On the vertical excitation energy of cyclopentadiene

The vertical excitation energy for the lowest valence pi-->pi(*) transition of cyclopentadiene is investigated. Using a combination of high-level theoretical methods and spectroscopic simulations, the vertical separation at the ground state geometry is estimated to be 5.43+/-0.05 eV. This value is intermediate between those calculated with coupled-cluster and multireference perturbation theory methods and is about 0.13 eV higher than the observed maximum in the absorption profile.     

Variable temperature system using vortex tube cooling and fiber optic temperature measurement for low temperature magic angle spinning NMR

We describe the construction and operation of a variable temperature (VT) system for a high field fast magic angle spinning (MAS) probe. The probe is used in NMR investigations of biological macromolecules, where stable setting and continuous measurement of the temperature over periods of several days are required in order to prevent sample overheating and degradation. The VT system described is used at and below room temperature. A vortex tube is used to provide cooling in the temperature range of -20 to 20 degrees C, while a liquid nitrogen-cooled heat exchanger is used below -20 degrees C. Using this arrangement, the lowest temperature that is practically achievable is -140 degrees C. Measurement of the air temperature near the spinning rotor is accomplished using a fiber optic thermometer that utilizes the temperature dependence of the absorption edge of GaAs. The absorption edge of GaAs also has a magnetic field dependence that we have measured and corrected for. This dependence was calibrated at several field strengths using the well-known temperature dependence of the (1)H chemical shift difference of the protons in methanol.     

Analysis of the phase transitions in alkyl-mica by density and pressure profiles

In a previous work [Heinz, Castelijns, and Suter, J. Am. Chem. Soc. 115, 9500 (2003)], we developed an accurate force field and simulated the phase transitions in C18-mica (octadecyltrimethylammonium-mica) as well as the absence of such transitions in 2C18-mica (dioctadecyldimethylammonium-mica) between room temperature and 100 degrees C. Here we analyze (i) average z coordinates of the carbon atoms and interdigitation of the hydrocarbon bilayers, (ii) density profiles, and (iii) pressure profiles of the structures along all Cartesian axes. In C18-mica, the standard deviation in the z coordinate for the chain atoms is high and more than doubles in the disordered phase. The order-disorder transition is accompanied by a change in the orientation of the ammonium head group, as well as decreasing tensile and shear stress in the disordered phase. In 2C18-mica, the standard deviation in the z coordinate for the chain atoms is low and does not increase remarkably on heating. The backbones display a highly regular structure, which is slightly obscured by rotations in the C18 backbones and minor head group displacements at 100 degrees C. Close contacts between the bulky head groups with sidearms cause significant local pressure which is in part not relieved at 100 degrees C. An increase of the basal-plane spacing at higher temperature is found in both systems due to larger separation between the two hydrocarbon layers and an increased z spacing between adjacent chain atoms (=decreased tilt of the chains relative to the surface normal), and, in C18-mica only, a stronger upward orientation of the C18 chain at the ammonium head group. The likelihood for chain interdigitation between the two hydrocarbon layers is 24%-30% for C18-mica, and 65%-26% for 2C18-mica (for 20-100 degrees C).     

Microfluidic biosensing systems. Part II. Monitoring the dynamic production of glucose and ethanol from microchip-immobilised yeast cells using enzymatic chemiluminescent micro-biosensors

A microfluidic flow injection (microFIA) system was employed for handling and monitoring of cell-released products from living cells immobilised on silicon microchips. The dynamic release of glucose and ethanol produced from sucrose by immobilised Saccharomyces cerevisiae cells was determined using microchip biosensors (micro-biosensors) with either co-immobilised glucose oxidase-horseradish peroxidase (GOX-HRP), or alcohol oxidase-horseradish peroxidase (AOX-HRP), catalysing a series of reactions ending up with chemiluminescence (CL) generated from HRP-catalysed oxidation of luminol in presence of p-iodophenol (PIP). The yeast cells were attached by first treating them with polyethylenimine (PEI) followed by adsorption to the microchip surface. The cell loss during assaying was evaluated qualitatively using scanning electron microscopy (SEM), showing that no cells were lost after 35 min liquid handling of the cell chip at 10 microl min(-1). The enzymes were immobilised on microchips via PEI-treatment followed by glutaraldehyde (GA) activation. The GOX-HRP micro-biosensors could be used during five days without any noticeable decrease in response, while the AOX-HRP micro-biosensors showed continuously decreasing activity, but could still be used employing calibration correction. The glucose and ethanol released from the immobilised yeast chips were quantitatively monitored, by varying the incubation time with sucrose, showing the possibilities and advantages of using a microfluidic system set-up for cell-based assays.     

Quantitative SIMS depth profiling of diffusion barrier gate-oxynitride structures in TFT-LCDs

Gate oxynitride structures of TFT-LCDs were investigated by SIMS, and successful solutions are demonstrated to overcome difficulties arising due to the charging effects of the multilayer systems, the matrix effect of the method, and the small pattern sizes of the samples. Because of the excellent reproducibility achieved by applying exponential relative sensitivity functions for quantitative analysis, minor differences in the barrier gate-oxynitride composition deposited on molybdenum capped aluminium-neodymium metallisation electrodes were determined between the centre and the edge of the TFT-LCD substrates. No differences were found for molybdenum-tungsten metallisations. Furthermore, at the edge of the glass substrates, aluminium, neodymium, and molybdenum SIMS depth profiles show an exponential trend. With TEM micrographs an inhomogeneous thickness of the molybdenum capping is revealed as the source of this effect, which influences the electrical behaviour of the device.The production process was improved after these results and the aging behaviour of TFT-LCDs was investigated in order to explain the change in control voltage occurring during the lifetime of the displays. SIMS and TEM show an enrichment of neodymium at the interface to the molybdenum layer, confirming good diffusion protection of the molybdenum barrier during accelerated aging. The reason for the shift of the control voltage was finally located by semi-quantitative depth profiling of the sodium diffusion originating from the glass substrate. Molybdenum-tungsten was a much better buffer for the highly-mobile charge carriers than aluminium-neodymium. Best results were achieved with PVD silicon oxynitride as diffusion barrier and gate insulator deposited on aluminium-neodymium metallisation layers.     

