Gear effect—10 : Conformational aspects of the positive or negative buttressing effects of methyl groups: polymethylpyridines

The effect of the shape of a methyl group on reactivity, which cannot be accounted for by considering a methyl group as a spherical substituent with the appropriate van der Waals radius, was considered in kinetics of alkylalion of substituted pyridines and barriers to rotation and ground state conformations of an isopropyl group attached to a planar framework. The perturbation of a methyl group by an o-methyl group is accounted for by a unique conformational explanation which involves the polyhedral shape of the methyl group.     

Plutonium(IV) mononitrate and dinitrate complex formation in acid solutions as a function of ionic strength

Titrations of Pu(IV) with HNO₃ in a series of aqueous HClO₄ solutions ranging in ionic strength from 2 to 19 molal were followed using visible and near-infrared absorption spectrophotometry. The Pu 5f-5f spectra in the visible and near IR range change with complex formation. At each ionic strength, a series of spectra were obtained by varying nitrate concentration. Each series was deconvoluted into spectra of Pu⁴⁺ (aq), Pu(NO₃)³⁻ and Pu(NO₃)₂ ²⁺ complexes, and simultaneously their formation constants were determined. When corrected for the incomplete dissociation of nitric acid, the ionic strength dependence of each formation constant can be described by two parameters, β⁰ and Δε using the formulae of specific ion interaction theory.     

The association energy of aggregates of divalent impurities and vacancies in NaCl-type crystals (point charge approximation)

The formation and association energies for the different aggregates of divalent metal impurities and cation vacancies are derived by considerations of the sums over all lattice vectors. This gives a simple formula in the point charge approximation if an infinite lattice is assumed. Because of the neglection of the polarization of the ions this method yields a higher value for these energies, as a comparison with the literature for the case of dipoles shows. But nevertheless it is a first possibility for a correct estimation of these energies also for higher aggregates.     

Raman Spectroscopic Studies of Methane Gas Hydrates

Abstract

A brief review of the Raman spectroscopic studies of methane gas hydrates is given, supported by some new measurements done in our laboratory.     

Trifluoromethylsulfenylation of Masked Carbonyl Compounds

Incorporation of fluorine and fluorine containing groups such as trifluoromethyl and trifluoromethylthio moieties considerably enhances the biopharmacological properties of the parent precursors. Trifluoromethylsulfenylation of masked carbonyl functions, such as the enamines using N-(trifluoromethylthio)phthalimide is described in this communication.     

The Effect of α-, β- and γ-Cyclodextrin on Wheat Dough and Bread Properties

Cyclodextrins (CDs) are cyclic oligosaccharides that have found widespread application in numerous fields. CDs have revealed a number of various health benefits, making them potentially useful food supplements and nutraceuticals. In this study, the impact of α-, β-, and γ-CD at different concentrations (up to 8% of the flour weight) on the wheat dough and bread properties were investigated. The impact on dough properties was assessed by alveograph analysis, and it was found that especially β-CD affected the viscoelastic properties. This behavior correlates well with a direct interaction of the CDs with the proteins of the gluten network. The impact on bread volume and bread staling was also assessed. The bread volume was in general not significantly affected by the addition of up to 4% CD, except for 4% α-CD, which slightly increased the bread volume. Larger concentrations of CDs lead to decreasing bread volumes. Bread staling was investigated by texture analysis and low field nuclear magnetic resonance spectroscopy (LF-NMR) measurements, and no effect of the addition of CDs on the staling was observed. Up to 4% CD can, therefore, be added to wheat bread with only minor effects on the dough and bread properties.     

Molecular mechanics calculations of conjugated amides and an ab initio investigation of acrylamide and its β-amino derivative: Conformational analysis and rotational barriers

Conformations and rotational barriers in a series of conjugated primary and tertiary amides have been analyzed by a modified MM2(91) force field, which treats the amide nitrogen as part of the conjugated system by redefining the atom type for the nitrogen. Ab initio molecular orbital calculations at the MP2/6-31G* level have been performed on the stable conformers and transition structures of acrylamide and β-trans-aminoacrylamide. The results have been used, with published experimental and computational data, to generate parameters for the MM2 force field. The force field has been applied to various conjugated amides, such as reduced nicotinamide adenine dinucleotide (NADH) and NAD⁺ analogues, nicotinamide, urea, vinylogous urea derivatives, and nucleic acid bases. The fundamental difference between primary and tertiary conjugated amides with respect to both conformation and barrier is highlighted. © 1996 by John Wiley & Sons, Inc.     

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.     

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.