One-pot fabrication of magnetic adsorbent based on polymeric ionic liquid/aminated carbon nanotubes composite for efficient capture of synthetic auxins in complex samples prior to chromatographic analysis.

Efficient enrichment is a challenging and indispensable step in the quantification of polar synthetic auxins in complex samples. In the current study, a new magnetic adsorbent based on polymeric ionic liquid/aminated carbon nanotube composite was fabricated with a one-pot precipitation copolymerization strategy and employed as the extraction phase of magnetic solid phase extraction of synthetic auxins. Various characterization techniques were utilized to inspect the morphology, structure, magnetic property, and functional groups of the prepared adsorbent. Under the optimal conditions, the obtained adsorbent displayed satisfactory capture performance towards studied auxins through multiple interactions. Adsorption studies evidenced that the adsorption procedure of the developed method towards analytes was fit for the Freundlich adsorption model and pseudo-second-order kinetics. Combining with high-performance liquid chromatography, sensitive and reliable method for the identification and quantification of trace synthetic auxins in environmental water and fruit juice samples was developed. The obtained limits of detection for water and fruit juice samples located in the ranges of 0.0059-0.013 and 0.018-0.031 µg/L, respectively. Recoveries in actual samples with different fortified contents varied from 82.2% to 117%, with satisfactory reproducibility. The results will evidence that the introduced extraction technique is a useful alternative for the entrapment of trace synthetic auxins from complex samples.

One-pot fabrication of functional magnetic adsorbent for efficient capture of mercury species in aqueous samples prior to HPLC analysis.

Efficient extraction is a vital step in mercury speciation. In this context, using 4-vinylbenzeneboronic acid and 9-vinylanthracene as functional monomers, a new magnetic adsorbent was fabricated according to one-pot hydrothermal approach. Various characterization results prove the as-prepared adsorbent presented abundant functional groups and saturation magnetism. Combining with magnetic solid phase extraction (MSPE), the adsorbent exhibited satisfactory entrapment performance towards different mercury species which had been pre-coordinated with dithizone to form metal-organic coordination. A series of parameters influencing the extraction performance were inspected in detail. Under the most beneficial conditions, sensitive and reliable approach to quantify trace methylmercury, ethylmercury, phenylmercury and inorganic mercury in aqueous samples was developed by the combination of HPLC/DAD. Limits of detection and precision located in the ranges of 0.012-0.074 µg/L and 2.5-9.8%, respectively. Recoveries with low, medium and high fortified contents in actual waters varied from 79.8 to 119%. Confirmatory experiments were performed to evidence the accuracy and reliability of established approach. In addition, a possible mechanism was suggested based on the chemical nature of analytes, extraction conditions and characterization results.

["One-pot" preparation of aminated carbon nanotube-modified magnetic nanoparticles and their application to the quantification of phenoxyacetic acid herbicides in cereal and vegetable samples].

