Reactions on polymers with amine groups. III. Description of the addition reaction of pyridine and imidazole compounds with α,β-unsaturated monocarboxylic acids

A detailed study of the synthesis of betaine products that result from addition reactions of poly (4-vinylpyridine) and poly (N-vinylimidazole) as well as of their model compounds, with α,β-unsaturated monocarboxylic acids is presented. A reaction mechanism based on experimental observations and proved by kinetic analysis is proposed. It consists of two reactions: the addition, which involves two molecules of acid and leads to X⁺B⁻-like structures, where the cation X⁺ results from the addition of the amino nitrogen to the double bond of acid and B⁻ is the carboxyl anion, and an equilibrium reaction between X⁺B⁻ and the betaine structure X^±. The latter occurs only in protic solvents and is coupled with the addition reaction. The process was especially investigated in methanol, because this solvent allows determination of the kinetic parameters. Some values of the addition rate constants are given. The study is based on ¹H-NMR measurements and observations. © 1996 John Wiley & Sons, Inc.     

Crystal and molecular structures of diastereomeric 2-phosphoryl-, 2-thiophosphoryl-, and 2-selenophosphoryl-substituted 1,3-dithianes

The crystal and molecular structures of five pairs of diastereomeric cis- and trans-2-phosphoryl-, 2-thiophosphoryl-, and 2-selenophosphoryl-5-t-butyl-1,3-dithianes have been determined. For all the examined compounds, all of the basic geometrical parameters, such as bond lengths, bond and torsion angles, and the deformation of a chair conformation of the six-membered heterocyclic rings, have been established. The differences in corresponding bond lengths and valence angles in diastereomeric cis- and trans-2-P-substituted 1,3-dithianes are discussed.     

Crystal and molecular structure of cyclic sulfoxides: 2-cyano-2-ethoxycarbonyl-3,6-dihydro-4,5-dimethyl-2H-thiapyran 1-oxide and 2-phenyl-2-methoxycarbonyl-3,6-dihydro-2H-thiapyran 1-oxide

Crystal and molecular structures of the title compounds 1b and 1c have been determined by the X-ray method. Crystals of 1b are monoclinic, space group P2₁/c, and crystals of 1c are orthorhombic, space group P2₁2₁2₁. The sulfinyl oxygen atom and the alkoxycarbonyl group in both compounds are trans oriented, and the six-membered rings adopt a sofa conformation. The differences between conformation, bond lengths, and angles in the compounds investigated are discussed. © John Wiley & Sons, Inc.     

Chloro­bis­[4,4‐bis(hydroxy­methyl)‐2‐(2‐pyridyl)‐4,5‐di­hydro­oxazole‐N,N′]copper(II) chloride hemi­hydrate

The title compound, [CuCl(C₁₀H₁₂N₂O₃)₂]Cl·0.5H₂O, is composed of discrete complex cations, Cl^? anions and water mol­ecules. The O atom of the water mol­ecule lies on a twofold rotation axis. The [CuN₄Cl] coordination polyhedron is intermediate between square pyramidal and trigonal bipy­ramidal.     

Some results for a class of generalized polynomials

A class of generalized polynomials is considered consisting of the null spaces of certain differential operators with constant coefficients. This class strictly contains ordinary polynomials and appropriately scaled trigonometric polynomials. An analog of the classical Bernstein operator is introduced and it is shown that generalized Bernstein polynomials of a continuous function converge to this function. A convergence result is also proved for degree elevation of the generalized polynomials. Moreover, the geometric nature of these functions is discussed and a connection with certain rational parametric curves is established. This revised version was published online in June 2006 with corrections to the Cover Date.     

Dry Friction Model of Percussive Drilling

It is postulated that the main mechanism of the enhancement of material removal rate (MRR) in percussive drilling is associated with generating impact forces, which act on the workpiece and help to develop micro-cracking in the cutting zone. The inherent non-linearity of the discontinuous impact process is modelled as a frictional pair, to generate the pattern of the impact forces. A novel formula for calculating the MRR is proposed, which explains the experimentally observed fall in MRR at higher static forces.     

