Cellular rubber: Dependency between relaxation time and pretreatment

In this contribution we investigate experimentally a porous carbon-filled rubber. The main focus is on the dependency of the mechanical behaviour using different pretreatments. Therfore, cyclic tests and relaxation tests with different pretreatment are performed. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Simultaneous measurement of proline and related compounds in oak leaves by high-performance ligand-exchange chromatography and electrospray ionization mass spectrometry for environmental stress studies

A mass spectrometer was coupled to high-performance ligand-exchange liquid chromatography (HPLEC) for simultaneous analysis of stress associated solutes such as proline, hydroxyproline, methylproline, glycine betaine and trigonelline extracted from leaves of drought stressed oaks and an internal standard namely N-acetylproline. Methanol/chloroform/water extracts were analyzed using an Aminex HPX-87C column and specifically quantified by the positive ion mode of an electrospray ionisation-mass spectrometry (ESI-MS) in single ion monitoring (SIM) mode. The recovery of N-acetyl proline added to oak leaf extracts ranged from 85.2 to 122.1% for an intra-day study. Standard calibration curves showed good linearity in the measured range from 0.3125 to 10 μmol L⁻¹ with the lowest correlation coefficient of 0.99961 for trigonelline. The advantages of this alternative procedure, compared to previously published methods using fluorescence or amperometric detections, are the simultaneous and direct detection of osmoprotectants in a single chromatographic run, a minimal sample preparation, a good specificity and reduced limits of quantification, ranging from 0.1 to 0.6 μmol L⁻¹. Fifty-six days of water deficit exposure resulted in increased foliar free proline levels (2.4-fold, P < 0.001, 155 μmol g⁻¹ FW) and glycine betaine contents (2.5-fold, P < 0.05, 175 μmol g⁻¹ FW) of drought stressed oak compared to control.     

Safety and Quality Aspects of Acrylic Monomers

Summary : Acrylic monomers are important intermediates for the chemical industry. Especially acrylic acid (AA) is the basis for various reactions, such as polymerizations and esterifications and is, therefore, responsible for high product diversity. Spontaneous polymerization is a safety problem during the transportation and storage of acrylic monomers. In the production process, polymerization leads to blockages in the apparatus. For the prevention of these issues, special stabilizer systems are used such as hydroquinone monomethyl ether (MeHQ)/oxygen and phenothiazine (PTZ). The reactions of these stabilizer systems are not well understood at the moment. Therefore a lot of expertise and experience are necessary to guarantee safe handling. In this paper some methods for the investigation of stability related reaction kinetics are presented. A better comprehension of the mechanism of the polymerization inhibition is generated by the kinetic simulation with these data.     

Real Interpolation of Sobolev Spaces Associated to a Weight

We hereby study the interpolation property of Sobolev spaces of order 1 denoted by \(W^{1}_{p,V}\), arising from Schrödinger operators with positive potential. We show that for 1?≤?p ₁?p?p ₂?q ₀ with p?>?s ₀, \(W^{1}_{p,V}\) is a real interpolation space between \(W_{p_1,V}^{1}\) and \(W_{p_2,V}^{1}\) on some classes of manifolds and Lie groups. The constants s ₀, q ₀ depend on our hypotheses.     

Facilitating access to the most easily ionized molecule: an improved synthesis of the key intermediate, W2(hpp)4Cl2, and related compounds

A far superior synthesis is reported for W(2)(hpp)(4)Cl(2), a key intermediate in the synthesis of the most easily ionized closed-shell molecule W(2)(hpp)(4) (hpp = the anion of the bicyclic guanidine compound 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine). At 200 degrees C, the one-pot reaction of the air-stable and commercially available compounds W(CO)(6) and Hhpp in o-dichlorobenzene produces W(2)(hpp)(4)Cl(2) in multigram quantities with isolated yields of over 90%. At lower temperatures, the reaction can lead to other compounds such as W(Hhpp)(2)(CO)(4) or W(2)(mu-CO)(2)(mu-hpp)(2)(eta(2)-hpp)(2), which are isolable in good purity depending upon the specific conditions employed. These compounds provide insight into the reaction pathway to W(2)(hpp)(4)Cl(2) and W(2)(hpp)(4). Two additional derivatives, W(2)(hpp)(4)X(2) where X is PF(6)(-) or the anion tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (TFPB), have also been synthesized and structurally characterized. A comparison of the electrode potentials of W(2)(mu-CO)(2)(mu-hpp)(2)(eta(2)-hpp)(2) and the di-p-anisylformamidinate analogue shows that oxidation of the hpp compound is significantly displaced (1.12 V) and shows that the bicyclic guanidinate ligand is considerably better than the formamidinate anion at stabilizing high oxidation states. A differential pulse voltammogram of W(2)(hpp)(4)(TFPB)(2) in THF shows two reduction processes with an E(1/2) of -0.97 V for the first and -1.81 V (vs Ag/AgCl) for the second. DFT calculations on the W(2)(hpp)(4)(2+) units in W(2)(hpp)(4)X(2) compounds show that the metal-metal bonding orbitals are destabilized by the axial ligands, which accounts for significant variations in the W-W distances. The low-energy gas-phase ionizations of W(2)(hpp)(4) are also reported and discussed.     