Phenoxyacetic acid herbicides (PAs) are widely used to control the growth of broad-leaf weeds in corn, tobacco, etc. The presence of PAs in plants even at low concentrations (at the ng/L to µg/L scale) may induce severe effects and lead to human health risks. Hence, a sensitive and reliable method for the determination of PAs at trace levels in cereals and vegetables is highly desired. Magnetic solid-phase extraction (MSPE) has attracted considerable attention on account of its benefits such as ease of separation, less solvent consumption, and good service life. In this study, aminated carbon nanotube-modified magnetic nanoparticles (NH2-CNTs@M) were prepared by a convenient and simple "one-pot" strategy and employed as the adsorbent for the MSPE of PAs in crops. The fabrication procedure is very convenient. In detail, the aminated carbon nanotubes, Fe(Ⅱ), Fe(Ⅲ), and isopropanol were mixed in one pot with mechanical stirring and reacted for 2.0 h at 80 ℃. The spectroscopic properties, morphology, and magnetic properties of the synthetic adsorbent were characterized by Fourier Transform-infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results revealed that the size of Fe3O4, diameter of NH2-CNTs, and the magnetic saturation values of NH2-CNTs@M were 30 nm, 40 nm, and 44.2 emu/g, respectively. Additionally, the results of FT-IR and TEM characterization confirmed the successful fabrication of NH2-CNTs@M by this "one-pot" hydrothermal approach. The NH2-CNTs@M displayed satisfactory capability to capture PAs through π-π, hydrophobic, and hydrogen-bonding interactions. To realize the best extraction performance, the key parameters, including the amount of adsorbent, formic acid concentration in the eluent, adsorption and desorption time, sample pH, and ionic strength in the sample matrices, were inspected and studied in detail. The optimal conditions were as follows: amount of NH2-CNTs@M, 30 mg; desorption solvent, 0.5 mL acetonitrile containing 2.0% (v/v) formic acid; adsorption and desorption times, 8.0 and 3.0 min, respectively; the sample pH was adjusted to 6.0, and no salt was added to the sample. Under the optimized extraction conditions, a sensitive, quick, and environmentally friendly method for the determination of the studied PAs in cereal and vegetable samples was established by the combination of NH2-CNTs@M/MSPE with high performance liquid chromatography-diode array detection (HPLC-DAD). The enrichment factors for the studied PAs varied from 73 to 90. The limits of detection (S/N=3) for the PAs in the cereal and vegetable matrixes were in the ranges of 0.32-1.6 µg/kg and 0.53-1.6 µg/kg, respectively; and the limits of quantification (S/N=10) for the PAs in the cereal and vegetable matrixes were 0.94-4.8 µg/kg and 1.6-4.8 µg/kg. The developed method also showed wide linear ranges and good precision. Finally, the established NH2-CNTs@M/MSPE-HPLC-DAD approach was applied to measure trace levels of PAs in cereals and vegetables, and good fortified recoveries (72.3% to 113%) and repeatability (RSDs below 10%) were obtained. The established approach has several advantages over the existing methods, such as high analytical speed, low LODs, and eco-friendliness.

One-pot fabrication of poly (ionic liquid)s functionalized magnetic adsorbent for efficient enrichment of phenylurea herbicides in environmental waters.

Efficient capture is an essential procedure in the highly sensitive monitoring of phenylurea herbicides (PUHs) in various environmental waters. Herein, a new poly (ionic liquid)s functionalized magnetic adsorbent (PFMA) was conveniently fabricated by means of "one-pot" strategy. The preparation procedure was quite simple by mixing 1-allyl-3-methylimidazoliumbis[(trifluoromethy)sulfonyl]imide, ethylene glycol dimethacrylate, Fe3+, Fe2+, mixed solution of dimethyl sulfoxide/H2O and azobisisobutyronitrile in one pot, and the total reaction time was just 3.0 h which was far shorter than that needed in previous approaches. A series of characterized techniques were employed to observe and inspect the morphology, structure and magnetic properties of prepared PFMA. Results revealed that the adsorbent contained abundant functional groups and superior magnetic property. Combing with magnetic solid-phase extraction (MSPE) format, the resultant PFMA displayed high capture capability towards studied PUHs through multiple interactions, and the enrichment factors were in the range of 126-227. Under the selected extraction parameters, the introduced PFMA/MSPE was combined with HPLC equipped with diode array detector (HPLC/DAD) to measure investigated PUHs at trace levels in various environmental waters. Wide linear range (0.010-200 µg/L), low limit of detection (0.0025-0.015 µg/L) and good precision (RSDs<10%) were achieved. The reliability and practicality of established approach was demonstrated by quantifying trace studied PUHs in various waters. Satisfactory fortified recoveries (80.2-119%) and repeatability were achieved. The results well evidence that the prepared PFMA is a good alternative for capture PUHs, and the introduced approach has wide prospect in the analyzing trace levels of PUHs in water and other complex samples.

γ-glutamylcysteine suppresses cadmium-induced apoptosis in PC12 cells via regulating oxidative stress.

