HPLC-DAD分析金线莲中天麻素和天麻苷元

研究超声-微波协同法提取金线莲中的天麻素和天麻苷元,并对提取条件进行了优化.应用高效液相-二极管阵列检测法分析提取物中的天麻素和天麻苷元.研究结果表明:金线莲中天麻素、天麻苷元和其他杂质成分能够很好的分离,且两者的含量分别为1.430及0.562 mg/g,相对标准偏差为0.94%和0.25%.方法准确、快速、灵敏度高、重现性好.     

Solution or Gas Phase? Oxidation and Radical Formation in Electrospray Ionization Mass Spectrometry (ESI MS)

The relationship between one‐electron (e^?) oxidation processes and the formation of radical cations of endogenous and exogenous compounds in vivo is of considerable interest. This paper reports on the experiments that allow FTICR mass spectrometric (MS) detection of ion signals that are consistent with the formation of radical cations of caffeine (CA) and theophylline (TP) during electrospray ionization (ESI) in ESI FTICR MS and in on‐line electrochemistry (EC)/ESI FTICR MS in positive mode. Significantly, the signals of the radicals of CA^?+ and TP^?+can be enhanced by simple modifications of the operating conditions in ESI MS, facilitating investigations of radical formation and related reactions.     

Square‐Wave Voltammetry of Electroinactive Surfactants

Under the influence of previously published and some new theoretical results, potential‐ dependent adsorption and desorption of model electroinactive surfactants Triton X‐100 (T‐X‐100 or polyethylene glycol p‐(1,1,3,3‐tetramethylbutyl)‐phenyl ether) and sodium dodecyl sulfate (SDS) on the static mercury drop electrode (SMDE) were studied by square‐wave voltammetry (SWV). Although (according to the theory) the resulting current – potential curve should consist of two highly separated peaks, only desorption signal could be seen on each experimentally obtained voltammogram, most probably because of the limitations concerning the available potential range. Different properties of the recorded peak are in good agreement with the theory indicating that square‐wave voltammetry could be treated as a potential tool for tensammetric studies of electroinactive surface active substances.     

Mass spectrometry detection of minor new meridianins from the antarctic colonial ascidians Aplidium falklandicum and Aplidium meridianum

Taking into account the broad biological activities found in the meridianin indole alkaloids isolated to date, we have re‐examined the organic extracts of an Antarctic collection of the tunicates Aplidium meridianum and A. falklandicum (Chordata: Ascidiacea) by HPLC in conjunction with a high‐resolution mass spectrometer (HPLC‐MS). A new set of analogs of meridianins A–G has been detected, and their structures are proposed on the basis of the molecular formulae identified by LC‐HRMS analysis using a C18 column with a gradient of water/acetonitrile and an LTQ‐FT‐MS Orbitrap detector. Remarkably, dimers derived from meridianin A and from meridianin B or E were also detected. Our findings provide further evidence of the broad variability within the meridianin‐like derivatives of this highly bioactive alkaloid family. Copyright © 2015 John Wiley & Sons, Ltd.     

Isolation and Crystal Structure of Ent-kaurane Diterpenes from Rubus corchorifolius L. f.

In this study, ent-Kaurane-3β,16β,17-triol(1) and ent-kaurane-2α,16β,17-triol(2), were isolated from the leaves of Rubus corchorifolius L. f. Their structures were elucidated based on extensive spectroscopic analysis. NMR experiments identified the two compounds and X-ray crystallographic analysis confirmed their crystal structures. The crystal of 1 belongs to monoclinic with space group P21 and a = 10.7641(3), b = 7.2789(3), c = 11.7862(4) , β = 95.275(3)°, V = 919.55(6) 3, Z = 2, C20H34O4, Mr = 322.49 g/mol, Dc = 1.230 g/m3, F(000) = 376, λ = 1.54178 , μ = 0.661 mm-1, R = 0.0319, and wR = 0.0811 for 10889 observed reflections(Ⅰ 2σ(Ⅰ)). The crystal of 2 is classified as orthorhombic with space group P212121 and a = 10.7641(3), b = 12.72224(19), c = 21.3929(3) , V = 1748.94(4) 3, Z = 4, C20H34O4, Mr = 322.47, Dc = 1.225 Mg/m3 F(000) = 712, λ = 1.54184 , μ = 0.625 mm-1, R = 0.0303 and w R = 0.0759 for 10470 observed reflections(Ⅰ 2σ(Ⅰ)). Meanwhile, the compound revealed low inhibitory activities toward Hep G2, MCF-7, and SCG-7901 cells.     

