Quaternary Centers by Nickel‐Catalyzed Cross‐Coupling of Tertiary Carboxylic Acids and (Hetero)Aryl Zinc Reagents

This work bridges a gap in the cross‐coupling of aliphatic redox‐active esters with aryl zinc reagents. Previously limited to primary, secondary, and specialized tertiary centers, a new protocol has been devised to enable the coupling of general tertiary systems using nickel catalysis. The scope of this operationally simple method is broad, and it can be used to simplify the synthesis of medicinally relevant motifs bearing quaternary centers.     

Ionic Liquid Based Polymer Gel Electrolytes for Use with Germanium Thin Film Anodes in Lithium Ion Batteries

Thermally stable, flexible polymer gel electrolytes with high ionic conductivity are prepared by mixing the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (C₄mpyrTFSI), LiTFSI and poly(vinylidene difluoride-co-hexafluoropropylene (PVDF-HFP). FT-IR and Raman spectroscopy show that an amorphous film is obtained for high (60 %) C₄mpyrTFSI contents. Thermogravimetric analysis (TGA) confirms that the polymer gels are stable below ∼300 °C in both nitrogen and air environments. Ionic conductivity of 1.9×10⁻³ S cm⁻² at room temperature is achieved for the 60 % ionic liquid loaded gel. Germanium (Ge) anodes maintain a coulombic efficiency above 95 % after 90 cycles in potential cycling tests with the 60 % C₄mpyrTFSI polymer gel.     

Structure Analysis of Solid Lipid Nanoparticles for Drug Delivery: A Combined USANS/SANS Study

Suspensions of solid lipid nanoparticles (SLNs) stabilized with emulsifiers have been extensively investigated (since the 1990s) as drug carriers, although details of their ultrastructure are poorly defined. Previously, a novel microwave‐assisted microemulsion‐based technique to prepare SLNs was reported. To understand the detailed internal structure of these SLNs, ultra‐small angle neutron scattering (USANS) and small angle neutron scattering (SANS) experiments are conducted on suspensions of hydrogenated stearic acid SLNs stabilized with hydrogenated Tween 20 surfactant in D₂O. Together, SANS and USANS gives a combined Q range of 0.000047 to 0.6 Å^?1 (corresponding to a size range of ≈1 nm–15 µm). This extended Q range allows a comprehensive understanding of the hierarchical structure of SLNs. The data are consistent with the multi‐length scale structure of SLNs having polydispersed large particles with roughened surfaces at the microscale level. At the nanoscale level, the results are consistent with the SLNs having an ellipsoidal shape intermediate between spheres and rods, with a crossover from mass fractals to surface fractals. The elucidation of this structure is particularly important given that the structure influences the stability and drug release properties of the nanoparticles. These results assist in the development of systems with desired shape and properties.     

Enhanced energy storage in polyvinylidenefluoride (PVDF) + BaZrO<Subscript>3</Subscript> electroactive nanocomposites

PVDF + BaZrO₃ electroactive nanocomposite thin film has been prepared by solution casting method. The structural analysis was carried out by using x-ray diffraction pattern and atomic force microscopy (AFM). Generally, the performance of dielectric capacitors toward higher energy density and higher operating temperatures has been drawing increased interest. In this regard, the present study was focussed on the fabrication and characterization of PVDF + BaZrO₃ electroactive nanocomposites in view of enhancing the energy density at elevated temperature. Cole-Cole plot is an agreement with multiple relaxation process in electroactive nanocomposites. Dielectric energy storage performance is assessed for PVDF nanocomposites with different wt% of BaZrO₃ at different frequencies and temperature. It has been observed that with increase of temperature, the permittivity increased while the energy density slightly decreased but significantly higher than pure polymer PVDF. A high energy density of 6.88 J/cm³ was obtained for BaZrO₃ electroactive nanocomposites at 50 °C and 5.06 J/cm³ at 70 °C. Overall, the testing results indicate that using nanocomposites of PVDF and BaZrO₃ as a dielectric component is promising for implementation to preserve high energy density values up to temperatures of 70 °C.The enhancement of dielectric permittivity and the energy density is attributed due to increase of interracial charge density. The effect of BaZrO₃ nanoparticles in energy density of PVDF is first time reported.     

