Hybrid membranes were prepared by incorporating silica with propyl-imidazoline groups in polybenzimidazoles (phthalide-containing PBI or PBI based on 2,6- or 2,5-pyridinedicarboxylic acids). The influence effects of the silica precursor hydrolysis conditions on the conductivity of the hybrid membranes are studied. Ionic conductivity, water uptake, phosphoric acid doping, and gas permeability of the obtained materials were found to depend on the preparation method and the silica loading. The materials with 10 wt% of functionalized silica present the highest conductivity. A decrease of hydrogen permeability is observed for low silica loadings.

Rigid amphipathic fusion inhibitors are potent broad-spectrum antivirals based on the perylene scaffold, usually decorated with a hydrophylic group linked via ethynyl or triazole. We have sequentially simplified these structures by removing sugar moiety, then converting uridine to aniline, then moving to perylenylthiophenecarboxilic acids and to perylenylcarboxylic acid. All these polyaromatic compounds, as well as antibiotic heliomycin, still showed pronounced activity against tick-borne encephalitis virus (TBEV) with limited toxicity in porcine embryo kidney (PEK) cell line. 5-(Perylen-3-yl)-2-thiophenecarboxylic acid (5a) showed the highest antiviral activity with 50% effective concentration of approx. 1.6 nM.

An attractive strategy for C−Se bond formation by Ullmann-type copper(I)-promoted cross-coupling is developed. A wide range of aryliodides reacts with various disubstituted 2- selenohydantoins under mild conditions and provides Se-arylated imidazolines in moderate to high yields. Computational mechanistic studies show the oxidative addition/intramolecular reductive elimination likely to be the lowest-energy pathway. Cytotoxic activity of all 43 reaction products has been tested in vitro against MCF7 and A549 cancer cell lines with VA13 and MCF10a control cells.

Cation-exchange membranes containing sulfo R–SO3M and sulfonylimide functional groups [R–SO2NSO2–X]M, where X¼CCl3, CF3, Ph, p-NO2Ph, p-CF3Ph and Mþ¼Li/Na/H, have been synthesized by the Hinsberg reaction from the polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene block copolymer. The obtained membranes have been characterized using ATR IR spectroscopy, CHNS elemental analysis, TGA, DSC, SEM and X-ray diffraction analysis, as well as mechanical properties were determined. Ionic conductivity of plasticized polymer electrolytes, containing mixtures of ethylene carbonate, propylene carbonate and ethylene carbonate, dimethylacetamide were investigated by impedance spectroscopy. It was demonstrated that membranes containing trifluorosulfonylimide functional groups have the highest ionic conductivity. The maximum ionic conductivity at 25 �C was observed for the membrane in contact with an ethylene carbonate – dimethylacetamide mixture.

A novel anion-exchange membrane has been manufactured by chloromethylation and subsequent quaternization of polystyrene within a graft copolymer films based on UV-oxidized polymethylpentene. Particular attention is given to the kinetics of chloromethylation and the influence of the reaction conditions on the properties of the anion-exchange membranes. By means of variation of the polystyrene content and its crosslinking degree we have obtained membranes that have an ion-exchange capacity from 1.1 to 2.9 mmole g−1, anion transport numbers between 91.0 and 95.5% and specific ionic conductivities (σ25
Cl− Þ ranging from 2 to 25 mS cm−1. The developed membranes due to their low thickness and high conductivities have a remarkably low surface ionic resistance of around 0.6 Ωcm2. It was calculated that the use of the developed materials will increase the efficiency of reverse electrodialysis energy production by 8–10% compared to the state of the art membranes.

Magnetic nanocomposites involving tetraborate ion (TB)-intercalated Mg–Al-layered double hydroxide (LDH) shell supported on magnesium ferrite core particles are synthesized, characterized, and compared with their non-magnetic analogues. The compositions of the obtained nanocomposites were determined and structural investigations were made by powder X-ray diffraction and Fourier transform infrared spectroscopy. Particle characteristics were examined by size distribution, specific surface area measurements, scanning electron microscopy and transmission electron microscopy. Room-temperature magnetic measurements were performed with a vibrating sample magnetometer. The dynamics and structure of the interlayer water molecules and borate ions were studied by molecular dynamics simulations. Analytical and modeling studies verified that the TB ions were arranged between the LDH layers in oblique positions. The products were found to carry ca. 6% boron (10**17 B atom/μg nanocomposite). The magnetic nanocomposite showed superparamagnetic properties and can potentially find applications in biomedical fields for the site-specific delivery of bio-potent boron agents.

