The temperature-dependent domains, SHG effect and piezoelectric coefficient of TGS

The temperature-dependent,second-order,nonlinear,optical coefficient(x^（2）).piezoelectric coefficient (d₃₃),pyroelectric coefficient（Ps） and domains on triglycine sulfate（TGS） reported herein provide a clue for us to investigate these as a typical second-order phase transition.The symmetry breaking occurrence is definitely confirmed by the temperature-dependent x^（2） in which x^（2） displays a limited value at the ferroelectric phase,indicating the space group（P2₁） chosen is correct,and when x^（2） basically maintains a zero value at the paraelectric phase,indicating the space group should be centric.Interestingly,after normalization of x^（2）,d₃₃ or Ps,the change trend with temperature is basically overlapped,probably abiding by Landau theory.Moreover,temperature-dependent domains directly show the symmetry breaking occurrence.     

Hydrothermal synthesis method of 5-(4'-methylbiphenyl-2-yl)-1H-tetrazole

A clean and safe synthesis method of 5-(4’-methylbiphenyl-2-yl)-1H-tetrazole was found:under hydrothermal conditions,1.2 equiv.of 4’-methylbiphenyl-2-carbonitrile react with 1 equiv.of sodium azide in a mixed solvent of propane-1,2-diol/H2O,with 1.5 equiv.of ammonium chloride and 0.2 equiv.of ammonium fluoride as catalyst.After simple post-processing,the yield can be improved to 95%,and the purity of the product is 99%without further recrystallization.     

Effective synthesis of benzyl halides triggered by in situ prepared hypervalent halides

An effective approach for the direct benzylhalogenation with in situ generation of hypervalent halides has been developed.A variety of benzyl halides are produced in moderate to excellent yields(up to 99%) with high regioselectivities.UV absorption spectrum is employed to detect the formation of ferr-butyl hypoiodite.     

可逆Diels-Alder反应

通过高效的反应精确合成功能分子已成为现代化学发展的趋势之一。基于呋喃/马来酰亚胺(MI)之间的Diels-Alder(D-A)反应作为一种高效的和高选择性的点击反应,克服了铜催化的叠氮/炔之间的1,3-偶极环化加成(CuAAC)反应中引起的金属污染等缺点,为生物医药载体、功能性材料的制备提供更可行的途径。同时,呋喃/MI之间的D-A反应具备原料易得、反应条件温和及易发生retro D-A(rD-A)反应等优点,在制备响应性材料领域备受关注。本文综述了近年基于呋喃/MI的可逆D-A反应在响应性聚合物合成、智能材料、生物分子及表面修饰等方面的应用,并展望了D-A反应的发展前景。     

Determination of ecgonine and seven other cocaine metabolites in human urine and whole blood by ultra-high-pressure liquid chromatography–quadrupole time-of-flight mass spectrometry

Ecgonine is suggested to be a promising marker of cocaine (COC) ingestion. A combined mass spectrometry (MS) and tandem MS (MS/MS) method was developed to simultaneously determine ecgonine and seven other metabolites of cocaine in human urine and whole blood with ultra-high-pressure liquid chromatography coupled with quadrupole time-of-flight mass spectrometry. The compounds were extracted from as little as 100 μL of sample by solid-phase extraction with a 96-well μElution solid-phase extraction plate. The protonated molecules or fragment ions at accurate mass acquired in MS mode were used to quantify specific analytes, following by dedicated MS/MS identification. The assay was linear in the range from 5 to 50-100 ng/mL for urine samples, except for ecgonine methyl ester (10-200 ng/mL) and ecgonine (40-400 ng/mL), and was linear from 1-2 to 50 ng/mL for whole blood samples, except for ecgonine methyl ester (20-1,000 ng/mL) and ecgonine (40-2,000 ng/mL). The correlation coefficients were all greater than 0.99. The limits of detection ranged from 0.2 to 16 ng/mL, and the lower limits of quantification ranged from 1 to 40 ng/mL. The repeatability and intermediate precision were 18.1 % or less. The accuracy was in the range from 80.0 to 122.9 %, process efficiencies were in the range from 8.6 to 177.4 %, matrix effects were in the range from 28.7 to 171.0 %, and extraction recoveries were in the range from 41.0 to 114.3 %, except for ecgonine (12.8 % and 9.3 % at low and high concentrations, respectively). This method was highly sensitive in comparison with previously published methods. The validated method was successfully applied to the analysis of real samples derived from forensic cases, and the results verified that, on the basis of data from four positive samples, ecgonine is a promising marker of cocaine ingestion.

