Poly(dimethylsiloxane) microchip: microchannel with integrated open electrospray tip

A polymer microchip with an open tip for electrospray mass spectrometry is presented. The tip consists of a groove with parallel walls where a droplet can form at the end surface. A lid covers the whole chip except at the microchannel tip, which is left open. Poly(dimethylsiloxane) (PDMS) microchips were cast using a nickel mould which in turn was replicated from a dry etched silicon wafer. Tips with microchannel widths of around 50 microm could easily be replicated. Since the tip had no cover, the assembly of microchip and cover was simplified. A total ion current variation of 5% during 300 s was achieved for a 1 microM myoglobin solution. The non-complex design of the cover makes it suitable for versatile tests of chip prototypes. The nickel mould was found to be useful for PDMS microstructure fabrication. Also, such a robust mould allows casting electrospray tips in more rigid thermoset materials.     

Defects and stresses in MBE-grown GaN and Al0.3Ga0.7N layers doped by silicon using silane

The electric and structural characteristics of silicon-doped GaN and Al_0.3Ga_0.7N layers grown by molecular beam epitaxy (MBE) using silane have been analyzed by the Hall effect, Raman spectroscopy, and high-resolution X-ray diffractometry. It is established that the electron concentration linearly increases up to n = 4 × 10²⁰ cm^?3 with an increase in the silane flow rate for GaN:Si, whereas the corresponding dependence for Al_0.3Ga_0.7N:Si is sublinear and the maximum electron concentration is found to be n = 4 × 10¹⁹ cm^?3. X-ray measurements of sample macrobending indicate a decrease in biaxial compressive stress with an increase in the electron concentration in both GaN:Si and Al_0.3Ga_0.7N:Si layers. The parameters of the dislocation structure, estimated from the measured broadenings of X-ray reflections, are analyzed.     

FLOW BEHAVIOR AND MASS TRANSFER IN THREE-PHASE EXTERNAL-LOOP AIRLIFT REACTORS WITH LARGE PARTICLES

The flow behavior and mass transfer in a three-phase external-loop airlift reactor can be improved by adding large particles. The mass transfer and liquid dispersion behavior for a three-phase external-loop reactor with large particles are studied in terms of the effect of the diameter and loading of the large particles on the liquid dispersion coefficient and mass transfer coefficient, The results showed that increasing the diameter or loading of the large particles tend to decrease dispersion and intensify mass transfer, and that an increase in the diameter of the large particles remarkably decreases the particle loop rate, while the effect of fine particles is much less notable.     

On-line electrochemically controlled solid-phase extraction interfaced to electrospray and inductively coupled plasma mass spectrometry

Electrochemically controlled solid-phase extractions of anions were interfaced on-line to electrospray mass spectrometry (ESI-MS) and inductively coupled plasma mass spectrometry (ICP-MS), using polypyrrole coated electrodes and a thin-layer electrochemical (EC) flow cell. The results indicate that electrochemically controlled solid-phase extraction (EC-SPE) can be used as a versatile potential controlled sample preparation technique for a range of anions and that the properties of the polypyrrole coatings can be modified by altering the electrodeposition conditions. In the present study, the influence of interfering anions (i.e., fluoride and sulfate), and the anion used during the electropolymerisation, on the bromide extraction recovery was investigated for EC-SPE interfaced to ICP-MS. The results of these experiments show that the interference due to the presence of similar concentrations of sulfate can be reduced when using a polypyrrole coating electropolymerised in the presence of bromide ions. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) measurements were also used to study the morphology of the coatings, as well as the variations in the film thickness within the coatings. The effect of different desorption techniques on the bromide preconcentration factor in the ICP-MS on-line flow system was also examined. Stopped-flow desorption was found to give rise to significantly increased preconcentration factors in comparison with desorptions in flowing solutions. While the desorption efficiency depends on the type of desorption electrolyte (the electrolyte in which the desorption takes place), due to the competing influx of cations, the influence of the pH on the switching charge of the polypyrrole coating was found to be small, at constant ionic strength. To study the applicability of the EC-SPE technique with respect to real samples, investigations were also made with tap water samples spiked with different bromide concentrations. The results of these experiments, which were carried out using a modified thin-layer EC flow cell allowing in situ polymerisation of polypyrrole yielding a polymer plug covering the cross section of the channel, demonstrate that 3 microM concentrations of bromide could be detected in the tap water sample. This demonstrates that the extraction technique allows extractions of low concentrations of ions in the presence of significantly higher concentrations of other similar ions. The fact that the extraction and desorption steps are electrochemically controlled makes EC-SPE particularly well suited for inclusion in miniaturised lab-on-a-chip systems.     

