Experimental study of coherence vortices: local properties of phase singularities in a spatial coherence function

By controlling the irradiance of an extended quasimonochromatic, spatially incoherent source, an optical field is generated that exhibits spatial coherence with phase singularities, called coherence vortices. A simple optical geometry for direct visualization of coherence vortices is proposed, and the local properties and the spatial evolution of coherence vortex are experimentally investigated. To our knowledge, this is the first direct and quantitative experimental measurement of a generic coherence vortex.     

High frequency attenuation measurements of lipid encapsulated contrast agents

A number of recent studies have indicated the potential of ultrasound contrast agent imaging at high ultrasound frequencies. However, the acoustic properties of microbubbles at frequencies above 10 MHz remain poorly understood at present. In this study we characterize the high frequency attenuation properties of (1) BR14, (2) BR14 that has been mechanically filtered (1 and 2 microm pore sizes) to exclude larger bubbles, and (3) the micron to submicron agent BG2423. A narrowband pulse-echo substitution method is employed with a series of four transducers covering the frequency range from 2 to 50 MHz. For BR14, attenuation decreases rapidly from 2 to 10 MHz and then more gradually from 10 to 50 MHz. For 2 microm filtration, the attenuation peaks between 10 and 15 MHz. For 1 microm filtration, attenuation continues to rise until 50 MHz. The agent BG2423 exhibits a diffuse attenuation peak in the range of 15-25 MHz and remains high until 50 MHz. These results demonstrate a strong influence of bubble size on high frequency attenuation curves, with bubble diameters of 1-2 microm and below having more pronounced acoustic activity at frequencies above 10 MHz.     

On the Use of Mössbauer Spectroscopy for Characterisation of Iron Oxides and Oxyhydroxides in Soils

Hyperfine Interactions - An empirical expression for the dependence of the magnetic hyperfine field on the aluminium content and the particle size in iron oxides and oxyhydroxides is often used in...     

Characterizations by Automorphism Groups of Some Rank 3 Buildings — II: A Half Strongly-Transitive Locally Finite Triangle Building is a Bruhat—Tits Building

We complete the proof of the fact that every locally finite triangle building with a half strongly-transitive automorphism group G (e.g., this happens when is defined via a (B, N)-pair in G) is a Bruhat—Tits building associated with a classical linear group over a locally finite local skewfield.     

Design and peptide-based validation of phage display antibodies for proteomic biochips

To validate potential application of phage display-antibody arrays for high-throughput screening on a novel proteomics biochip, we examined the epitopes versus the full protein of glucose-6-phosphate-dehydrogenase (G6PD) from yeast. In a predictive approach, we used the Hopp-Woods method and compared the results with antibodies directed against the entire enzyme. In total, 16 peptides of a length of 11 amino acids each fulfilling the desired criteria were identified and synthesized. Subsequently, antibodies against G6PD were raised using a phage display library. Selective interaction of the antibodies with certain peptides facilitated the identification of epitopes predicted by the hydropathic profile. The setup was adapted to a novel biochip system based on surface-enhanced absorption for direct CCD-camera based screening.     

Isotope effects on the unimolecular dissociation of ionized 3-methyl-2-butanol: reactions via a long-lived C-H-C hydrogen-bridged ion-neutral complex

A pronounced isotope effect causes metastable CD3CHOHCH(CH3)2+* ions to expell C3H6D2 in preference to C3H7D in a ratio of approximately 33:1; a number of related compounds show similar effects. High-level ab initio calculations suggest that the reactant alcohol molecular ion possesses an extraordinarily long alpha-carbon-carbon bond and that the reaction proceeds via the formation of an intermediate hydrogen-bridged complex of propane and ionized vinyl alcohol, in which the bridging hydrogen atom is almost midway between the two carbon termini. The isotopic preference reflects the difference between the zero-point vibrational energies of the isotopically different product pairs rather than kinetic isotope effects on the hydrogen atom transfer reactions that precede dissociation.     

Non-metal-catalysed intramolecular alkyne cyclotrimerization reactions promoted by focussed microwave heating in batch and flow modes

A number of oligomeric alkynes underwent [2 + 2 + 2] intramolecular trimerization to afford arenes under metal-free conditions using focussed microwave heating.     

Differences between retentions of various classes of aromatic hydrocarbons in reversed-phase high-performance liquid chromatography. Implications of using retention data for characterizing hydrophobicity

Capacity factors of a series of alkylbenzenes (C1-C10), 12 chlorobenzenes, 9 chlorotoluenes, 17 chloronaphthalenes and 65 chlorobiphenyls have been measured on an octadecylsilica column. Aqueous methanol of four different compositions (80-95% methanol) was used as eluent. Logarithms of capacity factors of all eluites are linearly related to the amount of organic modifier in the eluent. In addition, linear relationships between the solvent strength and the logarithms of capacity factors extrapolated to zero methanol have been revealed. The proportionality factors are dependent on the structures of the eluites. Thermodynamic consideration of the retention processes shows that, within each type of eluite, enthalpy-entropy compensation is found. The compensation temperatures are not significantly different for the various types of eluite. Furthermore, it is shown that the compensation temperatures increase with increasing water content of the eluent. Since the intercepts of the delta G0-delta H0 plots are not equal for the various types of eluite, it was concluded that the distribution processes causing retention of benzene, naphthalene and biphenyl are different. When only the free energies of retention (i.e. the capacity factors) of different types of eluite are compared, no accurate information on the hydrophobicity of the eluites can be obtained if aqueous methanol is used as eluent. Therefore the possibilities for relating or predicting other physico-chemical parameters of the test compounds, such as octan-1-ol-water partition coefficients with isocratic retention data, will be limited.     

Similarity between condensed phase and gas phase chemistry: Fragmentation of peptides containing oxidized cysteine residues and its implications for proteomics

Amino acid residues containing thioethers are easily oxidized during protein purification, derivatization, and/or digestion. For instance, oxidation of methionine residues in proteins during SDS-PAGE is commonly observed. Under low energy collision induced dissociation this gives rise to a second series of fragment ion of lower abundance that are shifted by -64 Da when compared to the oxidized methionine-containing fragments. We report here that alkylated cysteine residues can be found in their oxidized form too, indicating that the oxidation of thioethers can occur during and following protein digestion and not only during SDS-PAGE or reduction and alkylation. Collision induced dissociation experiments on the singly- and multiply-charged species reveals that these peptides preferentially undergo elimination reactions that forms a dehydroalanine from the oxidized, alkylated cysteine residue. This contrasts to the less abundant elimination reaction of peptides containing oxidized methionines which cannot form an alpha,beta-unsaturated compound, but parallels the condensed phased chemistry of sulfoxides. The masses of both precursor and product ions are shifted such that these peptides cannot be identified in database searches with current algorithms. Incorporation of this fragmentation pattern is important for the isotope-coded affinity tag approach since this method is based on peptides containing cysteine residues.     

Rearrangement and hydrogen abstraction reactions of amine cation radicals: a gas-phase analogy to the Hofmann-Löffler-Freytag reaction

Low-energy molecular ions of gas-phase primary and secondary aliphatic amines undergo reciprocal NH/CH exchange of hydrogen atoms prior to fragmentation on the microsecond time-scale; the subsequent decomposition reactions are significantly different from those observed in the mass spectrometer ion source.