X-ray and X-ray photoelectron spectra of vanadium oxides

X-ray (XS) and X-ray photoelectron (XPS) spectra are reported for vanadium oxides. Because of the multivalent character of vanadium in the oxide system high quality measurements can be used for chemical shift investigation. Both inner level and valence band spectroscopy give information on the electronic structure and their systematic change with increasing oxidation state. The experimental results are discussed favourable in terms of molecular orbital theory (MO-theory). The complete set of XS and XPS data reported here for V-oxides allows the identification of unknown vanadium oxidation states too.     

Antimicrobial Polyketide Metabolites from Penicillium bissettii and P. glabrum

Screening of several fungi from the New Zealand International Collection of Microorganisms from Plants identified two strains of Penicillium, P. bissettii and P. glabrum, which exhibited antimicrobial activity against Escherichia coli, Klebsiella pneumoniae, and Staphylococcus aureus. Further investigation into the natural products of the fungi, through extraction and fractionation, led to the isolation of five known polyketide metabolites, penicillic acid (1), citromycetin (2), penialdin A (3), penialdin F (4), and myxotrichin B (5). Semi-synthetic derivatization of 1 led to the discovery of a novel dihydro (1a) derivative that provided evidence for the existence of the much-speculated open-chained form of 1. Upon investigation of the antimicrobial activities of the natural products and derivatives, both penicillic acid (1) and penialdin F (4) were found to inhibit the growth of Methicillin-resistant S. aureus. Penialdin F (4) was also found to have some inhibitory activity against Mycobacterium abscessus and M. marinum along with citromycetin (2).     

Ultimate toughness of amorphous polymers

The deformation and toughness of amorphous glassy polymers is discussed in terms of both the molecular network structure and the microscopic structure at length scales of 50–300 nm. Two model systems were used: polystyrene-poly(2,6-dimethyl-1,4-phenylene ether) blends (PS-PPE; where PS possesses a low entanglement density and PPE a relatively high entanglement density) and epoxides based on diglycidyl ether of bisphenol A (DGEBA) with crosslink densities comparable with up to values much higher than the thermoplastic model system. The microscopic structure was controlled by the addition of different amounts of non-adhering core-shell-rubber particles. Toughness is mainly determined by the maximum macroscopic draw ratio since the yield stress of most polymers approximately is identical (50–80 MPa). It is shown that the theoretical maximum draw ratio, derived from the maximum (entanglement or crosslink) network deformation, is obtained macroscopically when the characteristic length scale of the microstructure of the material is below a certain dimension; i.e. the critical matrix ligament thickness between added non-adhering rubbery particles (‘holes’). The value of the critical matrix ligament thickness (ID_c) uniquely depends on the molecular structure: at an increasing network density, ID_c increases independent of the nature of the network structure (entanglements or crosslinks). A simple model is presented based on an energy criterion to account for the phenomenon of a critical ligament thickness and to describe its strain-rate and temperature dependency.     

A Mechanism of High-Tc Superconductivity Relating to Perovskite Crystal Structure

A mechanism of high-T_c superconductivity related to the perovskite crystal structure is proposed by a “phonon attenuation model”, which means that in the perovskite-like crystal structure, a number of “ordering” vacancies or holes occur due to the non-stoichiometric structure features. Such a reticular “spongly-like” structure facilitates lattice thermovibration attenuation perovskite (phonon attenuation) during temperature reduction. This leads to an abrupt drop of the resistivity, owing to the conduction electrons transmitted through the media without collision with irregularities in the lattice due to the lattice thermovibration. This probably is the main reason for high-T_c superconductivity of the perovskite cuprates.     

Large-scale production of polypropylenimine dendrimers

The synthesis and characterization of a new series of polypropylenimine dendrimers is reported. Using a repetition of the sequence of a Michael addition to a primary amine, followed by a heterogeneously catalyzed hydrogenation, ultra-pure polypropylenimine macromolecules with molecular weights up to 6912 are synthesized. The reaction sequence allows the preparation of these dendrimers at very large scales, whilst the availability of a simple purification in the sequence affords ultra-pure samples. The polypropylenimine dendrimers are fully characterized; apart from the first 0.5 generation they are all oils, possess a Tg in the range from −90 to −40 °C, are unexpectedly stable, and their intrinsic viscosity drops after generation 4.     

NMR measurement of the surface dynamics of poly(dimethylsiloxane) adsorbed on silica gel

CPMAS-DD ¹³C NMR spectroscopy was used to examine the mobility of poly(dimethylsiloxane) adsorbed on silica gel (PDMS/SiO₂) at submonolayer coverages. The spin-lattice relaxation time in the rotating frame (T_1ρH) decreased linearly with increasing loading. This is consistent with a decrease in the mobility of the polymer segments as the loading is increased. The decrease in mobility results from interpolymer interference. We propose a model that explains these results in terms of a surface intrinsic viscosity that incorporates the polymer-polymer interactions on the surface.     

