HPLC-MS/MS enantioseparation of triazole fungicides using polysaccharide-based stationary phases

The enantiomeric separation of 21 triazole fungicides was carried out on four polysaccharide-derived chiral stationary phases in the reversed phase separation mode using high performance liquid chromatography coupled with tandem mass spectrometry. All fungicides were detected in electrospray ionization (ESI) positive mode with selected reaction monitoring (SRM). Complete enantioseparation was achieved for 21 fungicides except for difenoconazole based on cellulose tris (3,5-dimethylphenylcarbamate) and cellulose tris (3-chloro-4-methylphenyl carbamate) columns by optimizing experimental conditions including mobile phase and column temperature. Mobile phase was 0.1% formic acid aqueous solution mixed with methanol or acetonitrile in different proportions. Among all the fungicides, 15 with two enantiomers and three with four stereoisomers (bitertanol, bromuconazole, and cyproconazole) were successfully separated at 25°C. Enantioseparation for the other three fungicides (propiconazole, triadimenol, and difenoconazole) with four stereoisomers could be achieved by changing the column temperature from 10 to 40°C. Propiconazole and triadimenol were enantioseparated on baseline at 40 and at 35°C, respectively, and difenoconazole was enantioseparated partially with the R(s) > 1.1 at 25°C. Moreover, linearities and limits of detection (LODs) of 21 fungicides except for difenoconazole were studied, showing coefficients of determination (R(2)) higher than 0.99 and LODs lower than 2.5 μg/L.     

Morphine-induced conditioned place preference in mice: Metabolomic profiling of brain tissue to find “molecular switch” of drug abuse by gas chromatography/mass spectrometry

Conditioned place preference (CPP) is a widely used model to explore the mechanism of context-dependent learning. In this work, we developed a GC–MS method to investigate the metabolites in mice brain which was used to study the mechanism of context-dependent learning associated with rewarding effect of morphine. Metabolites were extracted from brain tissues and derivatized followed by analysis by gas chromatography/mass spectrometry (GC–MS). In total, 69 peaks were identified as known compounds. By a Wilcoxon ran sum test with p value ≤0.05, 21 metabolites were selected and considered as the potential biomarkers of morphine in mice brain. Using principal component analysis (PCA) and receiver-operator characteristic (ROC) curves, a model was constructed with a combination of these 21 metabolic markers. Multivariate statistics of the model yielded separation between the two groups with an area under the curve value of 0.947. Some metabolites were further discussed in detail about their pathway. Results showed that our technique can be successfully applied to profile for biomarkers and in understanding molecular mechanisms of drug abuse.     

Fluorescence properties of novel rare earth complexes using carboxyl-containing polyaryletherketones as macromolecular ligands

The fluorescence properties of a series of rare earth (Re³⁺ = Eu³⁺, Tb³⁺) polymeric complexes (PEK-Re³⁺-HLs) using three high-T_g novel carboxyl-containing polyaryletherketones (PEK) as macromolecular ligands and small molecules (HL) such as 1,10-phenanthroline (Phen), dibenzoylmethane (DBM) and 8-hydroxyquinoline (HQ) as co-ligands were investigated by means of fluorescence excitation and emission spectroscopy as well as fluorescence lifetime measurement methods. Among them, PEK-1-Re³⁺-Phens, in which the Re³⁺ ions were coordinated simultaneously with Phen and PEK-1 containing both carboxyl and bulky isopropyl groups on the polymer backbone, exhibited strong fluorescence intensities, long lifetimes, and good film-formation properties. The smooth films of PEK-1-Eu³⁺-Phen and PEK-1-Tb³⁺-Phen, cast from their DMF solutions, could emit bright red and green light under the UV lamp of 365 nm, respectively, which characteristics are of great significance for their potential applications in the large area display material fields. The excellent fluorescence properties of complexes in this study were attributed to the synergistic effects of PEK-1 ligand and Phen co-ligand. Especially, the rigid twisted structure and the bulky isopropyl substituents on PEK-1 backbone forced the coordinated rare earth ion moieties apart, and thus the probability of non-radiative decay rate of Re³⁺ ions at the excited levels were decreased to a large extent.     

Pd–Co bimetallic nanoparticles supported on graphene as a highly active catalyst for Suzuki–Miyaura and Sonogashira cross-coupling reactions

Graphene (G) supported Pd–Co bimetallic nanoparticles (NPs) as a highly active catalyst was prepared by a chemical reduction method and used for coupling reactions. With the characterization of X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and Raman spectrum, the composition of resulting Pd–Co material was identified to be alloy structural. The Pd–Co (1:1)/G exhibited the highest catalytic activity for the Sonogashira-type coupling reactions and also exerted satisfied catalytic activity and recycle stability for Suzuki–Miyaura cross-coupling reactions. This Pd–Co/G material also possessed other advantages such as low-cost, easy recycled from reaction system by a magnet for their magnetic property, and easy experimental handling.     

