CuI/Fe3O4 NPs@Biimidazole IL‐KCC‐1 as a leach proof nanocatalyst for the synthesis of imidazo[1,2‐a]pyridines in aqueous medium

In the present work, an innovative leach proof nanocatalyst based on dendritic fibrous nanosilica (DFNS) modified with ionic liquid loaded Fe₃O₄ NPs and CuI salts was designed and applied for the rapid synthesis of imidazo[1,2‐a]pyridines from the reaction of phenyl acetylene, 2‐aminopyridine, and aldehydes in aqueous medium. The structure of the synthesized nanocatalyst was studied by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), Fourier transform infrared (FT‐IR), flame atomic absorption spectroscopy (FAAS), energy‐dispersive X‐ray (EDX), and X‐ray diffraction (XRD), vapor–liquid–solid (VLS), and adsorption/desorption analysis (Brunauer–Emmett–Teller [BET] equation) instrumental techniques. CuI/Fe₃O₄NPs@IL‐KCC‐1 with high surface area (225 m² g^?1) and porous structure not only exhibited excellent catalytic activity in aqueous media but also, with its good stability, simply recovered by an external magnet and recycled for eight cycles without significant loss in its intrinsic activity. Higher catalytic activity of CuI/Fe₃O₄NPs@IL‐KCC‐1 is due to exceptional dendritic fibrous structure of KCC‐1 and the ionic liquid groups that perform as strong anchors to the loaded magnetic nanoparticles (MNPs) and avoid leaching them from the pore of the nanocatalyst. Green reaction media, shorter reaction times, higher yields (71–97%), easy workup, and no need to use the chromatographic column are the advantages of the reported synthetic method.     

Effect of biaxial strain and hydrostatic pressure on the magnetic properties of bilayer CrI3

Two-dimensional van der Waals magnetic materials are intriguing for applications in the future spintronics devices, so it is crucial to explore strategy to control the magnetic properties. Here, we carried out first-principles calculations and Monte Carlo simulations to investigate the effect of biaxial strain and hydrostatic pressure on the magnetic properties of the bilayer CrI₃. We found that the magnetic anisotropy, intralayer and interlayer exchange interactions, and Curie temperature can be tuned by biaxial strain and hydrostatic pressure. Large compressive biaxial strain may induce a ferromagneticto-antiferromagnetic transition of both CrI₃ layers. The hydrostatic pressure could enhance the intralayer exchange interaction significantly and hence largely boost the Curie temperature. The effect of the biaxial strain and hydrostatic pressure revealed in the bilayer CrI₃ may be generalized to other two-dimensional magnetic materials.     

DSA、CTA联合MR影像评估AIS患者脑支循环及预后性关系

探讨数字减影血管成像(DSA)、计算机断层扫描血管成像(CTA)联合磁共振(MR)影像评估急性缺血性卒中(AIS)患者脑支循环及预后性关系。选取60例大脑中动脉M1段急性闭塞所致AIS患者为研究对象,根据DSA、CTA与MR影像对其脑侧支循环评估,比较患者基线资料、结局指标等,并分析预后性。结果发现:基于DSA、CTA与MR影像对AIS患者脑侧支循环评估结果一致性良好;3种影像模式下脑侧支循环良好组与不良组结局资料差异显著(P<0.05);多因素分析显示,FVH-ASPECTS评分、rLMC评分、ASITN/SIR分级量表均为AIS患者神经功能预后的独立影响因素。总之,DSA、CTA、MR影像对AIS患者脑侧支循环评估具有一致性,且FVH-ASPECTS评分、rLMC评分、ASITN/SIR分级量表均为AIS患者神经功能预后的独立影响因素。     

Pattern transition and regulation in a subthalamopallidal network under electromagnetic effect

