Highly diastereoselective approach to novel phenylindolizidinols via benzothieno analogues of tylophorine based on reductive desulfurization of benzo[b]thiophene

Chiral tetra- and hexahydro[1]benzothieno[2,3-f]indolizines 3–5, 9, and 11 were synthesized easily from benzo[b]thiophene-2-carboxaldehyde (1) and (S)-glutamic acid (2) in good overall yields and both high enantio- and diastereomeric purities. Applying a diastereoselective reductive desulfurization of benzo[b]thiophene followed by lactam reduction, epimeric alcohols 4a and 4b were readily converted into (7R or S,8aS)-phenylindolizidinols 6a,c. During these studies, the reduction of benzothienoindolizines 3–5, 9, 11, and 12, was investigated and the results obtained are also discussed.     

Traceability of absorbed dose in photon radiation therapy: from primary standard to patient treatment

The relevant standard quantity for radiation therapy is the absorbed dose to water. This quantity refers to the amount of energy locally absorbed in a small volume of water divided by the mass of this volume. The aim of this paper is to present a short overview on the establishment of traceability to national standards of absorbed doses delivered to patients in radiation therapy. The approach used at LNE-LNHB, the French national metrology laboratory for ionizing radiation, to determine the reference value of absorbed dose to water is presented and the chain of traceability from the reference value to the treatment of the patient is described.     

EPMA of Porous Media: A Monte Carlo Approach

 We examine the influence of the sample porosity on the X-ray emission from mesoporous alumina bombarded with kilovolt electrons. Experimental results show that there is a loss of X-rays (Al Kα and O Kα) from those samples when compared to a fully dense mono-crystalline alumina (sapphire), which depends on the X-ray line, the measurement time and the embedding medium. Both geometrical and charging effects may be responsibl e for this signal loss. Monte Carlo simulations of the X-ray intensity emitted from porous alumina, using different models to describe sample porosity, show that the geometrical effect of porosity itself cannot account for the X-ray loss. Charge trapping effect and/or its combination with porosity is therefore expected to be the major cause of the signal loss.     

Remark on stabilization of tree-shaped networks of strings

We consider a tree-shaped network of vibrating elastic strings, with feedback acting on the root of the tree. Using the d’Alembert representation formula, we show that the input-output map is bounded, i.e. this system is a well-posed system in the sense of G. Weiss (Trans. Am. Math. Soc. 342 (1994), 827–854). As a consequence we prove that the strings networks are not exponentially stable in the energy space. Moreover, we give explicit polynomial decay estimates valid for regular initial data.     

Electronic properties of multi-quantum dot structures in Cd 1-xZn xS alloy semiconductors

In this paper, we present a theoretical study of the quantized electronic states in Cd_1-xZn_xS quantum dots. The shape of the confining potential, the subband energies and their eigen envelope wave functions are calculated by solving a one-dimensional Schr?dinger equation. Electrons and holes are assumed to be confined in dots having a flattened cylindrical geometry with a finite barrier height at the boundary. Optical absorption measurements are used to fit the bandgap edge of the Cd_1-xZn_xS nanocrystals. An analysis of the electron band parameters has been made as a function of Zn composition. Two main features were revealed: (i) a multiplicity in Cd_1-xZn_xS quantum dots with different crystalline sizes has been found to fit accurately experimental data in the composition range 0 ≤x ≤0.2; (ii) the fit did not, however, show a multiplicity for x higher than 0.4. On the other hand, we have calculated the energy level structure of coupled Cd_1-xZn_xS semiconductor quantum dots using the tight-binding approximation. As is found the Zn composition x = 0.4 is expected to be the most favorable to give rise a superlattice behavior for the Cd_1-xZn_xS quantum dots studied.     

Nambu–Dirac Structures for Lie Algebroids

The theory of Nambu–Poisson structures on manifolds is extended to the context of Lie algebroids in a natural way based on the derived bracket associated with the Lie algebroid differential. A new way of combining Nambu–Poisson structures and triangular Lie bialgebroids is described in this work. Also, we introduce the concept of a higher order Dirac structure on a Lie algebroid. This allows to describe both Nambu–Poisson structures and Dirac structures on manifolds in the same setting.     

Nonlinear problems related to the Thomas-Fermi equation

Journal of Evolution Equations -     

An Unusual Family of Glycosylated Peptides Isolated from <Emphasis Type="BoldItalic">Dendroaspis angusticeps</Emphasis> Venom and Characterized by Combination of Collision Induced and Electron Transfer Dissociation

This study describes the structural characterization of a totally new family of peptides from the venom of the snake green mamba (Dendroaspis angusticeps). Interestingly, these peptides differ in several points from other already known mamba toxins. First of all, they exhibit very small molecular masses, ranging from 1.3 to 2.4 kDa. The molecular mass of classical mamba toxins is in the range of 7 to 25 kDa. Second, the new peptides do not contain disulfide bonds, a post-translational modification commonly encountered in animal toxins. The third difference is the very high proportion of proline residues in the sequence accounting for about one-third of the sequence. Finally, these new peptides reveal a carbohydrate moiety, indicating a glycosylation in the sequence. The last two features have made the structural characterization of the new peptides by mass spectrometry a real analytical challenge. Peptides were characterized by a combined use of MALDI- TOF/TOF and nanoESI-IT-ETD experiments to determine not only the peptide sequence but also the composition and the position of the carbohydrate moiety. Anyway, such small glycosylated and proline-rich toxins are totally different from any other known snake peptide and form, as a consequence, a new family of peptides.     

Long-lived, charge-shift states in heterometallic, porphyrin-based dendrimers formed via click chemistry

A series of multiporphyrin clusters has been synthesized and characterized in which there exists a logical gradient for either energy or electron transfer between the porphyrins. A central free-base porphyrin (FbP), for example, is equipped with peripheral zinc(II) porphyrins (ZnP) which act as ancillary light harvesters and transfer excitation energy to the FbP under visible light illumination. Additional energy-transfer steps occur at the triplet level, and the series is expanded by including magnesium(II) porphyrins and/or tin(IV) porphyrins as chromophores. Light-induced electron transfer is made possible by incorporating a gold(III) porphyrin (AuP(+)) into the array. Although interesting by themselves, these clusters serve as control compounds by which to understand the photophysical processes occurring within a three-stage dendrimer comprising an AuP(+) core, a second layer formed from four FbP units, and an outer layer containing 12 ZnP residues. Here, illumination into a peripheral ZnP leads to highly efficient electronic energy transfer to FbP, followed by charge transfer to the central AuP(+). Charge recombination within the resultant charge-shift state is intercepted by secondary hole transfer to the ZnP, which occurs with a quantum yield of around 20%. The final charge-shift state survives for some microseconds in fluid solution at room temperature.     

NMR evidence of the kinetic and thermodynamic products in the NIS promoted cyclization of 1-phenyl-4-pentenylamines. Synthesis and reactivity of trans-2-phenyl-5-iodopiperidines

The intramolecular reaction of secondary amines with tethered alkenes using NIS was studied, which gave insight into the kinetic vs. thermodynamic control of the iodoaminocyclization and the regioselectivity of the aziridinium ring-opening reactions, and led to functionalized piperidines.