Syntheses and luminescence of three lanthanide complexes constructed by flexible carboxylate ligand

Three new complexes, namely {[Ln(L)₃(2,2′-Bipy)] _n · H₂O} (Ln = Pr (I), Sm (II), and Nd (III)) (HL = 3-(2-hydroxyphenyl)propanoic acid), have been synthesized and structurally characterized. The structural determinations indicated (CIF files CCDC nos. 1472729 (I), 1472730 (II), 1472734 (III)) that I–III have similar dinuclear structures, which can be further linked into 2D sheet via the hydrogen bond interactions. Furthermore, the luminescent properties of I–III show the strong emissive power and feature.     

A dual chemosensor for Cu2+ and Fe3+ based on π-extend tetrathiafulvalene derivative

A new dual chemosensor (TTF-PBA) for Fe³⁺ and Cu²⁺ in different signal pathways was designed and synthesized. The absorption spectrum, fluorescence spectrum and cyclic voltammograms changed in the presence of Cu²⁺ and Fe³⁺. The optical color changed within 5 s from yellow to orange upon the addition of Cu²⁺, and it changed to dark yellow when Fe³⁺ existed. The cyclic voltammogram of Cu²⁺/TTF-PBA changed from E_ox = 0.50 V, E_red = 0.32 V to E_ox = 0.64 V, E_red = 0.80 V (vs Ag/AgCl) upon the addition of 2.0 equiv. Cu²⁺. As for Fe³⁺/TTF-PBA, its oxidation wave disappeared, and its reduction wave appeared at E_red = ?0.59 V (vs Ag/AgCl) upon the addition of 4.0 equv. Fe³⁺. The sensor displayed high selectivity for Cu²⁺ and Fe³⁺ over other ions including Pb²⁺, Zn²⁺, Ni²⁺, Ag⁺, Cr³⁺, Mn²⁺, Al³⁺, Co²⁺, Pd²⁺, Hg²⁺, Fe^2+, Cd²⁺, Ce³⁺, Bi³⁺ and Au³⁺, the detection limits for Cu²⁺ and Fe³⁺ ion reached as low as 5.33 × 10^?7 mol/L and 5.34 × 10^?7 mol/L, respectively. Furthermore, when Fe³⁺ existed, Cu²⁺ can be detected sequentially by the sensor through the absorption spectrum and the color change observed by naked-eyes.     

Determination and Characterization of the Uptake of Voriconazole in Human Lung Epithelial Cells by High-Performance Liquid Chromatography–Tandem Mass Spectrometry

Voriconazole is used to prevent invasive pulmonary aspergillosis. However, little is known about the concentrations of voriconazole in human lung epithelial cells (A549), which is the target for preventing invasive pulmonary aspergillosis. The goal of this study was to develop a high-performance liquid chromatography–tandem mass spectrometry method to quantify voriconazole in A549 cells. A triple-quadrupole mass spectrometer in selected reaction monitoring mode was used with positive electrospray ionization. The total duration of each run was 5?min. The calibration curves fit a least squares model for the voriconazole concentration ranging from 0.625 to 160?ng/mL. Intraday and interday coefficients of variation were less than 10%. Recoveries at the concentrations of the quality control samples where greater than 85%, and the matrix effects showed that the ratios of the peak response exhibited a 15% suppression of the signal in the matrix compared to water. Voriconazole may penetrate A549 cells. However, the voriconazole uptake was slow in A549 cells, reaching a plateau at 2?h, where the dose-dependent intracellular voriconazole concentrations were 1.98?±?0.38, 4.43?±?0.54, and 8.14?±?0.52?ng/mg protein for extracellular voriconazole concentrations of 5, 10, and 20?µg/mL, respectively. The uptake of voriconazole by A549 cells was linear at extracellular concentrations from 0 to 20?µg/mL. This study established a rapid and sensitive method suitable for determining voriconazole in A549 cells and described the kinetic properties of the absorption of voriconazole by A549 cells.     

Influence of peripheral alkyl chain length on the mesomorphic behaviours of hexasubstituted triphenylene 2,3-dicarboxylic esters

A comparative study of our established synthetic approaches to hexasubsituted triphenylenes 2,3-dicarboxylic esters containing four identical β-alkoxy and two adjacent β-alkoxycarbonyl side chains shows that the phase behaviours of small-sized discotic liquid crystals can be tailored over a wide range by simply varying the length of the peripheral alkyl chains. All the prepared esters in two series were observed to form a single hexagonal columnar phase, except for Tp4-1 having four β-butyloxy and two adjacent β-methoxycarbonyl chains which displays two columnar mesophase behaviours with a transition from the columnar plastic phase to hexagonal columnar phase. A significant difference between the two mesophase was observed in the variable temperature X-ray diffraction studies, and the mesophase assignment was also confirmed by polarising optical microscopy and differential scanning calorimetry. Moreover, the prepared esters in each series display the general trend of decreasing clearing temperature upon increasing alkoxy or alkoxycarbonyl chains length. The intermediate triphenylene 2,3-dicarboxylic acids were also found not only to exhibit columnar hexagonal mesophase over a narrower temperature range by maintaining high melting and clearing points but also to form organogel on mixing with toluene or dichloromethane with the assistance of hydrogen bonding.     

