Organocatalysis: quantum chemical modeling of nucleophilic addition to α,β‐unsaturated carbonyl compounds

One of the successful transformations within the field of organocatalysis, the organocatalytic asymmetric addition of nitromethane to α,β‐unsaturated aldehydes and ketones, has been studied by quantum chemical modeling. The level of accuracy of the hybrid density functional theory method B3LYP/6‐31G(d) was compared to a high level ab initio benchmark for this reaction. It is concluded that B3LYP/6‐31G(d) performs very well for this reaction type, giving good estimates of critical energies. The reaction between acrolein and nitromethane was studied in detail. The reaction mechanism revealed an intermediate oxazolidin structure, which is currently unknown. Alkyl substitution in various positions on the amine catalyst or α,β‐unsaturated carbonyl compound influences the reactivity in a predictive fashion. The iminium ion, prop‐2‐en‐iminium, is less activated towards nucleophilic attack compared to protonated acrolein. Copyright © 2007 John Wiley & Sons, Ltd.     

Microelectromagnet for magnetic manipulation in lab-on-a-chip systems

We demonstrate a simple scheme for fabrication of microelectromagnets consisting of planar spiral coils semi-encapsulated in soft magnetic yokes using conventional microfabrication techniques. The microelectromagnets are suitable for applications operating at frequencies below 250 kHz. Conventional fabrication schemes for planar microelectromagnets typically rely on five mask steps. We allow the current to flow in the soft magnetic yoke and thereby two mask steps are eliminated. We have characterized the electromagnets electrically, the results agree well with theory, and the implications arising from current flowing in the magnetic yoke are discussed. We have integrated the microelectromagnets with microfluidic channels, and demonstrated separation of commercially available magnetic beads from a fluid in a microfluidic system, i.e. a lab-on-a-chip system.     

Impact of 100 MeV Au on the surface of relaxed Si0.5Ge0.5 alloy films studied by atomic force microscopy

We demonstrate a gradual surface modification process of relaxed Si_0.5Ge_0.5 alloy films by 100 MeV Au beam with fluence varying between 5 × 10¹⁰ and 1 × 10¹² ions/cm² at 80 K by means of atomic force microscopy (AFM). Presence of Ge quantum dots (QDs) was found in the virgin sample. The disappearance of the QDs were noticed when the samples were irradiated with a fluence of 5 × 10¹⁰ ions/cm². Craters were found developing at a fluence of 1 × 10¹¹ ions/cm². Apart from the evolution of the craters, blisters were also detected at a fluence of 1 × 10¹² ions/cm². Variation of the average root mean square value of the surface roughness as a function of fluence was examined.     

New synthesis of 2',3'-didehydro-2',3'-dideoxynucleosides.

The 3'-iodonucleoside 4 and the 3'-O-methylsulfonylthymidine 9 have been synthesized by condensation of silylated uracils 2 with methyl 5-O-tert-butyldiphensilyl-2,3-dideoxy-3-iodo-D-threo-pentofuran oside (3) and methyl 5-O-tert-butyldiphenylsilyl-2-deoxy-3-methylsulfonyl-D-erythro- pentofuranoside (8), respectively. The nucleoside 4 and 9 produced the corresponding 2',3'-didehydro-2',3'-dideoxynucleosides 5 in an elimination reaction on treatment with sodium methoxide. The compounds 5b showed no antiviral activity against HIV-1.     

Effects of surface roughness on the electronic structure of metallic clusters

We study the electronic level density in spherical clusters. Due to the granularity of the ionic background the surface is irregular at the microscopical level. We show that this affects the shell structure and that the level statistics display from the bottom to the top of the spectrum a transition from a poissonian behaviour to one consistent with the predictions of random matrices theory.     

Complex point sources in probe-corrected cylindrical near-field scanning

A probe-corrected theory based on complex point sources is presented for computing the acoustic field of an arbitrary finite source from measurements of the near field on a cylindrical scanning surface. The complex point sources are used both as basis functions for the expansion of the field outside the scan cylinder and for the representation of the probe. The resulting probe-corrected formulas are considerably simpler than the standard probe-corrected formulas based on cylindrical waves. The new formulation makes simulations of near-field scanning systems much less computationally intensive than simulations based on standard theory. The complex point-source theory is validated through numerical examples involving a baffled circular piston transducer probe.