超声提取–离子色谱法测定土壤易溶盐中的氯离子和硫酸根离子

采用超声提取的方式,以离子色谱法测定土壤易溶盐中的氯离子和硫酸根离子。对实验条件进行了优化,色谱柱为NJ–SA–4A柱(250 mm×2 mm),保护柱为SI–92G柱(50 mm×4 mm),淋洗液为1.8 mmol/L Na_2CO_3–1.7mmol/L NaHCO_3,流量为1.0 m L/min;在40℃下,对土壤样品提取10 min。Cl~–和SO_4~(2–)在检测范围内均线性良好,线性相关系数为0.999 8,加标回收率分别为95.0%~99.0%,96.0%~101.0%,测定结果的相对标准偏差分别为1.4%,1.0%(n=4)。与传统的方法相比,该法试剂用量少,操作简单,可用于土壤易溶盐样品的测定。     

Immunosensor for α-fetoprotein based on a glassy carbon electrode modified with electrochemically deposited N-doped graphene,gold nanoparticles and chitosan

The authors describe a voltammetric immunosensor with antibody immobilized on a glassy carbon electrode (GCE) modified with N-doped graphene (N-GS), electrodeposited gold nanoparticles (AuNPs) and chitosan (Chit). The preparation is simple and the thickness of the electrodeposited films can be well controlled. Due to the specific advantages of N-GS, AuNPs and Chit, the electrode has a large specific surface, improved conductivity, high stability. A new label-free immunosensor for the model antigen (alpha fetoprotein, AFP) detection was then designed by employing N-GS-AuNP-Chit as the antibody immobilization and signal amplification platform. Differential pulse voltammetry and electrochemical impedance spectroscopy were used for the characterization of the stepwise assembly process. Under the optimized conditions, at a typical working potential of +0.20 V (vs. SCE), and by using hexacyanoferrate as an electrochemical probe, the immunosensor has a detection limit as low as 1.6 pg mL^?1 and a linear analytical range that extends from 5 pg mL^?1 to 50 ng mL^?1. AFP was quantified in spiked human serum samples with acceptable precision.

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Graphical Abstract Schematic of sensitive and effective label-free electrochemical immunosensor for the detection of AFP based on N-GS-AuNP-Chit as signal amplification matrix.

     

Ir(I)-catalyzed enantioselective hydrogenolysis of 3-aryl-3-hydroxyisoindolin-1-ones

An enantioselective hydrogenolysis of 3-aryl-3-hydroxyisoindolin-1-ones under H₂ has been developed by using Ir(I)/(R)-MeO-Biphep complex as a catalyst. Cyclic diaryl methylamides were obtained in moderate to excellent yields and up to 92% ee.     

Comparison of Gasoline-Ranged <Emphasis Type="Italic">n</Emphasis>-Alkanes Conversions Using Dielectric Barrier Discharge: A Kinetic Study

Here, we compared the conversion of gasoline-ranged n-alkanes (C₆–C₉) using dielectric barrier discharge. For an energy density of ~68 J/L and an initial n-alkane concentration of ~230 ppm, when carbon number increased from 6 to 9, the energy efficiency of n-alkane conversion increased from 117 to 240 mmol/kWh, CO _x selectivity decreased from 46 to 20%, and ozone concentration increased from 216 to 240 ppm. The effect of energy density and initial n-alkane concentration were also investigated. The understanding of initial step of conversion was greatly aided by a proposed kinetic model. The pathways of consecutive reactions from the initiation to products were also discussed.     

The Effect of Intermolecular Hydrogen Bonding on the Polyaniline Water Complex

The polyaniline water hydrogen-bonded complex was studied by first-principles calculation. The density functional theory method was used to calculate the structure characters, natural bond orbital charge distribution, infrared spectra and the frontier molecular orbital. Results showed that the H–O···H–N and C–N···H–O type intermolecular hydrogen bonds were formed. The bonds involved in the intermolecular H-bond were all influenced by the hydrogen bonding interaction. During the hydrogen bond formation, the polymer chains in the complexes were all charged, which can be an important factor contributing to the increase of electrical conductivity. The N1–H vibration was strongly influenced, and the locations as well as the intensities of N1–H absorption bands were all changed in the complexes. In the orbital transition of HOMO to LUMO, the electron density transferred from benzenoid ring to quinoid ring.     

Solubility of Nifedipine and Lacidipine in Supercritical CO<Subscript>2</Subscript>: Measurement and Correlation

Solubilities of two calcium channel blockers, nifedipine and lacidipine, were measured in supercritical carbon dioxide at T = (313, 323, and 333) K over the pressure range (12.0–36.0) MPa using a dynamic-analytical apparatus. The solubility values obtained are in the range of (0.18–7.05) × 10^?5 mol·mol^?1. The solubilities of the two solids show similar trends with a crossover region of the respective isotherms in the range 18.0–21.0 MPa. The experimental solubility data were correlated with several different models. The semi-empirical density-based models provided satisfactory correlation results with AARD values lower than 10%. According to the results of the Méndez-Santiago and Teja models, the measured solid solubility data are quite consistent at all experimental conditions, which indicates the reliability of the data. The compressed gas model of the Peng–Robinson equation of state, combined with the two parameter van der Waals mixing rule (PR-EoS-VDW2) model, gives better correlation results than the PR-EoS-VDW1 model. The expanded liquid model based on Scatchard–Hildebrand regular solution theory can be used for solubility prediction, but the correlation results for nifedipine and lacidipine by the model are inferior to the compressed gas models in this work.     

