Quantification of polychlorinated dibenzo-p-dioxins and dibenzofurans by direct injection of sample extract into the comprehensive multidimensional gas chromatograph/high-resolution time-of-flight mass spectrometer

Polychlorinated dibenzo-p-dioxins and dibenzofurans in crude extracts of fly ash and flue gas from municipal waste incinerators were quantified using a comprehensive multidimensional gas chromatograph (GC x GC) coupled to a high-resolution time-of-flight mass spectrometer (HR-TOFMS). For identification and quantification, we developed our own program to prepare 3D chromatograms of selected mass numbers from the data of the GC x GC/HR-TOFMS. Isolation of all congeners with a TCDD toxic equivalency factor from the other isomers by only one injection was confirmed. The instrumental detection limit of TCDD on the GC x GC/HR-TOFMS was 0.9 pg by the relative calibration method. Quantification of these substances in the crude extracts was achieved by direct injection to the GC x GC/HR-TOFMS. The results agree with the values obtained using a generic gas chromatography/high-resolution mass spectrometry (GC/HRMS) system. It was confirmed that measurement by high-resolution TOFMS and GC x GC effectively reduces interference from other chemicals.     

Synthesis of poly(6-azulenylethynyl)benzene derivatives as a multielectron redox system with liquid crystalline behavior

A series of poly(6-azulenylethynyl)benzenes substituted with n-hexyloxycarbonyl chains at 1,3-positions in azulene rings, i.e., hexakis-, 1,2,4,5-tetrakis-, 1,3,5-tris-, and 1,4-bis(6-azulenylethynyl)benzene derivatives 1, 2, 3, and 4b, have been prepared by a simple one-pot reaction involving repeated Pd-catalyzed alkynylation of halogenated arenes with substituted 6-ethynylazulene and/or ethynylated arenes with substituted 6-bromoazulene under Sonogashira-Hagihara conditions. The redox behavior of these novel poly(6-azulenylethynyl)benzene derivatives was examined by cyclic voltammetry (CV), which revealed the presumed multielectron redox properties. Compound 4b exhibited a one-step, two-electron reduction wave upon CV, which revealed the formation of the dianion stabilized by two 6-azulenylethynyl substituents under electrochemical reduction conditions. Four 6-azulenylethynyl substituents on a benzene ring in a 1,2,4,5 relationship increased the electron-accepting properties because of the formation of a stabilized closed-shell dianionic structure, whereas 3 was reduced at more negative reduction potentials. In contrast to the multistep redox behavior of 2, compound 1 was reduced in one step at -1.28 V upon CV. Compound 1 showed a wide temperature range of columnar mesophases (Col(ho) and Col(ro)) from 77.3 degrees C to the decomposition temperature at ca. 270 degrees C. Compounds 2, 3, and 4b exhibited columnar mesomorphism (Col(ro)) with crystalline polymorphs for 2, unusual triple-melting behavior for 3, and both double-melting behavior and columnar mesomorphism (Col(ho)) for 4b. Therefore, the investigated systems exemplify a new principle for multielectron redox behavior with liquid crystalline properties.     

硅基上Si1-xGex合金的外延生长及性能研究

硅基上高质量的异质外延生长是实现高性能微电子器件的基础,本文通过低温分子束外延技术在Si衬底上实现了全组分的Si1-x Gex(0相似文献   

Electrochemical fluorination of chlorine-containing ethers

The electrochemical fluorination of chlorine-containing ethers has been studied. In general, it was found that a chlorine bonded to an a-carbon atom in the ethers was readily removed during electrochemical reaction in anhydrous hydrogen fluoride, whilst a chlorine bonded to the β-carbon atom was retained to yield β-chlorinated polyfluoroethers.Through the use of this method, several new chloropolyfluoroethers, e.g. 2-chloro-1,1,2,2-tetrafluoroethyl difluoromethyl ether, 2,2-dichloro-1,1,2-trifluoroethyl trifluoromethyl ether 2,2-dichloro-1,1,2-trifluoroethyl difluoromethyl ether, 2,2-dichloro-1,1,2-trifluoroethyl chlorodifluoromethyl ether, 2-chloro-1,1,2,2-tetrafluoroethyl chlorodifluoromethyl ether and 2,2-trichloro-1,1-difluoroethyl trifluoromethyl ether, have isolated and characterized.     

