An Improved Measurement of Isotopic Ratios by High Resolution Mass Spectrometry

The study of protein kinetics requires an accurate measurement of isotopic ratios of peptides. Although Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometers yield accurate mass measurements of analytes, the isotopologue ratios are consistently lower than predicted. Recently, we demonstrated that the magnitude of the spectral error in the FT-ICR mass spectrometer is proportional to the scan duration of ions. Here, we present a novel isotopic ratio extrapolation (IRE) method for obtaining accurate isotopic ratio measurements. Accuracy is achieved by performing scans with different duration and extrapolation of the data to the initial moment of the ion rotation; IRE minimizes the absolute isotopic ratio error to ≤1 %. We demonstrate the application of IRE in protein turnover studies using ²H₂O-metabolic labeling. Overall, this technique allows accurate measurements of the isotopic ratios of proteolytic peptides, a critical step for enabling routine studies of proteome dynamics.      

Solid‐State Structural Transformations and Photoreactivity of 1D‐Ladder Coordination Polymers of PbII

An attempt has been made to design double‐stranded ladder‐like coordination polymers (CPs) of hemidirected Pb^II. Four CPs, [Pb(μ‐bpe)(O₂C‐C₆H₅)₂] ? 2H₂O ( 1 ), [Pb₂(μ‐bpe)₂(μ‐O₂C‐C₆H₅)₂(O₂C‐C₆H₅)₂] ( 2 ), [Pb₂(μ‐bpe)₂(μ‐O₂C‐p‐Tol)₂(O₂C‐p‐Tol)₂] ? 1.5 H₂O ( 3 ) and [Pb₂(μ‐bpe)₂(μ‐O₂C‐m‐Tol)₂(O₂C‐m‐Tol)₂] ( 4 ) (bpe=1,2‐bis(4′‐pyridyl)ethylene), have been synthesised and investigated for their solid‐state photoreactivity. CPs 2 – 4 , having a parallel orientation of bpe molecules in their ladder structures and being bridged by carboxylates, were found to be photoreactive, whereas CP 1 is a linear one‐dimensional (1D) CP with guest water molecules aggregating to form a hydrogen‐bonded 1D structure. The linear strands of 1 were found to pair up upon eliminating lattice water molecules by heating, which led to the solid‐state structural transformation of photostable linear 1D CP 1 into photoreactive ladder CP 2 . In the construction of the double‐stranded ladder‐like structures, the parallel alignment of C?C bonds in 2 – 4 is dictated by the chelating and μ₂‐η²:η¹ bridging modes of the benzoate and toluate ligands. The role of solvents in the formation of such double‐stranded ladder‐like structures has also been investigated. A single‐crystal‐to‐single‐crystal transformation occurred when 4 was irradiated under UV light to form [Pb₂(rctt‐tpcb)(μ‐O₂C‐m‐Tol)₂(O₂C‐m‐Tol)₂] ( 5 ).     

Fractional Order Analysis of Sephadex Gel Structures: NMR Measurements Reflecting Anomalous Diffusion

We report the appearance of anomalous water diffusion in hydrophilic Sephadex gels observed using pulse field gradient (PFG) nuclear magnetic resonance (NMR). The NMR diffusion data was collected using a Varian 14.1 Tesla imaging system with a home-built RF saddle coil. A fractional order analysis of the data was used to characterize heterogeneity in the gels for the dynamics of water diffusion in this restricted environment. Several recent studies of anomalous diffusion have used the stretched exponential function to model the decay of the NMR signal, i.e., exp[-(bD)(α)], where D is the apparent diffusion constant, b is determined the experimental conditions (gradient pulse separation, durations and strength), and α is a measure of structural complexity. In this work, we consider a different case where the spatial Laplacian in the Bloch-Torrey equation is generalized to a fractional order model of diffusivity via a complexity parameter, β, a space constant, μ, and a diffusion coefficient, D. This treatment reverts to the classical result for the integer order case. The fractional order decay model was fit to the diffusion-weighted signal attenuation for a range of b-values (0 < b < 4,000 s-mm(-2)). Throughout this range of b values, the parameters β, μ and D, were found to correlate with the porosity and tortuosity of the gel structure.     

Seifen

Ohne Zusammenfassung     

Multiple Ligand and Cell-Dependent States of Lateral Mobility of Plasmalemmal G Protein-Coupled Cholecystokinin Receptors

Lateral movement of receptor molecules in the plane of the plasmalemma has important implications for signal transduction and receptor regulation, yet mechanisms affecting such movement are not well understood. We have studied the lateral mobility of the G protein-coupled cholecystokinin (CCK) receptor expressed in the natural milieu of the rat pancreatic acinar cell and in a model cell system, the CHO-CCKR cell, after occupation with fluorescent agonist and antagonist. Lateral diffusion characteristics were distinct in each type of cell and for receptors occupied by each type of ligand, fluorescent agonist, rhodamine-Gly-[(Nle^28,31)CCK-26-33], and fluorescent antagonist, rhodamine-Gly-[(D-Trp³⁰,Nle^28,31)CCK-26-32]-phenethyl ester. Multiple states of mobility were detected for CCK receptors. The slowest population of mobile receptors on the CHO-CCKR cells moved at similar rates when occupied by both antagonist and agonist, while the faster-moving populations moved at a faster rate when occupied with antagonist than with agonist. The fastest component of mobile receptors may reflect unconstrained interactions of the antagonist-occupied receptors with signaling or anchoring structures, while the slowest component may represent the fraction of ligand-occupied receptors that ultimately undergo internalization. The intermediate mobility states may reflect receptor interactions with signal transduction and regulatory machinery. While only a single population of mobile receptors was demonstrable on the acinar cells, increased ligand concentrations (agonist and antagonist) resulted in increased percentages of mobile receptors, suggesting a stoichiometric limitation of immobilizing molecular constraints. Inhibition of protein kinase C had no significant effect on the lateral mobility of agonist-occupied CCK receptors.     

Zur Analyse von Eisen -und Stahl

Ohne Zusammenfassung     

Die Hauptprinzipien der Kolloidchemie

Ohne Zusammenfassung Vortrag, gehalten auf dem 4. Kolloid-Symposium, Cambridge. Uebersetzt von Rudolf K?hler, Leipzig.     

Apparate

Ohne Zusammenfassung     

Amplified Production of Singlet Oxygen in Aqueous Solution Using Metal Enhancement Effects

Studies involving metal enhancement effects have gained popularity, and enhancement of fluorescence due to the close proximity of a dye molecule to a metal nanoparticle is well documented. Although enhancement of singlet oxygen production by metal has been reported, studies are relatively scarce and so far only stationary silver island films have been proven to be adequate to do so. Herein, we describe the synthesis and characterization of core–shell nanoparticles on which a photosensitizer acting as source of singlet oxygen has been covalently attached to the nanoparticle surface. As a proof of concept, silver nanoparticles with a diameter around 68 nm were chosen as the metallic core, and were coated by a silica shell of about 22 nm in thickness. The silica shell plays a dual role as a spacer and a medium onto which the photosensitizer, rose bengal (RB), has been covalently attached. These novel core–shell nanoparticles allow for the amplification of singlet oxygen production by 3.8 times, which is similar to the amplification found for RB in proximity of silver island films.