Optimal topological test for degeneracies of real Hamiltonians

We consider adiabatic transport of eigenstates of real Hamiltonians around loops in parameter space. It is demonstrated that loops that map to nontrivial loops in the space of eigenbases must encircle degeneracies. Examples from Jahn-Teller theory are presented to illustrate the test. We show furthermore that the proposed test is optimal.     

A rat brain protein expression map including cytosolic and enriched mitochondrial and microsomal fractions

Proteomics is a powerful tool to screen brain protein expression but the methodology is hampered by low abundance of proteins or compartmentalization or overload of high-abundance proteins. It was therefore the aim of the study to determine the expression of brain proteins by using enriched cellular subfractions and pre-electrophoretic chromatographical separation of brain homogenates. We used two-dimensional electrophoresis with subsequent matrix-assisted laser desorption/ionization (MALDI) detection and characterization of brain proteins. Subfractionation into cytosolic, mitochondrial and microsomal compartments was performed by ultracentrifugation. Pre-electrophoretic fractionation of the cytosolic fractions was carried out by ion exchange column chromatography. We detected and identified a large series of 437 proteins in rat brain and have shown proteins specific for the individual subcellular compartments. These proteins included housekeeping, signaling, cytoskeletal, intermediary metabolism, antioxidant proteins on the one and neuron and synaptosomal specific proteins on the other hand. Using fractionations of brain homogenates we were able to improve the power of the method on forming the basis for brain protein expressional studies and providing a reference map as a powerful tool for the neuroscientist.     

Induced fit process in the selective distal binding of imidazoles in zinc(II) porphyrin receptors

The respective affinities of various imidazole derivatives, imidazole (ImH), 2-methylimidazole (2-MeImH), 2-phenylimidazole (2-PhImH), N-methylimidazole (N-MeIm), 2-methylbenzimidazole (2-MeBzImH), and 4,5-dimethylbenzimidazole (4,5-Me(2)BzImH), for two phenanthroline (Phen) strapped zinc(II) porphyrin receptors porphen-Zn 1-Zn and 2-Zn have been studied. The formation of a supplementary H-bond considerably enhances the affinity of the zinc(II)-porphen receptor for imidazoles unsubstituted on the pyrrolic nitrogen (ImH) versus N-substituted imidazoles such as N-MeIm. The ImHs subset porphen-Zn complexes are formed with association constants up to 4 orders of magnitude superior to those measured either for N-MeIm as substrate or TPP-Zn as receptor. Distal or proximal binding of the substrates was determined by (1)H NMR measurements and titration. In two cases, the very high stability of the inclusion complex enabled the use of 2D NMR techniques. Excellent correlation between solution and solid-state structures has been obtained. A total of six X-ray structures are detailed in this article showing that the evolution of the shape of the zinc(II) receptor is mostly dependent on the steric constraints induced by the substitution on the imidazole. Hindered guests also progressively induce considerable mobility restrictions and severe distortions on the receptor, especially in the case of 2-MeBzImH and 2-PhImH.     

Application of isomorphous replacement in the structure determination of a cubic liquid crystal phase and location of counterions

A second generation monodendron with dodecyl end-groups based on the AB(3) monomer 3,4,5-trihydroxy benzoate has previously been shown to form a thermotropic cubic phase with Pmthremacr;n symmetry (Balagurusamy et al., J. Am. Chem. Soc. 1997, 119, 1539). A structure consisting of spherical "micelles" was proposed originally, but an alternative choice of structure factor phases, giving a structure of interlocked squashed columns, could not be ruled out by diffraction data on the original material alone. We have therefore synthesized two selectively fluorinated equivalent compounds, the carboxylic acid and its Rb salt, to be able to apply a variant of the isomorphous replacement crystallographic technique. On the basis of the electron density maps of the new labeled compounds, reconstructed using small-angle X-ray diffraction intensities, the interlocking columns model is unequivocally rejected and the spheres model is upheld. Furthermore, the location of the metal cation in the center of the "micelles" is directly confirmed. Micellar diameter was shown to decrease on fluorination of the dodecyl chain ends, and increase significantly on introduction of Rb. This is interpreted in terms of changes in the number of wedge-shaped dendrons fitting into a spherical micelle due to their changing taper angle. It was found that the Rb-rich regions at the centers of six out of eight "micelles" in the unit cell are elongated in the direction of their closest packing. This adds support to the suggestion of a partial "column-like" character of stacked rows of such micelles, consistent with the position of the Pmthremacr;n phase next to the columnar phase in the phase sequence of most taper-shape compounds. The results illustrate the potential of isomorphous replacement, used a great deal in protein crystallography, in structure investigation of liquid crystals and supramolecular soft matter.     

Applications of high-order harmonics

We review applications of high-order harmonic generation in different fields of physics, from spectroscopic studies of atoms and molecules, to interferometry and plasma diagnostics and nonlinear optics.Received: 11 December 2002, Published online: 24 April 2003PACS: 32.80.Fb Photoionization of atoms and ions - 42.65.Ky Frequency conversion; harmonic generation, including higher-order harmonic generationD. Descamps: Present address: CEA/DRECAM/SPAM, CEN Saclay, 91105 Gif-sur-Yvette, France.