Rack-mounted chemistry IV: the thermal rearrangement of 7-oxabenzonorbornadienes into benzo[b]oxepines on and off the polycyclic rack

The thermal rearrangement of [3]polynorbornane bis-imide rack-mounted 7-oxabenzonorbornadienes has been conducted using flash vacuum pyrolysis (FVP) at 520 °C and is compared with the FVP of similar 7-oxabenzonorbornadienes off the rack. The isomerisation is considered to involve (a) C–O bond cleavage to a vinylogous 1,5-dipole, (b) formation of a benzene epoxide by nucleophilic ring-closure and (c) valence-isomerisation of the benzene epoxide to the oxepine. Competing fragmentation to the isobenzofuran by ejection of acetylene and other rearrangements become prominent pathways off the rack, whereas isomerisation to the oxepine is highly favored on the rack.     

Product Inhibited Enzymatic Reactions on the Rotating Disk Electrodes

A model of cyclic staircase voltammetry of enzymatic reactions on the rotating disk electrode is developed and the inhibition by the product is investigated. The responses are mostly time – dependent current – potential curves with maxima in the forward but not in the backward branch. If the maxima appear in both branches, the inhibition is potential – dependent either directly or indirectly. The source of the second maximum is explained.     

Vibrational Structure of the B—X System of Isotopic Ago Molecules

Spectra of ¹⁰⁷Ag¹⁸O and ¹⁰⁷Ag¹⁶O molecules have been obtained in a low-pressure arc in oxygen atmosphere, and recorded with medium dispersion. Vibrational assignments for the bands of B ²π —X²π system were verified by the study of the oxygen isotope effect, and the vibrational constants were obtained for the states involved in transitions.     

Spectrophotometric Investigation of the Celiprolol-Hydrochloride Ion-Pair

Celiprolol-hydrochloride has been determined using benzylorange and forming ion-pair. The absorbance of yellow coloured ion-pair is measured at 401 nm. Unknown concentrations of celiprolol-hydrochloride is calculated by using the calibration graph of the following calibration equation:

y = 0.1602 × + 0.0214

The conditional stability constant of the ion-pair at the optimum pH 6.2 and ionic strength 0.05 is found to be 5.63. The method is successfully applied to the determination of celiprolol-hydrochloride in pharmaceutical preparations.     

Some classes of finite homomorphism-homogeneous point-line geometries

In 2006, P. J. Cameron and J. Ne?et?ril introduced the following variant of homogeneity: we say that a structure is homomorphism-homogeneous if every homomorphism between finite substructures of the structure extends to an endomorphism of the structure. In this paper we classify finite homomorphism-homogeneous point-line geometries up to a certain point. We classify all disconnected point-line geometries, and all connected point-line geometries that contain a pair of intersecting proper lines (we say that a line is proper if it contains at least three points). In a way, this is the best one can hope for, since a recent result by Rusinov and Schweitzer implies that there is no polynomially computable characterization of finite connected homomorphism-homogeneous point-line geometries that do not contain a pair of intersecting proper lines (unless P=coNP).     

Hydrogenation of poly(myrcene) and poly(farnesene) using diimide reduction at ambient pressure

Ambient pressure chemical hydrogenation using p-toluene sulfonyl hydrazide (TSH) via thermal diimide formation (N₂H₂) permitted reduction of double bonds of poly(myrcene) (poly[Myr]) and poly(farnesene) (poly[Far]). Both pendent and backbone double bonds in poly(Myr) (M_n = 56 kg/mol) and poly(Far) (M_n = 62 kg/mol) synthesized by conventional free radical polymerization were hydrogenated to almost completion. Furthermore, TSH semi-batch addition efficiently hydrogenated double bonds, while avoiding undesired autohydrogenation of diimides that occurred in batch mode. Thermal stability improved for hydrogenated poly(Myr) and poly(Far), where temperature at 10% weight loss (T_10%) increased from 188 to 404°C for poly(Myr) and from 310 to 379°C for poly(Far). T_gs of poly(Myr) and poly(Far) also increased by about 10–25°C, indicating increased stiffness after hydrogenation. Finally, viscosities of poly(Myr) and poly(Far) were also increased after hydrogenation, and a greater increase was observed for poly(Myr) (by two orders of magnitude from 10² to 10⁴ Pa s) due to its M_n being much higher than its entanglement molecular weight. Poly(Far) viscosity only increased by 1.5 times after hydrogenation (~10⁴ Pa s), comparable to the poly(Myr) after hydrogenation, suggesting unsaturated poly(Far) was more entangled than unsaturated poly(Myr) because of its longer side chains.     

Stochastic analysis of the electromagnetic induction effect on a neuron’s action potential dynamics

Nonlinear Dynamics - The presence of time-varying electromagnetic fields across a neuron cell may cause changes in its electrical characteristics, most notably, in the action potential dynamics....     

Dissipative and generative fractional electric elements in modeling $${\varvec{RC}}$$ RC and $${\varvec{RL}}$$ RL circuits

Nonlinear Dynamics - Two types of constitutive equations consisting of instantaneous and power type hereditary contributions are proposed in order to model generalized capacitor (inductor). The...     

Dynamics and stability of evolutionary optimal strategies in duopoly

Central European Journal of Operations Research - In this paper, we analyse the company behaviour in duopoly taking into account the most common strategies, including dominant, reactive,...