Macromolecular metal complexes as catalysts with improved stability

Polymer-bound tertiary amine–copper complexes and polymer-bound phosphite–rhodium complexes were studied as catalysts for oxidative coupling of phenols and hydroformylation of alkenes, respectively. The activity and stability of these catalysts could be tuned or optimized by adapting the structure of the ligands and by changing the distance between adjacent ligands along the polymer chains. The latter effect has been described in terms of strain in the intermediate chain segments in the copper complexes or enhancement of the effective local ligand concentration around the rhodium complexes. So-called immobilized homogeneous catalysts were obtained by end-grafting of both types of macromolecular catalysts on to inert and insoluble silica particles. These immobilized polymeric catalysts could easily be separated and recovered. Under proper conditions a grafted polymerbound imidazole–copper complex and a new type of polymer-bound triphenyl–phosphite–rhodium complex showed excellent stability in continuous processes.     

Characterization of modification sites during peptide synthesis using liquid secondary ion/collision-induced dissociation mass spectrometry and a computer program

Side-reactions often occur during peptide synthesis resulting in modified amino acid moieties. To identify these residues, liquid secondary ion/collision-induced dissociation mass spectra were recorded. The main fragments are generated by cleavage of the peptide bond. To facilitate interpretation of the spectra and assignment of the structure, a simple, but flexible and efficient, computer program is presented. The program allows the verification of the correct structure of the synthesized peptides and the deduction of the type of side-products formed, such as alkylation of tryptophan residues.     

Fluctuations of g factors in metal nanoparticles: effects of electron-electron interaction and spin-orbit scattering

We investigate the combined effect of spin-orbit scattering and electron-electron interactions on the probability distribution of g factors of metal nanoparticles. Using random matrix theory, we find that even a relatively small interaction strength significantly increases g-factor fluctuations for not-too-strong spin-orbit scattering (ratio of spin-orbit rate and single-electron level spacing 1/tau(so)delta < or near 1), and leads to the possibility to observe g factors larger than 2.     

Stimulus-sensitive hydrogels and their applications in chemical (micro)analysis

In this tutorial review the use of stimulus-sensitive hydrogels as sensors and actuators for (micro)analytical applications is discussed. The first part of the article is aimed at making the reader familiar with stimulus-sensitive hydrogels, their chemical composition and their chemo-physical behavior. The prior art in the field, that comprises a number of sensors ranging from metal ion-sensitive sensors to antigen-sensitive sensors and a few actuators, is also treated in this part. The second part of the article focusses on the use of stimulus-sensitive hydrogels for microsensors and microactuators as well as their application in micro total analysis systems. The benefits of stimulus-sensitive hydrogels, their miniaturisation and the use of 365 nm UV-photolithography as a fast economical manufacturing technique are discussed.     

Ehrenfest-time dependence of weak localization in open quantum dots

Semiclassical theory predicts that the weak localization correction to the conductance of a ballistic chaotic cavity is suppressed if the Ehrenfest time exceeds the dwell time in the cavity [I. L. Aleiner and A. I. Larkin, Phys. Rev. B 54, 14423 (1996)]. We report numerical simulations of weak localization in the open quantum kicked rotator that confirm this prediction. Our results disagree with the "effective random matrix theory" of transport through ballistic chaotic cavities.     

Bound on anisotropy in itinerant ferromagnets from random impurities

We calculate the anisotropy energy of a single-domain ferromagnetic particle in which the only source of anisotropy is the presence of nonmagnetic impurities. Such anisotropy has easy-axis and easy-plane contributions, with random orientations of the axes. Typically the anisotropy energy is of order N1/2plankv/tau(so), where N is the number of electrons in the ferromagnetic particle and tau(so) is the spin-orbit time.