Total synthesis of alternariol

Total synthesis of alternariol, a toxic secondary metabolite of various Alternaria fungi, was achieved in seven steps starting with orcinol and 3,5-dimethoxybromobenzene. The longest linear sequence consists of six steps. Key reaction is a palladium-catalyzed Suzuki-type coupling of an orcinol-derived boronic acid with a brominated resorcylic aldehyde. The final demethylation furnished alternariol in 73% yield containing a smaller fraction of alternariol 9-methyl ether (approximately 20%).     

Sn-containing liquid crystalline side group homopolymers with two glass transitions

Three homologous tin-containing homopolymers with a terminal CN-dipole in the side group have been synthesized and characterized by dynamical calorimetry, polarization microscopy, X-ray and dielectric methods. AFM was used to evaluate the texture at room temperature. Four different phase transitions were detected by DSC. The high temperature phases were identified by polarization microscopy as SmA and SmC. AFM-measurements show focal-conic domains at room temperature and confirm so the smectic nature of all phases. X-ray measurements on nonoriented samples give hints to a phase segregation on nanometer scale. Dielectric investigation and temperature-modulated DSC (TMDSC) confirm clearly phase separation by appearance of two glass transitions related to the liquid order of the main chains and the liquid crystalline of the side groups.     

Organic mass spectrometry in archaeology: evidence for Brassicaceae seed oil in Egyptian ceramic lamps

An analytical procedure based on alkaline hydrolysis and silylation followed by GC/MS analysis was employed to study the formation of characteristic acidic compounds and the development of a distinctive chromatographic pattern in the course of accelerated ageing tests on Brassicaceae seed oil. On the basis of mass spectra of trimethylsilyl derivatives, the main degradation products were identified as alpha,omega-dicarboxylic, omega-hydroxycarboxylic and dihydroxycarboxylic acids, including 11,12-dihydroxyeicosanoic acid and 13,14-dihydroxydocosanoic acid. The mass spectra of both these compounds are characterised by fragment ions arising from the alpha cleavage of the bond between the two vicinal trimethylsiloxy groups, resulting in fragments at m/z 215 and 345 for 11,12-dihydroxyeicosanoic acid, and at m/z 215 and 373 for 13,14-dihydroxydocosanoic acid. Other significant fragment ion-radicals from rearrangement process at m/z [M - 90](+*), [M - 142](+*), 204 as well as fragment ions at m/z [M - 15](+), [M - 105](+), 217 are present in the mass spectra of both the compounds. The results obtained for reference materials were compared with those relating to archaeological organic materials recovered in Egyptian pottery lamps. The occurrence of the same characteristic degradation products found in the reference materials subjected to accelerated ageing indicates an unambiguous origin for the organic archaeological remains and represents the chemical evidence for the use of oil from seeds of Brassicaceae as illuminant.     

Electrodeposition of a nickel-based hydrotalcite on Pt nanoparticles for ethanol and glucose sensing

Two different substrates, GC and graphite electrodes, have been coated with electrodeposited Pt nanoparticles (PtNPs) of different morphologies and sizes (from 2 μm to 20 nm). The electrochemical behavior of the platinised GC electrodes has been mainly evaluated in terms of the increase of the real surface area. A nickel-based hydrotalcite-like compound (HT) has been electrosynthesised on the GC platinised electrodes, by the cathodic reduction of a 0.03 M Ni and Al nitrates solution, and the cyclic voltammetric responses to these electrodes have been measured in a 0.1 M NaOH solution. Finally, the electrocatalytic performances of the GC–PtNPs–HT electrodes to ethanol and glucose have been investigated and compared with the performances of HT electrodeposited onto bare Pt, in the same conditions.     

Determination of the surface characteristics of particulate fillers by inverse gas chromatography at infinite dilution: a critical approach

CaCO3 fillers were investigated by inverse gas chromatography (IGC) to determine the dispersion component of their surface tension as well as their acid-base character. Because of the high energy of the filler surface, it readily adsorbs water, thus the parameters measured by IGC depend on the conditioning temperature, as well as on the measurement conditions. As a consequence, the determined surface characteristics are not material constants; different fillers or the effect of coating can be compared only under standard conditions. The use of the same conditioning and measurement temperature eliminates the effect of measurement time. Under appropriate standard conditions the acid-base characteristics of the filler can be determined reliably. However, the accuracy of the determination and the value of the derived parameters depend very much on the selected approach and on the acid-base constants used for the probe molecules. A critical analysis of the approaches used in the current literature pointed out those that yield the most reasonable and accurate values. The results prove that the surface of CaCO3 is strongly basic in character. Coating significantly reduces basicity. Surprisingly, the filler coated with an amount of stearic acid resulting in minimum surface tension showed relatively strong acidity, which indicates a coating exceeding monolayer coverage and/or the uneven distribution of the surfactant on the surface.     