Although the significant roles of magnetic induction and electromagnetic radiation in the neural system have been widely studied, their influence on Parkinson's disease (PD) has yet to be well explored. By virtue of the magnetic flux variable, this paper studies the transition of firing patterns induced by magnetic induction and the regulation effect of external magnetic radiation on the firing activities of the subthalamopallidal network in basal ganglia. We find: (i) The network reproduces five typical waveforms corresponding to the severity of symptoms: weak cluster, episodic, continuous cluster, episodic, and continuous wave. (ii) Magnetic induction is a double-edged sword for the treatment of PD. Although the increase of magnetic coefficient may lead the physiological firing activity to transfer to pathological firing activity, it also can regulate the pathological intensity firing activity with excessive β-band power transferring to the physiological firing pattern with weak β-band power. (iii) External magnetic radiation could inhibit continuous tremulous firing and β-band power of subthalamic nucleus (STN), which means the severity of symptoms weakened. Especially, the bi-parameter plane of the regulation region shows that a short pulse period of magnetic radiation and a medium level of pulse percentage can well regulate pathological oscillation. This work helps to understand the firing activity of the subthalamopallidal network under electromagnetic effect. It may also provide insights into the mechanisms behind the electromagnetic therapy of PD-related firing activity.     

超导磁共振仪器设备国产化现状及挑战

磁共振在化学分析和医学影像等领域发挥着不可或缺的作用，而磁共振仪器设备是开展磁共振研究的必要前提.长期以来，国外仪器厂商在我国磁共振仪器市场居于垄断地位.近年来，随着我国在磁共振仪器研发和产业化方面不断取得进展，市场份额为外商垄断的局面已大为改观.本文调研综述了我国磁共振仪器设备研制的现状，以及面临的若干挑战.     

Comparative structural analysis of a histone-like protein from Spiroplasma melliferum in the crystalline state and in solution

A solution of a histone-like protein from Spiroplasma melliferum (HUSpm) was examined by small-angle X-ray scattering (SAXS). The experimental SAXS curve was compared with those calculated for the HUSpm structures from the PDB databank obtained by both X-ray diffraction analysis and nuclear magnetic resonance spectroscopy. The model of the HUSpm structure in solution, which best agrees with the experimental SAXS data, has a shorter distance between the centers of mass of the HUSpm monomers compared to the crystal structure, indicating that the HUSpm monomers can be located closer to each other in solution than in the crystalline state.     

Simultaneous determination of 75 abuse drugs including amphetamines,benzodiazepines, cocaine,opioids, piperazines,zolpidem and metabolites in human hair samples using liquid chromatography–tandem mass spectrometry

A liquid chromatography–tandem mass spectrometric method for the simultaneous determination of 75 abuse drugs and metabolites, including 19 benzodiazepines, 19 amphetamines, two opiates, eight opioids, cocaine, lysergic acid diethylamide, zolpidem, three piperazines and 21 metabolites in human hair samples, was developed and validated. Ten‐milligram hair samples were decontaminated, pulverized using a ball mill, extracted with 1 mL of methanol spiked with 28 deuterated internal standards in an ultrasonic bath for 60 min at 50°C, and purified with Q‐sep dispersive solid‐phase extraction tubes. The purified extracts were evaporated to dryness and the residue was dissolved in 0.1 mL of 10% methanol. The 75 analytes were analyzed on an Acquity HSS T3 column using gradient elution of methanol and 0.1% formic acid and quantified in multiple reaction monitoring mode with positive electrospray ionization. Calibration curves were linear (r ≥ 0.9951) from the lower limit of quantitation (2–200 pg/mg depending on the drug) to 2000 pg/mg. The coefficients of variation and accuracy for intra‐ and inter‐assay analysis at three QC levels were 4.3–12.9% and 89.2–109.1%, respectively. The overall mean recovery ranged from 87.1 to 105.3%. This method was successfully applied to the analysis of 11 forensic hair samples obtained from drug abusers.     

Highly sensitive and rapid determination of tacrolimus in peripheral blood mononuclear cells by liquid chromatography–tandem mass spectrometry

