Synthesis of polysiloxane xerogels with fluorine-containing groups in the surface layer and their sorption properties

Hydrolysis and polycondensation reactions of tetraethoxysilane (TEOS) with 3,3,3-trifluoropropyl-trimethoxysilane (TFMS) or 1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFES) were used to synthesize xerogels functionalized with fluorine-containing groups. According to transmission electron microscopy, the skeletons of synthesized polysiloxane xerogels have globular structures and consist of agglomerates of particles with fluorinated groups on their surfaces. FTIR spectroscopy showed that primary xerogel particles possess spatial polysiloxane networks, with fluorinated groups along with silanol groups and water in the surface layer. According to thermal analyses, the water content was 3–8 wt.%, and it decreased with increasing length of the fluorinated chain. Thermal destruction of the surface layer starts above 300 °C. The sorbents that were obtained were predominantly mesoporous materials with well-developed porous structures (S_BET = 400–960 m² g⁻¹, V_s = 0.66–0.93 cm³ g⁻¹). The influence of the TEOS/functional silane ratio and the natures of the functional groups on the structural and adsorptive properties were shown. The samples synthesized are organophilic. The affinity for n-hexane increases with increasing length of the fluorine-containing chain (PFES) and the content of fluorinated groups in the surface layer. The hybrid organic–inorganic materials that were obtained can be used for adsorption of hydrocarbons, including oil, from water.     

Photochemistry of dithiocarbamate Cu(II) complex in CCl4

Laser pulse photolysis was used to study the nature and reactions of intermediates in the photochemistry of the flat dithiocarbamate complex Cu(Et(2)dtc)(2) in CCl(4). A nanosecond laser pulse (355 nm) is shown to induce intermediate absorption bands of bivalent copper complex whose coordination sphere contains a dithiocarbamate radical Et(2)dtc(?) and a chloride ion at the axial position ([(Et(2)dtc)Cu(Et(2)dtc(?))Cl(a)]). At room temperature during some microseconds after the laser pulse, this intermediate interacts with the initial complex to form presumably a dimer [Cu(2)(Et(2)dtc)(3)(Et(2)dtc(?))Cl]. The latter vanishes in the second-order reaction. Analysis of kinetic and spectral features gives the arguments for the formation of a cluster [Cu(2)(Et(2)dtc)(3)Cl-tds-Cu(2)(Et(2)dtc)(3)Cl], which produces a new absorption band at 345 nm. The cluster decomposes in ～5 ms into final products, a binuclear complex [Cu(2)(Et(2)dtc)(3)Cl] and tetraethylthiuramdisulfide (Et(4)tds).     

Hypergraph list coloring and Euclidean Ramsey theory

A hypergraph is simple if it has no two edges sharing more than a single vertex. It is s‐list colorable (or s‐choosable) if for any assignment of a list of s colors to each of its vertices, there is a vertex coloring assigning to each vertex a color from its list, so that no edge is monochromatic. We prove that for every positive integer r, there is a function d_r(s) such that no r‐uniform simple hypergraph with average degree at least d_r(s) is s‐list‐colorable. This extends a similar result for graphs, due to the first author, but does not give as good estimates of d_r(s) as are known for d₂(s), since our proof only shows that for each fixed r ≥ 2, d_r(s) ≤ 2 We use the result to prove that for any finite set of points X in the plane, and for any finite integer s, one can assign a list of s distinct colors to each point of the plane so that any coloring of the plane that colors each point by a color from its list contains a monochromatic isometric copy of X. © 2011 Wiley Periodicals, Inc. Random Struct. Alg., 2011     

Immunocytochemical Localization of XRCC1 and γH2AX Foci Induced by Tightly Focused Femtosecond Laser Radiation in Cultured Human Cells

