On the consequences of material frame-indifference in algebraic stress models

The principle of material frame-indifference (MFI) is a fundamental and controversial principle of continuum mechanics that has been invoked recently to derive nonlinear algebraic models for stresses of viscoelastic liquids. The purpose of the present study is to identify regions of a flow field where MFI should be considered. Such regions are identified by computing the angular velocity of the principal directions of the rate-of-deformation tensor in order to obtain an Euclidean objective vorticity tensor. An analysis is carried out for uniform shear and extensional flows, and for a Couette flow. The method is then applied to the planar flow through an abrupt 4:1 contraction and to the two-dimensional stream past a circular cylinder. The main results are: (1) MFI should be taken into account in regions characterized by the transition between two different kinematics and a significant velocity magnitude, and (2) MFI can be safely ignored in regions of pure viscometric behaviour as well as in recirculation regions. The consequences of MFI being taken into account are then examined upon using the Euclidean objective vorticity tensor in a simple algebraic constitutive law for viscoelastic fluids.     

Conformational Analysis of Epiquinine and Epiquinidine

The conformational potential energy surfaces for the epiquinine and epiquinidine molecules were analyzed in gas phase and water solution using semiempirical and ab initio levels of theory. The results obtained showed that the main conformation of the nonactive threo epimers is distinct from those observed for the active parent compounds quinine and quinidine. This result might be used, on a qualitative way, to understand the loss of activity of the threo epimers and allow selecting important conformations to be considered in molecular modeling quantitative studies addressing the drug–receptor interactions.     

Conformational analysis of the antimalarial agent quinine

Quinine, an active antimalarial compound, is one of the most abundant constituents extracted from the bark ofCinchona trees. The activity differences among structurally related molecules appear to depend on the absolute stereochemistry of some functional groups, a result that has stimulated a detailed conformational analysis of these molecules of biological interest. In the present study the potential energy surface (PES) for the antimalarial agent quinine (C₂₀H₂₄O₂N₂) has been comprehensively investigated using the molecular mechanics (MM) and quantum mechanical semiem-pirical AM1 and PM3 methods. Six distinct minimum-energy structures are located on the multidimensional PES and also characterized as true minima through harmonic frequency analysis. The relative stabilities and thermodynamic properties are reported. The coexistence of different conformers is discussed for the first time in the literature based on the calculated transition-state (TS) structures connecting the six minima located on the PES for the quinine molecule. The theoretical results reported in the present study are in agreement with the experimental proposal, based on NMR data, that there are two possible forms for the quinine molecule in solution.     

Absorption spectroscopy of mid and neighboring Z plasmas: Iron, nickel,copper and germanium

Opacities of four medium Z element plasmas (iron, nickel, copper and germanium) have been measured at the LULI-2000 facility in similar conditions: temperatures between 15 and 25 eV and densities between 2 and 10 mg/cm³, in a wavelength range (8–18 Å) including the strong 2p–3d structures.Two laser beams from the LULI facility were used in the nanosecond-picosecond configuration. The NANO-2000 beam (at λ = 0.53 μm) heated a gold hohlraum with an energy between 30 and 150 J with a duration of 0.6 ns. Samples covering half a hohlraum hole were thus radiatively heated. The picosecond pulse PICO-2000 beam (at λ = 1.053 μm) has been used to produce a short (about 10 ps) X-ray backlighter in order to reduce time variations of temperatures and densities during the measurement. A crystal high-resolution spectrometer was used as the main diagnostic to record at the same time the non-absorbed and the absorbed backlighter spectra. Radiation temperatures were measured using a broadband spectrometer. 1D and 2D simulations have been performed in order to estimate hydrodynamic plasmas parameters.The measured spectra have been compared with theoretical ones obtained using either the superconfiguration code SCO or the detailed term accounting code HULLAC. These comparisons allow us to check the modeling of the statistical broadening and of the spin-orbit splitting of the 2p–3d transitions and related effects such as the interaction between relativistic subconfigurations belonging to the same non-relativistic configuration.     

