An imidazolium ionic-liquid-modified phenolic resin (ILPR) was synthesized using 3-aminophenol as a functional monomer, glyoxylic acid as a green cross-linker, and polyethylene glycol 6000 as a porogen. The obtained ILPR showed better extraction of benzoylurea plant hormones thidiazuron and forchlorfenuron than the unmodified phenolic resin because the imidazolium IL provides more interaction modes with the analytes. ILPR, as a tailored adsorbent for solid-phase extraction, was coupled with high-performance liquid chromatography (ILPR‒SPE‒HPLC) for the simultaneous determination of thidiazuron and forchlorfenuron in cucumbers. Good linearity of the ILPR‒SPE‒HPLC method was obtained, ranging from 0.0100 to 5.00 µg g-1 with a correlation coefficient (r) ≥ 0.9999. The recoveries of spiked samples ranged from 91.4% to 100.7% with a relative standard deviation of ≤ 6.0%.

Green synthesis of hydrophilic protein-imprinted resin with specific recognition of bovine serum albumin in aqueous matrix.

The synthesis of biomacromolecule imprinted materials is a challenge with the bulkiness and instability of macromolecule, such as protein. A green strategy to prepare hydrophilic protein-imprinted resin (HPIR) was firstly developed using resorcinol and melamine as double functional monomers, hexamethylenetetramine instead of formaldehyde as crosslinker, water as solvent, and bovine serum albumin (BSA) as a dual-function template. BSA as dual-function template could not only act as template but also porogen in the preparation of HPIR. According to the adsorption experiments, the adsorption kinetics of BSA on HPIR obeyed pseudo-second-order adsorption kinetics and the equilibrium data were best described by Langmuir isotherm model. The adsorption capability was 44.3459 mg g-1 (25 °C), and the imprinted factor for binding BSA is 5.78. HPIR showed high adsorption capacity, fast mass transfer rate, and specific selectivity towards BSA in aqueous solvent. More importantly, HPIR can be applied to selectively adsorb target protein BSA in urine without the matrix interference of biological matrix, therefore, it is promising for HPIR to be applied to proteomics, diagnostics, and pharmaceutics.

Ionic Liquid-Hybrid Molecularly Imprinted Material-Filter Solid-Phase Extraction Coupled with HPLC for Determination of 6-Benzyladenine and 4-Chlorophenoxyacetic Acid in Bean Sprouts.

A new method involving ionic liquid-hybrid molecularly imprinted material-filter solid-phase extraction coupled to high-performance liquid chromatography (IL-HIM-FSPE-HPLC) was developed for the simultaneous isolation and determination of 6-benzyladenine (6-BA) and 4-chlorophenoxyacetic acid (4-CPA) in bean sprouts. Sample preconcentration was performed using a modified filter, with the new IL-HIM as the adsorbent, which shows double adsorption. The first adsorption involves special recognition of molecular imprinting, and the second involves ion exchange and electrostatic attraction caused by the ionic liquid. This method combines the advantages of ionic liquids, hybrid materials, and molecularly imprinted polymers and was successfully applied to determine 6-BA and 4-CPA in bean sprouts. The adsorption of 6-BA to IL-HIM is based on selective imprinted recognition, whereas the adsorption of 4-CPA is mainly dependent on ion-exchange interactions.

Synthesis of mimic molecularly imprinted ordered mesoporous silica adsorbent by thermally reversible semicovalent approach for pipette-tip solid-phase extraction-liquid chromatography fluorescence determination of estradiol in milk.

A mimic molecularly imprinted ordered mesoporous silica (MIOMS) adsorbent was prepared utilizing a thermally reversible semicovalent approach. The thermally reversible covalent template-monomer complex was firstly synthesized by employing 4,4'-sulfonyldiphenol (BPS) and (3-isocyanatopropyl) triethoxysilane (ICPTES) as template and monomer, respectively. The template-monomer complex was incorporated into ordered mesoporous silica via a simple self-assembly process. The adsorption experiment illustrated that the imprint-removed silica (MIOMS-ir) had higher special recognition ability (250µgg(-1)) for estradiol (E2) than the non-imprinted silica (NIOMS-ir) (25µgg(-1)). MIOMS-ir was applied as an adsorbent in pipette-tip solid-phase extraction (PT-SPE) coupled with liquid chromatography-fluorescence detector (LC-FLD) for determination of E2 in milk samples. Under the optimized conditions, only 3mg of the adsorbent, 0.3mL of water as washing solvent, and 0.5mL of acetonitrile-acetic acid (96:4, v/v) as elution solvent were used in the pretreatment procedure of milk samples. Good calibration linearity was obtained in a range of 25ngL(-1) to 1000ngL(-1), and the recoveries at three spiked levels were ranged from 95.4% to 107.0% with relative standard deviations (RSDs) ≤3.1% (n=3). The proposed MIOMS-ir-PT-SPE-LC-FLD method combined the advantages of PT-SPE and ordered mesoporous material such as ease assembly, low cost, high extraction efficiency and large specific surface area, so it is a potential pretreatment strategy for the extraction and determination of E2 in complex milk samples.

