Modeling of the Simultaneous Hydrogen Evolution and Cobalt Electrodeposition

A mathematical model of simultaneous cobalt deposition and hydrogen evolution was developed and applied to the electroreduction process of 5 mM Co²⁺ ions investigated by cyclic voltammetry (CV) technique at different hydrogen ion concentrations (pH=2, 3, 4). The kinetic parameters of such a complex process were determined, and the validity of the model and its sensitivity to changes in individual parameters were verified. The relative value of the approximate standard deviation (ASD_%) was used to determine the degree of fit of the model to the experimental data. The catalytic effect of cobalt on the hydrogen evolution process was comprehensively confirmed.     

Gelfand-Kirillov dimension of algebras with locally nilpotent derivations

Let R be a finitely generated algebra over a field of characteristic 0 with a locally nilpotent derivation δ ≠ 0. We show that if {ie313-1}, where the invariants {ie313-2} are prime and satisfy a polynomial identity, then {ie313-3}. Furthermore, when R is a domain, the same conclusion holds without the assumption that R is finitely generated. This enables us to obtain a result on skew polynomial rings. These results extend work of Bell and Smoktunowicz on domains with GK dimension in the interval [2, 3).     

Can 2‐acylpyrroles form an intramolecular hydrogen bond?

The formation of intramolecular hydrogen bonding by certain N‐substituted 2‐acylpyrroles has been demonstrated by B3LYP/aug‐cc‐pVDZ calculations, the quantum theory of atoms in molecules, and the natural bond orbital method. Total electron energy densities H_BCP at the bond critical point of the H?O bond were applied to analyze the strength of these interactions. The relations between quantum theory of atoms in molecules, carbonyl stretching vibrational modes ν_{C = O}, and natural bond orbital parameters associated with the formation of the C–H?O interaction have been established. The short contacts were found experimentally in the crystal structure of a new 2‐acylpyrrole derivative 5‐chloro‐2‐oxopentyl‐1‐(5‐chloro‐2‐oxopentyl)pyrrolo‐2‐carboxylate. The influence of 2‐ and N‐substitution of 2‐acylpyrroles on C‐H?O interaction energy is discussed. It was found that the methylene group may act as a proton donor leading to a red‐shift or blue‐shift phenomenon of the ν_C–H stretching mode. Copyright © 2015 John Wiley & Sons, Ltd.     

Modelling the surface free energy parameters of polyurethane coats—part 2. Waterborne coats obtained from cationomer polyurethanes

Polyurethane cationomer coats were synthesised on the basis of typical diisocyanates, properly selected polyether polyols, HO-tertiary amines and HCOOH as quaternisation reagents. The values of their surface free energy (SFE) parameters were obtained by the van Oss-Good method, with the use of the contact angle values which had been found by the goniometric method. Based on the obtained findings, empirical models were developed which made it possible to anticipate the effects of the raw material types on the SFE values of the produced coats. The possibility was noted to adjust the SFE values within 25–50 mJ/m² by selecting carefully suitable parent substances. The principal consequences for the formation of improved hydrophobicity coats, applicable inter alia specialised protective coatings, were found to come not only from diisocyanate and polyol types but also from the alkylammonium cation structure which results from the use of different tertiary amines. The fundamental SFE lowering effect was noted when tertiary amines with 0–15 % of the 2,2,3,3-tetrafluoro-1,4-butanediol as a fluorinated chain extender was incorporated into polymer chains.     

Stereochemistry of the reaction of ribonucleoside cyclic 3′,5′-phosphorothioates with oxiranes

The stereochemical course of the epoxide-induced oxidative rearrangement of ribonucleoside cyclic 3′,5′-phosphorothioates into the corresponding 2′,3′-phosphates has been determined using styrene [¹⁸O] oxide and (S_p)-uridine cyclic 3′,5′-phosphorothioate. The evidence of full stereoselectivity of this reaction is presented and mechanistic implications of the presence of the nucleoside 2′-hydroxyl group are discussed in terms of a classical Hamer Mechanism.     

