Xanthate based radical cascade toward multicomponent formation of pyrrolopyrimidines

A short sequential synthesis of pyrrolidino- pyridines and pyrimidines illustrates the potential of combining Ugi-Smiles couplings with radical tin-free processes.     

f‐Element Half‐Sandwich Complexes: A Tetrasilylcyclobutadienyl–Uranium(IV)–Tris(tetrahydroborate) Anion Pianostool Complex

Despite there being numerous examples of f‐element compounds supported by cyclopentadienyl, arene, cycloheptatrienyl, and cyclooctatetraenyl ligands (C_5–8), cyclobutadienyl (C₄) complexes remain exceedingly rare. Here, we report that reaction of [Li₂{C₄(SiMe₃)₄}(THF)₂] ( 1 ) with [U(BH₄)₃(THF)₂] ( 2 ) gives the pianostool complex [U{C₄(SiMe₃)₄}(BH₄)₃][Li(THF)₄] ( 3 ), where use of a borohydride and preformed C₄‐unit circumvents difficulties in product isolation and closing a C₄‐ring at uranium. Complex 3 is an unprecedented example of an f‐element half‐sandwich cyclobutadienyl complex, and it is only the second example of an actinide‐cyclobutadienyl complex, the other being an inverse‐sandwich. The U?C distances are short (av. 2.513 Å), reflecting the formal 2? charge of the C₄‐unit, and the SiMe₃ groups are displaced from the C₄‐plane, which we propose maximises U?C₄ orbital overlap. DFT calculations identify two quasi‐degenerate U?C₄ π‐bonds utilising the ψ₂ and ψ₃ molecular orbitals of the C₄‐unit, but the potential δ‐bond using the ψ₄ orbital is vacant.     

Use of Doubly Charged Precursors to Validate Dissociation Mechanisms of Singly Charged Poly(Dimethylsiloxane) Oligomers

Collision-induced dissociation of doubly charged poly(dimethylsiloxane) (PDMS) molecules was investigated to provide experimental evidence for fragmentation reactions proposed to occur upon activation of singly charged oligomers. This study focuses on two PDMS species holding trimethylsilyl or methoxy end-groups and cationized with ammonium. In both cases, introduction of the additional charge did not induce significant differences in dissociation behavior, and the use of doubly charged precursors enabled the occurrence of charge-separation reactions, allowing molecules always eliminated as neutrals upon activation of singly charged oligomers to be detected as cationized species. In the case of trimethylsilyl-terminated oligomers, random location of the adducted charge combined with rapid consecutive reactions proposed to occur from singly charged precursors could be validated based on MS/MS data of doubly charged oligomers. In the case of methoxy-terminated PDMS, favored interaction of the adducted ammonium with both end-groups, proposed to rationalize the dissociation behavior of singly charged molecules, was also supported by MS/MS data obtained for molecules adducted with two ammonium cations.

Formation and structural,energetic and dynamic properties of cyclodextrin host tubes and included guest molecules

Experimental data about 3D arrangements and building modes of cyclodextrin (CD) tubes are scarce, though investigations of such assemblies are particularly interesting for a vast array of applications related to organic tubes in general. Opting for a theoretical approach, we studied the organisation of CD tubes by three schemes: a structural examination of geometries from the Cambridge Structural Database, simulated annealing studies based on classical force fields to evaluate the stability of tubular arrangements, and an incremental construction procedure of the tubes by molecular dynamics. For β-CDs, the investigations pointed to a head-to-head configuration, while γ-CDs favoured a head-to-head+tail-to-head triplet. The position and interactions of water molecules inside the obtained tubular arrangements were studied as well. Various complexes for diphenylpolyenes and styrene included in the β- and γ-CDs tubes were considered and compared based on structural, energetic and dynamic criteria.     

