Isolation of the new minor constituents dihydropyranochromone and furanocoumarin from fruits of Peucedanum alsaticum L. by high-speed counter-current chromatography

A preparative high-speed counter-current chromatography (HSCCC) method was successfully used for isolation of two new minor compounds – alsaticol and alsaticocoumarin A. A two-phase solvent system composed of n-hexane–ethyl acetate–methanol–water (1:1:1:1) was developed. Compounds were obtained from the dichloromethane extract of Peucedanum alsaticum fruits and their identification was performed with NMR and MS methods. Optimized HSCCC offers a rapid method of obtaining new natural compounds.     

Epigenetics: an important challenge for ICP-MS in metallomics studies

Trace metal analysis has been long regarded as one of the principle tasks in areas of chemical analysis. At the early stage of instrumental development, total concentration was assessed in a variety of samples, yielding results, among others, for environmental, biological, and clinical samples. With the power of newer analytical techniques, such as inductively coupled plasma mass spectrometry (ICP-MS), accurate quantitative results can now be obtained at ultra-trace levels not only for metals, but also for metalloids and several non-metals. Even though the importance of trace elements in many biological processes is widely accepted, the elucidation of their biological pathways, understanding specific biological functions, or possible toxicological aspects is still a challenge and a driving force to further develop analytical methodology. Over the past decades, the scientific interest has moved from total element determination to include speciation analysis, which provides quantitative information of one or more individual element species in a sample. More recently, metallomics has been introduced as a more expanded concept, in which the global role of all metal/metalloids in a given system is considered. Owing to the multi-elemental focus of metallomics research, the use of ICP-MS becomes indispensable. Furthermore, considering the biological role of metals/metalloids and the use of elements as internal or external molecular tags, epigenetics should be considered as an important emerging application for metallomics studies and approaches. Among a variety of epigenetic factors, essential nutrients, but also environmental toxins, have been shown to affect DNA methylation, modification of histone proteins, and RNA interference, all of them being implicated in cancer, cardiovascular disease, and several inherited conditions. Recent studies suggest that epigenetics may be a critical pathway by which metals produce health effects. In this Trends article, the basic epigenetic concepts are introduced, followed by the early applications of ICP-MS classified as: (i) detection of ³¹P as a natural element tag for DNA, (ii) analysis of DNA adducts with metal-based drugs, (iii) element species as epigenetic factors.     

Di-ionizable p-tert-butylcalix[4]arene-1,2-crown-5 and -crown-6 compounds in the cone conformation: synthesis and alkaline earth metal cation extraction

Di-ionizable p-tert-butylcalix[4]arene-1,2-crown-5 and -crown-6 ethers in the cone conformation were prepared and their conformations and regioselectivities were verified by NMR spectroscopy. The metal ion-complexing properties of these ligands were evaluated by competitive solvent extractions of alkaline earth metal cations from water into chloroform. The ligands were found to be efficient extractants with selectivity for Ba(2+). The maximal loadings were 95-100% as calculated for formation of 1 : 1 ionized ligand-metal ion complexes. With the variation of proton-ionizable groups, which were oxyacetic acid moieties and N-(X)sulfonyl oxyacetamide units with X = methyl, phenyl, 4-nitrophenyl, and trifluoromethyl, "tunable" acidity was obtained.     

Fluorescence lifetimes study of alpha-tocopherol and biological prenylquinols in organic solvents and model membranes

We have found that for biological prenyllipids, such as plastoquinol-9, alpha-tocopherol quinol, and alpha-tocopherol, the shortest fluorescence lifetimes were found in aprotic solvents (hexane, ethyl acetate) whereas the longest lifetimes were those of ubiquinonol-10 in these solvents. For all the investigated prenyllipids, fluorescence lifetime in alcohols increased along with an increase in solvent viscosity. In a concentrated hexane solution, the lifetimes of prenylquinols considerably decreased. This contrasts with methanol solutions, which is probably due to the self-association of these compounds in aprotic solvents. We have also found a correlation of the Stokes shift of prenyllipids fluorescence with the orientation polarizability of the solvents. Based on data obtained in organic solvents, measurements of the fluorescence lifetimes of prenyllipids in liposomes allowed an estimation of the relative distance of their fluorescent rings from the liposome membrane surface, and was found to be the shortest for alpha-tocopherol quinol in egg yolk phosphatidylcholine liposomes, and increased in the following order: alpha-tocopherol in dipalmitoyl phosphatidylcholine liposomes < alpha-tocopherol < plastoquinol-9 < ubiquinol-10 in egg-yolk phosphatidylcholine liposomes.     

