Chemical versus Electrochemical Synthesis of Carbon Nano‐onion/Polypyrrole Composites for Supercapacitor Electrodes

The development of high‐surface‐area carbon electrodes with a defined pore size distribution and the incorporation of pseudo‐active materials to optimize the overall capacitance and conductivity without destroying the stability are at present important research areas. Composite electrodes of carbon nano‐onions (CNOs) and polypyrrole (Ppy) were fabricated to improve the specific capacitance of a supercapacitor. The carbon nanostructures were uniformly coated with Ppy by chemical polymerization or by electrochemical potentiostatic deposition to form homogenous composites or bilayers. The materials were characterized by transmission‐ and scanning electron microscopy, differential thermogravimetric analyses, FTIR spectroscopy, piezoelectric microgravimetry, and cyclic voltammetry. The composites show higher mechanical and electrochemical stabilities, with high specific capacitances of up to about 800 F g^?1 for the CNOs/SDS/Ppy composites (chemical synthesis) and about 1300 F g^?1 for the CNOs/Ppy bilayer (electrochemical deposition).     

Derivatisation in gas chromatographic determination of acidic herbicides in aqueous environmental samples

This paper reviews derivatisation processes applied in chromatographic determination of acidic herbicides (with carboxyl and phenol groups), mainly in aqueous environmental samples. The discussion focuses on the basic derivatisation reactions used to convert herbicides to derivatives to make them analysable by gas chromatography, and possibly to reduce detection limits and/or increase extraction recovery from aqueous samples. The reactions are transesterification, esterification, silylation, alkylation, and extractive and pyrolytic alkylation. The reagents used to conduct the reactions are numerous. Diazomethane is a very efficient methylation reagent but explosive and toxic. Methyl iodide also ensures rapid and efficient methylation. Benzyl bromide can be used directly in water but derivatisation yield is low and reproducibility is poor. Butyl chloroformate and dimethyl sulfite can also be used for derivatisation in water, and acetic anhydride can be used for in-situ derivatisation of phenolic herbicides. For increasing selectivity of GC detection pentafluorobenzyl bromide (for ECD) and (2-cyanethyl)dimethyl(diethylamino)silane (for NPD) have been applied. Very characteristic ions are produced in mass spectra if silyl groups are introduced, e.g. by using bis(trimethylsilyl)trifluoroacetamide. Tetramethylammonium, trimethylphenylammonium, tetraalkylammonium, and trimethylsulfonium hydroxides and salts can by used for derivatisation at elevated temperature in the GC injection port. Extractive alkylation is relatively efficient if tetraalkylammonium salts with long chain alkyl groups are used.     

Synthesis and Biological Activity of Ferrocenyl and Ruthenocenyl Analogues of Etoposide: Discovery of a Novel Dual Inhibitor of Topoisomerase II Activity and Tubulin Polymerization

Two series of the ferrocenyl and ruthenocenyl analogues of etoposide bearing 1,2,3-triazolyl or aminoalkyl linker were synthesized and evaluated for their cytotoxic properties, influence on the cell cycle, ability to induce tubulin polymerization, and inhibition of topoisomerase II activity. We found that the replacement of the etoposide carbohydrate moiety with a metallocenyl group led to organometallic conjugates exhibiting differentiated antiproliferative activity. Biological studies demonstrated that two ferrocenylalkylamino conjugates were notably more active than etoposide, with submicromolar or low-micromolar IC₅₀ values towards SW620, etoposide-resistant SW620E, and methotrexate-resistant SW620M cancer cell lines. Moreover, the simplest ferrocenylmethylamino conjugate exerted dual inhibitory action against tubulin polymerization and topoisomerase II activity while other studied compounds affected only topoisomerase II activity.     

