Pyridine-based lanthanide complexes combining MRI and NIR luminescence activities

A series of novel triazole derivative pyridine-based polyamino-polycarboxylate ligands has been synthesized for lanthanide complexation. This versatile platform of chelating agents combines advantageous properties for both magnetic resonance (MR) and optical imaging applications of the corresponding Gd(3+) and near-infrared luminescent lanthanide complexes. The thermodynamic stability constants of the Ln(3+) complexes, as assessed by pH potentiometric measurements, are in the range log K(LnL)=17-19, with a high selectivity for lanthanides over Ca(2+), Cu(2+), and Zn(2+). The complexes are bishydrated, an important advantage to obtain high relaxivities for the Gd(3+) chelates. The water exchange of the Gd(3+) complexes (k(ex)(298)=7.7-9.3×10(6) s(-1)) is faster than that of clinically used magnetic resonance imaging (MRI) contrast agents and proceeds through a dissociatively activated mechanism, as evidenced by the positive activation volumes (ΔV(≠)=7.2-8.8 cm(3) mol(-1)). The new triazole ligands allow a considerable shift towards lower excitation energies of the luminescent lanthanide complexes as compared to the parent pyridinic complex, which is a significant advantage in the perspective of biological applications. In addition, they provide increased epsilon values resulting in a larger number of emitted photons and better detection sensitivity. The most conjugated system PheTPy, bearing a phenyl-triazole pendant on the pyridine ring, is particularly promising as it displays the lowest excitation and triplet-state energies associated with good quantum yields for both Nd(3+) and Yb(3+) complexes. Cellular and in vivo toxicity studies in mice evidenced the non-toxicity and the safe use of such bishydrated complexes in animal experiments. Overall, these pyridinic ligands constitute a highly versatile platform for the simultaneous optimization of both MRI and optical properties of the Gd(3+) and the luminescent lanthanide complexes, respectively.     

Role of the middle residue in the triple tryptophan electron transfer chain of DNA photolyase: ultrafast spectroscopy of a Trp-->Phe mutant

Photoreduction of the semi-reduced flavin adenine dinucleotide cofactor FADH* in DNA photolyase from Escherichia coli into FADH- involves three tryptophan (W) residues that form a closely spaced electron-transfer chain FADH*-W382-W359-W306. To investigate this process, we have constructed a mutant photolyase in which W359 is replaced by phenylalanine (F). Monitoring its photoproducts by femtosecond spectroscopy, the excited-state FADH* was found to decay in approximately 30 ps, similar as in wild type (WT) photolyase. In contrast to WT, however, in W359F mutant photolyase the ground-state FADH* fully recovered virtually concomitantly with the decay of its excited state and, despite the presence of the primary electron donor W382, no measurable flavin reduction was observed at any time. Thus, W359F photolyase appears to behave like many other flavoproteins, where flavin excited states are quenched by very short-lived oxidation of aromatic residues. Our analysis indicates that both charge recombination of the primary charge separation state FADH-W382*+ and (in WT) electron transfer from W359 to W382*+ occur with time constants <4 ps, considerably faster than the initial W382-->FADH* electron-transfer step. Our results provide a first experimental indication that electron transfer between aromatic residues can take place on the time scale of approximately 10(-12) s.     

Characterization of heat-wave propagation through laser-driven Ti-doped underdense plasma

The propagation of a laser-driven heat-wave into a Ti-doped aerogel target was investigated. The temporal evolution of the electron temperature was derived by means of Ti K-shell X-ray spectroscopy, and compared with two-dimensional radiation hydrodynamic simulations. Reasonable agreement was obtained in the early stage of the heat-wave propagation. In the later phase, laser absorption, the propagation of the heat-wave, and hydrodynamic motion interact in a complex manner, and the plasma is mostly re-heated by collision and stagnation at the target central axis.     