Quantum chemical modeling of reaction mechanism for 2-oxoglutarate dependent enzymes: effect of substitution of iron by nickel and cobalt

Enzymatic hydroxylation reactions carried out by 2-oxoglutarate (2OG) dependent iron-containing oxygenases were recently implicated in oxygen sensing. In addition to oxygen depletion, two metals, cobalt and nickel, are capable of inducing hypoxic stress in cells by inhibiting oxygenase activity. Two possible scenarios have been proposed for the explanation of the hypoxic effects of cobalt and nickel: oxidation of enzyme-bound iron following cobalt or nickel exposure, and substitution of iron by cobalt or nickel. Here, by using density functional theory calculations, we modeled the reaction route from the reaction components to the high-spin metal-oxide intermediate in the activation of oxygen molecule by 2OG-dependent enzymes for three metal ions Fe(II), Ni(II), and Co(II) in the active site. An initial molecular model was constructed based on the crystal structure of iron-containing asparaginyl hydroxylase (FIH-1). Nickel- and cobalt-containing enzymes were modeled by a consequent replacement of the iron in the active center. The energy profiles connecting stationary points on the potential surfaces were computed by using the intrinsic reaction coordinate (IRC) technique from the located transition states. The results of calculations show that the substitution of iron by nickel or cobalt modifies the reaction energy profile; however, qualitatively, the reaction mechanism remains essentially the same. Thus, we would postulate that if the iron ion in the active site were substitutable by nickel and/or cobalt ions enzyme activity would be considerably altered due to high activation barriers.     

Dynamics of induction charging for multiple particle agglomerations with a thin conducting surface layer

In electrostatic applications, particles are typically stacked in an arbitrary array. In this paper, multiple particle agglomerations with a finite volume conductivity, surface conductivity and permittivity have been simulated. Upon exposure to the electric field, electric shielding can occur due to the proximity of other particles, which greatly reduces the maximum accumulated charge and affects the charging time. All results have been obtained using the COMSOL commercial software. The simulation results show that shielding the electric field from a given particle reduces its saturation charge and the rate of charge accumulation was mainly affected by the volume and surface conductivities.     

The uniqueness of endpoints for set-valued dynamical systems of contractions of Meir–Keeler type in uniform spaces

In this paper, the concept of the set-valued dynamical systems of contractions of Meir–Keeler type in uniform spaces is introduced and conditions guaranteeing the existence and uniqueness of endpoints of these contractions and the convergence to these endpoints of all generalized sequences of iterations of these contractions are established. The definition and the result presented here are new for set-valued dynamical systems in uniform, locally convex and metric spaces and even for single-valued maps. Examples show a fundamental difference between our result and the well-known ones.     

Improving Fe3Al alloy resistance against high temperature oxidation by pack cementation process

The paper presents the results of oxidation tests of Fe₃Al-based alloys containing additions of Cr, Zr, B, and C, with and without an aluminide coating. The coating was formed by a pack cementation process in which the surface of material got enriched in aluminum. The Al-rich layer was intended to enhance the tendency of Al₂O₃ formation. The slow-growing Al₂O₃ scale provides the best corrosion protection for structural materials at high temperatures. The cyclic oxidation tests were performed in laboratory air at 1373 K. The structure and composition of oxide scales as well as their adherence were evaluated and compared for the materials with and without aluminide coatings. Surface enrichment in aluminum and effect minor addition of Zr on oxidation behavior was discussed.     

Measurement of Ibuprofen Binding to Mixed Monolayers Containing β-Cyclodextrin Active Sites

A molecular imprinting method involving a three-step sequential self-assembly procedure was applied to prepare gold electrodes responsive towards ibuprofen. The electrode modified with the cyclodextrin derivative binds ferrocene to form an electroactive complex with the ferrocene oxidation current decreasing in the presence of ibuprofen in the solution. The competition of ferrocene and ibuprofen for the cyclodextrin cavities in the monolayer provided a means for the determination of the binding constants of ibuprofen with two derivatives of lipoylamide β-cyclodextrin of different hydrophobicity.