After solid organ transplantation, tacrolimus is given to prevent rejection. Therapeutic drug monitoring is used to reach target concentrations of tacrolimus in whole blood. Because the site of action of tacrolimus is the lymphocyte, and tacrolimus binds ~80% to erythrocytes, the intracellular tacrolimus concentration in lymphocytes is possibly more relevant. For this purpose, we aimed to develop, improve and validate a UPLC–MS/MS method to measure tacrolimus concentrations in isolated peripheral blood mononuclear cells (PBMCs). PBMCs were isolated using a Ficoll separation technique, followed by a washing step using red blood cell lysis. A cell suspension of 50 μL containing 1 million PBMCs was used in combination with MagSiMUS‐TDM^PREP. To each sample we added 30 μL lysis buffer, 20 μL reconstitution buffer containing ¹³C²H₄‐tacrolimus as internal standard, 40 μL MagSiMUS‐TDM^PREP Type I Particle Mix and 175 μL Organic Precipitation Reagent VI for methanol‐based protein precipitation. A 10 μL aliquot of the supernatant was injected into the UPLC–MS/MS system. The method was validated, resulting in high sensitivity and specificity. The method was linear (r² = 0.997) over the range 5.0–1250 pg/1 × 10⁶ PBMCs. The inaccuracy was <5% and the imprecision was <15%. The washing steps following Ficoll isolation could be performed at either room temperature or on ice, with no effect of the temperature on the results. A method for the analysis of tacrolimus concentrations in PBMCs was developed and successfully validated. Further research will be performed to investigate the correlation between concentrations in PBMCs and clinical outcome.     

Analysis of F-53B,Gen-X,ADONA, and emerging fluoroalkylether substances in environmental and biomonitoring samples: A review

The persistent, bioaccumulative, and toxic properties of certain per- and polyfluoroalkyl substances (PFAS) raise concerns for environmental and human health. This has led to the gradual phase-out from production and commerce of some legacy PFAS. Fluoroalkylether compounds (ether-PFAS) are among the fluorinated alternative chemicals that are beginning to be reported in impacted and background environments. Extensive monitoring activities were conducted since 2015–2019 to bridge knowledge gaps on the environmental fate and effects of ether-PFAS including F-53B (6:2 chlorinated polyfluoroalkyl ether sulfonate [6:2 Cl-PFAES] and 8:2 Cl-PFAES), Gen-X (hexafluoropropylene oxide dimer acid [HFPO-DA]), and ADONA (dodecafluoro-3H-4,8-dioxanonanoate). In recent years, advances in nontarget screening using high-resolution mass spectrometry have revealed the identities of other infrequently monitored ether-PFAS. In this critical review, we provide an up-to-date inventory of the structures of ether-PFAS discovered in the recent literature. Their environmental occurrence, fate, and effects are discussed on a comparative perspective with some legacy PFAS such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS). Information on the methods employed for the quantitative and semi-quantitative analysis of ether-PFAS is also provided, including sample preparation and mass spectrometry analysis, analytical performance, and limitations. In particular, the compiled database of MS/MS fragment ions (n = 111) can be useful in spectrum interpretation of novel ether-PFAS. The concluding remarks open on possible research avenues and the challenges that remain to be addressed.     

Novel palladium nanoparticles supported on β‐cyclodextrin@graphene oxide as magnetically recyclable catalyst for Suzuki–Miyaura cross‐coupling reaction with two different approaches in bio‐based solvents

A novel nanocatalyst was designed and prepared. Initially, the surface of magnetic graphene oxide (M‐GO) was modified using thionyl chloride, tris(hydroxymethyl)aminomethane and acryloyl chloride as linkers which provide reactive C═C bonds for the polymerization of vinylic monomers. Separately, β‐cyclodextrin (β‐CD) was treated with acryloyl chloride to provide a modified β‐CD. Then, in the presence methylenebisacrylamide as a cross‐linker, monomers of modified β‐CD and acrylamide were polymerized on the surface of the pre‐prepared M‐GO. Finally, palladium acetate and sodium borohydride were added to this composite to afford supported palladium nanoparticles. This fabricated nanocomposite was fully characterized using various techniques. The efficiency of this easily separable and reusable heterogeneous catalyst was successfully examined in Suzuki–Miyaura cross‐coupling reactions of aryl halides and boronic acid as well as in modified Suzuki–Miyaura cross‐coupling reactions of N‐acylsuccinimides and boronic acid in green media. The results showed that the nanocatalyst was efficient in coupling reactions for direct formation of the corresponding biphenyl as well as benzophenone derivatives in green media based on bio‐based solvents. In addition, the nanocatalyst was easily separable, using an external magnet, and could be reused several times without significant loss of activity under the optimum reaction conditions.