Electron attachment rate constant measurement by photoemission electron attachment ion mobility spectrometry (PE-EA-IMS)

Photoemission electron attachment ion mobility spectrometry (PE-EA-IMS), with a source of photoelectrons induced by vacuum ultraviolet radiation on a metal surface, has been developed to study electron attachment reaction at atmospheric pressure using nitrogen as the buffer gas. Based on the negative ion mobility spectra, the rate constants for electron attachment to tetrachloromethane and chloroform were measured at ambient temperature as a function of the average electron energy in the range from 0.29 to 0.96 eV. The experimental results are in good agreement with the data reported in the literature.     

Rigid NON- and NSN-ligand complexes of tetravalent and trivalent uranium: comparison of U-OAr2 and U-SAr2 bonding

A rigid NSN-donor proligand, 4,5-bis(2,6-diisopropylanilino)-2,7-di-tert-butyl-9,9-dimethylthioxanthene (H(2)[TXA(2)], 1) was prepared by palladium-catalyzed coupling of 2,6-diisopropylaniline with 4,5-dibromo-2,7-di-tert-butyl-9,9-dimethylthioxanthene. Deprotonation of 1 using (n)BuLi provided Li(2)(DME)(2)[TXA(2)] (2), and subsequent reaction with UCl(4) afforded [Li(DME)(3)][(TXA(2))UCl(3)] (4). The analogous NON-donor ligated complex [(XA(2))UCl(3)K(DME)(3)] [3; XA(2) = 4,5-bis(2,6-diisopropylanilino)-2,7-di-tert-butyl-9,9-dimethylxanthene] was prepared by the reaction of K(2)(DME)(x)[XA(2)] with UCl(4). A cyclic voltammogram (CV) of 3 in THF/[NBu(4)][B(C(6)F(5))(4)] at 200 mV s(-1) showed an irreversible reduction to uranium(III) at E(pc) = -2.46 V versus FeCp(2)(0/+1), followed by a product wave at E(1/2) = -1.83 V. Complex 4 also underwent irreversible reduction to uranium(iii) [E(pc) = -2.56 V], resulting in an irreversible product peak at E(pa) = -1.83 V. One-electron reduction of complexes 3 and 4 using K(naphthalenide) under an argon atmosphere in DME yielded 6-coordinate [(XA(2))UCl(DME)] (5) and the thermally unstable 7-coordinate [(TXA(2))U(DME)Cl(2)Li(DME)(2)] (6), respectively. The U-S distances in 4 and 6 are uncommonly short, the C-S-U angles are unusually acute, and the thioxanthene backbone of the TXA(2) ligand is significantly bent. By contrast, the xanthene backbone in XA(2) complexes 3 and 5 is planar. However, κ(3)-coordination and an approximately meridional arrangement of the ancillary ligand donor atoms is maintained in all complexes. DFT and Atoms in Molecules (AIM) calculations were carried out on 3, 4, 5, 6, [(XA(2))UCl(3)](-) (3B), [(TXA(2))UCl(2)(DME)](-) (6B) and [(TXA(2))UCl(DME)] (6C) to probe the extent of covalency in U-SAr(2) bonding relative to U-OAr(2) bonding.     

Improved performance of surface‐enhanced Raman scattering on silver substrates prepared in nitric acid solutions

In this work, we propose a new electrochemical method to prepare surface‐enhanced Raman scattering (SERS)‐active silver substrates in nitric acid solutions. Experimental results indicate that the SERS intensity of adsorbed Rhodamine 6G (R6G) can be significantly increased, as compared with that of R6G adsorbed on a SERS‐active Ag substrate prepared by an electrochemical method in a chloride‐containing solution, which was generally employed in the literature. Moreover, the SERS of R6G on the newly developed substrate (prepared in a nitric acid solution) still performs well at a high temperature of 250 °C. However, the enhancement capability of the SERS‐active substrate prepared in a chloride‐containing solution is seriously destroyed at temperatures higher than 150 °C. Further investigations indicate that the oxidation states of roughened Ag substrates prepared in nitric acid solutions under different experiment conditions have less influence on the corresponding SERS performances. Instead, different surface morphologies of roughened Ag substrates and different contents of nitrogen‐containing dopping ions on the roughened Ag substrates demonstrate significant effects on the corresponding SERS performances. Copyright © 2011 John Wiley & Sons, Ltd.     

