Fleeting Beauty—The World of Plant Fragrances and Their Application

This article is devoted to some aspects of the fragrant substances of plant origin applied in the food industry and perfumery as well. Since antiquity many extractive techniques have been developed to obtain essential oils. Some of them are still applied, but new ones, like microwave or ultrasound-assisted extractions, are more and more popular and they save time and cost. Independently of the procedure, the resulting essential oils are the source of many so-called isolates. These can be applied as food additives, medicines, or can be used as starting materials for organic synthesis. Some substances exist in very small amounts in plant material so the extraction is not economically profitable but, after their chemical structures were established and synthetic procedures were developed, in some cases they are prepared on an industrial scale. The substances described below are only a small fraction of the 2000–3000 fragrant molecules used to make our life more enjoyable, either in food or perfumes. Additionally, a few examples of allelopathic fragrant compounds, present in their natural state, will be denoted and some of their biocidal features will be mentioned as an arising “green” knowledge in agriculture.     

The impact of sterol structure on the interactions with sphingomyelin in mixed langmuir monolayers

In this work, the Langmuir monolayer technique was applied to study the interactions between sphingomyelin and various sterols differing in the structure of the side chain (cholesterol, beta-sitosterol, stigmasterol). The mean area per molecule and the excess free energy of mixing values were analyzed in the context of sterol-induced condensing effect and interactions between molecules in the mixed monolayers. Moreover, the compression modulus values were calculated and widely discussed from the point of view of the ordering effect of sterols. It was found that all of the sterols investigated form the most stable monolayers with sphingomyelin at 2:1 sphingomyelin:sterol proportion and the strongest interactions exist between molecules in cholesterol-containing films. Moreover, cholesterol provokes the strongest area condensation and reveals the highest ordering properties, while plant sterols were found to differ only slightly with regards to their ordering properties. Additionally, the ordering effect of the sterols on dipalmitoylphosphatidylcholine (DPPC) films was analyzed and compared to that on sphingomyelin films.     

Calorimetric characterization of 2′,3′-dideoxyinosine water solution

A study of 2′,3′-dideoxyinosine (ddI) stability and its interaction with human serum albumin (HSA) was carried out by differential scanning microcalorimetry DSC. Scan rate dependent and irreversible endothermic thermal degradation of ddI was analyzed with use of kinetic approach. Observed process could be interpreted in terms of simple first-order one step kinetic model. Moreover it was shown that ddI bound weakly to the human serum albumin and stabilized this protein.     

Introducing hydrophilic carbon nanoparticles into hydrophilic sol-gel film electrodes

A hydrophilic carbon nanoparticle–sol-gel electrode with good electrical conductivity within the sol-gel matrix is prepared. Sulfonated carbon nanoparticles with high hydrophilicity and of 10–20 nm diameter (Emperor 2000) are co-deposited onto tin-doped indium oxide substrates employing a sol-gel technique. The resulting carbon nanoparticle-sol-gel composite electrodes are characterized as a function of composition and salt (KCl) additive. Scanning electron microscopy and voltammetry in the absence and in the presence of a solution redox system suggest that the composite electrode films can be made electrically conducting and highly porous to promote electron transport and transfer. The effect of the presence of hydrophilic carbon nanoparticles is explored for the following processes: (1) double layer charging, (2) diffusion and adsorption of the electrochemically reversible solution redox system 1,1′-ferrocenedimethanol, (3) electron transfer to the electrochemically irreversible redox system hydrogen peroxide, and (4) electron transfer to the redox liquid tert-butylferrocene deposited into the porous composite electrode film. The extended electrochemically active hydrophilic surface area is beneficial in particular for surface sensitive processes (1) and (3), and it provides an extended solid|organic liquid|aqueous solution boundary for reaction (4). The carbon nanoparticle–sol-gel composite electrodes are optimized to provide good electrical conductivity and to remain stable during electrochemical investigation.     

Wettability of a glass surface in the presence of two nonionic surfactant mixtures