Annulation reaction of methyl 2-(benzo[b][1,4]thiazin-3-ylidene)acetate with β-nitrostyrenes and 3-nitrochromenes

The acid catalyzed domino reaction of β-nitrostyrenes with methyl 2-(benzo[b][1,4]thiazin-3-ylidene)acetate, which were previously prepared from the cyclization of 2-aminobenzenethiol and methyl 4-chloroacetoacetate, resulted in 2-arylbenzo[b]pyrrolo[1,2-d][1,4]thiazine-3-carboxylates in high yields. Under same reaction conditions, the similar reaction with 3-nitrochromenes afforded corresponding benzo[b]chromeno[4′,3':4,5]pyrrolo[1,2-d][1,4]thiazine derivatives in good yields.     

Facile fabrication of asphaltene-derived graphene-polyurethane sponges for efficient and selective oil-water separation

Based on the natural graphene-structure in the raw asphaltene material, a graphene-polyurethane sponge (GPU) oil-absorption material was prepared via a facile and inexpensive route of dip-coated sponge carbonization, which used low-value petroleum asphlatene as the dip-coating reagent and polyurethane sponges as the template. The GPU presents high hydrophobic and super oleophilic properties, as well as the excellent oil absorption performance. And its chloroform absorption capacity could reach 123 times its original mass, which is significantly higher than that of most reported oil absorbents. Furthermore, the GPU exhibits good recyclability. It has the promising applications in the pollution control of spilt oil.     

Effect of temperature on the organized self-assembly of SDS/β-Cyclodextrin aqueous solution by dielectric relaxation behavior

The temperature dependence of microstructures of SDS/β-cyclodextrin aqueous solution was investigated by impedance analyzer at the temperature range of 15°C to 55°C. The dielectric relaxation behaviors were observed from 15°C to 35°C, which was attributed to the Maxwell-Wagner interfacial polarization. The microstructure transition of the SDS/β-cyclodextrin aqueous solution from micro-tube to vesicle and then to monomer with increasing temperature was confirmed by conjointly analyzing dielectric parameters, confocal laser scanning microscopy, and infrared spectra. Furthermore, the dielectric analysis was proved to be useful to study surfactant-based organized self-assembly.     

Modeling liquid-liquid interface level in a horizontal three-phase separator with a bucket and weir

The flow behavior in a three-phase separator with a bucket and weir was analyzed, and a theoretical equation for calculating the liquid-liquid interface level (H_H) in gravity separation zone was derived. The analysis indicates that the H_H increases as the flow rate and the density ratio of heavy to light liquid increase, and decreases linearly with increasing height difference between heavy and light liquid overflow weirs. The calculated H_H under different operating conditions is in good agreement with the experimental. With the proposed equation, the thicknesses of heavy and light liquid layers can be calculated, and then the minimum lengths of two phase layers required for separation can be determined separately. From the minimum lengths it can be clearly indicated that the governing step of liquid-liquid separation is in heavy or light liquid layers, hence the sizing of the separator can be optimized.     

An In situ Study on the Orderly Crystal Growth of Pluronic F127 Block Copolymer Blended with and without Ionic Liquid during Isothermal Crystallization

Isothermal crystallization behavior of Pluronic F127 blended with and without an ionic liquid (IL) was investigated by in situ polarized optical microscopy (POM) and Fourier transform infrared spectroscopy (FTIR). For the pure F127, the POM and FTIR results showed that the spherulite size and crystallinity of F127 increased with the melting temperature increasing to 60, 80, and 135°C. This could be explained by the flexibility of the polymer chain at high melting temperatures. For the F127 blended with IL, the POM results showed that the morphology of F127 evolved from spherulite to dendritic segregation and fibrous crystal with the increasing IL content. FTIR results indicated that hydrogen bonds were formed between F127 and IL, and the intensity of the hydrogen bonds became strengthened gradually with increasing IL content. The effect of hydrogen bonds on the morphology evolution of F127/IL is discussed.     

Mechanism of the Enhanced Electrochemical Properties of LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> Cathode Materials by a Pre-Sintering Process

α-NaFeO₂ layered LiNi_1/3Co_1/3Mn_1/3O₂ cathode materials were synthesized by mechanical milling accompanied by the solid phase sintering. The sample exhibited a good crystallinity and layered structure while sintered at 900°C, which can be further improved by adding a pre-sintering process at 500°C before high temperature sintering. The sample with a pre-sintering process presents an average particle size about 0.6 μm, and a hexagonal crystalline structure. The optimally fabricated sample showed a first charge capacity of 210.2 mA h/g, discharge capacity of 171.2 mA h/g with a current rate of 0.2 C within the voltage range of 2.7~4.5 V. With increasing the current rate to 1 C, the charge–discharge capacity faded quickly during the cycling process, which can be partially recovered while operated at a low current rate. However, the capacity fading at a current rate of 2 C was largely irreversible. The evolution of the surface chemical states was evaluated using X-ray photoelectron spectroscopy on the charged and discharged samples to understand the high rate capacity fading.