Insights into the electronic structure of Cu(II) bound to an imidazole analogue of westiellamide.

Three synthetic analogues of westiallamide, H3L(wa), have previously been synthesized (H3L(1-3)) that have a common backbone (derived from l-valine) with H3L(wa) but differ in their heterocyclic rings (imidazole, oxazole, thiazole, and oxazoline). Herein we explore in detail through high-resolution pulsed electron paramagnetic resonance (EPR) and magnetic circular dichroism (MCD) spectroscopy in conjunction with density functional theory (DFT) the geometric and electronic structures of the mono- and dinuclear Cu(II) complexes of these cyclic pseudo hexapeptides. Orientation-selective hyperfine sublevel correlation, electron nuclear double resonance, and three-pulse electron spin echo envelope modulation spectroscopy of [Cu(II)(H2L(1))(MeOH)2](+) reveal delocalization of the unpaired electron spin onto the ligating and distal nitrogens of the coordinated heterocyclic rings and that they are magnetically inequivalent. DFT calculations confirm this and show similar spin densities on the distal heteroatoms in the heterocyclic rings coordinated to the Cu(II) ion in the other cyclic pseudo hexapeptide [Cu(II)(H2L(2,3,wa))(MeOH)2](+) complexes. The magnetic inequivalencies in [Cu(II)(H2L(1))(MeOH)2](+) arise from different orientations of the heterocyclic rings coordinated to the Cu(II) ion, and the delocalization of the unpaired electron onto the distal heteroatoms within these N-methylimidazole rings depends upon their location with respect to the Cu(II) d(x(2)-y(2)) orbital. A systematic study of DFT functionals and basis sets was undertaken to examine the ability to reproduce the experimentally determined spin Hamiltonian parameters. Inclusion of spin-orbit coupling (SOC) using MAG-ReSpect or ORCA with a BHLYP/IGLO-II Wachters setup with SOC corrections and ∼38% Hartree-Fock exchange gave the best predictions of the g and A((63)Cu) matrices. DFT calculations of the (14)N hyperfine and quadrupole parameters for the distal nitrogens of the coordinated heterocyclic rings in [Cu(II)(H2L(1))(MeOH)2](+) with the B1LYP functional and the SVP basis set were in excellent agreement with the experimental data, though other choices of functional and basis set also provided reasonable values. MCD, EPR, mass spectrometry, and DFT showed that preparation of the dinuclear Cu(II) complex in a 1:1 MeOH/glycerol mixture (necessary for MCD) resulted in the exchange of the bridging methoxide ligand for glycerol with a corresponding decrease in the magnitude of the exchange coupling.

Exposure to secondhand smoke in Germany: air contamination due to smoking in German restaurants, bars, and other venues.

This study quantified exposure to secondhand smoke in German restaurants, bars, and entertainment venues by determining the concentration of respirable suspended particles measuring 2.5 microm or less (PM2.5) in indoor air. The measurements were taken using an inconspicuous device placed on the investigator's table in the venue. The concentration of particulate matter in the indoor air was measured for a minimum of 30 min. A total of 39 restaurants, 20 coffee bars, 12 bars, 9 discothèques, and 20 restaurant cars in trains were visited throughout Germany from September 30 to October 31, 2005. The readings disclosed a median PM2.5 of 260 microg/m3 and an arithmetic mean PM2.5 of 333 microg/m3. Median values were 378 microg/m3 in bars, 131 microg/m3 in cafes, and 173 microg/m3 in restaurants. The highest medians were measured in discothèques and restaurant cars, with values averaging 432 microg/m3 and 525 microg/m3 PM2.5, respectively. This study was the first to show the magnitude and extent of exposure to secondhand smoke on such an extensive scale in Germany. The contaminated air due to smoking is a human carcinogenic and major health hazard, which would be prevented most effectively and completely by implementing a ban on smoking. This study is important for the ongoing national debate in Germany as well as for debates in all countries without smoke-free air legislation, which includes most countries around the world.