Use of Induced Circularly Polarized Luminescence (CPL) from Racemic D3 Lanthanide Complexes to Determine the Absolute Configuration of Amino Acids

The perturbation of the racemic equilibrium of luminescent D₃ lanthanide(III) complexes by added chiral agents, such as amino acids, may be a useful technique for determining the absolute configuration of the added species. It is shown in this work, however, that simple interpretation of the equilibrium shift of racemic tris-terdentate complexes of Tb(III) with 2,6-pyridine-dicarboxylate by amino acids, as measured by the sign of the resultant circularly polarized luminescence (CPL) in terms of specific structural characteristics is not possible. CPL results for a number of derivatized amino acids are also presented, and some insights into the nature of the chiral discriminatory forces that might be exploited in this kind of study are discussed.     

Nonlinear resonant ultrasound spectroscopy (NRUS) applied to damage assessment in bone

Nonlinear resonant ultrasound spectroscopy (NRUS) is a resonance-based technique exploiting the significant nonlinear behavior of damaged materials. In NRUS, the resonant frequency(ies) of an object is studied as a function of the excitation level. As the excitation level increases, the elastic nonlinearity is manifest by a shift in the resonance frequency. This study shows the feasibility of this technique for application to damage assessment in bone. Two samples of bovine cortical bone were subjected to progressive damage induced by application of mechanical cycling. Before cycling commenced, and at each step in the cycling process, NRUS was applied for damage assessment. For independent assessment of damage, high-energy x-ray computed tomography imaging was performed but was only useful in identifying the prominent cracks. As the integral quantity of damage increased, NRUS revealed a corresponding increase in the nonlinear response. The measured change in nonlinear response is much more sensitive than the change in linear modulus. The results suggest that NRUS could be a potential tool for micro-damage assessment in bone. Further work must be carried out for a better understanding of the physical nature of damaged bone and for the ultimate goal of the challenging in vivo implementation of the technique.     

Coherent control of a V-type three-level system in a single quantum dot

In a semiconductor quantum dot, the IIx and IIy transitions to the polarization eigenstates, |x> and |y>, naturally form a three-level V-type system. Using low-temperature polarized photoluminescence spectroscopy, we have investigated the exciton dynamics arising under strong laser excitation. We also explicitly solved the density matrix equations for comparison with the experimental data. The polarization of the exciting field controls the coupling between the otherwise orthogonal states. In particular, when the system is initialized into \Y>, a polarization-tailored pulse can swap the population into |x>, and vice versa, effectively operating on the exciton spin.     

Single and double metallic layer-containing ruthenium dendrimers. Synthesis and catalytic properties

The reaction of a series of phosphanyl-terminated carbosilane dendrimers displaying only one phosphorus ligand per arm with [RuCl(2)(p-cymene)](2) resulted in the grafting of RuCl(p-cymene) moieties on the periphery of the dendrimer. In these species, the chloride ligand is easily displaced by the organic bases pyridine, 4-cyanopyridine and 4,4[prime or minute]-bipyridine to afford new cationic metallodendrimers. NMR studies have confirmed the chirality of the ruthenium centre. The species containing 4,4[prime or minute]-bipyridine reacts through the uncoordinated pyridyl nitrogen with a new equivalent of [RuCl(2)(p-cymene)](2) or [RhCl(CO)(2)](2) to lead to homo- or hetero-bimetallic layer-containing dendrimeric systems. The ruthenodendrimers were tested as catalysts in the transfer hydrogenation of cyclohexanone by propan-2-ol and their activity compared with that of some analogous mononuclear ruthenium(ii) complexes.     

