Mass spectrometric methods for distinguishing structural isomers of glutathione conjugates of estrone and estradiol

Collisionally activated decompositions (CAD) of [M+H]⁺ ions from two sets (estrone and estradiol) of three isomeric glutathione (GSH) conjugates were studied by using five tandem mass spectrometric methods: (1) low energy (LE) CAD in an ion trap, (2) LE CAD in a triple quadrupole, (3) electrospray ionization (ESI)-source CAD in a tandem four sector, (4) high energy (HE) CAD of both ESI-produced and fast-atom bombardment (FAB)-produced ions in a tandem four-sector mass spectrometer, and (5) metastable-ion decompositions of FAB-produced ions. Four types of fragment ions are produced. The first type, formed from cleavage of the peptide backbone, gives rise to modified b₂, modified y₂, y₂, and b₁ ions. These fragments are observed with all the methods and show that the catechol estrogen attachment is at the cysteine moiety of the GSH. Internal fragment ions are the second type, and they also support that the modification is at cysteine. The third type involves fragmentation of the C–S bond to give an ion containing the steroid bonded to the sulfur. The fourth type of fragment ion is similar to the third but involves oxidation of the steroid ring and reduction of the GSH moiety; it is the most isomer specific of the four. The isomer-specific ions are of relatively low abundance in the product-ion spectra taken on the triple quadrupole and ion trap, but their abundances can be improved by increasing the collision energy. ESI source-CAD and the HE-CAD spectra of the isomers are the most distinctive because abundant product ions of all four types are seen in a single spectrum.     

Stable polymeric microballoons as multifunctional device for biomedical uses: synthesis and characterization

Gas filled hollow microparticles, i.e., microbubbles and microballoons, are soft matter devices used in a number of diverse applications ranging from protein separation and purification in food science to drilling technology and ultrasound imaging. Aqueous dispersions of these mesoscopic systems are characterized by the stabilization of the air/water interface by a thin shell of phospholipid bilayer or multilayers or by a denatured and cross-linked proteic matrix. We present a study of a type of microballoons based on modified poly(vinyl alcohol), PVA, a synthetic biocompatible polymer, with new structural features. A cross-linking reaction carried out at the air/water interface provides polymeric air-filled microbubbles with average dimensions depending on the reaction temperature. Characterization of diameters and shell thicknesses for microbubbles obtained at different temperatures has been carried out. Conversion to solvent-filled hollow microcapsules is possible by soaking microbubbles in dimethyl sulfoxide. Microcapsules permeability to fluorescent labeled dextran molecular weight standards was correlated to the mesh size of the polymer network of the shell. Microbubbles were covalently grafted under very mild conditions with beta-cyclodextrin and poly-l-lysine with a view to assay the capability of the device for delivery of hydrophobic drugs or DNA. PVA based microballoons show a remarkable shelf life of several months, their external surface can be decorated with many biologically relevant molecules. These features, together with a tested biocompatibility, make them attractive candidates for use as multifunctional device for diagnosis and therapeutic purposes, i.e., as ultrasound reflectors in ecographic investigation and as drug platforms for in situ sonoporation.     

6-alkyl and 5,6-dialkyl-2-methoxy-4(3H)- pyrimidinones in the transformations of pyrimidines—2: Synthesis and conversion into alkyluracils and 2-alkoxy-4(3H)-pyrimidinones

The synthesis of 6-alkyl and 5,6-dialkyl-2-methoxy-4(3H)-pyrimidinones 3 is described. Their versatility to be transformed into 6-alkyl and 5,6-dialkyluracils 4(a-h), 6-alkyl and 5,6-dialkyl-3-methyluracils 7(a,e,f) and 6-alkyl and 5,6-dialkyl-2-alkoxy-4(3H)-pyrimidinones 5(a-i) is also shown.     

Concerted and stepwise proton-coupled electron transfers in aquo/hydroxo complex couples in water: oxidative electrochemistry of [Os(II)(bpy)(2)(py)(OH(2))](2+)

Successive oxidation of transition metal(II) aqua complexes (M(II)OH(2) to M(III)OH) is a domain in which proton-coupled electron transfer reactions are extremely common. The mechanism of these PCET reactions-concerted or stepwise-is an important issue in the understanding and design of natural or artificial systems catalyzing the formation of dioxygen by four-electron oxidation of water. Concerted proton-coupled electron transfer from an aqua metal(II) to a hydroxo metal(III) complex requires the close proximity of a proton-accepting group with a pK value between those of the aqua complexes. Otherwise, stepwise electron-proton or proton-electron pathways involving high-energy intermediates are followed. Concerted proton-electron pathways involving water as proton-acceptor or proton-donor group are inefficient. Cyclic voltammetry of the title complex in buffered aqueous solution and re-examination of previous results for the same complex attached to an electrode surface are used to establish these conclusions, which provide a starting point on the route to higher degrees of oxidation, such as those involved in the catalysis of water oxidation.     

Sonochemical synthesis of liquid-encapsulated lysozyme microspheres

Liquid-encapsulated lysozyme microspheres were successfully synthesized using a sonochemical method. The encapsulation of four different liquids, namely, sunflower oil, tetradecane, dodecane and perfluorohexane on the formation, stability and morphology of the lysozyme microspheres was studied. Among the four different liquids used for encapsulation, perfluorohexane-filled microspheres were found to be most stable in the dried state with a narrow size distribution. In order to explore the possibility of encapsulating biofunctional molecules (e.g., drugs) within these microspheres, liquids containing a fluorescent dye (Nile red) were encapsulated and the ultrasound-induced release of these dye-loaded liquids was studied. The fluorescence data for the liquid-filled lysozyme microspheres demonstrated the potential use of the sonochemical technique for synthesizing these “vehicles” for the encapsulation and the controlled delivery of dyes, flavours, fragrances or drugs.     

