Melanin from epidermal human melanocytes: Study by pyrolytic GC/MS

Pigmentation of human skin is determined by the presence of melanin, the polymeric pigment that is produced in melanocytes and transferred to adjacent keratinocytes. Epidermal melanocytes produce two distinct types of melanin pigments: eumelanin, composed mainly of indole-type monomers, and pheomelanin that contains benzothiazine-type backbone. Eumelanin protects skin against UV-induced damages, whereas pheomelanin is believed to act as a potent UV photosensitizer and promote carcinogenesis. In this study, pyrolysis in combination with gas chromatography and mass spectrometry (Py-GC/MS) was applied for structural studies of the epidermal pigment isolated from the cultured human melanocytes. The analysis was preceded by investigations of DOPA-originated synthetic eumelanin and pheomelanin standards. This allowed determination of pyrolytic markers for both types of melanin pigments. To obtain additional information on the natural pigment structure, the samples were thermally degraded in the presence of tetramethylammonium hydroxide as the derivatizing agent. It was shown that the analyzed pigment from normal human epidermal melanocytes derived from moderately pigmented skin is of eumelanin type with little incorporation of a pheomelanin component. The results indicate that Py-GC/MS is a rapid and efficient technique for the differentiation of epidermal melanin types and may be an alternative to commonly used methods based on chemical degradation.     

Ab initio calculations of dispersion coefficients for nucleic acid base pairs

The results of ab initio calculations of two- and three-body dispersion coefficients for the four most important nucleic acid bases are reported. The isotropic as well as anisotropic coefficients were found by using the time-dependent Hartree-Fock approach and the aug-cc-pVDZ basis set. Single and double excitation coupled-cluster theory with noniterative treatment of triple excitations [CCSD(T)] was used to find the values of static polarizabilities which were subsequently used to estimate the values of the CCSD(T) dispersion coefficients. A comparison of these estimated CCSD(T) dispersion coefficients with coefficients found by using empirical approaches based on atomic contributions revealed that the latter are not reliable.     

Addition of γ-silyloxyallyltins on ethyl glyoxylate: evaluation of the influence of the experimental conditions on the stereochemical course of the reaction

Ethyl glyoxylate was reacted with α-substituted γ-(t-butyldimethylsilyloxy)-allyltributyltin in order to obtain selectively each diastereomer of ethyl 3-(t-butyldimethylsilyloxy)-2-hydroxyhex-4-enoate and subsequently the corresponding diols. Diastereomers syn-E, anti-E and anti-Z were obtained in good yields with good to high selectivities and the obtained results were rationalized by consideration of cyclic or open transition states in agreement with the experimental conditions and with the structure of the starting reagents.     

Conductance of alpha-helical peptides trapped within molecular junctions

Self-assembled monolayers of alpha-helical peptides on a gold surface were employed as model systems for the investigation of mediated electron transfer. The peptides contained 14, 15, 16, and 17 amino acid residues. The measurements of electron transmission through single molecules of helical peptides were performed using scanning tunneling spectroscopy (STS). The molecules were trapped between the gold tip and the substrate. Electrical contact between the molecule and the gold probe was achieved by the use of peptides containing thiol groups present at each end of the helix. The conductance behavior of the peptides was examined as a function of tip-substrate distance at fixed bias voltage. Measurements performed with peptides containing different numbers of amino acid residues indicate that the distance dependence of electron transmission through an alpha-helix is weaker than that through simple n-alkyl bridges.     

On -cobordisms of spherical space forms

Given a manifold of dimension at least 4 whose universal covering is homeomorphic to a sphere, the main result states that a compact manifold is isomorphic to a cylinder if and only if is homotopy equivalent to this cylinder and the boundary is isomorphic to two copies of ; this holds in the smooth, PL and topological categories. The result yields a classification of smooth, finite group actions on homotopy spheres (in dimensions ) with exactly two singular points.

     

Existence and uniqueness of a Nash equilibrium feedback for a simple nonzero-sum differential game

Existence and uniqueness of a Nash equilibrium feedback is established for a simple class nonzero-sum differential games on the line.     

Flammability of wood-polypropylene composites

Addition of wood particles to polymers can cause a change of properties of the composites which depends on features of lignocellulosic materials and those of polymers. It is also observed in the flammability characteristics of the composites.In this work, the flammability of polypropylene composites with pine wood particles obtained by extrusion and press moulding was analyzed. The amount of wood particles was 50%. Polymers with various melt flow index (MFI) were used (Malen F-401, PP HY-202 and Malen S-702).The samples were tested using Cone Calorimeter at heat flux of 35 kW/m². Heat release rate (HRR) curves of composites show that thermal decomposition depends on the kind of polypropylene used. In the presence of PP HY-202 and Malen S-702, the flammability characteristic is similar to that of lignocellulosic materials, in contrast to composites with matrices prepared from Malen F-401. The observed phenomenon is interpreted in terms of the wettability of particles of pine wood by polymers of varying melt viscosity.     

Electrical behavior of molecular junctions incorporating alpha-helical peptide

We synthesized an alpha-helical peptide containing two terminal thiol groups and demonstrated the method of preparation of a self-assembled monolayer (SAM) on gold with uniform orientation of the molecules on the surface. The monolayers were employed as model systems for the investigations of mediated electron transfer. The measurements of electron transfer efficiency through the peptide were performed using scanning tunneling spectroscopy (STS). The molecules were trapped between the gold tip and the substrate using a Au-S linkage. The electron transfer behavior of the peptide was examined as a function of the tip-substrate distance at fixed bias voltage and as a function of bias voltage at a fixed distance between the tip and the substrate. The data obtained from these experiments indicated that the electron transfer through alpha-helical peptide is very efficient, and its conductivity is comparable to those observed for dodecanedithiol. There is also a directional dependence of electron transmission through the peptide, which is connected with the electric field generated by the molecular dipole of the helix.     

Formation and stabilization of persistent free radicals

We demonstrate that stable and relatively unreactive “environmentally persistent free radicals (PFRs)” can be readily formed in the post-flame and cool-zone regions of combustion systems and other thermal processes. These resonance-stabilized radicals, including semiquinones, phenoxyls, and cyclopentadienyls, can be formed by the thermal decomposition of molecular precursors including catechols, hydroquinones and phenols. Association with the surfaces of fine particles imparts additional stabilization to these radicals such that they can persist almost indefinitely in the environment. A mechanism of chemisorption and electron transfer from the molecular adsorbate to a redox-active transition metal or other receptor is shown through experiment, and supported by molecular orbital calculations, to result in PFR formation. Both oxygen-centered and carbon-centered PFRs are possible that can significantly affect their environmental and biological reactivity.