Due to their high durability and immobilization properties, cementitious materials have found a considerable application in the design and construction of radioactive waste repositories in the last decades. During cement paste production, organic additives are introduced to modify various properties of cement. The presence of such organic complexants may negatively affect the immobilizing properties of cement with respect to radionuclides. For better understanding and prediction of the effects of interactions between organic molecules and cementitious materials with radionuclides, we have developed several representative models consisting of three principal components: (i) calcium silicate hydrate (C-S-H) phase - the main binding phase of cement; (ii) gluconate, a simple well-described molecule, as a representative of organic additives; (iii) U(VI), as one of the most studied radionuclides of the actinide series. The C-S-H phase with low Ca/Si ratio (~0.83) typical for “low-pH” and degraded cement pastes has been selected for this modelling study. Structural, and energetic aspects of the sorption processes of uranyl, gluconate, and their mutual correlations on the surface of cement were quantitatively modeled by classical molecular dynamics (MD) and potential of mean force (PMF) calculations. The ternary surface complex formation between uranyl hydroxides and Ca2+ cations at the C-S-H aqueous interfaces is shown to have an important role in the overall sorption process. In the presence of gluconate, U(VI) sorption on C-S-H is facilitated by weakening the Ca2+ binding with the surface. Additionally, Na+ is proven to be an important competitor for certain surface sorption sites and can potentially affect the equilibrium properties of the interface.

The siloxane surface of uncharged clays is known to be hydrophobic, which is supported by strong experimental and theoretical evidence. For the siloxane surface of charged clays, like smectites, the picture is not as clear. We are aiming to clarify this issue by molecular simulations in which smectite surface hydrophobicity is quantified through the separate contribution of the surface itself, and the contribution due to the presence of charge-balancing cations on the surface. In order to explore systematically the effects of the total smectite charge and its distribution in the structure, a series of molecular dynamics (MD) simulations was performed for several models of dioctahedral smectites and compared with the results for uncharged pyrophyllite.

The largest difference between the simulation results for smectite models with naturally present surface counterions and the models where these ions were artificially removed from the surface, while maintaining the same total charge balance of the model, is in the shape of the water coverage. In the former case, full surface wetting is observed and a relatively flat water film is forming on the surface. Its irregularity and thickness is connected with number of ions on the surface. However, in all cases of smectite surfaces artificially devoid of ions, a water droplet is always formed and the wetting is incomplete. The contact angles of the water droplets on charged montmorillonites are very similar to that on uncharged pyrophyllite surface and range roughly between 110o and 90o. These angles are also affected by the distribution of the octahedral and tetrahedral substitutions in the structure and by their ratio. In the case of purely tetrahedral substitutions the contact angle on the bare smectite surface can be as low as ~60o, but still far from complete wetting.

The angular distributions of the H2O dipole vectors as a function of distance from the smectite surface show two preferred surface-oriented types of water molecules when counterions are present, and the total surface is highly hydrophilic. However, for surfaces devoid of ions, a population with dipole angles close to ~90o is dominating, and the smectite surfaces can be considered hydrophobic. It can be thus concluded that, independent of the structural charge, bare smectite surfaces by themselves are either hydrophobic or only moderately hydrophilic. Their experimentally observed highly hydrophilic character is almost entirely due to the charge balancing cations present on the surface.

We performed constant reservoir composition molecular dynamics (CRC-MD) simulations at 323 K and 124 bar to quantitatively study the partitioning of fluid species between the nano- and mesopores of clay and a bulk reservoir containing an equimolar mixture of CO2 and CH4. The results show that the basal (001) and protonated edge (010) surfaces of illite both demonstrate a strong preference for CO2 over CH4 adsorption; that the (001) surfaces show a stronger preference for CO2 than the (010) surfaces, especially with K+ as the exchangeable cation; and that the structuring of the near-surface CO2 by K+ is stronger than that by Na+. The protonated (010) surfaces have a somewhat greater preference for CH4, with the concentration near them close to that in the bulk fluid. The effects of the surfaces on the fluid composition extend to approximately 2.0 nm from them, with the fluid composition at the center of the pore becoming essentially the same as the bulk composition at a pore thickness of ~5.7 nm. The preference of nano- and mesopores bounded by clay minerals for CO2 over CH4 suggests that injection of CO2 into tight reservoirs is likely to displace CH4 into larger pores, thus enhancing its production.