Chemical composition and evaluation of antinociceptive activity of the essential oil of Stevia serrata Cav. from Guatemala

The composition and the antinociceptive activity of the essential oil of Stevia serrata Cav. from a population located in the west highlands of Guatemala were evaluated. A yield of 0.2% (w/w) of essential oil was obtained by hydrodistillation of the dried aerial parts of the plant. The essential oil analysed by GC-FID and GC-MS showed a high content of sesquiterpenoids, with chamazulene (60.1%) as the major component and 91.5% of the essential oil composition was identified. To evaluate antinociceptive activity in mice, the essential oil of S. serrata Cav. was administered as gavage, using three different doses. In the formalin test, the animals were pre-treated with oral doses of the essential oil before the administration of formalin. Oral administration of S. serrata Cav. essential oil produced a marked antinociceptive activity. Therefore, the plant could be domesticated as a source of essential oil rich in chamazulene for developing medicinal products.     

Trifaceted Mickey Mouse Amphiphiles for Programmable Self-Assembly,DNA Complexation and Organ-Selective Gene Delivery

Instilling segregated cationic and lipophilic domains with an angular disposition in a trehalose-based trifaceted macrocyclic scaffold allows engineering patchy molecular nanoparticles leveraging directional interactions that emulate those controlling self-assembling processes in viral capsids. The resulting trilobular amphiphilic derivatives, featuring a Mickey Mouse architecture, can electrostatically interact with plasmid DNA (pDNA) and further engage in hydrophobic contacts to promote condensation into transfectious nanocomplexes. Notably, the topology and internal structure of the cyclooligosaccharide/pDNA co-assemblies can be molded by fine-tuning the valency and characteristics of the cationic and lipophilic patches, which strongly impacts the transfection efficacy in vitro and in vivo. Outstanding organ selectivities can then be programmed with no need of incorporating a biorecognizable motif in the formulation. The results provide a versatile strategy for the construction of fully synthetic and perfectly monodisperse nonviral gene delivery systems uniquely suited for optimization schemes by making cyclooligosaccharide patchiness the focus.     

Understanding Electrogenerated Chemiluminescence Efficiency in Blue‐Shifted Iridium(III)‐Complexes: An Experimental and Theoretical Study

Compared to tris(2‐phenylpyridine)iridium(III) ([Ir(ppy)₃]), iridium(III) complexes containing difluorophenylpyridine (df‐ppy) and/or an ancillary triazolylpyridine ligand [3‐phenyl‐1,2,4‐triazol‐5‐ylpyridinato (ptp) or 1‐benzyl‐1,2,3‐triazol‐4‐ylpyridine (ptb)] exhibit considerable hypsochromic shifts (ca. 25–60 nm), due to the significant stabilising effect of these ligands on the HOMO energy, whilst having relatively little effect on the LUMO. Despite their lower photoluminescence quantum yields compared with [Ir(ppy)₃] and [Ir(df‐ppy)₃], the iridium(III) complexes containing triazolylpyridine ligands gave greater electrogenerated chemiluminescence (ECL) intensities (using tri‐n‐propylamine (TPA) as a co‐reactant), which can in part be ascribed to the more energetically favourable reactions of the oxidised complex (M⁺) with both TPA and its neutral radical oxidation product. The calculated iridium(III) complex LUMO energies were shown to be a good predictor of the corresponding M⁺ LUMO energies, and both HOMO and LUMO levels are related to ECL efficiency. The theoretical and experimental data together show that the best strategy for the design of efficient new blue‐shifted electrochemiluminophores is to aim to stabilise the HOMO, while only moderately stabilising the LUMO, thereby increasing the energy gap but ensuring favourable thermodynamics and kinetics for the ECL reaction. Of the iridium(III) complexes examined, [Ir(df‐ppy)₂(ptb)]⁺ was most attractive as a blue‐emitter for ECL detection, featuring a large hypsochromic shift (λ_max=454 and 484 nm), superior co‐reactant ECL intensity than the archetypal homoleptic green and blue emitters: [Ir(ppy)₃] and [Ir(df‐ppy)₃] (by over 16‐fold and threefold, respectively), and greater solubility in polar solvents.