Manganese doping effects on interband electronic transitions,lattice vibrations,and dielectric functions of perovskite-type Ba<Subscript>0.4</Subscript>Sr<Subscript>0.6</Subscript>TiO<Subscript>3</Subscript> ferroelectric ceramics

The Ba_0.4Sr_0.6−x Mn _x TiO₃ (BSMT) ceramics with different Mn composition (from 1% to 10%) have been prepared via the conventional solid-state reaction sintering. The X-ray diffraction analysis shows that the ceramics are polycrystalline with the single perovskite phase. The lattice vibrations and optical properties have been investigated using Raman scattering, spectroscopic ellipsometry (SE), and infrared reflectance spectra. It was found that the optical bandgap for the BSMT ceramics is varied between 3.40 and 3.65 eV. The three first-order Raman-active phonon modes can be observed, and the frequency of the A ₁(LO₃)/E(LO) mode shows a blue shift of 8 cm⁻¹ with the Mn composition, which can be attributed to the distortion of the TiO₆ octahedron. With increasing Mn composition, the frequency of the infrared-active TO₄ mode decreases from 532 to 520 cm⁻¹, owing to the local variation of the lattice constant induced by the Mn incorporation. Moreover, the optical functions of the ceramics from the far-infrared to ultraviolet region are obtained based on the SE and reflectance spectra, which is useful for the potential applications in ferroelectric-based optoelectronic devices.     

Template-assisted assembly: scanning tunneling microscopy study of solvent-dependent adlattices of alkyl-derivatized tetrathiafulvalene

The self-assembly of an adsorbate as a function of the strength of solvent-substrate adsorption is an important yet relatively unexplored subject. In this study, how the strength of solvent-substrate adsorption and solvent-solvent attraction affects the assembly of tetrakis(octadecylthio)tetrathiafulvalene (1) is scrutinized by scanning tunneling microscopy (STM). For solvents with strong intermolecular interactions and adsorption onto graphite, such as long n-alkanes (C(n)H(2n+2), n ≥ 13), STM reveals that the solvent molecules form lamellae which become a template to direct the assembly of 1 into one-dimensional arrays. The lengths of one of the unit cell vectors for the assemblies are increased and well correlated with the solvent sizes. In situ STM monitoring of 1 introduced onto graphite with preadsorbed n-tetradecane adlattices shows that the developed assemblies of 1 have striped features aligned parallel to the underlying template. In contrast, for solvents with weak adsorption, such as short n-alkanes (C(n)H(2n+2), n ≤ 12), toluene, and 1,2,4-trichlorobenzene, the adlattice structures of 1 are solvent-independent.     

利用Diels-Alder反应构建桉烷类倍半萜骨架关键中间体的研究

以3-甲基-1,3-间苯二酚和异戊醛为原料分别合成亲双烯2-甲氧基-6-甲基对苯醌和双烯1-甲氧基-3-异丙基-1,3-丁二烯,通过Diels-Alder反应,高区域选择性地得到桉烷类倍半萜骨架中间体2c.     

Aqueous phase synthesis of palladium tripod nanostructures for sonogashira coupling reactions

In this work, palladium tripod nanocrystals have been synthesized by mixing an aqueous solution of cetyltrimethylammonium bromide (CTAB) surfactant, Na(2)PdCl(4), copper acetate, and ascorbic acid at 30 °C for 3 h. Addition of a small amount of copper ion source is critical to the formation of these tripods with a pod length reaching 100 nm. The incorporation of Cu atoms into the Pd tripods has been verified. The entire Pd tripod is single-crystalline with their branches growing along the [111] and [200] directions. Formation of side branches can be observed in some tripods. Triangular nanoplates are initially formed and evolved into the tripod structure in 20-30 min of reaction. Further growth leads to elongation of the pods. The large Pd tripods can serve as active and recyclable catalysts for a broad range of Sonogashira coupling reactions in water using a variety of aromatic halides containing electron-donating and -withdrawing substituents.     

A new dual immunoassay for tumor markers based on chemiluminescence signal amplification by magnetic mesoporous silica and enzyme modified gold nanoparticles

A sensitive dual immunoassay was proposed for the determination of carcinoembryonic antigen (CEA) and α-fetoprotein (AFP) based on signal amplification. Monoclonal antibodies immobilized on magnetic mesoporous silica particles (Fe(3)O(4)/SiO(2)) were prepared as the primary probe. Horseradish peroxidase (HRP) labeled antibodies co-coated with HRP on gold nanoparticles (AuNPs) were used as the secondary probe to achieve signal amplification. HRP tags were retained in the flow cells after a sandwich immunoassay. By controlling two switches on the two channels, chemiluminescent substrates were injected orderly man way, and then signals for CEA and AFP were sequentially detected by HRP-luminol-H(2)O(2). Due to the increased amount of HRP on AuNPs and the increased amount of monoclonal antibodies on Fe(3)O(4)/SiO(2), the signals were largely amplified. Under the optimal conditions, CEA and AFP could be detected in the linear ranges of 1.0 - 80 and 1.0 - 75 ng mL(-1) with detection limits of 0.25 and 0.5 ng mL(-1), respectively.