A Titanium-doped-sapphire laser source with tunable frequency,single-mode emission,and adjustable pulse duration

We present a laser source with several desirable characteristics, such as tunable wavelength in the near infrared, single-longitudinal-mode emission and variable pulse temporal duration in the nanosecond regime. The laser is based on an injection-seeded Titanium-doped-sapphire ring cavity. Our experiments show how the pulse duration can be varied in a controllable fashion either by changing the cavity length or by changing the pump energy. We present a theoretical model which successfully reproduces the experimental results by treating the operation of this type of laser as a gain-switching technique. As far as the stabilization of the laser cavity, we also present a novel solution involving the use of an avalanche photodiode.     

Water, solute, and segmental dynamics in polysaccharide hydrogels

Polysaccharide hydrogels have found several applications in the food industry, in biomedicine, and cosmetics. The study of polysaccharide hydrogels offers a challenging scenario of intrinsic heterogeneities in the crosslinking density and large time and space ranges that characterize a number of dynamic processes entailing segmental motions, water diffusion, and small-molecule diffusion. The understanding of such complex features is essential because of the extensive use of polysaccharidic moieties in the food industry, biomedical devices, and cosmetics. The study of phenomena occurring at the nanoscale to the mesoscale requires the combination of investigative tools to probe different time and distance scales and the structural characterization of the networks by established methodologies such as swelling and elastic modulus measurements. Elastic and quasielastic neutron scattering, and fluorescence recovery after photobleaching are emerging methodologies in this field. In this feature article we focus, somewhat arbitrarily, on these new approaches because other techniques, such as low-resolution proton NMR relaxometry and rheology, have been already described thoroughly in the literature. Case examples of polysaccharide hydrogels studied by neutron scattering and fluorescence recovery are presented here as contributions to the comprehension of the dynamic behavior of physical and chemical hydrogels based on polysaccharides. Quasielastic incoherent neutron scattering experiment on a Sephadex hydrogel sample at different temperatures.     

Investigation of structural and electronic properties of β- HgS: Molecular dynamics simulations

The pressure induced phase transition of β-HgS is studied using an ab initio molecular dynamics simulation. The structural phase transformation from the zinc-blende structure to the NaCl-type structure (space group $Fm\overline{3}m$) and from this structure to CsCl-type structure ($Pm\overline{3}m$) with the application of hydrostatic pressure is predicted. Additionally, the electronic properties of HgS and various physical properties such as the lattice constants, the bulk modulus and the pressure derivative of the bulk modulus are revealed. Furthermore, these phase transitions are obtained using the total energy and enthalpy calculations. According to these calculations these transformations are occurring at about 20?GPa and 28?GPa for $F\overline{4}3m$ →$Fm\overline{3}m$ and $Fm\overline{3}m$ →$Pm\overline{3}m$, respectively.     

Jittering wave-packet models for subsonic jet noise

Three simplified wave-packet models of the coherent structures in subsonic jets are presented. The models comprise convected wave-packets with time-dependent amplitudes and spatial extents. The dependence of the radiated sound on the temporal variations of the amplitude and spatial extent of the modulations are studied separately in the first two model problems, being considered together in the third. Analytical expressions for the radiated sound pressure are obtained for the first and third models.Results show that temporally localised changes in the wave-packet can lead to radiation patterns which are directional and which comprise high-amplitude bursts; such intermittency is observed in subsonic jets at the end of the potential core, and so the models may help explain the higher noise levels and intermittent character of the sound radiated to low emission angles for subsonic jets. By means of an efficiency metric, relating the radiated acoustic power to the fluctuation energy of the source, we show that the source becomes more powerful as its temporal localisation is increased. This result extends that of Sandham et al. (Journal of Sound and Vibration 294(1) (2006) 355–361) who found similar behaviour for an infinitely extended wavy-wall.The pertinence of the model is assessed using two sets of data for a Mach 0.9 jet. One corresponds to a direct numerical simulation (DNS) of a Reynolds number 3600 turbulent jet and the other to a large eddy simulation (LES) of a Reynolds number 4×10⁵ jet. Both time-averaged and time-dependent amplitudes and spatial extents are extracted from the velocity field of the numerical data. Computing the sound field generated by the wave-packet models we find for both simulations that while the wave-packet with a time-averaged envelope shows discrepancies of more than an order of magnitude with the sound field, when the wave-packet ‘jitters’ in a way similar to the intermittency displayed by the simulations, we obtain agreement to within 1.5 dB at low axial angles. This shows that the ‘jitter’ of the wave-packet is a salient source feature, and one which should be modelled explicitly.     

Method for high-resolution frequency measurements in the extreme ultraviolet regime: random-sampling Ramsey spectroscopy

Ramsey-like schemes have been recently introduced in combination with high-order laser harmonic sources for high-resolution spectroscopic studies in the extreme ultraviolet (XUV). Here we demonstrate a novel method, combining measurements only in a limited subset of randomly chosen time-sampling intervals, which lead us to perform the first high-resolution XUV spectroscopy of atomic argon with a simple split-pulse setup. Providing an experimentally simple and convenient solution to the problem of performing high-resolution absolute frequency measurements in the XUV, our approach will help paving new roads into this challenging spectral territory.