A novel method to prepare microcellular poly(vinyl alcohol) foam based on thermal processing and supercritical fluid

Combining the thermal processing and supercritical fluid technology develops a novel preparation method of microcellular poly(vinyl alcohol) (PVA). Water, as the plasticizer in system, can form the hydrogen bonding with pendant hydroxyl of PVA and weaken its strong intermolecular and intramolecular forces to realize the thermal processing. Supercritical carbon dioxide (sc‐CO₂) can easily dissolve into water‐plasticized PVA (WPVA) because of the destruction of crystal region caused by water, and the enhanced sc‐CO₂ solubility can greatly improve the foamability of WPVA. The porous structure generates through the saturation of sc‐CO₂ in WPVA sample and followed by pressure drop‐induced phase separation. The foaming behavior of WPVA was studied as a function of saturation pressure, foaming temperature, and saturation time. The cell density, cell size, and distribution of the obtained foam can be controlled by tuning processing conditions. The results revealed that the cell size decreased, and its distribution narrowed with saturation pressure increasing, or decrease of foaming temperature. But excessively increasing the saturation time generated a negative effect on the foaming behavior owing to the deteriorated plasticization effect resulted from the loss of water. Copyright © 2016 John Wiley & Sons, Ltd.     

Ionic liquid functionalized graphene oxide for enhancement of styrene‐butadiene rubber nanocomposites

Ionic liquid 1‐allyl‐3‐methyl‐imidazolium chloride (AMICl) is used to fine‐tune the surface properties of graphene oxide (GO) sheets for fabricating ionic liquid functionalized GO (GO‐IL)/styrene‐butadiene rubber (SBR) nanocomposites. The morphology and structure of GO‐IL are characterized using atomic force microscope, X‐ray diffraction, differential scanning calorimetry, X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, UV‐vis spectra and Raman spectra. The interaction between GO and AMICl molecules as well as the effects of GO‐IL on the mechanical properties, thermal conductivity and solvent resistance of SBR are thoroughly studied. It is found that AMICl molecules can interact with GO via the combination of hydrogen bond and cation–π interaction. GO‐IL can be well‐dispersed in the SBR matrix, as confirmed by X‐ray diffraction and scanning electron microscope. Therefore, the SBR nanocomposites incorporating GO‐IL exhibit greatly enhanced performance. The tensile strength, tear strength, thermal conductivity and solvent resistance of GO‐IL/SBR nanocomposite with 5 parts per hundred rubber GO‐IL are increased by 505, 362, 34 and 31%, respectively, compared with neat SBR. This method provides a new insight into the fabrication of multifunctional GO‐based rubber composites. Copyright © 2016 John Wiley & Sons, Ltd.     

Ligand and base additive effects on the reversibility of nucleophilic addition in palladium-catalyzed allylic aminations monitored by nucleophile crossover

A nucleophile crossover experiment was used to monitor the reversibility of nucleophilic addition of benzylamine to π-allylpalladium complexes. Dppe, dppp, dppb, and PHOX showed more crossover than PPh₃ and dppm in both DMF and dichloromethane. Crossover was inhibited by the addition of DBU or Cs₂CO₃, but much less elimination to diene side products was observed with Cs₂CO₃. Analysis of percent crossover vs. percent reaction completion using the PHOX ligand revealed that with added DBU or Cs₂CO₃ crossover only began occurring after 100% completion had been reached.     

衍生化β-环糊精手性固定相高效液相色谱法拆分米那普仑对映体及其分离机制

建立了新型抗抑郁药米那普仑在环糊精手性固定相上的高效液相色谱拆分方法。在反相色谱条件下采用未衍生化β-环糊精(Cyclobond I 2000)、乙酰基-β-环糊精(AC-β-CD)、2,3-二甲基-β-环糊精(DM-β-CD)、3,5-二甲基苯基氨基甲酸酯-β-环糊精(DMP-β-CD)4种手性柱分离米那普仑对映体。考察了固定相、流动相比例、pH、流速和柱温对拆分的影响。利用分子对接和结合能计算方法,研究米那普仑分子与AC-β-CD的对接过程,探讨其可能的分离机制。优化后的拆分条件如下:固定相为乙酰基-β-环糊精手性柱Astec CYCLOBONDTMI 2000 AC(25 cm×4.6 mm,5μm),流动相为乙腈-0.1%(体积分数)pH 5.0醋酸三乙胺溶液(TEAA)(5∶95,v/v),流速为0.4mL/min,柱温为25℃,检测波长为220 nm。在此条件下,米那普仑对映体获得快速拆分,分离度(Rs)为1.74,理论塔板数为10 125。分子模拟结果表明引起手性识别的作用力主要是环糊精衍生化的乙酰基导致的氢键作用差异。该方法快速、高效、重现性好。