Vibronic coupling in organic semiconductors: the case of fused polycyclic benzene-thiophene structures

The nature of vibronic coupling in fused polycyclic benzene-thiophene structures has been studied using an approach that combines high-resolution gas-phase photoelectron spectroscopy measurements with first-principles quantum-mechanical calculations. The results indicate that in general the electron-vibrational coupling is stronger than the hole-vibrational coupling. In acenedithiophenes, the main contributions to the hole-vibrational coupling arise from medium- and high-frequency vibrations. In thienobisbenzothiophenes, however, the interaction of holes with low-frequency vibrations becomes significant and is larger than the corresponding electron-vibrational interaction. This finding is in striking contrast with the characteristic pattern in oligoacenes and acenedithiophenes in which the low-frequency vibrations contribute substantially only to the electron-vibrational coupling. The impact of isomerism has been studied as well.     

The Si-Si effect on ionization of beta-disilanyl sulfides and selenides

The ionization energies of conformationally constrained, newly synthesized beta-disilanyl sulfides and selenides were determined by photoelectron spectroscopy. These ionization energies reflect substantial (0.53-0.75 eV) orbital destabilizations. The basis for these destabilizations was investigated by theoretical calculations, which reveal geometry-dependent interaction between sulfur or selenium lone pair orbitals and sigma-orbitals, especially Si-Si sigma-orbitals. These results presage facile redox chemistry for these compounds and significantly extend the concept of sigma-stabilization of electron-deficient centers.     

Influence of particle-particle interactions and particles rotational motion in traveling wave dielectrophoresis

Traveling wave dielectrophoresis provides an interesting method for the controlled movement of microsized particles in suspended mixtures, and as such is a promising tool in microfluidic technology. In this case, the electrostatic force acting on the particles has two components: one due to the spatially varying magnitude of the electric field and the other due to the spatially varying phase. The actual movement of the particle is determined by the combined effect of these two forces and corresponding torques, the viscous drag exerted by the fluid on the particle, and the electrostatic and hydrodynamic particle-particle interactions. This paper presents the first numerical simulations of the motion of particles subjected to all previous forces and torques. Our technique is based on a finite-element scheme in which the particles are moved using a direct simulation scheme respecting the fundamental equations of motion for both the fluid and the solid particles. The fluid-particle motion is resolved by the method of distributed Lagrange multipliers and the electrostatic forces are computed using the point-dipole approximation. Our simulations show that the particle behavior strongly depends on the mismatch of the dielectric properties between the particles and the fluid, and that the particle-particle interaction force as well as particles rotation speeds play crucial roles in the various regimes.     

Elastomeric materials: Theoretical investigation and experiments

In this contribution we investigate an incompressible carbon–filled rubber experimentally and theoretically. On the experimental side we perform uniaxial tension tests and theoretically we use two different constitutive models, the Arruda–Boyce–Model and the Yeoh–Model, to describe the experimental observed behaviour. The model parameters are identified by a comercial fitting tool Origin Pro from National Instruments. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Mapping Dicorynia guianensis Amsh. wood constituents by submicron resolution cluster‐TOF‐SIMS imaging

The preparation of tropical wood surface sections for time‐of‐flight secondary ion mass spectrometry imaging is described, and the use of delayed extraction of secondary ions and its interest for the analysis of vegetal surface are shown. The method has been applied to the study by time‐of‐flight secondary ion mass spectrometry imaging with a resolution of less than one micron of a tropical wood species, Dicorynia guianensis, which is one of the most exploited wood in French Guiana for its durable heartwood. The heartwood of this species exhibits an economical importance, but its production is not controlled in forestry. Results show an increase of tryptamine from the transition zone and a concomitant decrease of inorganic ions and starch fragment ions. These experiments lead to a better understanding of the heartwood formation and the origin of the natural durability of D. guianensis. Copyright © 2016 John Wiley & Sons, Ltd.