Measurements of the advancing contact angle (theta) were carried out for aqueous solution of p-(1,1,3,3-tetramethylbutyl)phenoxypoly(ethylene glycol), Triton X-100 (TX100), and Triton X-165 (TX165) mixtures on glass. The obtained results indicate that the wettability of glass depends on the concentration and composition of the surfactant mixture. The relationship between the contact angle and concentration suggests that the lowest wettability corresponds to the concentration of TX100 and TX165 and their mixture near the critical micelle concentration (CMC). The minimum of the dependence between the contact angle and composition of the mixtures for each concentration at a monomer mole fraction of TX100, alpha, equals 0.2 and 0.4 points to synergism in the wettability of the glass surface. In contrast to the results of Zisman ( Zisman, W. A. In Contact Angle, Wettability and Adhesion; Gould, R. F., Ed.; Advances in Chemistry Series 43; American Chemical Society Washington, DC, 1964; p 1 ) there was no linear dependence between cos theta and the surface tension of aqueous solutions of TX100 and TX165 mixtures for all studied systems, but a linear dependence exists between the adhesional tension and surface tension for glass, practically, in the whole concentration range of surfactants studied, the slopes of which are positive in the range of 0.43-0.67. These positive slopes indicate that the interactions between the water molecules and glass surface might be stronger than those between the surface and surfactant molecules. So, the surface excess of surfactant concentration at the glass-water interface is probably negative, and the possibility for surfactant to adsorb at the glass/water film-water interface is higher than that at the glass-water interface. This conclusion is confirmed by the values of the work of adhesion of "pure" surfactants, aqueous solutions of surfactants, and aqueous solutions of their mixtures to the glass surface and by the negative values of glass-water interfacial tension determined from the Young equation in the range of surfactant concentrations corresponding to their unsaturated monolayer at the water-air interface.     

Synthesis and biochemical evaluation of selective inhibitors of class II fructose bisphosphate aldolases: towards new synthetic antibiotics

We report the synthesis and biochemical evaluation of selective inhibitors of class II (zinc-dependent) fructose bisphosphate aldolases. The most active compound is a simplified analogue of fructose bisphosphate, bearing a well-positioned metal chelating group. It is a powerful and highly selective competitive inhibitor of isolated class II aldolases. We report crystallographic studies of this inhibitor bound in the active site of the Helicobacter pylori enzyme. The compound also shows activity against Mycobacterium tuberculosis isolates.     

Is the Hoveyda–Grubbs Complex a Vinylogous Fischer‐Type Carbene? Aromaticity‐Controlled Activity of Ruthenium Metathesis Catalysts

Three naphthalene-based analogues (4 a-c) of the Hoveyda-Grubbs metathesis catalyst exhibited immense differences in reactivity. Systematic structural and spectroscopic studies revealed that the ruthenafurane ring present in all 2-isopropoxyarylidene chelates possesses some aromatic character, which inhibits catalyst activity. This aromatic stabilization within the chelate ring may be controlled by variation of the polycyclic core topology as was demonstrated for tetraline and phenanthrene derivatives (4 d, e). General conclusions about a new mode of ligand-structure tuning in catalytic systems are presented.     

Ab Initio Study of H-Bond Dynamics in Three-Component Crystals Comprising (DABCOH+)n Polycationic Chains

In this work, the dynamic character of hydrogen-bond (H-bond) networks in two three-component crystals comprising polycationic chains was described. The first studied system was 1,4-diazabicyclo[2.2.2]octan-1-ium (DABCOH⁺) sulfamate monohydrate, known for its large negative linear compressibility. The second analyzed material was the newly obtained polar salt co-crystal: 1,4-diazabicyclo[2.2.2]octan-1-ium sulfamate urea. X-ray diffraction measurements enabled us to study the H-bond systems in both crystals using the graph set analysis. Obtained structures served as the initial models for Born-Oppenheimer molecular dynamics computations. A detailed study of intermolecular interactions and power spectra was conducted. The analysis of time and space correlations between the changes in H-bonds enabled the detection of proton transfer occurring in both systems at 300 K. Further study of those dynamic phenomena was done using the Energy Decomposition Analysis for selected trajectory fragments. Our work should improve the understanding of dielectric and ferroelectric properties of hybrid organic-inorganic materials.     

SEM and TEM analysis of composite of ZrO2-Ti system

3Y-ZrO₂-Ti composites obtained by slip casting method were studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Moreover, the Vickers hardness was measured. The experiments show the complex microstructure of composites. The tetragonal zirconium dioxide (t-ZrO₂) and monoclinic zirconium dioxide (m-ZrO₂) as a composite matrix were detected at XRD analysis. SEM observations revealed that Ti -rich phase are uniform distributed in composites. Moreover, the large and very fine precipitations were found. The very fine Ti rich precipitations were located at ZrO₂ grain boundaries as well as in the triple-points. TEM experiments confirmed that in the sintered composites 3Y-ZrO₂ – 10%Ti the uniaxial ZrO₂ grains (100–600 nm), fine monoclinic martensitic plates and fine round monoclinic particles (20–40 nm) of ZrTiO₂ phase were exist. The complex microstructures of 3Y-ZrO₂-Ti composites have a high hardness as a result of existing fine ZrTiO₂ and other Ti oxides precipitations.