A MALDI-chip integrated system with a monitoring window

The integration of a monitoring port along the microfluidic path of a MALDI-chip integrated device is described. Optimization of the microreactor design allows longer reaction and measuring times. The Schiff base reaction between 4-tert-butylaniline (1) and 4-tert-butylbenzaldehyde (2) in ethanol was carried out on-chip in the MALDI ionization chamber and the formed imine 3 was detected in real time, demonstrating the feasibility of the "monitoring window" approach. This preliminary result opens the way to on-chip kinetic studies by MALDI-MS, by opening multiple monitoring windows along the microchannel.     

Synthesis of new boron complexes: application to transfer hydrogenation of acetophenone derivatives

Two new boron complexes were synthesized from N‐[3‐(methylmercapto)aniline]‐3,5‐di‐tert‐butylsalicylaldimine ( LH ) with boron reagent BPh₃ or BF₃.Et₂O. These boron complexes are stable and easily soluble in protic solvents such as ethanol (C₂H₅OH) but hardly soluble in nonprotic solvents such as chloroform (CHCl₃), dichloromethane (CH₂Cl₂) and tetrahydrofuran (THF). All new boron complexes have been fully characterized by both analytical and spectroscopic methods. The catalytic activities of complexes [LBPh₂], 2 , and [LBF₂], 3 , in the transfer hydrogenation of acetophenone derivatives were tested. Stable boron complexes were found to be efficient catalysts in the transfer hydrogenation of aromatic ketones in good conversions up to 99% in the presence of iso‐PrOH/KOH. Copyright © 2011 John Wiley & Sons, Ltd.     

Double sequences and Orlicz functions

In this paper we define strong A-convergence with respect to an Orlicz function for double sequences. We show, on bounded double sequences, that statistical convergence and strong A-convergence with respect to any Orlicz function are equivalent. This eliminates a condition of Demirci for bounded single (ordinary) sequences.     

Reactions of NO in a Positive Streamer Corona Plasma

The reaction of NO in a streamer corona plasma is studied systematically as a function of the composition of the gas mixture, the initial concentration of NO, and the discharge repetition rate. The experimental results show that the reactions of NO depend strongly on the composition of the gas mixture. Reduction is observed in the absence of oxidants such as oxygen and water, but at very high energy cost (>200 eV/NO). In the presence of both these oxidants, more than 90% of the NO conversion is oxidation. The lowest energy costs, 24 eV/NO for He mixtures and 45 eV/NO for N ₂ mixtures, are obtained at water and oxygen concentration above 3% and at low discharge repetition rates (<10 Hz). Chemical kinetics calculations of the production of radicals in the plasma show a good agreement with the value derived from the experiments.     

Synthesis,electrochemical and in situ spectroelectrochemical studies of new transition metal complexes with two new Schiff-bases containing N2O2/N2O4 donor groups

New Schiff-base copper and cobalt complexes, [Cu(L¹)], [Cu(L²)] and [Co(L¹)], [Co(L²)] (where L¹ = N-N′-bis(3,5-di-tert-butylsalicylaldimine)-1,4-cyclohexane bis(methylamine) and L² = N-N′-bis(3,5-di-tert-butylsalicylaldimine)-1,8-diamino-3,6-dioxaoctane), were synthesized and characterized using elemental analysis, IR spectra, UV–Vis spectra, magnetic susceptibility measurements, ¹H and ¹³C NMR spectroscopy, thermal analysis and molar conductance (Λ_M). Their electro-spectrochemical properties were investigated using cyclic voltammetric (CV) and thin-layer spectroelectrochemical techniques in a dichloromethane solution (CH₂Cl₂). The CV of [Cu(L²)] showed a lower oxidation potential than that of [Cu(L¹)] under the same experimental conditions. The oxidation wave (II) of [Cu(L²)] was accompanied by an EC process (II′), which was not observed for [Cu(L¹)]. Also, [Cu(L²)] exhibited a reduction process, but [Cu(L¹)] did not. These results indicate that the Cu(II) ion in [Cu(L²)] is coordinated by N₂O₄ donor sites while [Cu(L¹)] presents a square-planar structure with N₂O₂ donor sites. Both oxidation processes for [Co(L¹)] and [Co(L²)] are based on the cobalt center, and they are assigned to Co(II)/Co(III) couples. The spectroelectrochemical results indicate that the oxidized species of [Cu(L²)] is similar to that of [Cu(L¹)], the only difference being that the absorption bands of the oxidized species for [Cu(L²)] shift to lower energy compared with those of [Cu(L¹)] because of their different coordination environment. The geometry of [Cu(L²)] changed into square-planar after the complex was totally oxidized and the neutral complex was only recovered following the EC process, as observed from the CV of [Cu(L²)]. For the two cobalt complexes, the bands corresponding to the π → π^∗transitions disappeared and new bands with small red shifts and of lower intensity were observed during the oxidation process. These new bands are attributed to the LMCT transition as observed in the case of the oxidation processes of the cobalt complexes.     