[Design, synthesis and evaluation of 4-pyridinylthiazole-2-amines as acetylcholinesterase inhibitors].

Alzheimer's disease (AD) is a degenerative disease of the nervous system. Compound I reported to have inhibitory activity on AChE was used as a lead compound in this study, and 4-pyridinylthiazole-2-amines were designed by optimizing compound I structure. The new compounds were synthesized from acetylpyridines through five-steps of reaction, and their inhibition activities on AChE were measured in vitro by Ellman method. The new compounds exhibited a clear inhibitory activity on AChE in vitro. The bioactivity of compound 13c was the best among them, and its IC(50) value was 0.15 µmol·L(-1), which was better than that of rivastigmine and compound I in the control. Meanwhile, it exhibited little inhibition on butyrylcholinesterase. So the selective inhibitory activities of 4-pyridinylthiazole-2-amines to acetylcholinesterase were worth of studying furtherly.

3-chloromethylene-6-fluorothiochroman-4-one, A novel DNA Topoisomerase poison.

3-Chloromethylene-6-fluorothiochroman-4-one (CMFT) is a novel thiochromanones derivative that has better anti-tumor activity. In this paper, we will compare the antitumor activity of the cis-trans isomers, and explore their inhibiting effects on human topoisomerase I and topoisomerase II in cell free reaction system. The MTT method was used to study inhibition rates; the AO/EB double staining and TUNEL assay was used to assess proportion of apoptotic cells. The inhibition of CMFT to Topo I and II could be identified by adding CMFT solutions to Topo-DNA reaction mixtures and observing the relative quantities of relaxed strands and supercoils in electrophoresis assay. Results showed that CMFT had dramatic anti-tumor activities at low concentrations and the activity of CMFT trans-isomer is more significant. Use of AO/EB double staining and TUNEL indicated that CMFT induces apoptosis. DNA relaxation assays and DNA cleavage and relegation assays were performed and showed a higher potential to interact with topoisomerase I (Topo I) and topoisomerase II (Topo II) and it was verified that CMFT is a Topo poison which could be one of the mechanisms that induce cell apoptosis. Our results provide preliminary data for further investigation for the mechanism of CMFT of the apoptotic mechanism.

Short-chain fatty acids suppress lipopolysaccharide-induced production of nitric oxide and proinflammatory cytokines through inhibition of NF-κB pathway in RAW264.7 cells.

Short-chain fatty acids (SCFAs) produced by the colonic bacterial fermentation of dietary fiber contribute a significant proportion of daily energy requirement. Furthermore, these compounds are modulators of macrophage function and potential targets for the development of new drugs. The aims of this study were to evaluate the effects of three types of SCFAs (sodium acetate (NaAc), sodium propionate (NaP), and sodium butyrate (NaB)) on the production of NO and inducible nitric oxide synthase (iNOS) and proinflammatory and antiinflammatory cytokines (tumor necrosis factor-α (TNF-α) and interleukin (IL-1, IL-6, and IL-10)) and to observe the effect of NaAc on inhibiting lipopolysaccharide (LPS)-induced NF-κB activation in LPS-stimulated RAW264.7 cells. The results show that three types of SCFAs (acetate, propionate, and butyrate) reduced the production of proinflammatory factors, including TNF-α, IL-1ß, IL-6, and NO, and inhibited the vitality of iNOS. Meanwhile, SCFAs enhanced the production of antiinflammatory cytokine IL-10 in lower concentrations (1-1,200 µmol/L). Like NaB, NaAC inhibited LPS-induced NF-κB activation. These results may hold promise on the role that SCFAs have on the prevention and treatment of various inflammatory conditions.

Preparation and characterization of temperature-responsive poly(N-isopropylacrylamide-co-N,N'-methylenebisacrylamide) monolith for HPLC.

A temperature-responsive poly(N-isopropylacrylamide-co-N,N'-methylenebisacrylamide) [poly(NIPAAm-co-BIS)] monolith was prepared via a free-radical polymerization technique using an aqueous redox initiator in solution at -12°C. The effect of the % T (total monomer concentration/100 mL) and % C (cross-linker concentration/100 mL) on the visual form was investigated. The effect of the porogen on the pore structure was characterized by SEM. Under the optimum condition, the monolith for HPLC was successfully prepared and its mechanical strength and permeability have been studied. Furthermore, a temperature-dependent resolution of aromatic ketones was achieved using only water as mobile phase. The increasing interaction between solutes and the monolith was observed when temperature increased. The theoretical plate number of every analyte was more than 10(4).