Theoretical and experimental study of the nonlinear resonance vibration of cementitious materials with an application to damage characterization

This paper presents a theoretical and experimental study of the nonlinear flexural vibration of a cement-based material with distributed microcracks caused by an important deterioration mechanism, alkali-silica reaction (ASR). The general equation of motion is derived for the flexural vibration of a slender beam with the nonlinear hysteretic constitutive relationship for consolidated materials, and then an approximate formula for excitation-dependent resonance frequency is obtained. A downward shift of the resonance frequency is related to the nonlinearity parameters defined in the constitutive relationship. Vibration experiments are conducted on standard mortar bar samples undergoing progressive ASR damage. The absolute nonlinearity parameters are determined from these experimental results using the theoretical solution in order to investigate their dependence on the damage state of the material. With the progress of the ASR damage, the absolute value of the hysteresis nonlinearity parameter increases by as much as six times from the intact (undamaged) state in the sample with highly reactive aggregate; this is in contrast to a change of about 16% in the linear resonance frequency. It is demonstrated that the combined theoretical and experimental approach developed in this research can be used to quantitatively characterize ASR damage in mortar samples and other cement-based materials.     

From Si nanowire to SiC nanotube

Si nanowires (NWs), with diameters of about 800 nm and lengths of about 10 ??m, previously synthesized by the VLS method with gold catalyst, were carburized at 1,100 °C under methane for conversion into SiC nanostructures. These experiments have shown that Si NWs have been transformed into SiC nanotubes (NTs) with approximately the same sizes. Nanotubes?? sidewall thickness varies from 20 to 150 nm depending on the NTs?? height. These SiC nanotubes are hexagonal in shape and polycrystalline. A model of growth based on the out-diffusion of Si through the SiC layer was proposed to explain the transformation from Si nanowires to SiC nanotubes. This model was completed with thermodynamic calculations on the Si?CH₂?CCH₄?CO₂ system and with results from complementary experiment using propane precursor. Routes for obtaining crystalline SiC NTs using this reaction are proposed.     

Leptocarposide: a new triterpenoid glycoside from Ludwigia leptocarpa (Onagraceae)

A new triterpenoid bidesmoside (leptocarposide) possessing an acyl group in their glycosidic moiety (1), together with the known luteolin‐8‐C‐glucoside (2) and 1‐O‐β‐d ‐glucopyranosyl‐(2S,3R,8E)‐2‐[(2′R)‐2‐hydroxypalmitoylamino]‐8‐octadecen‐1,3‐diol (3) was isolated from the n‐butanol‐soluble fraction of whole plant of Ludwigia leptocarpa (Nutt) Hara (Onagraceae). Structure of compound 1 has been assigned on the basis of spectroscopic data (¹H and ¹³C NMR, ¹H‐¹H COSY, HSQC, HMBC, and ROESY), mass spectrometry, and by comparison with the literature. This compound was further screened for its potential antioxidant properties by using the radical scavenging assay model 2,2‐diphenyl‐1‐picrylhydrazyl and reveals non‐potent antioxidant activities, while compound 2 shows SC₅₀ of 0,038 mM. Copyright © 2013 John Wiley & Sons, Ltd.     

Determination of block size in poly(ethylene oxide)‐b‐polystyrene block copolymers by matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry

Characterization of block size in poly(ethylene oxide)‐b‐poly(styrene) (PEO‐b‐PS) block copolymers could be achieved by matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF‐MS) after scission of the macromolecules into their constituent blocks. The performed hydrolytic cleavage was demonstrated to specifically occur on the targeted ester function in the junction group, yielding two homopolymers consisting of the constitutive initial blocks. This approach allows the use of well‐established MALDI protocols for a complete copolymer characterization while circumventing difficulties inherent to amphiphilic macromolecule ionization. Although the labile end‐group in PS homopolymer was modified by the MALDI process, PS block size could be determined from MS data since polymer chains were shown to remain intact during ionization. This methodology has been validated for a PEO‐b‐PS sample series, with two PEO of number average molecular weight (M_n) of 2000 and 5000 g mol^?1 and M_n(PS) ranging from 4000 to 21,000 g mol^?1. Weight average molecular weight (M_w), and thus polydispersity index, could also be reached for each segment and were consistent with values obtained by size exclusion chromatography. This approach is particularly valuable in the case of amphiphilic copolymers for which M_n values as determined by liquid state nuclear magnetic resonance might be affected by micelle formation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3380–3390, 2009