Microfabrication of FeMnPt films involving magnetic phase change due to structural transformation caused by ion irradiation

Correlations between crystal structures and magnetic properties of Fe_1–xMn_x Pt films were studied. The disordered films with x ≥ 0.44 had paramagnetic properties and the ordered films with x ≥ 0.46 had antiferromagnetic properties, viz. a difference of 0.02 in the x ‐value (i.e., 1.0 at%) was found. At x = 0.44 with the ordered structure, the uniaxial magnetocrystalline anisotropy was about 2.1 × 10⁷ erg cm^–3. A microfabrication process involving the slight composition difference of 0.02, which results in ferromagnetic–paramagnetic phase change due to the structural transformation caused by ion irradiation, was investigated. Only the area irradiated by Mn ions changed from ferromagnetic to paramagnetic phase. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Deprotonated Amines Formed Through Coordination to Sulfur/Oxygen-Bridged Incomplete Cubane-Type Molybdenum Clusters

Oxygen/sulfur-bridged incomplete cubane-type molybdenum aqua clusters [Mo₃( ₃-S)(-X)(-S)₂(H₂O)₉]⁴⁺ (X=O, S) in hydrochloric acid react with dien (diethylenetriamine) to give [Mo₃( ₃-S)(-X)(-S)₂(dien^–)(dien)₂]Cl₃·nH₂O [1, X=O, n=3; 2, X=S, n=4; dien^–=NH₂(CH₂)₂NH(CH₂)₂NH^–], respectively, where each cluster has a deprotonated dien. The X-ray structural analysis of 1 revealed proton dissociation from an amino group of one of the three dien ligands: one Mo–N distance [1.987(4) Å] is clearly shorter than the other eight Mo–N distances [2.229(3)–2.276(3) Å]. The ¹H NMR spectra of the Mo–dien clusters 1 and 2 in D₂O show two well-resolved methylene proton signals in the 2.8- to 3.0-ppm region, which indicates that both deprotonated amines in 1 and 2 receive D⁺ ions from solvent D₂O. The factors for the proton dissociation are discussed.     

Alternative optimality criteria of portfolio selection based upon threshold stopping rule

This paper proposes two types of alternative criteria of optimality for the continuous time portfolio selection problem. The optimality criteria, the so–called Laplace–Stieltjes transform (LST) criteria, are based on the assumption that the financial agent has a target level for the wealth accumulation process. These criteria are closely related to the so–called threshold stopping investment rule. We analytically derive the LST criteria and numerically compare them with the well–known Kelly criterion. It is shown that the portfolio strategies suggested may overcome the problem that the growth portfolio is often overestimated in several investment situations.     

Some electronic properties and morphological features of hybrid material DNA–SWCNT thin films

Thin films of hybrid material (ssDNA–SWCNT) prepared by ultrasonic mixing of both materials in water have been examined from the viewpoint of electrical, magnetic and optical properties, and morphological features to probe the possibly induced novel functions due to mutual interactions. Enclosing of DNA molecules inside a SWCNT is confirmed by the image and its motion. The temperature dependence of electrical resistivities is best-fitted to the two-dimensional variable-range-hopping regime. The radial breathing mode of the Raman spectra of the SWCNT exhibits significant modification due to interaction with DNA. The expected change in magnetic susceptibilities is not found in this case.     

Photo-Driven Iron-Induced Non-Oxidative Coupling of Methane to Ethane

Photo-driven CH₄ conversion to multi-carbon products and H₂ is attractive but challenging, and the development of efficient catalytic systems is critical. Herein, we construct a solar-energy-driven redox cycle for combining CH₄ conversion and H₂ production using iron ions. A photo-driven iron-induced reaction system was developed, which is efficient at selective coupling of CH₄ as well as conversion of benzene and cyclohexane under mild conditions. For CH₄ conversion, 94 % C₂ selectivity and a C₂H₆ formation rate of 8.4 μmol h⁻¹ is achieved. Mechanistic studies reveal that CH₄ coupling is induced by hydroxyl radical, which is generated by photo-driven intermolecular charge migration of an Fe³⁺ complex. The delicate coordination structure of the [Fe(H₂O)₅OH]²⁺ complex ensures selective C−H bond activation and C−C coupling of CH₄. The produced Fe²⁺ can be used to reduce the potential for electrolytic H₂ production, and then turns back into Fe³⁺, forming an energy-saving and sustainable recyclable system.