Multimeric cyclic RGD peptides as potential tools for tumor targeting: solid-phase peptide synthesis and chemoselective oxime ligation

The alpha v beta 3 integrin receptor plays an important role in human metastasis and tumor-induced angiogenesis. Targeting this receptor may provide information about the receptor status of the tumor and enable specific therapeutic planning. Solid-phase peptide synthesis of multimeric cyclo(-RGDfE-)-peptides is described, which offer the possibility of enhanced integrin targeting due to polyvalency effects. These peptides contain an aminooxy group for versatile chemoselective oxime ligation. Conjugation with para-trimethylstannylbenzaldehyde results in a precursor for radioiododestannylation, which would allow them to be used as potential tools for targeting and imaging alpha v beta 3-expressing tumor cells. The conjugates were obtained in good yield without the need of a protection strategy and under mild conditions.     

Additions D'α-chloronitriles sur les olefines par catalyse redox

α-Chloronitriles are shown to add to α-olefins and conjugated dienes, with ferrous chloride or preferably cuprous chloride in the presence of 2,2′-bipyridyl or 1,10-phenanthroline as catalysts     

Electrokinetic DNA transport in 20 nm-high nanoslits: evidence for movement through a wall-adsorbed

The electrokinetic transport behavior of λ-DNA (48 kbp) in 20 nm-high fused-silica nanoslits in the presence of short-chain PVP is investigated. Mobility and video data show a number of phenomena that are typical of DNA transport through gels or polymer solutions, thus indicative of rigid migration obstacles in the DNA pathway. Calculations show that a several nanometer thin layer of wall-adsorbed PVP ('nano-gel') can provide such a rigid obstacle matrix to the DNA. Such ultrathin wall-adsorbed polymer layers represent a new type of matrix for electrokinetic DNA separation.     

Rapid synthesis of 1,3,5-substituted 1,2,4-triazoles from carboxylic acids, amidines, and hydrazines

A general method for the synthesis of 1,3,5-trisubstituted 1,2,4-triazoles has been developed from reaction of carboxylic acids, primary amidines, and monosubstituted hydrazines. This highly regioselective and one-pot process provides rapid access to highly diverse triazoles.     

Addition du chloracetate de methyle sur les olefines

α-Chloroesters add to olefins or dienes under redox catalysis by cuprous chloride in the presence of Bipy or Phen, leading to γ-chloroesters or unsaturated esters.     

A heterogeneous modeling method for porous media flows

This paper presents a new heterogeneous multiscale modeling method for porous media flows. Physics at the global level is governed by one set of PDEs, while features in the solution that are beyond the resolution capacity of the global model are accounted for by the next refined set of governing equations. In this method, the global or coarse model is given by the Darcy equation, while the local or refined model is given by the Darcy–Stokes equation. Concurrent domain decomposition where global and local models are applied to adjacent subdomains, as well as overlapping domain decomposition where global and local models coexist on overlapping domains, is considered. An interface operator is developed for the case where global and local models commute along the common interface. For the overlapping decomposition, a residual‐based coupling technique is developed that consistently facilitates bottom‐up embedding of scale effects from the local Darcy–Stokes model into the global Darcy model. Numerical results are presented for nonoverlapping and overlapping domain decompositions for various benchmark problems. Computed results show that the hierarchically coupled models accurately account for the heterogeneity of the medium and efficiently incorporate local features into the global response. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthèse partielle de la (20S)-ψ-vincamine et de la (20S)-épi-16ψ-vincamine

Partial Synthesis of (20S)-ψ-Vincamine and (20S)-epi-16ψVincamine An attempt of classification of the indole alkaloids is presented; (20S)-ψ-vincamine. (20S)-16-épi-ψ-vincamine and (20S)-ψ-apo-vincamine have been prepared from catharanthine by partial synthesis.     

Thermal rearrangements of some indole alkaloid derivatives

Under both static and flow thermolysis conditions, several compounds with an “aspidosperma” framework rearranged to “vinca” derivatives. Thus (-)1,2-dehydroaspidospermidine ($\text{4}$) rearranged to (-) gave vincane $\text{14}$. Compound $\text{6}$ rearranged to vincamine ($\text{13a}$) and 16-epi vincamine ($\text{13b}$) under either condition ; increasing the temperature resulted in formation of apovincamine ($\text{19}$) (pyrolysis) or vincamone thermolysis).     

Conception and Evaluation of a Library of Cleavable Mass Tags for Digital Polymers Sequencing

A library of phosphoramidite monomers containing a main-chain cleavable alkoxyamine and a side-chain substituent of variable molar mass (i.e. mass tag) was prepared in this work. These monomers can be used in automated solid-phase phosphoramidite chemistry and therefore incorporated periodically as spacers inside digitally-encoded poly(phosphodiester) chains. Consequently, the formed polymers contain tagged cleavable sites that guide their fragmentation in mass spectrometry sequencing and enhance their digital readability. The spacers were all prepared via a seven steps synthetic procedure. They were afterwards tested for the synthesis and sequencing of model digital polymers. Uniform digitally-encoded polymers were obtained as major species in all cases, even though some minor defects were sometimes detected. Furthermore, the polymers were decoded in pseudo-MS³ conditions, thus confirming the reliability and versatility of the spacers library.