Selective oxidation of anthracene to 9,10-anthraquinone over silica supported vanadium catalyst

The inner-ring oxidation of anthracene over V₂O₅/SiO₂ catalyst was investigated at various oxygen concentrations, contact times of the reactants and reaction temperatures. Up to 90 % yield to 9,10-anthraquinone is obtained at 218-220^oC.     

Chemical modifications of Au/SiO2 template substrates for patterned biofunctional surfaces

The aim of this work was to create patterned surfaces for localized and specific biochemical recognition. For this purpose, we have developed a protocol for orthogonal and material-selective surface modifications of microfabricated patterned surfaces composed of SiO(2) areas (100 μm diameter) surrounded by Au. The SiO(2) spots were chemically modified by a sequence of reactions (silanization using an amine-terminated silane (APTES), followed by amine coupling of a biotin analogue and biospecific recognition) to achieve efficient immobilization of streptavidin in a functional form. The surrounding Au was rendered inert to protein adsorption by modification by HS(CH(2))(10)CONH(CH(2))(2)(OCH(2)CH(2))(7)OH (thiol-OEG). The surface modification protocol was developed by testing separately homogeneous SiO(2) and Au surfaces, to obtain the two following results: (i) SiO(2) surfaces which allowed the grafting of streptavidin, and subsequent immobilization of biotinylated antibodies, and (ii) Au surfaces showing almost no affinity for the same streptavidin and antibody solutions. The surface interactions were monitored by quartz crystal microbalance with dissipation monitoring (QCM-D), and chemical analyses were performed by polarization modulation-reflexion absorption infrared spectroscopy (PM-RAIRS) and X-ray photoelectron spectroscopy (XPS) to assess the validity of the initial orthogonal assembly of APTES and thiol-OEG. Eventually, microscopy imaging of the modified Au/SiO(2) patterned substrates validated the specific binding of streptavidin on the SiO(2)/APTES areas, as well as the subsequent binding of biotinylated anti-rIgG and further detection of fluorescent rIgG on the functionalized SiO(2) areas. These results demonstrate a successful protocol for the preparation of patterned biofunctional surfaces, based on microfabricated Au/SiO(2) templates and supported by careful surface analysis. The strong immobilization of the biomolecules resulting from the described protocol is advantageous in particular for micropatterned substrates for cell-surface interactions.     

Eigenmode structure in solar-wind Langmuir waves

We show that observed spatial- and frequency-domain signatures of intense solar-wind Langmuir waves can be described as eigenmodes trapped in a parabolic density well. Measured solar-wind electric field spectra and waveforms are compared with 1D linear solutions and, in many cases, can be represented by 1-3 low-order eigenstates. To our knowledge, this report is the first observational confirmation of Langmuir eigenmodes in space. These results suggest that linear eigenmodes may be the starting point of the nonlinear evolution, critical for producing solar type II and type III radio bursts.     

Observation of hydrogenlike and heliumlike krypton spectra

Hydrogenlike and heliumliken=2→n=1 lines in Kr have been produced and studied for the first time. HydrogenlikeL y α lines have been observed and the fine structure interval has been determined. The absolute energy of the¹P₁,³P₂,³P₁ lines of heliumlike Kr have been measured and compared to Multiconfigurational Dirac-Fock Calculations.     

Energy transfer in dioxane liquid scintillators

The study of the radiation yields of free radical formation in deaerated dioxane solutions containing a fluorescent solute (PPO or PBD) or a chlorinated compound (CCl₄ or CHCl₃) shows that there are two possible mechanisms for energy transfer from superexcited states: transfer of the electronic excitation energy, and the ionc mechanism which involves the electrons formed by autoionization. We propose a kinetic scheme which agrees with experimental results.     

Translocation of bioactive peptides across cell membranes by carbon nanotubes

Functionalised carbon nanotubes are able to cross the cell membrane and to accumulate in the cytoplasm or reach the nucleus without being toxic for the cell up to 10 [micro sign]M.     

高电荷态离子束的应用(摘要)

The ECR ion sources have mainly been used until now for injection of cyclotrons and a large number of these sources are presently in operation through the world.Most cyclotrons are used today for nuclear physics researches but an increasing number of these accelerators are now devoted to medical applications.The ECR ion sources have also been extensively used for producing low energy beams for academic researches in atomic and surface physics.These studies led to very encouraging results opening the way to industrial applications. In this talk some of the most promising applications of HCI beams will be reviewed.The development of these applications will require some important improvements of the ECR sources which will be discussed.A special emphasis will be given to the respective roles of ECR and EBIS ion sources in these industrial applications, and some economic and market considerations discussed.     