制备工艺对Mn-Fe/ZSM-5催化剂在NH3-SCR催化还原反应中催化性能的影响

分别采用共沉淀法和浸渍法、不同铁前驱物以及不同焙烧温度等研究了制备工艺对Mn-Fe/ZSM-5催化剂的结构、化学组分及NH3-SCR活性的影响。结果显示,当采用Fe(NO3)3作为Fe前驱物,并用共沉淀法制备、300°C焙烧条件下得到的MFZ-CP-N-300样品低温活性最优,在120°C时,其NO的转化率达到96.7%,120-300°C范围内NO转化率始终保持在95%以上。同时利用XRD、NH3-TPD、XPS、SEM、TEM、氮吸附等手段对催化剂结构、晶相、酸位、锰铁氧化物的化学形态及表面的形貌特征进行表征分析。结果表明锰铁氧化物分别以MnO2-Mn2O3和Fe2O3的形式高度分散于催化剂表面,特别是当Mn4+/Mn3+比例为1.254时,有较强的表面中强酸和较多的酸位数,从而增加了NH3的吸附能力,提高NO的转化率。     

Direct Determination of Trace Dopamine in an Ascorbic Acid Solution at a Bare Glassy Carbon Electrode Using Differential Pulse Voltammetry

It is difficult to monitor dopamine (DA) accurately with a bare glassy carbon electrode because of the interference of ascorbic acid (AA). In this paper, a method for the determination of DA in an AA solution using differential pulse voltammetry was established. Because AA loses its electrochemical activity after being oxidized, hydrogen peroxide was used to oxidize AA, and the interference of AA was completely eliminated. As a result, trace DA could be directly determined in the AA solution with a bare glassy carbon electrode. When trace DA was determined in a 1.0 mmol L^?1 AA solution, there was a wide linear range from 3.0×10^?8 mol L^?1 to 1.0×10^?5 mol L^?1. The application of this method was demonstrated by the selective measurement of DA in an injection without pretreatment.     

Controlled Light‐Mediated Preparation of Gold Nanoparticles by a Norrish Type I Reaction of Photoactive Polymers

Gold nanoparticles (AuNPs) are subjects of broad interest in scientific community due to their promising physicochemical properties. Herein we report the facile and controlled light‐mediated preparation of gold nanoparticles through a Norrish type I reaction of photoactive polymers. These carefully designed polymers act as reagents for the photochemical reduction of gold ions, as well as stabilizers for the in situ generated AuNPs. Manipulating the length and composition of the photoactive polymers allows for control of AuNP size. Nanoparticle diameter can be controlled from 1.5 nm to 9.6 nm.     

Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)2(μ,η6:η6‐P6)] Towards the “Naked” Cations Cu+, Ag+, and Tl+

Although the cyclo‐P₆ complex [(Cp*Mo)₂(μ,η⁶:η⁶‐P₆)] ( 1 ) was reported 30 years ago, little is known about its chemistry. Herein, we report a high‐yielding synthesis of 1 , the complex 2 , which contains an unprecedented cyclo‐P₁₀ ligand, and the reactivity of 1 towards the “naked” cations Cu⁺, Ag⁺, and Tl⁺. Besides the formation of the single oxidation products 3 a,b which have a bisallylic distorted cyclo‐P₆ middle deck, the [M( 1 )₂]⁺ complexes are described which show distorted square‐planar (M=Cu( 4 a ), Ag( 4 b )) or distorted tetrahedral coordinated (M=Cu( 5 )) M⁺ cations. The choice of solvent enabled control over the reaction outcome for Cu⁺, as proved by powder XRD and supported by DFT calculations. The reaction with Tl⁺ affords a layered two‐dimensional coordination network in the solid state.     

Electrochemically controlled in-tube solid phase microextraction

We report a new in-tube solid phase microextraction approach named electrochemically controlled in-tube solid phase microextraction (EC in-tube SPME). This approach, which combined electrochemistry and in-tube SPME, led to decrease in total analysis time and increase in sensitivity. At first, pyrrole was elctropolymerized on the inner surface of a stainless steel tube. Then, the polypyrrole (PPy)-coated in-tube SPME was coupled on-line to liquid chromatography (HPLC) to achieve automated in-tube SPME–HPLC analysis. After the completion of EC-in-tube SPME–HPLC setup, the PPy-coated tube was used as working electrode for uptake of diclofenac as target analyte. Extraction ability of the tube in presence and in absence of applied electrical field was investigated. It was found that, under the same extraction conditions, the extraction efficiency could be greatly enhanced by using the constant potential. Important factors are also optimized. The detection limit (S/N = 3) and precision were 0.1 μg L⁻¹ and 4.4%, respectively.