Substituent effect in anionic polymerization of β-lactones initiated by alkali metal alkoxides

The influence of methyl substituent on the mechanism of the ring-opening polymerization of β-lactones initiated by alkali metal alkoxides is discussed. Attention has been paid to the effect of the substituent position in the monomer molecule on the ring-opening mechanism, the 3,3-dimethyl-2-oxetanone (pivalolactone), 4-methyl-2-oxetanone (β-butyrolactone) and 2-oxetanone (β-propiolactone) being chosen as model monomers. Moreover, it was found unexpectedly that in the case of pivalolactone polymerization, besides open-chain polymers, cyclic oligomers are produced.     

Barrier Dispersion-Based Coatings Containing Natural and Paraffin Waxes

Petroleum, synthetic, and natural waxes have been used as hydrophobic bases for dispersions intended for use as barrier coatings for packaging paper. Oil-in-water dispersions with alkaline pH were prepared by a two-step homogenization procedure containing paraffin wax, with various characteristics, the Fischer–Tropsch synthesis product or beeswax. The size of the dispersed particles determined by dynamic light scattering depended on the type of hydrophobic base used and was in the range of 350–440 nm. The ability of dispersion particles in aggregation driven by electrostatic attraction, evaluated by Zeta potential analysis by electrophoretic light scattering, was from −26 to −50 mV. Static multiply light scattering was used for 30 days of stability assessment and helped to select the dispersion with a Sarawax SX70 wax base as the most stable. Dispersions were further used for coating the backing of kraft paper by the Meyer rod method. Coated paper with an applied coating of 6 g/m² had very good hydrophobic properties (Cobb60 < 4 g/m²), sufficient strength properties, and air permeation, which enabled its application as a packaging material. The dispersions based on Sarawax SX70 wax were evaluated as the best coating for Mondi ProVantage Kraftliner 125 g/m² backing paper. Good hydrophobic properties and strength properties indicate the possibility of using the SX70-based wax dispersion coating as a replacement for PFAS coatings in some applications.     

The Effect of the Modification of Carbon Spheres with ZnCl2 on the Adsorption Properties towards CO2

Zinc chloride and potassium oxalate are often applied as activating agents for carbon materials. In this work, we present the preparation of ZnO/carbon spheres composites using resorcinol-formaldehyde resin as a carbon source in a solvothermal reactor heated with microwaves. Zinc chloride as a zinc oxide source and potassium oxalate as an activating agent were applied. The effect of their addition and preparation conditions on the adsorption properties towards carbon dioxide at 0 °C and 25 °C were investigated. Additionally, for all tested sorbents, the CO₂ sorption tests at 40 °C, carried out utilizing a thermobalance, confirmed the trend of sorption capacity measured at 0 and 25 °C. Furthermore, the sample activated using potassium oxalate and modified using zinc chloride (a carbon-to-zinc ratio equal to 10:1) displayed not only a high CO₂ adsorption capacity (2.69 mmol CO₂/g at 40 °C) but also exhibited a stable performance during the consecutive multicycle adsorption–desorption process.     

Differential Entropy and Dynamics of Uncertainty

We analyze the functioning of Gibbs-type entropy functionals in the time domain, with emphasis on Shannon and Kullback-Leibler entropies of time-dependent continuous probability distributions. The Shannon entropy validity is extended to probability distributions inferred from L ²(R ⁿ ) quantum wave packets. In contrast to the von Neumann entropy which simply vanishes on pure states, the differential entropy quantifies the degree of probability (de)localization and its time development. The associated dynamics of the Fisher information functional quantifies nontrivial power transfer processes in the mean, both in dissipative and quantum mechanical cases. PACS NUMBERS: 05.45.+b, 02.50.-r, 03.65.Ta, 03.67.-a     

Simplified spectral phase interferometry for direct electric-field reconstruction by using a thick nonlinear crystal

We propose and demonstrate a novel implementation of spectral-shearing interferometry (SSI) for reconstructing the electric field of ultrashort pulses by utilizing asymmetric group velocity matching in a long nonlinear crystal. The proposed configuration eliminates the requirement for a linearly chirped auxiliary pulse that is in common in all existing SSI methods, relying on nonlinear conversion to produce a spectral shear.