Reversal of elution order of N‐(2,4‐dinitrophenyl)‐proline and N‐(2,4‐dinitrophenyl)‐serine in HPLC by BSA chiral stationary phase

N‐(2,4‐dinitrophenyl)‐proline and N‐(2,4‐dinitrophenyl)‐serine were enantiomerically resolved on the BSA chiral stationary phase by HPLC in reversed‐phase mode. Effects of chromatographic conditions on enantioseparation and elution order have been investigated in detail. For these two samples, reversal of enantiomer elution order was observed by changing buffer pH, the content of acetonitrile, or alcohol modifiers in mobile phase, which is firstly reported in the BSA chiral stationary phase studies. More interestingly, combined effect between buffer pH and the content of acetonitrile was also observed. In addition, coelution range of enantiomers varied along with the content of acetonitrile in mobile phase.     

Adsorption behavior of uranium on polyvinyl alcohol-g-amidoxime: Physicochemical properties, kinetic and thermodynamic aspects

Amidoxime-based adsorbents are widely studied as the main adsorbent in the recovery of uranium from seawater.However,the adsorption rate and loading capacity of such adsorbents should be further improved due to the economic viability consideration.In this paper,polyvinyl alcohol functionalized with amidoxime(PVA-g-AO)has been prepared as a new adsorbent for uranium(Ⅵ)adsorption from aqueous solution.The physicochemical properties of PVA-g-AO were investigated using infrared spectroscopy(IR),scanning electron microscope(SEM),X-ray diffraction(XRD),and X-ray photoelectron spectroscopy(XPS).Results showed that the ligand monomers were successfully grafted onto the matrixes.The XRD and XPS analysis showed that uranium was adsorbed in metal ionic form rather than in crystal form.Uranyl(U(Ⅵ))adsorption properties onto PVA-g-AO were evaluated.The adsorption of U(Ⅵ)by PVA-g-AO was fast,with an equilibrium time of less than 50 min.Additionally the maximum adsorption capacity reached 42.84 mg/g at pH 4.0.     

Five New Cycloartane‐Type Triterpenoid Saponins from Nervilia fordii

Five new cycloartane glycosides, nervisides D–H ( 1 – 5 ), were isolated from the AcOEt‐ and H₂O‐soluble portions of the 90% EtOH extract of the aerial part of the plant Nervilia fordii. The structures of the isolated glycosides were elucidated by extensive spectroscopic analysis including HR‐ESI‐MS and NMR data. The isolated nervisides D–H were evaluated for the cytotoxic activity in vitro against human‐tumor cell lines (CNE, Hep‐2 and HepG2) with the MTT method.     

A Stereoselective Synthetic Route To (E)-α,β-Unsaturated Thioesters

Terminal alkynes 1 react with Cp₂Zr(H)Cl (Cp = η⁵-C₅H₅) and CO to give acylzirconocene chloride derivatives 2, which are trapped with arylsulfenyl chlorides to afford (E)-α,β-unsaturated thioesters.     

Microstructural evolution during oxidative ablation in air for polyacrylonitrile based carbon fibers with different graphite degrees

Polyacrylonitrile‐based carbon fibers with different graphite degrees were oxidative ablated at 500 and 600 °C in air. By Thermal gravimetric (TG), Raman spectroscopy, X‐ray diffraction, and SEM, the mass loss, microstructure, and surface morphology of carbon fibers were investigated. The mass loss of carbon fiber increases linearly with increasing oxidative ablated time under 500 and 600 °C. The carbon fiber with higher graphite degree shows higher oxidative resistance, and the surface roughness increases gradually because of chemical ablation during the whole oxidation. A gloss morphology appears on the surface primarily because of physical denudation for carbon fibers with lower graphite degree and then burn off according to carbon and oxygen reaction. The crystallite size (La) decreases significantly, while interlayer spacing(d₀₀₂) remains nearly unchanged. SEM observation suggests the two kinds of ablation mechanisms for carbon fibers with different graphite degrees indicating that CC band in sp³ hybridization prefers to be attacked by oxygen molecule more than that in sp² hybridization during oxidation ablation in air. Copyright © 2012 John Wiley & Sons, Ltd.