Traceability of pH measurements by glass electrode cells: performance characteristic of pH electrodes by multi-point calibration

Routine pH measurements are carried out with pH meter-glass electrode assemblies. In most cases the glass and reference electrodes are thereby fashioned into a single probe, the so-called 'combination electrode' or simply 'the pH electrode'. The use of these electrodes is subject to various effects, described below, producing uncertainties of unknown magnitude. Therefore, the measurement of pH of a sample requires a suitable calibration by certified standard buffer solutions (CRMs) traceable to primary pH standards. The procedures in use are based on calibrations at one point, at two points bracketing the sample pH and at a series of points, the so-called multi-point calibration. The multi-point calibration (MPC) is recommended if minimum uncertainty and maximum consistency are required over a wide range of unknown pH values. Details of uncertainty computations for the two-point and MPC procedure are given. Furthermore, the multi-point calibration is a useful tool to characterise the performance of pH electrodes. This is demonstrated with different commercial pH electrodes. ELECTRONIC SUPPLEMENTARY MATERIAL is available if you access this article at http://dx.doi.org/10.1007/s00216-002-1506-5. On that page (frame on the left side), a link takes you directly to the supplementary material.     

Development of a microfluidic confocal fluorescence detection system for the hyphenation of nano-LC to on-line biochemical assays

One way to profile complex mixtures for receptor affinity is to couple liquid chromatography (LC) on-line to biochemical detection (BCD). A drawback of this hyphenated screening approach is the relatively high consumption of sample, receptor protein and (fluorescently labeled) tracer ligand. Here, we worked toward minimization of sample and reagent consumption, by coupling nano-LC on-line to a light-emitting diode (LED) based capillary confocal fluorescence detection system capable of on-line BCD with low-flow rates. In this fluorescence detection system, a capillary with an extended light path (bubble cell) was used as a detection cell in order to enhance sensitivity. The technology was applied to a fluorescent enhancement bioassay for the acetylcholine binding protein, a structural analog of the extracellular ligand-binding domain of neuronal nicotinic acetylcholine receptors. In the miniaturized setup, the sensitive and low void volume LED-induced confocal fluorescence detection system operated in flow injection analysis mode allowing the measurement of IC₅₀ values, which were comparable with those measured by a conventional plate reader bioassay. The current setup uses 50 nL as injection volume with a carrier flow rate of 400 nL/min. Finally, coupling of the detection system to gradient reversed-phase nano-LC allowed analysis of mixtures in order to identify the bioactive compounds present by injecting 10 nL of each mixture.     

Structural elucidation of biologically active neomycin N‐octyl derivatives in a regioisomeric mixture by means of liquid chromatography/ion trap time‐of‐flight mass spectrometry

Structural elucidation of six regioisomers of mono‐N‐octyl derivatized neomycin is achieved using MSⁿ (up to n = 4) on an ion trap time‐of‐flight (IT‐TOF) instrument equipped with electrospray ionization. The mixture of six derivatized neomycin analogues was generated by reductive amination in a shotgun synthetic approach. In parallel to the liquid chromatography/mass spectrometry (LC/MS) detection, the antibacterial activity of the neomycin regioisomers was tested by post‐column addition of buffer and bacterial inocula, subsequent microfractionation of the resulting mixture, incubation, and finally a chemiluminescence‐based bioactivity measurement based on the production of bacterial ATP. The MS‐based high‐resolution screening approach described can be applied in medicinal chemistry to help in designing and producing new antibiotic substances, which is particularly challenging due to the high functionality of most antibiotic substances, therefore requiring advanced (hyphenated) separation and detection techniques for compound mixtures. Copyright © 2010 John Wiley & Sons, Ltd.     

Effect of Pr-Ca substitution on the transport and magnetic behavior of LaMnO3 perovskite

The effect of simultaneous substitution of a fluctuating cation and a divalent cation in LaMnO₃ perovskite modifies the properties of the material to exhibit large valence colossal magnetoresistance (CMR) effect. A good example of these properties is (La_1−2x Pr _x Ca _x )MnO₃ (LPCMO) type CMR material. In this communication it is reported that, with the increase in x (for x=0.1, 0.15, 0.2), the T _c varies between 100 and 120 K with improvisation in metal-insulator transition. Interestingly, resistance increases with x from few hundred ohms to few kilo ohms with corresponding decrease in the unit cell volume. The results of the studies using X-ray diffraction (XRD), electrical resistivity, magnetoresistance and ac susceptibility measurements on LPCMO samples for understanding the structural, transport and magnetic properties are discussed in detail.     

A study of the formation and application of new chiral water soluble lanthanoid benzoates using real-time infrared spectroscopy

A range of water soluble lanthanoid benzoate complexes of composition [Ln(Bz)₃(H₂O)_n] (Ln = La, Gd, Ho and Yb; Bz = 3,5-bis((R)-2,3-dihydroxypropoxy)benzoate and 3,4,5-tris((R)-2,3-dihydroxypropoxy)benzoate) have been prepared by reaction of lanthanoid bicarbonates with three equivalents of the corresponding optically active benzoic acid in water. Application of [Ln(Bz)₃(H₂O)_n] as asymmetric catalysts for epoxide ring opening reactions has been investigated using styrene oxide, showing complete conversion after 20 h, albeit with no significant enantiomeric excess observed. The formation of the lanthanoid complexes and subsequent catalytic conversion of styrene oxide to phenylethane-1,2-diol were monitored using real-time infrared (RTIR) spectroscopy, yielding information about reaction pathways and intermediates.