Cadmium (Cd) is a highly toxic environmental pollutant, leading to the occurrence and development of multiple neurological diseases. γ-glutamylcysteine (γ-GC) is a dipeptide formed by the condensation of l-glutamic acid and l-cysteine, which has antioxidant, anti-inflammatory, and chelating properties. The purpose of this study is to investigate the effect of γ-GC on Cd-induced apoptosis in PC12 cells. PC12 cells were pretreated with or without γ-GC (2 mM or 4 mM) for 2 h and exposed to Cd (10 µM) for 12 h, and survival, apoptosis, and oxidative stress of PC12 cells were detected after different treatments. The results showed that γ-GC significantly inhibited cell viability reduction, apoptosis, and depolarization of mitochondrial transmembrane potential in Cd-treated PC12 cells, as indicated by CCK-8 assay, flow cytometry, TUNEL staining, and JC-1 detection. Western blot showed that γ-GC down-regulated the ratio of Bax/Bcl-2 and the protein levels of cytosolic cytopigment c, cleaved-caspase-9, cleaved-caspase-3, and cleaved-PARP. Mechanistically, γ-GC suppressed Cd-induced ROS production, MDA accumulation, and GSH depletion, and increased the activity of antioxidant enzymes. Cd-induced activation of MAPK and PI3K/Akt signaling pathways were inhibited by γ-GC treatment, while sustained phosphorylation of JNK, p38, or Akt reversed anti-apoptotic effects of γ-GC. These results suggested that γ-GC inhibited Cd-induced apoptosis in PC12 cells through decreasing oxidative stress and inhibiting the activation of MAPK and PI3K/Akt signaling pathways. γ-GC could be used as a potential protective agent against Cd neurotoxicity.

One-Pot Strategy as a Green and Rapid Method to Fabricate Magnetic Molecularly Imprinted Nanoparticles for Selective Capture of Sulfonylurea Herbicides.

Magnetic solid-phase extraction (MSPE) based on molecularly imprinted nanoparticles (MINs) has attracted wide attention in sample pretreatment because it combines the merits of high selectivity and quick extraction procedures. However, laborious, time and solvent-consuming steps were involved in the synthesis of magnetic imprinted particles in existing approaches. To circumvent this dilemma, a green and rapid "one-pot" strategy was proposed to prepare MINs. Halosulfuron-methyl (HSM) was selected as a template molecule, and Gaussian 09 simulation software was employed to screen the 2,4,6-trivinylboroxin pyridine complex (TBP) as a functional monomer. Subsequently, the fabrication was simply conducted using a hydrothermal approach by mixing self-assembly solution of TBP-HSM, Fe3+, Fe2+, dimethyl sulfoxide, and azobisisobutyronitrile in one-pot with a total reaction time of 3.0 h. Various characterized results well evidenced the successful imprint of HSM and the resultant HSM-MINs presented satisfying superparamagnetism and saturation magnetism. Under the optimized parameters, the obtained HSM-MINs displayed good recognition capability and selectivity toward HSM (recognition coefficient was 2.60), as well as a satisfactory saturation adsorption capacity (1781 µg/g). The quantification of sulfonylurea herbicides at trace levels in environmental water and soil samples was selected as a paradigm to demonstrate the practicality and reliability of HSM-MINs/MSPE. The present study provides a convenient, reliable, and green approach for fabricating a magnetic molecular-imprinting adsorbent for MSPE.

l-Theanine attenuates neointimal hyperplasia via suppression of vascular smooth muscle cell phenotypic modulation.

Neointimal hyperplasia is a prominent pathological phenomenon in the process of stent restenosis. Abnormal proliferation and migration of vascular smooth muscle cells (VSMCs) play major pathological processes involved in the development of restenosis. l-Theanine, one of the major amino acid components in green tea, has been reported to improve vascular function. Here we display the effects of l-theanine on neointima formation and the underlying mechanism. In the rat carotid-artery balloon-injury model, l-theanine greatly inhibited neointima formation and prevented VSMCs from a contractile phenotype switching to a synthetic phenotype. In vitro study showed that l-theanine significantly inhibited PDGF-BB-induced VSMC proliferation and migration, which was comparable with the effect of l-theanine on AngII-induced VSMC proliferation and migration. Western blot analysis demonstrated that l-theanine suppressed PDGF-BB and AngII-induced reduction of SMA and SM22α and increment of OPN, suggesting that l-theanine inhibited the transformation of VSMCs from contractile to the synthetic phenotype. Further experiments showed that l-theanine exhibits potential preventive effects on neointimal hyperplasia and related vascular remodeling via inhibition of phosphorylation of Elk-1 and activation of MAPK1. The present study provides the new experimental evidence that l-theanine has potential clinical application as an anti-restenosis agent for the prevention of restenosis.