Derivatization and mass spectrometric behaviour of catecholamines and their 3-O-methylated metabolites

A method has been developed for the derivatization of both catecholamines (dopamine, noradrenaline and adrenaline) and their 3-O-methylated metabolites (3-methoxytyramine, normetanephrine and metanephrine) in a single run. The compounds were first incubated with methanolic hydrochloric acid to methylate those compounds that contain a benzylic hydroxyl group and were subsequently converted into their pentafluoropropionyl derivatives. The derivatives thus prepared, showed good gas chromatographic and electron-impact mass spectrometric properties and can be analysed in a single gas chromatographic run. The effect of the derivatization on exchange reactions in the aromatic ring was investigated because standard compounds with deuterium label in that part of the molecule are often used in isotope dilution measurements. The exchange of deuterium for hydrogen in the aromatic ring under derivatization conditions was found to be limited.     

Investigation of low-voltage on-resonance ion selection for Fourier transform mass spectrometry

Low-voltage on-resonance ion selection (LOIS) was recently introduced as an alternative technique for ion selection and storage. Under high pressure conditions and similar to the technique of quadrupolar axialization, unwanted (unselected) trapped ions are eliminated from the analysis cell through collisions with cell plates following orbital expansion. The ions remaining after tens of seconds of mass selection can be detected with better coherence, leading to improvements in ion detection and sensitivity. Here, experiments designed to test ion remeasurement and ion transfer capabilities are presented. Simulations of ion motion give insight into the possible mechanism of ion cooling, which does not appear to be the same as that of the axialization process. Because of its ease of use, lack of need for additional hardware devices, and comparable ion selection results, LOIS is an attractive alternative for trapped ion experiments.     

Synthesis,spectral characterization,electrochemical studies and catalytic properties in Suzuki–Miyaura coupling reactions of the mononuclear PdII,trinuclear PdII(BPh2)2 and RuII?PdII?RuII type complexes containing 4‐amino‐1‐benzyl piperidine and phenyl groups

The ligand containing the 4‐amino‐1‐benzyl piperidine group, N, N′‐(4‐amino‐1‐benzyl piperidine)‐glyoxime, (LH₂) (1) was prepared from 4‐amino‐1‐benzyl piperidine with anti‐dichloroglyoxime at ? 15 °C in absolute Tetrahydrofuran (THF). In the trinuclear [Pd(L)₂Ru₂(phen)₄](ClO₄)₂ (4) and [Pd(L)₂Ru₂(bpy)₄](ClO₄)₂ (5) metal complexes, the Pd^II ion centered into the main oxime core by the coordination of the imino groups while the two Ru^II ions coordinated dianionic oxygen donors of the oxime groups and linked to the ligands of 1,10‐phenanthroline and 2,2′‐bipyridine. The mono and trinuclear metal complexes were characterized by elemental analyses, FT‐IR, UV–vis, ¹H and ¹³C‐NMR spectra, magnetic susceptibility measurements, molar conductivity, cyclic voltammetry, mass spectra, X‐ray powder techniques and their morphology by SEM measurements. The cyclic voltammetric results show that the cathodic peak (E_pc) potential of (3) shifts towards more positive values compared with that of (2) as a result of the BPh₂⁺‐bridged complex formation. The Suzuki–Miyaura reaction was used to investigate their activity as catalyst either prepared in‐situ or from well‐defined complexes. Copyright © 2008 John Wiley & Sons, Ltd.     

Electrokinetic pumping and detection of low-volume flows in nanochannels

Electrokinetic pumping of low-volume rates was performed on-chip in channels of small cross sectional area and height in the sub-microm range. The flow was detected with the current monitoring technique by monitoring the change in resistance of the fluid in the channel upon the electroosmosis-driven displacement of an electrolyte solution by a second electrolyte solution. Flow rates in the order of 0.1 pL/s were successfully generated and detected. The channels were fabricated with the sacrificial layer technology.