A new hybrid target concept for multi-keV X-ray sources

A novel concept for using hybrid targets to create multi-keV X-ray sources was tested on the GEKKO XII facility of the OSAKA University and on the OMEGA facility of the University of Rochester. The sources were made via laser irradiation of a titanium foil placed at the end of a plastic cylinder, filled with a very low-density (2 and 5 mg/cm³) silicon-dioxide aerogel that was designed to control the longitudinal expansion of the titanium plasma. Preliminary calculations were used to determine optimal conditions for the aerogel density, cylinder diameter and length that maximize multi-keV X-ray emission. The X-ray emission power was measured on OMEGA using absolutely calibrated broad-band, diode-based CEA diagnostics, in addition to high resolution crystal spectrometers. On GEKKO XII, the heat wave propagation velocity in the aerogel was also measured with an X-ray framing camera. The advantage of using the thermal wave generated in the aerogel to heat a solid material to increase the conversion efficiency has not been fully demonstrated in these experiments. However, it was shown that a 5 mg/cm³ aerogel placed in front of a titanium foil can improve the x-ray conversion efficiency with respect to the case of 2 mg/cm³ for some target diameter and length.     

Fast purification of cyclodextrin-glucosyltransferase fromBacillus circulans E 192 by affinity chromatography using an epichlorhydrin-reticulated copolymer of beta-cyclodextrin

Summary Bacillus circulans E 192 Cyclodextrin-glucosyltransferase was purified 40 fold to homogeneity on a large scale, by affinity chromatogrpahy on a β-CD copolymer cross-linked with epichlorhydrin. A preliminary step was necessary to remove maltooligosaccharides and cyclomaltooligosaccharides from the crude extract. The simplest method consists in performing the affinity chromatography directly from a redissolved 65% saturation ammonium sulfate precipitate of the crude extract. Five successive affinity runs of Cetavlon — treated concentrated extract gave about one gram of pure CGTase with a 70% yield, using 50 g of a 750 U/g β-CD copolymer. This rapid purification is described and the advantages of the method are discussed.     

Subsurface-channeling-like energy loss structure of the skipping motion on an ionic crystal

The skipping motion of Ne+ ions in grazing scattering from the LiF(001) surface is studied for velocity below 0.1 a.u. with a time-of-flight technique. It is demonstrated that suppression of electronic excitation and dominance of optical phonon excitation in the projectile stopping results in an odd 1,3,5,... progression of the energy loss peaks, a feature usually ascribed to subsurface channeling. The experimental findings are well reproduced by parameter-free model calculations where thermal vibrations are the dominant cause for the ion trapping and detrapping.     

Comparison of X-ray source concepts for radiographic purposes at OMEGA

As multi-keV X-ray sources, seven targets including thick and thin foils, metal-lined halfraums and a foil combined with a plastic cylinder, have been shot on Omega in September 2011. Titanium was used as X-ray emitting material for all the sources. Using experimental data and FCI2 simulation results, we have, for each source type, characterized the emission lobes and determined the spatial directions of maximum multi-keV energy. These results demonstrate the benefit of using a laser drive with a pre-pulse for both thick and thin foils. The favorable effect of a confinement cylinder for the X-ray emitted from front side by a thin foil has also been experimentally found but is not yet confirmed by the simulations. The temporal waveforms of the X-ray power obtained from the different sources as well as the emission spots at the times of maximum emission are also compared.     

Analysis of oligosaccharides using aminobonded silica gel and a ternary eluent with evaporative light scattering detection

Using two commercial, amino bonded, silica gel columns, binary eluents (methanol/water, acetonitrile/methanol) and ternary eluents (acetonitrile/methanol/water) are evaluated for their ability to separate oligosaccharides in comparison with classical acetonitrile/water eluents. Chromatographic data on glucose, maltose, raffinose, stachyose and maltodextrin are reported. Mobile phases consisting of acetonitrile/water or acetonitrile/methanol/water produce the best separations. Phase hydrolysis is evaluated using an evaporative light scattering detector. The reduction of the water content in the eluent stabilizes the aminocolumns and the life time of the amino columns should be improved with the ternary eluent. Moreover, a better detection limit can be obtained. Capabilties to run gradient elution without baseline drift are clearly demonstrated.     

Electron bihole complex formation in neutralization of Ne+ on LiF(001).

Neutralization of low keV Ne+ ions at a LiF(001) surface is studied in a grazing incidence geometry. The combination of energy loss and electron spectroscopy in coincidence reveals two neutralization channels of comparable importance. Besides the Auger process, the Ne+ neutralization can proceed via peculiar target excitation, corresponding to the formation of an electron bihole complex termed trion.