Positive Effect of Cannabis sativa L. Herb Extracts on Skin Cells and Assessment of Cannabinoid-Based Hydrogels Properties

The skin is an organ that is constantly exposed to many external factors that can affect its structure and function. Due to the presence of different cannabinoid receptors on many types of skin cells, cannabinoids can interact directly with them. Therefore, as part of this work, the impact of two types of Cannabis sativa L. herb extracts on keratinocytes and fibroblasts was assessed. The content of biologically active compounds such as phenols, flavonoids, chlorophylls and cannabinoids was evaluated. The antioxidant capacity of prepared extracts using the DPPH radical, H₂DCFDA probe and measurement of superoxide dismutase activity was also assessed. The cytotoxicity of hemp extracts was determined using the Alamar Blue, Neutral Red and LDH assays. The ability of the extracts to inhibit the activity of matrix metalloproteinases, collagenase and elastase, was assessed. Preparations of model hydrogels were also prepared and their effect on transepidermal water loss and skin hydration was measured. The obtained results indicate that hemp extracts can be a valuable source of biologically active substances that reduce oxidative stress, inhibit skin aging processes and positively affect the viability of skin cells. The analysis also showed that hydrogels based on cannabis extracts have a positive effect on skin hydration.     

Isomerization of a peptidic fragment studied theoretically in vacuum and in explicit water solvent at finite temperature

The cis-trans isomerization of N-methylacetamide, a molecular model of the polypeptide chain, is examined via umbrella sampling Car-Parrinello MD and classical MD, in both gas and solution phases at 300 K. A new analysis of the C(O)-N bond interconversion and a full examination of the solvent shell structure are presented.     

Synthesis and characterization of hyperbranched polyesters from glycerol‐based AB2 monomer

This article describes the synthesis of a new glycerol‐based AB₂ type monomer—ethyl{3‐[2‐hydroxy‐1‐(hydroxymethyl)ethoxy]propyl}thioacetate ( 4 ) and its application for the preparation of hyperbranched polyesters. The polycondensation of 4 has been performed over a wide range of catalysts and reaction conditions leading to polymers containing solely primary hydroxyl groups. The polycondensation progress has been monitored by means of ¹H NMR. The degree of branching of the polymers showed to be in the range of 0.5 ± 0.03. The obtained polyesters easily undergo hydrolysis or alcoholysis and may be of interest as recycled materials. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3860–3868, 2009     

Structure and hydrogen bonding in neat N-methylacetamide: classical molecular dynamics and Raman spectroscopy studies of a liquid of peptidic fragments

The results of classical molecular dynamics (MD) simulations and Raman spectroscopy studies of neat liquid N-methylacetamide (NMA), the simplest model system relevant to the peptides, are reported as a function of temperature and pressure. The MD simulations predict that near ambient conditions, the molecules form a hydrogen bond network consisting primarily of linear chains. Both the links between molecules within the hydrogen-bonded chains and the associations between chains are stabilized by weak methyl-donated "improper" hydrogen bonds. The three-dimensional structural motifs observed in the liquid show some similarity to protein beta-sheets. The temperature and pressure dependence of the hydrogen bond network, as probed by the mode frequency of the experimentally determined amide-I Raman band, blue shifts on heating and red shifts under compression, respectively, suggesting weakened and enhanced hydrogen bonding in response to temperature and pressure increases. Disruption of the hydrogen-bonding network is clearly observed in the simulation data as temperature is increased, whereas the improper hydrogen bonding is enhanced under compression to reduce the energetic cost of increasing the packing fraction. Because of the neglect of polarizability in the molecular model, the computed dielectric constant is underestimated compared to the experimental value, indicating that the simulation may underestimate dipolar coupling in the liquid.     

Complexation copper(II) or magnesium ions with d-glucuronic acid – potentiometric,spectral and theoretical studies

Results of potentiometric and spectral studies have shown that in d-glucuronic acid (GluA) with Cu²⁺ or Mg²⁺ systems, the complexes ML and ML(OH)_x are formed. Overall stability constants (log β) and equilibrium constants (log K_e) were calculated for all complex forms. The mode of coordination for each form was concluded on the basis of spectral values, Vis, EPR, and chemical shifts in the ¹³C NMR. According to spectral analysis, Cu(GluA) exists in two possible forms, which confirm the occurrence of the coordination dichotomy in the system. The main center of interactions in the hydroxyl complexes Cu(GluA)(OH)_x and MgGluA are oxygens from the carboxyl group. Differences in the coordination mode in the copper(II) and magnesium systems at low pH were observed.