UV laser ablation of GdCa4O(BO3)3 (GdCOB) investigated by Fourier transform ion cyclotron resonance mass spectrometry

The ions generated by laser ablation (LA) of calcium and gadolinium oxoborate GdCa4O(BO3)3 (GdCOB) were investigated by Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS), a powerful tool for the characterization of ionic species produced by laser interaction with solid material. In order to better understand the matter transfer and the mechanism of thin film growth by pulsed-laser deposition (PLD), cationic and anionic clusters generated by UV laser ablation of GdCOB bulk material were studied. Laser ablation of GdCOB leads to the formation of various cluster ions which result from association of CaO, BO and B2O3 building blocks (BB) with different charge carriers (CC): H+, BO+, GdO+ in positive ion mode, and BO2-, OK-, OH-, Cl-, WO3- in negative ion mode. LA-FTICRMS investigations allow us to assign a valence state to each metallic atom included in each BB. A +II chemical state may be associated with calcium and +II and +III ones to boron. UV laser ablation of GdCOB therefore induces reduction processes of boron species in the gas phase. The oxygen reactive atmosphere used during PLD experiments allows the growth of stoichiometric thin films by fixation of oxygen on the ablated species.     

Measurement of RLT and ATL in the 4He(e, e’p)3H reaction at pmiss of 130-300 MeV/ c

We have measured the ⁴He(e, ep)³H reaction at missing momenta of 130-300 MeV/c using the three-spectrometer facility at the Mainz microtron MAMI. Data were taken in perpendicular kinematics to allow us to determine the response function R_LT and the asymmetry term A_TL. The data are compared to both relativistic and non-relativistic calculations.     

Spermine participates in oxidative damage of guanosine and 8-oxoguanosine leading to deoxyribosylurea formation

Oxidation of single- or double-stranded DNA containing a 7,8-dihydro-8-oxoguanosine lesion with the one-electron oxidant Na2IrCl6 in the presence of spermine led to formation of a covalent adduct that was analyzed by gel electrophoresis, HPLC, ESI-MS, and UV-vis. The adduct was labile to heat, exhibiting a t1/2 of 12 h at 37 degrees C, and the ultimate hydrolysis product was characterized as a deoxyribosylurea lesion. Data from model studies with 1,3-diaminopropane vs 1,4-diaminobutane are consistent with initial formation of a C5 spermine adduct from a dehydro-8-oxoguanosine intermediate, followed by rearrangement to a spiroaminal subject to slow hydrolysis at C4 of the purine. Spermine adducts could also be formed from oxidation of the analogous G-containing oligomer from reaction with singlet oxygen, albeit in lower yield. These results are surprising in light of the traditional view that spermine is radioprotective against DNA oxidation.     

Measurement of the subcycle timing of attosecond XUV bursts in high-harmonic generation

The absolute timing of the high-harmonic attosecond pulse train with respect to the generating IR pump cycle has been measured for the first time. The attosecond pulses occur 190+/-20 as after each pump field maxima (twice per optical cycle), in agreement with the "short" quantum path of the quasiclassical model of harmonic generation.     

Evidence for a new class of defects in highly n-doped Si: donor-pair-vacancy-interstitial complexes

Electron channeling experiments performed on individually scanned, single columns of atoms show that in highly n-type Si grown at low temperatures the primary electrically deactivating defect cannot belong to either the widely accepted class of donor-vacancy clusters or a recently proposed class of donor pairs. First-principles calculations suggest a new class of defects consisting of two dopant donor atoms near a displaced Si atom, which forms a vacancy-interstitial pair. These complexes are consistent with the present experimental results, the measured open volume of the defects, the observed electrical activity as a function of dopant concentration, and the enhanced diffusion of impurities in the presence of deactivated dopants.     

Characterization of spiroiminodihydantoin as a product of one-electron oxidation of 8-Oxo-7,8-dihydroguanosine

[reaction: see text] Further oxidation of the common DNA lesion 8-oxo-7,8-dihydroguanosine by one-electron oxidants such as IrCl6(2-), Fe(CN)6(3-), or SO4-* leads to two major products, depending upon reaction conditions. In nucleosides at pH 7, 22 degrees C, the principal product is shown herein to be a spiroiminodihydantoin nucleoside, as a diastereomeric mixture, that can be characterized by NMR, ESI-MS/MS, and independent synthesis.