改进型单晶炉提拉系统偏心平衡研究

随着光伏行业的快速发展, 对硅单晶的品质和长晶装备的稳定性的要求也不断提高。直拉法是生产硅单晶的主要方法,通过提高单晶炉副室的高度以扩大单晶硅的生产规模。由于副室高度的大幅增加,且单晶炉提拉头质心相对于旋转轴心有一定距离,对单晶炉整体稳定性有较大影响,从而降低了单晶硅的生产质量。针对此问题,对单晶炉建立可靠的力学分析模型,采用数值仿真方法,对单晶炉整体进行动力学响应分析,计算得到副室高度增加后的单晶炉工作时中钨丝绳下端晶棒的运动规律以及最大摆动幅度,为改进设计提供依据。数值仿真分析表明提高单晶炉副室高度后,提拉头较大的质心偏心是单晶炉提拉系统发生摆动的主要原因。在此基础上提出在提拉头上添加质心调节装置,通过控制系统调节可保证提拉头质心位置在旋转轴线上以降低提拉系统的摆动。     

Design,Synthesis, and In Vitro and In Vivo Antifungal Activity of Novel Triazoles Containing Phenylethynyl Pyrazole Side Chains

A series of triazole derivatives containing phenylethynyl pyrazole moiety as side chain were designed, synthesized, and most of them exhibited good in vitro antifungal activities. Especially, compounds 5k and 6c showed excellent in vitro activities against C. albicans (MIC = 0.125, 0.0625 μg/mL), C. neoformans (MIC = 0.125, 0.0625 μg/mL), and A. fumigatus (MIC = 8.0, 4.0 μg/mL). Compound 6c also exerted superior activity to compound 5k and fluconazole in inhibiting hyphae growth of C. albicans and inhibiting drug-resistant strains of C. albicans, and it could reduce fungal burdens in mice kidney at a dosage of 1.0 mg/kg. An in vivo efficacy evaluation indicated that 6c could effectively protect mice models from C. albicans infection at doses of 0.5, 1.0, and 2.0 mg/kg. These results suggested that compound 6c deserves further investigation.     

Evaluation of granule structure and strength properties of green packed beds in iron ore sintering using high-resolution X-ray tomography and uniaxial compression testing

The strength properties of green sinter beds,including the Young's modulus and maximum bed strain,were evaluated using uniaxial compression tests.The green-sint...     

Deep Multilabel Multilingual Document Learning for Cross-Lingual Document Retrieval

Cross-lingual document retrieval, which aims to take a query in one language to retrieve relevant documents in another, has attracted strong research interest in the last decades. Most studies on this task start with cross-lingual comparisons at the word level and then represent documents via word embeddings, which leads to insufficient structure information. In this work, the cross-lingual comparison at the document level is achieved through the cross-lingual semantic space. Our method, MDL (deep multilabel multilingual document learning), leverages a six-layer fully connected network to project cross-lingual documents into a shared semantic space. The semantic distances can be calculated when the cross-lingual documents are transformed into embeddings in semantic space. The supervision signals are automatically extracted from the data and then used to construct the semantic space via a linear classifier. The ambiguity of manual labels could be avoided and the multilabel supervision signals can be acquired instead of a single label. The representation of the semantic space is enriched by multilabel supervision signals, which improves the discriminative ability of the embeddings. The MDL is easy to extend to other fields since it does not depend on specific data. Furthermore, MDL is more efficient than the models training all languages jointly, since each language is trained individually. Experiments on Wikipedia data showed that the proposed method outperforms the state-of-the-art cross-lingual document retrieval methods.     

Mesoporous sodium four-coordinate aluminosilicate nanoparticles modulate dendritic cell pyroptosis and activate innate and adaptive immunity

Pyroptosis is a programmed cell death widely studied in cancer cells for tumour inhibition, but rarely in dendritic cell (DC) activation for vaccine development. Here, we report the synthesis of sodium stabilized mesoporous aluminosilicate nanoparticles as DC pyroptosis modulators and antigen carriers. By surface modification of sodium-stabilized four-coordinate aluminium species on dendritic mesoporous silica nanoparticles, the resultant Na-^IVAl-DMSN significantly activated DC through caspase-1 dependent pyroptosis via pH responsive intracellular ion exchange. The released proinflammatory cellular contents further mediated DC hyperactivation with prolonged cytokine release. In vivo studies showed that Na-^IVAl-DMSN induced enhanced cellular immunity mediated by natural killer (NK) cells, cytotoxic T cells, and memory T cells as well as humoral immune response. Our results provide a new principle for the design of next-generation nanoadjuvants for vaccine applications.

Na-^IVAl-DMSN acts as both antigen carriers and modulators to “hyperactivate” dendritic cells (DCs) via potassium (K⁺) efflux dependent pyroptosis, eventually leading to enhanced adaptive and innate immunity.     

Asymptotic behavior for a nematic liquid crystal model with different kinematic transport properties

We study the asymptotic behavior of global classical solutions to hydrodynamical systems modeling the nematic liquid crystal flows under kinematic transports for molecules of different shapes. The coupling system consists of Navier–Stokes equations and kinematic transport equations for the molecular orientations. We prove the convergence of global solutions to single steady states as time tends to infinity as well as estimates on the convergence rate both in 2D for arbitrary regular initial data and in 3D for certain particular cases.