Probing lead(II) bonding environments in 4-substituted pyridine adducts of (2,6-Me2C6H3S)2Pb: an X-ray structural and solid-state 207Pb NMR study

The effect of subtle changes in the sigma-electron donor ability of 4-substituted pyridine ligands on the lead(II) coordination environment of (2,6-Me(2)C(6)H(3)S)(2)Pb (1) adducts has been examined. The reaction of 1 with a series of 4-substituted pyridines in toluene or dichloromethane results in the formation of 1:1 complexes [(2,6-Me(2)C(6)H(3)S)(2)Pb(pyCOH)](2) (3), [(2,6-Me(2)C(6)H(3)S)(2)Pb(pyOMe)](2) (4), and (2,6-Me(2)C(6)H(3)S)(2)Pb(pyNMe(2)) (5) (pyCOH = 4-pyridinecarboxaldehyde; pyOMe = 4-methoxypyridine; pyNMe2 = 4-dimethylaminopyridine), all of which have been structurally characterized by X-ray crystallography. The structures of 3 and 4 are dimeric and have psi-trigonal bipyramidal S(3)N bonding environments, with the 4-substituted pyridine nitrogen and bridging sulfur atoms in axial positions and two thiolate sulfur atoms in equatorial sites. Conversely, compound 5 is monomeric and exhibits a psi-trigonal pyramidal S(2)N bonding environment at lead(II). The observed structures may be rationalized in terms of a simple valence bond model and the sigma-electron donor ability of the 4-pyridine ligands as derived from the analysis of proton affinity values. Solid-state (207)Pb NMR experiments are applied in combination with density functional theory (DFT) calculations to provide further insight into the nature of bonding in 4, 5, and (2,6-Me(2)C(6)H(3)S)(2)Pb(py)(2) (2). The lead chemical shielding (CS) tensor parameters of 2, 4, and 5 reveal some of the largest chemical shielding anisotropies (CSA) observed in lead coordination complexes to date. DFT calculations using the Amsterdam Density Functional (ADF) program, which take into account relativistic effects using the zeroth-order regular approximation (ZORA), yield lead CS tensor components and orientations. Paramagnetic contributions to the lead CS tensor from individual pairs of occupied and virtual molecular orbitals (MOs) are examined to gain insight into the origin of the large CSA. The CS tensor is primarily influenced by mixing of the occupied MOs localized on the sulfur and lead atoms with virtual MOs largely comprised of lead 6p orbitals.     

Triterpenoid Saponins from the Cultivar “Green Elf” of Pittosporum tenuifolium

Four oleanane-type glycosides were isolated from a horticultural cultivar “Green Elf” of the endemic Pittosporum tenuifolium (Pittosporaceae) from New Zealand: three acylated barringtogenol C glycosides from the leaves, with two previously undescribed 3-O-β-d-glucopyranosyl-(1→2)-[α-l-arabinopyranosyl-(1→3)]-β-d-glucuronopyranosyl-21-O-angeloyl-28-O-acetylbarringtogenol C, 3-O-β-d-galactopyranosyl-(1→2)-[α-l-arabinopyranosyl-(1→3)]-β-d-glucuronopyranosyl-21-O-angeloyl-28-O-acetylbarringtogenol C, and the known 3-O-β-d-glucopyranosyl-(1→2)-[α-l-arabinopyranosyl-(1→3)]-β-d-glucuronopyranosyl-21-O-angeloyl-28-O-acetylbarringtogenol C (Eryngioside L). From the roots, the known 3-O-β-d-glucopyranosyl-(1→2)-β-d-galactopyranosyl-(1→2)-β-d-glucuronopyranosyloleanolic acid (Sandrosaponin X) was identified. Their structures were elucidated by spectroscopic methods including 1D- and 2D-NMR experiments and mass spectrometry (ESI-MS). According to their structural similarities with gymnemic acids, the inhibitory activities on the sweet taste TAS1R2/TAS1R3 receptor of an aqueous ethanolic extract of the leaves and roots, a crude saponin mixture, 3-O-β-d-glucopyranosyl-(1→2)-[α-l-arabinopyranosyl-(1→3)]-β-d-glucuronopyranosyl-21-O-angeloyl-28-O-acetylbarringtogenol C, and Eryngioside L were evaluated.     

Investigation of detonation initiation in aluminium suspensions

Detonation initiation is investigated in aluminium/oxygen and aluminium/air mixtures. Critical conditions for initiation of spherical detonations are examined in analogy with the criteria defined for gaseous mixtures, which correlate critical parameters of detonation initiation to the characteristic size of the cellular structure. However, experimental data on the detonation cell size in these two-phase mixtures are very scarce, on account of the difficulty to perform large-scale experiments. Therefore, 2D numerical simulations of the detonation cellular structure have been undertaken, with the same combustion model for Al/air and Al/O₂ mixtures. The cell size is found to be λ = 37.5 cm for a rich (r = 1.61) aluminium–air mixture, and λ = 7.5 cm for a stoichiometric aluminium-oxygen mixture, which is in reasonable agreement with available experimental data. Calculations performed in large-scale configurations (up to 25 m in length and 1.5 m in lateral direction) suggest that the critical initiation energy and predetonation radius for direct initiation of the unconfined detonation in the aluminium–air mixture are, respectively, 10 kg of TNT and 8 m. Moreover, numerical simulations reveal that the structure of the detonation wave behind the leading front is even more complicated than in pure gaseous mixtures, due to two-phase flow effects. This paper is based on work that was presented at the 21st International Colloquium on the Dynamics of Explosions and Reactive Systems, Poitiers, France, July 23–27, 2007.