Magnetic Phase Diagram of the MnxFe2−xP1−ySiy System

The phase diagram of the magnetocaloric Mn_xFe_2−xP_1−ySi_y quaternary compounds was established by characterising the structure, thermal and magnetic properties in a wide range of compositions (for a Mn fraction of 0.3 ≤ x < 2.0 and a Si fraction of 0.33 ≤ y ≤ 0.60). The highest ferromagnetic transition temperature (Mn_0.3Fe_1.7P_0.6Si_0.4, T_C = 470 K) is found for low Mn and high Si contents, while the lowest is found for low Fe and Si contents (Mn_1.7Fe_0.3P_0.6Si_0.4, T_C = 65 K) in the Mn_xFe_2−xP_1−ySi_y phase diagram. The largest hysteresis (91 K) was observed for a metal ratio close to Fe:Mn = 1:1 (corresponding to x = 0.9, y = 0.33). Both Mn-rich with high Si and Fe-rich samples with low Si concentration were found to show low hysteresis (≤2 K). These compositions with a low hysteresis form promising candidate materials for thermomagnetic applications.     

“Titration” polymerization of monovinylacetylene

A polymer consisting of a saturated carbon backbone with pendent acetylenic groups was prepared from monovinylacetylene. A titration was performed between the monomer and tertiary butyllithium, its lithiating agent. The charge transfer complex formed between the solvent THF and the tertiary butyllithium was used as an indicator of the unreacted butyllithium. Hence, a stoichiometric quantity of tertiary butyllithium was added dropwise to a solution of monovinylacetylene in THF to form lithiovinylacetylene. The addition of a slight excess of butyllithium led to the polymerization of the lithiated monomer. The obtained polymer was reprotonated and characterized. This polymerization was evaluated as a possible route to synthesize poly(vinylacetylene) with processable molecular weights, for its application as a potential carbon fiber precursor. © 1996 John Wiley & Sons, Inc.     

Nonlinear optical polymers. Second harmonic generation in corona-poled thin films

The synthesis and second harmonic coefficients, d_3,1 and d_3,3 as well as the related susceptibilities χ⁽²⁾_zzz of five series of (NLO-dye methacrylate)-(methyl methacrylate) copolymers were investigated. The NLO-chromophores bound covalently to the polymer backbone were 5-(2,2-dicyanovinyl)-or 4-(2-cyano-2-methoxycarbonyl)vinyl-1-piperidino-2-thiophene (P₁ and P₂), 4-nitro-4′-alkoxy-stilbene (P₃), 4-nitro-3′-methoxy-4′-alkoxystilbene (P₄) and 4-nitro-4′-alkoxy-α-cyano stilbene (P₅). The second order nonlinear optical properties of corona-poled aligned thin polymer films, using a needle electrode in order to induce noncentrosymmetry, were evaluated. Nonlinear susceptibilities, χ⁽²⁾_zzz, of the films were derived from the analysis of full-angle Maker fringe patterns at 1064 nm, χ⁽²⁾_zzz values as high as 1.98×10⁻⁷ esu for P₂ copolymers and of 1.19×10⁻⁷ esu for P₃ copolymers could be achieved.     

Modeling Geometric State for Fluids in Porous Media: Evolution of the Euler Characteristic

Multiphase flow in porous media is strongly influenced by the pore-scale arrangement of fluids. Reservoir-scale constitutive relationships capture these effects in a phenomenological way, relying only on fluid saturation to characterize the macroscopic behavior. Working toward a more rigorous framework, we make use of the fact that the momentary state of such a system is uniquely characterized by the geometry of the pore-scale fluid distribution. We consider how fluids evolve as they undergo topological changes induced by pore-scale displacement events. Changes to the topology of an object are fundamentally discrete events. We describe how discontinuities arise, characterize the possible topological transformations and analyze the associated source terms based on geometric evolution equations. Geometric evolution is shown to be hierarchical in nature, with a topological source term that constrains how a structure can evolve with time. The challenge associated with predicting topological changes is addressed by constructing a universal geometric state function that predicts the possible states based on a non-dimensional relationship with two degrees of freedom. The approach is validated using fluid configurations from both capillary and viscous regimes in ten different porous media with porosity between 0.10 and 0.38. We show that the non-dimensional relationship is independent of both the material type and flow regime. We demonstrate that the state function can be used to predict history-dependent behavior associated with the evolution of the Euler characteristic during two-fluid flow.