Homogenization of transmission conditions for analysis of acoustic waves in domains with perforated barriers

We consider structures like the muffler of the engine exhaust, where the acoustic waves propagate through periodically perforated barriers. Recently we proposed a homogenized model [6] of the acoustic transmission through the layer with embedded rigid obstacles of arbitrary shapes, which represent the perforation. The homogenized model describes relationship between jump of the acoustic pressures p⁺ and p⁻ at the discontinuity interface Γ₀ and the transverse acoustic velocity g^0±, on introducing in–layer acoustic pressure p⁰ which describes wave propagation along the interface. The coupling between the transversely and the tangential acoustic velocities may become important for certain types of perforations. A sensitivity study was done which reveals remarkable dependence of wave transmission losses on the geometry of the perforation. Examples of 3D perforation geometries were treated. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Void collapse in an elastic solid

Radial deformations of an infinite medium surrounding a traction-free spherical cavity are considered. The body is composed of an isotropic, incompressible elastic material and is subjected to a uniform pressure at infinity. The possibility of void collapse (i.e. the void radius becoming zero at a finite value of the applied stress) is examined. This does not occur in all materials. The class of materials that do exhibit this phenomenon is determined, and for such materials, an explicit expression for the value of the applied pressure at which collapse occurs is derived. The stability of the deformation and the influence of a finite outer radius are also considered. The results are illustrated for a particular class of power-law materials. In certain respects, the present results for void collapse are complementary to Ball (1982)'s results for cavitation in an incompressible elastic material.Some brief observations on void collapse in compressible materials are made. The collapse of a void under non-symmetric conditions is also discussed by utilizing a solution obtained by Varley and Cumberbatch (1977, 1980).The results reported here were obtained in the course of an investigation supported in part by the U.S. Army Research Office.     

1H and 13C NMR assignments for two new xanthones from the endophytic fungus Xylaria sp. FRR 5657

The complete 1H and 13C NMR assignments are reported for the new natural products, 7-hydroxy-3-(hydroxymethyl)-1-methoxy-9H-xanthen-9-one (1) and 2,5-dihydroxy-8-methoxy-6-methyl-9-oxo-9H-xanthene -1-carboxylic acid (2). Both of these secondary metabolites were isolated from the fermentation culture of the endophytic fungus Xylaria sp. FRR 5657. 1D and 2D NMR experiments that included 1H, gCOSY, gHSQC and gHMBC were used for the determination of the structure and assignment of these xanthones.     

The Crystal Structure of a Homodimeric Pseudomonas Glyoxalase I Enzyme Reveals Asymmetric Metallation Commensurate with Half‐of‐Sites Activity

The Zn inactive class of glyoxalase I (Glo1) metalloenzymes are typically homodimeric with two metal‐dependent active sites. While the two active sites share identical amino acid composition, this class of enzyme is optimally active with only one metal per homodimer. We have determined the X‐ray crystal structure of GloA2, a Zn inactive Glo1 enzyme from Pseudomonas aeruginosa. The presented structures exhibit an unprecedented metal‐binding arrangement consistent with half‐of‐sites activity: one active site contains a single activating Ni²⁺ ion, whereas the other contains two inactivating Zn²⁺ ions. Enzymological experiments prompted by the binuclear Zn²⁺ site identified a novel catalytic property of GloA2. The enzyme can function as a Zn²⁺/Co²⁺‐dependent hydrolase, in addition to its previously determined glyoxalase I activity. The presented findings demonstrate that GloA2 can accommodate two distinct metal‐binding arrangements simultaneously, each of which catalyzes a different reaction.     

Recognition of CG inversions in DNA triple helices by methylated 3H-pyrrolo[2,3-d]pyrimidin-2(7H)-one nucleoside analogues

Substituted 3H-pyrrolo[2,3-d]pyrimidin-2(7H)-one nucleoside analogues have been synthesised from 5-alkynyl-uridine derivatives, incorporated into triplex forming oligonucleotides (TFOs) and found to selectively bind CG inversions with enhanced affinity compared to T.