Preparation of highly fluorinated and boron-rich adsorbent for magnetic solid-phase extraction of fluoroquinolones in water and milk samples.

Effective extraction is an indispensable procedure for the sensitive analysis of fluoroquinolones (FQs) in complex samples. According to the molecular properties of FQs, a new highly fluorinated and boron-rich adsorbent (FBA) was synthesized and employed as the extraction phase of magnetic solid-phase extraction (MSPE). Results revealed that the prepared FBA displayed satisfactory extraction capability for FQs through fluorophilic and B-N coordination interactions. Besides, the synthesized FBA also exhibited strong magnetic responsiveness and good life-span. Under the most favorable conditions, the FBA/MSPE was combined with high-performance liquid chromatography with diode array detection (HPLC-DAD) to sensitively quantify trace levels of FQs in environmental water and milk samples. The developed approach showed good linearity within the studied concentration range, satisfactory precision and low limits of detection (0.0049-0.016 µg/L for water sample and 0.010-0.046 µg/kg for milk sample). In the analysis of target FQs in real samples, the recoveries of different fortified concentrations were in the ranges of 80.1-120% and 78.9-119% for water and milk samples, respectively. The relative standard deviations for reproducibility were all below 11%. The results well evidence that the introduced FBA/MSPE is a promising extraction technology for FQs, and the established FBA/MSPE-HPLC/DAD approach is suitable to measure low concentrations of FQs in water and milk samples.

Dual functional monomers modified magnetic adsorbent for the enrichment of non-steroidal anti-inflammatory drugs in water and urine samples.

According to the molecular properties of non-steroidal anti-inflammatory drugs (NSADs), a new adsorbent for magnetic solid phase extraction (MSPE) was designed and synthesized. Triethyl-(4-vinylbenzyl)aminium chloride and 4-vinylbenzeneboronic acid were utilized as dual functional monomers to copolymerize with divinylbenzene on the surface of pre-modified Fe3O4 nanoparticles. The prepared magnetic adsorbent (Fe3O4@TCVA) was characterized by elemental analysis, Fourier transform infrared, scanning electron microscopy, transmission electron microscopy and vibrating sample magnetometer. Due to the abundant boronic acid, quaternary amine and phenyl groups, the Fe3O4@TCVA displayed satisfactory extraction performance for target NSADs (diclofenac acid, ibuprofen and mefenamic acid) by means of B-N coordination, anion-exchange, π-π and hydrophobic interactions. Under the optimized conditions, the Fe3O4@TCVA/MSPE was combined with high-performance liquid chromatography with diode array detection (HPLC-DAD) to sensitively analyze NSADs in water and human urine samples. Results indicated that the limits of detection for water and urine samples were in the ranges of 0.014-0.031 µg/L and 0.029-0.11 µg/L, respectively. The relative standard deviations for the intra-day and inter-day assay variability were below 10%. The applicability of the proposed Fe3O4@TCVA/MSPE-HPLC-DAD method was demonstrated by the successful extraction and quantification of trace levels of NSADs in real water and human urine samples. Satisfactory spiked recovery and reproducibility were achieved.

Allylthiourea functionalized magnetic adsorbent for the extraction of cadmium, copper and lead ions prior to their determination by atomic absorption spectrometry.