Geländer Molecules with Orthogonal Joints: Synthesis of Macrocyclic Dimers

Orthogonal joints, understood as connections with an angle of 90°, were introduced in the design of the “Geländer” model compounds 1 and 2 . The banister, consisting of a conjugated carbazole dimer linked by either 1,3-butadiyne ( 2 ) or a single thiophene ( 1 ), wraps around an axis composed of a phthalimide dimer due to the dimensional mismatch of both subunits, which are interconnected by phenylene rungs. The “Geländer” structure was assembled from a monomer comprising the 1,4-diaminobenzene rung with one amino substituent as part of a 4-bromo phthalimide subunit forming the orthogonal junction to the axis, and the other as part of a masked 2-ethynyl carbazole as orthogonal joint to the banister. The macrocycle was obtained by two sequential homocoupling steps. A first dimerization by a reductive homocoupling assembled the axis, while an oxidative acetylene coupling served as ring-closing reaction. The formed butadiyne was further derivatized to a thiophene, rendering all carbons of the model compound sp² hybridized. Both helical structures were fully characterized and chirally resolved. Assignment of the enantiomers was achieved by simulation of chiroptical properties and enantiopure synthesis.     

Optimization of gain-assisted waveguiding in metal-dielectric nanowires

We theoretically demonstrate that, for a given diameter of the core-pumped metal-dielectric nanowire, there is an optimum thickness of the metallic cladding that provides the maximum propagation length of the lowest-order surface plasmon polariton (SPP) modes. If the nanowire is fabricated with the optimum cladding thickness, the lowest pumping power is required to fully compensate for the SPP propagation losses. We also show that a strong confinement of SPPs within the nanowire can be achieved, but at the expense of either high optical gains or large nanowire diameters. For example, a gain of 565 cm(-1) would suffice to make up for the decay of SPPs in a 250-nm-thick silver-GaAs nanowire; the confinement of optical power within such nanowires exceeds 90%, which makes them ideal interconnects for nanophotonic circuitry.     

Minimization of negative phenomena arising at rectification of reactive mixtures

Using the technology of ethyl alcohol production as an example, a scheme of the transformation of admixed components in rectifying columns was considered and procedures for the minimization of negative side processes by chemical and instrumental-technological methods were offered.     

A top down approach to protein structural studies using chemical cross-linking and Fourier transform mass spectrometry

Mass spectrometric analysis of wild-type proteins that have been covalently modified by bifunctional cross-linking reagents and then digested proteolytically can be used to obtain low-resolution distance constraints, which can be useful for protein structure determination. Limitations of this approach include time-consuming separation steps, such as the separation of internally cross-linked protein monomers from covalent dimers, and a susceptibility to artifacts due to low levels of natural and man-made peptide modifications that can be mistaken for cross-linked species. The results presented here show that when a crude cross-linked protein mixture is injected into an electrospray ionization Fourier transform mass spectrometry (ESI-FTMS) instrument, the cross-link positions can be localized by fragmentation and mass spectrometry on the 'gas-phase purified' singly internally cross-linked monomer. Our results show that reaction of ubiquitin with the homobifunctional lysine-lysine cross-linking reagent dissuccinimidyl suberate (DSS) resulted in two cross-links consistent with the known ubiquitin tertiary structure (K6-K11 and K48-K63). Because no protein or peptide chemistry steps are needed, other than the initial cross-linking, this new top down approach appears well suited for high-throughput experiments with multiple cross-linkers and reaction conditions. Published in 2002 by John Wiley & Sons, Ltd.