To assess the prospects for using intense femtosecond laser radiation in biomedicine, it is necessary to understand the mechanisms of its action on biological macromolecules, especially on the informational macromolecule—DNA. The aim of this work was to study the immunocytochemical localization of DNA repair protein foci (XRCC1 and γH2AX) induced by tightly focused femtosecond laser radiation in human cancer A549 cells. The results showed that no XRCC1 or γH2AX foci tracks were observed 30 min after cell irradiation with femtosecond pulses of 10¹¹ W∙cm⁻² peak power density. An increase in the pulse power density to 2 × 10¹¹ W∙cm⁻² led to the formation of linear tracks consisting both of XRCC1 and γH2AX protein foci localized in the places where the laser beam passed through the cell nuclei. A further increase in the pulse power density to 4 × 10¹¹ W∙cm⁻² led to the appearance of nuclei with total immunocytochemical staining for XRCC1 and γH2AX on the path of the laser beam. Thus, femtosecond laser radiation can be considered as a tool for local ionization of biological material, and this ionization will lead to similar effects obtained using ionizing radiation.     

Determination of nanostructure of liposomes containing two model drugs by X‐ray scattering from a synchrotron source

Small‐angle X‐ray scattering has been employed to study how the introduction of paracetamol and acetylsalicylic acid into a liposome bilayer system affects the system's nanostructure. An X‐ray scattering model, developed for multilamellar liposome systems [Pabst et al. (2000), Phys. Rev. E, 62 , 4000–4009], has been used to fit the experimental data and to extract information on how structural parameters, such as the number and thickness of the bilayers of the liposomes, thickness of the water layer in between the bilayers, size and volume of the head and tail groups, are affected by the drugs and their concentration. Even though the experimental data reveal a complicated picture of the drug–bilayer interaction, they clearly show a correlation between nanostructure, drug and concentration in some aspects. The localization of the drugs in the bilayers is discussed.     

Shallow Donors and Deep-Level Color Centers in Bulk AlN Crystals: EPR, ENDOR, ODMR and Optical Studies

The results of studies of shallow donors and deep-level color centers in bulk AlN crystals are presented. Two shallow donors (presumably oxygen located on the nitrogen site and carbon located on the aluminum site) are suggested to exhibit the DX-relaxation. Third shallow donor (presumably silicon on the Al site) shows the shallow donor behavior up to the room temperature and can be observed without light excitation at temperatures above 200 K. The values of the Bohr radius of the shallow donors are estimated. The structure of deep-level color centers (neutral nitrogen vacancy V _N) in bulk AlN crystals is determined and analyzed by electron paramagnetic resonance, electron-nuclear double resonance, optical absorption and thermoluminescence induced by X-ray irradiation. Spin-dependent recombination processes in AlN crystals are studied by means of optically detected magnetic resonance.     

Coding of Gibbs function flows from nucleotide pools

The biochemical machinery of living systems obeys kinetic laws, but is driven by Gibbs function flows. Both the kinetic and thermodynamic aspects of Gibbs gain, transmission, and utilization are considered. An information-theoretic approach is used to find conditions under which the kinetics encodes the associated Gibbs function flow with the lowest possible error.     

Stability in the Erdős–Gallai Theorem on cycles and paths,II

The Erd?s–Gallai Theorem states that for $k\ge 3$, any $n$-vertex graph with no cycle of length at least $k$ has at most $\frac{1}{2}(k?1)(n?1)$ edges. A stronger version of the Erd?s–Gallai Theorem was given by Kopylov: If $G$ is a 2-connected $n$-vertex graph with no cycle of length at least $k$, then $e\left(G\right)\le max\{h(n,k,2),h(n,k,?\frac{k?1}{2}?)\}$, where $h(n,k,a)?\left(\genfrac{}{}{0ex}{}{k?a}{2}\right)+a(n?k+a)$. Furthermore, Kopylov presented the two possible extremal graphs, one with $h(n,k,2)$ edges and one with $h(n,k,?\frac{k?1}{2}?)$ edges.In this paper, we complete a stability theorem which strengthens Kopylov’s result. In particular, we show that for $k\ge 3$ odd and all $n\ge k$, every $n$-vertex 2-connected graph $G$ with no cycle of length at least $k$ is a subgraph of one of the two extremal graphs or $e\left(G\right)\le max\{h(n,k,3),h(n,k,\frac{k?3}{2})\}$. The upper bound for $e\left(G\right)$ here is tight.