A quick and sensitive method was developed for the trace determination of Cd(II), Pb(II) and Cu(II) ions in water and bean samples. It is based on a combination of magnetic solid phase extraction (MSPE) and graphite furnace atomic absorption spectrometry (GFAAS). Allylthiourea (which contains abundant sulfur and nitrogen atoms) was copolymerized with ethylene dimethacrylate on the surface of magnetite (Fe3O4) nanoparticles to prepare a new adsorbent for use in MSPE. Various technologies were used to characterize the morphology, spectroscopic and magnetic properties of the adsorbent, and several parameters that affect the extraction performance were optimized. The adsorbent can enrich Cd(II), Pb(II) and Cu(II) ions via chelation interaction. Following elution with 0.1 mol·L-1 HNO3, the ions were quantified by GFAAS. Under the most favorable conditions, the limits of detection are from 3.3-7.2 ng·L-1 for water samples, and 1.1-1.5 µg·kg-1 for beans. The method displays wide linear analytical ranges and good precision. It was successfully applied to the determination of the metal ions in water and bean samples. The recoveries from spiked samples ranged between 80.5 and 114% in water, and from 82.2 to 118% in bean samples. The relative standard deviations of reproducibility were < 10%. Graphical abstract Schematic presentation of the magetic solid phase extraction (MSPE) for the analysis of Cd(II), Pb(II) and Cu(II). MNP: magnetic nanoparticles; ATED: allylthiourea ethylene dimethacrylate copolymer.

One-pot preparation of magnetic carbon adsorbent derived from pomelo peel for magnetic solid-phase extraction of pollutants in environmental waters.

In this work, magnetic carbon material derived from pomelo peels (MCMPs) was conveniently fabricated utilizing one-pot synthesis method and employed as adsorbent of magnetic solid-phase extraction (MSPE). Several characterized measures including infrared spectroscopy, scanning electron microscopy, transmission electron microscopy and vibrating sample magnetometer were used to investigate the morphology, spectroscopic and magnetic properties of prepared adsorbent. Apolar parabens and polar fluoroquinolones (FQs) were used to investigate the extraction performance of MCMPs. Under the optimized extraction conditions, the MCMPs displayed satisfactory extraction performance for target analytes. At the same time, the MCMPs/MSPE was combined with HPLC-DAD for the sensitive determination of parabens and FQs in real-life water samples. Results showed that the limits of detection (S/N = 3) for parabens and FQs were in the ranges of 0.011-0.053 µg/L and 0.012-0.46 µg/L, respectively. The spiked recoveries were in the range of 76.6-116% for parabens and 80.2-114% for FQs with good repeatability (relative standard deviations less than 10%). In comparison to reported methods, the developed MCMPs/MSPE-HPLC-DAD showed some merits including low-cost, simplicity, satisfactory sensitivity and green non-pollution.

[Post-transplant kidney from C-III donation after cardiac death of children: a clinicopathologic study of 20 cases].

OBJECTIVE: To study the clinical and histopathologic features of post-transplant kidney biopsy tissues from pediatric C-III donors. METHODS: The clinical and pathologic features of 20 cases (22 case-times) of renal transplant biopsies from pediatric cadaveric donors were analyzed by light microscopy and immunohistochemistry according to the Banff system of working classification of renal allograft pathology. Biopsies were compared to those from adult C-III donors and adult cadaveric donors. RESULTS: Sixteen cases (72.7%) showed renal allograft drug toxicity damage by Tacrolimus, seven cases (31.8%) showed degeneration and necrosis of renal tubular epithelial cells, four cases (18.2%) showed T cell-mediated acute rejection and six cases (27.3%) showed renal interstitial inflammation. There were two cases (9.1%) of renal dysplasia and one case (4.5%) of renal infarction. There was insufficient evidence for diagnosis of renal allograft nephropathy. Compared to post-transplant kidney from adult C-III donors, the proportion of drug toxicity damage was higher (P<0.05). Compared to post-transplant kidney from adult cadavers, the proportions of drug toxicity damage, degeneration and necrosis of renal tubular epithelial cells were higher (P<0.05) while the proportion of acute rejection was lower (P<0.05). CONCLUSIONS: The pathologic changes in the post-transplant kidneys from pediatric donors are different from those from adult donors. Optimal long-term outcome can be accomplished by effective treatment based on timely or procedural biopsy.