The photoenol tautomer of 5-methyl-1, 4-naphthoquinone

Irradiation of pale yellow 5-methyl-1, 4-naphthoquinone ( 1 , Scheme 1) yields the blue photoenol 4-hydroxy-5-methylidene-1(5H)-naphthalenone (2) which is stable at 77 K. At room temperature the enol retautomerizes to starting material, the reaction rate being strongly dependent on the hydrogen-bond-acceptor basicity of the solvent. The enol is trapped in the presence of acid by protonation at the remaining carbonyl oxygen atom and subsequent electrophilic reaction of the exocylclic methylene group.     

The physicochemical and biological properties of zinc(II) complexes

Spectroscopic (IR), thermoanalytical (TG/DTG, DTA) and biological methods were applied to investigate physicochemical and biological properties of seven zinc(II) complex compounds of the following formula Zn(HCOO)₂·2H₂O (I), Zn(HCOO)₂·tph (II), Zn(CH₃COO)₂·2H₂O (III), Zn(CH₃COO)₂·tph (IV), Zn(CH₃COO)₂·2phen (V), Zn(CH₃CH₂COO)₂·2H₂O (VI), Zn(CH₃CH₂CH₂COO)₂·2H₂O (VII), where tph=theophylline, phen=phenazone. The formation of various intermediates during thermal decomposition suggests the dependence on the length of aliphatic carboxylic chain and type of N-donor ligand (tph, phen). The final product of the thermal decomposition was ZnO. The antimicrobial activity of these complexes were tested against G⁺ and G^– bacteria. Strong inhibitive effect was observed towards E. coli, salmonellae and Staph. aureus.     

A two-state model for selective solubilization of benzene-limonene mixtures in sodium dihexyl sulfosuccinate microemulsions

When surfactants are used to solubilize oil, the oil to be solubilized is often a mixture of components with differing properties, for example, solubilization of drug molecules in microemulsion formulations, remediation of organic polluted aquifers using surfactants, and so forth. Previous research has demonstrated that selective solubilization of one organic component over the other may occur if the organic components are dissimilar. In this research, we investigated selective solubilization from benzene-limonene mixtures in Winsor type I and III microemulsion systems containing water, sodium di-n-hexyl sulfosuccinate, and NaCl. The effect of the oil phase composition and the electrolyte concentration on the selectivity was studied. It was found that the selectivity toward benzene was highest at low electrolyte and benzene concentrations, decreasing as the electrolyte or benzene concentration increased. The results are discussed on the basis of the two-state solubilization theory and by correlating the curvature of the surfactant film in the microemulsion with changes of the electrolyte concentration and the oil phase composition. A simple mathematical model is developed for the selectivity, which combines the two-state solubilization theory and the net-average curvature model of microemulsion solubilization to yield close agreement with the experimental data.     

Performance and selectivity of polymeric pseudostationary phases for the electrokinetic separation of amino acid derivatives and peptides

Two polymeric pseudostationary phases, one an acrylamide polymer and the second a siloxane polymer, have been investigated for the separation of naphthalene-2,3-dicarboxaldehyde (NDA)-derivatized amino acids and small peptides. The dervatized amino acids were detected by UV absorbance and laser-induced fluorescence (LIF) detection. The polymers provided very high efficiency and good selectivity for the separation of the amino acids. The separation selectivity using the polymers was significantly different from that of SDS micelles, and there were subtle differences in selectivities between the polymers. Although very good detection limits were obtained with LIF detection, a significant background signal was observed when the polymers were not washed to remove fluorescent impurities. The polymers did not separate the peptides very well. It is postulated that the fixed covalent structure of the polymers prevents them from interacting strongly or efficiently with the peptides, which are large in relation to the analytes typically separated by electrokinetic chromatography using polymers.     

Novel strategies for isolation and characterization of cyclotides: the discovery of bioactive macrocyclic plant polypeptides in the Violaceae

This review focuses on the discovery of cyclotides in the Violaceae, their isolation and their anti-cancer effects. These macrocyclic plant peptides consist of about 30 amino acids, including three conserved disulfide bonds in a cystine knotted arrangement, which renders them a remarkable stability. Their unique structure, combined with a wide array of biological activities, makes them of great interest as possible leads in drug development or as carriers of grafted peptide sequences. Here we describe the work conducted in our laboratory, which started with the overall aim of identifying peptides and small proteins of the size 10-50 amino acid residues in plants with novel chemical structures and biological profiles with a potential for drug development or for use as pharmacological tools. Thus we developed a fractionation protocol to directly address major challenges encountered when dealing with plant material, such as removal of chlorophyll, polyphenols, and low molecular compounds omnipresent in plants. Using this protocol, we then discovered a suite of cyclotides, the varv peptides, from the plant Viola arvensis (Violaceae). Following this, separation methods directly targeting cyclotides were developed, e.g. by adsorption, ion exchange chromatography and solvent-solvent partitioning, which then were used in the isolation of additional cyclotides. To structurally examine cyclotides we have also developed methods based on mass spectrometry for cyclotide sequencing and mapping of disulfide bonds. Finally, to assess structure-activity relationships, regarding their anti-cancer and cytotoxic effects that we focus upon, we have also characterized the three dimensional structure of cyclotides by homology modeling techniques.