Potential of capillary-column-switching liquid chromatography-tandem mass spectrometry for the quantitative trace analysis of small molecules. Application to the on-line screening of drugs in water

We have investigated the potential of capillary-column-switching liquid chromatography coupled to tandem mass spectrometry (cLC-MS-MS) for the quantitative on-line trace analysis of target compounds in aqueous solutions. The technical design of the nano-scale cLC system developed at our Institute for peptide and protein identification has been tested and evaluated for the direct trace analysis of drugs in water samples. Sulphametoxazole, bezafibrate, metoprolol, carbamazepine and bisoprolol occurring frequently in Dutch waters, were selected as test compounds. Adequate conditions for trapping, elution and MS-MS detection were investigated by employing laboratory made 200 microm i.d. capillary columns packed with 5 microm aqua C18 material. In the final cLC-MS-MS conditions, a 1 cm length trapping column and a 4 cm length analytical column were selected. Under these conditions, the target compounds could be directly determined in water down to a level of around 50 ng/l employing only 25 microl of water sample. Validation was done by recovery experiments in ground-, surface- and drinking-water matrices as well as by the analysis of water samples with incurred residues and previously analyzed with a conventional procedure involving off-line solid-phase extraction and narrow-bore LC with MS-MS detection. The new methodology provided recoveries (50-500 ng/l level) between 50 and 114% with RSDs (n = 3, each level) below 20% for most of the compounds. Despite the somewhat less analytical performance in comparison to the conventional procedure, the on-line approach of the new methodology is very suitable for screening of drugs in aqueous samples.     

Conditional Response to Stress in Yeast

Summary. All living cells respond to sudden, adverse changes in their environment by evoking a stress response. Here we focus mainly on the response of the model eukaryotic organism Saccharomyces cerevisiae (bakers yeast) to an increase in external osmolarity. We summarize data demonstrating that stress responses largely depend on the existing environmental growth conditions. Nutrients and other medium parameters such as external pH determine how yeast cells sense osmotic stress circumstances and subsequently elicit adaptive responses. It is likely that the composition of cell wall and plasma membrane plays an important role in this process.Received September 3, 2002; accepted September 13, 2002 Published online May 26, 2003     

New chiral diamide ligands containing redox-active hydroquinone groups. Synthesis and results in the palladium(II)-catalyzed 1,4-diacetoxylation of 1,3-dienes

Chiral ligands 8-11, 22 and 23 were synthesized from different chiral diamines as a new class of ligands for the Pd(II)-catalyzed 1,4-diacetoxylation of 1,3-dienes. The synthesis from the diamines and protected benzoic acids was performed in a few simple steps and gave the ligands in high overall yields. The hydroquinone groups present in the ligands are in situ oxidized to benzoquinone to give the active ligands. Application of these ligands in the 1,4-diacetoxylation reaction afforded the oxidation product with high regio- and diastereoselectivity and an enantiomeric excess up to 42% was obtained. Possible coordination modes of the metal to the ligand are discussed, and experiments were made to investigate the coordination by varying the reaction conditions or making changes to the ligands.     

Surface effects in the esterification of 9-pyrenebutyric acid within a glass micro reactor

Surface phenomena are an important contribution to the "chip effect", leading to higher yields and shorter reaction times, as demonstrated for the acid-catalysed esterification of 9-pyrenebutyric acid within a glass fabricated micro reactor.     

Small scale velocity jumps in shear turbulence

We measure structure functions and structures in uniformly sheared strong turbulence using an array of hot-wire velocity sensors. We find that the large-scale shear persists down to the smallest scales. There is a marked asymmetry between velocity increments measured in the shear direction, and those measured in the plane perpendicular to it. In the shear direction the scaling exponents tend to a constant, signifying the presence of small-scale cliffs. Direct evidence for those is presented by the spatial structure of the strongest velocity gradients.     

Trapezoidal and midpoint splittings for initial-boundary value problems

In this paper we consider various multi-component splittings based on the trapezoidal rule and the implicit midpoint rule. It will be shown that an important requirement on such methods is internal stability. The methods will be applied to initial-boundary value problems. Along with a theoretical analysis, some numerical test results will be presented.

     

Globular proteins at solid/liquid interfaces

Seven years have passed since one of us (W.N.) published the last comprehensive review on the mechanism of globular protein adsorption to solid/water interfaces. Since that time, annual contributions to the field have steadily increased and substantial progress has been made in a number of important areas. This review takes a fresh look at the driving force for protein adsorption by combining recent advances with key results from the past. The analysis indicates that four effects, namely structural rearrangements in the protein molecule, dehydration of (parts of) the sorbent surface, redistribution of charged groups in the interfacial layer, and protein surface polarity usually make the primary contributions to the overall adsorption behavior.