New type of inorganic filler with a core-shell structure

We tried to use a new kind of filler with “core-shell” structure as a crosslinking agent for carboxylated butadiene-acrylonitrile rubber. We thought that the substance would be better dispersed in the polymer matrix than zinc oxide. Silica (ZnO/SiO₂) whose surface was modified with amorphous zinc oxide from zinc nitrate was used. Its properties were investigated using gas chromatography. Finally we obtained unconventional networks containing ionic and complex bonds (as a result of reaction of elastomers' functional groups i.e. carboxyl groups with the appropriate neutralizing agent as metal oxide). Ionic clusters were formed in vulcanizates which influenced the mechanical properties and crosslinking efficiency. We confirmed the presence of these unconventional bonds by IR spectroscopy and DMTA analyses.     

Simulation of the Solid State Vibrational Spectra of Aminodichloroborane and Ammonia Boron Trichloride

This is the second part of a quantum chemical investigation on the reaction between boron trichloride and ammonia. In part I [9] we focused on the energetic course of successive chlorine substitutions which are relevant for the chemical vapor deposition of BN. In this work we analyze in detail the vibrational spectra of reaction products accessible at room temperature. Regarding an experimental IR spectrum of the condensation product of the reaction between BCl₃ and NH₃ [10], there are more signals than expected for monomeric aminodichloroborane. Since this molecule shows the tendency to oligomerize, we have studied whether the presence of aminodichloroborane dimers or trimers or an impurity of the ammonia boron trichloride complex – an intermediate from which aminodichloroborane is formed – can explain the shape of the measured spectrum. To this end we have calculated the vibrational frequencies of monomeric, dimeric, and trimeric BCl₂NH₂, H₃N · BCl₃, and several van der Waals complexes at the level of a Møller‐Plesset second order perturbation theory. For the verification of the methodology, the vibrational frequencies of the dimethylaminodichloroborane molecule have been determined, in good accord with experimental gas phase spectra. Also the solid state spectrum of H₃N · BCl₃ is well reproduced by the computed vibrational spectrum of the monomeric adduct and a hydrogen‐bonded aggregate. Our studies concerning the spectrum of the condensation product of the reaction of boron trichloride with ammonia indicate that the substance investigated by Kwon and McGee had contained, besides monomeric aminodichloroborane, also its trimer and ammonia boron trichloride.     

Cancer Influences the Elemental Composition of the Myocardium More Strongly than Conjugated Linoleic Acids-Chemometric Approach to Cardio-Oncological Studies

The aim of the study was to verify in a cardio-oncological model experiment if conjugated linoleic acids (CLA) fed to rats with mammary tumors affect the content of selected macro- and microelements in their myocardium. The diet of Sprague–Dawley females was supplemented either with CLA isomers or with safflower oil. In hearts of rats suffering from breast cancer, selected elements were analyzed with a quadrupole mass spectrometer with inductively coupled plasma ionization (ICP-MS). In order to better understand the data trends, cluster analysis, principal component analysis and linear discriminant analysis were applied. Mammary tumors influenced macro- and microelements content in the myocardium to a greater extent than applied diet supplementation. Significant influences of diet (p = 0.0192), mammary tumors (p = 0.0200) and interactions of both factors (p = 0.0151) were documented in terms of Fe content. CLA significantly decreased the contents of Cu and Mn (p = 0.0158 and p = 0.0265, respectively). The level of Ni was significantly higher (p = 0.0073), which was more pronounced in groups supplemented with CLA. The obtained results confirmed antioxidant properties of CLA and the relationship with Se deposition. Chemometric techniques distinctly showed that the coexisting pathological process induced differences to the greater extent than diet supplementation in the elemental content in the myocardium, which may impinge on cardiac tissue’s susceptibility to injuries.     

Ab initio prediction of 15N-NMR chemical shift in α-boron nitride based on an analysis of connectivities

Hydrogen-saturated cut-outs of hexagonal boron nitride have been used to model the solid state. Model compounds have been geometry optimized by means of density functional theory, whereas chemical shift calculations have been carried out at the coupled-perturbed Hartree–Fock level of theory employing gauge-including atomic orbital (GIAO) basis sets. The reliability of results has been tested against experimental values for chemical shifts in stable molecules with similar structural elements. With increasing cluster size, viz. a vanishing influence of the saturating hydrogens on the innermost nitrogen atoms, we find a convergence of ¹⁵N chemical shifts. A classification scheme for the chemical environment of a nitrogen atom has been set up according to its bonding graph including the second coordination sphere. For a given connectivity, chemical shifts vary within a few parts per million, thus enabling us to predict a ¹⁵N-NMR chemical shift of −285 ± 5 ppm for solid α-boron nitride. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 716–725, 1998