Chirality-Controlled Self-Assembly of Amphiphilic Dibenzo[6]helicenes into Langmuir-Blodgett Thin Films.

Racemic and highly enantioenriched 3-methoxycarbonyl, 3-carboxy, and 3-hydroxymethyl derivatives of dibenzo[6]helicene were prepared. The Langmuir layers of these helicenes were formed at the air-water interface and transferred onto solid substrates to afford Langmuir-Blodgett films, which were then studied by ambient atomic force microscopy and (chir)optical spectroscopy. Significant differences were found in the behaviour of the Langmuir layers as well as in the morphology, UV/Vis, electronic circular dichroism (ECD), and fluorescence spectra of the Langmuir-Blodgett thin films depending on the molecular chirality and nature of the polar group. The experimental results were supported by molecular dynamics simulations.

The effects of formation and functionalization of graphene-based membranes on their gas and water vapor permeation properties.

The gas and water vapor permeabilities of graphene-based membranes can be affected by the presence of different functional groups directly bound to the graphene network. In this work, one type of carboxylated graphene oxide (GO-COOH) and two types of graphene oxide synthesized i) under strong oxidative conditions directly from graphite (GO-1) and ii) under mild oxidative conditions from exfoliated graphene (GO-2) were used as precursors of self-standing membranes prepared with thicknesses in the range of 12-55 µm via slow-vacuum filtration preparation method. It was observed that the permeabilities for all tested gases decreased in order GO-2 > GO-1 > GO-COOH and depended on both the arrangement of graphene sheets and their functionalization. The GO-1 membrane with a high content of oxygen-containing groups showed the best performance for water vapor permeability. The GO-2 membrane with a thickness of 43 µm exhibited a disordered GO sheet morphology and, therefore, unique gas-separation performance towards H2/CO2 gas pair, showing high hydrogen permeability while keeping extremely high H2/CO2 ideal selectivity that exceeds the Robeson 2008 upper bound of polymer membranes.

Push-pull amino-nitro helicenes: synthesis, (chir)optical properties and self-assembly into thin films.

A series of regioisomeric push-pull amino-nitro [6]helicenes and a related [7]helicene derivative were prepared and their racemates resolved into enantiomers. Compared to the parent helicenes, they exhibit red-shifted UV-Vis spectra, pronounced dipole moments, altered chiroptical properties such as remarkable optical rotatory power, and can form nanocrystalline Langmuir-Blodgett films.

Room-temperature synthesis of nanoceria for degradation of organophosphate pesticides and its regeneration and reuse.

A simple low-temperature water-based and one-pot synthesis was developed for the preparation of nanocrystalline CeO2 that was used for degradation of the toxic organophosphate pesticide parathion methyl. By changing the reaction temperature in the range from 5 °C to 95 °C, several properties (i.e., crystallinity, grain size and surface area) of nanoceria can be easily controlled. The catalytic decomposition of parathion methyl to its degradation product 4-nitrophenol was highly dependent on the CeO2 preparation temperature. It was demonstrated that at low temperature (i.e. 5 °C), CeO2 with very small crystallites (<2 nm) and high surface area can be obtained. For practical use, it was demonstrated that highly crystalline CeO2 can be prepared at room-temperature (30 °C) in at least 100 g batches. It was shown that precipitated nanoceria had high thermal stability and its post-synthesis annealing up to 400 °C did not significantly alter the material properties and hence the catalytic activity. Furthermore, as shown by the reusability tests, the sorbent can be reactivated by simply washing with water which demonstrated its durability.

Removal of anthracycline cytostatics from aquatic environment: Comparison of nanocrystalline titanium dioxide and decontamination agents.

Anthracyclines are a class of pharmaceuticals used in cancer treatment have the potential to negatively impact the environment. To study the possibilities of anthracyclines (represented by pirarubicin and valrubicin) removal, chemical inactivation using NaOH (0.01 M) and NaClO (5%) as decontamination agents and adsorption to powdered nanocrystalline titanium dioxide (TiO2) were compared. The titanium dioxide (TiO2) nanoparticles were prepared via homogeneous precipitation of an aqueous solution of titanium (IV) oxy-sulfate (TiOSO4) at different amount (5-120 g) with urea. The as-prepared TiO2 samples were characterized by XRD, HRSEM and nitrogen physisorption. The adsorption process of anthracycline cytostatics was determined followed by high-performance liquid chromatography coupled with mass spectrometry (LC-MS) and an in-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) technique. It was found that NaClO decomposes anthracyclines to form various transformation products (TPs). No TPs were identified after the reaction of valrubicin with a NaOH solution as well as in the presence of TiO2 nanoparticles. The best degree of removal, 100% of pirarubicin and 85% of valrubicin, has been achieved in a sample with 120 grams of TiOSO4 (TIT120) and TiO2 with 60 grams (TIT60), respectively.

Ultrasound exfoliation of inorganic analogues of graphene.

High-intensity ultrasound exfoliation of a bulk-layered material is an attractive route for large-scale preparation of monolayers. The monolayer slices could potentially be prepared with a high yield (up to 100%) in a few minutes. Exfoliation of natural minerals (such as tungstenite and molybdenite) or bulk synthetic materials (including hexagonal boron nitride (h-BN), hexagonal boron carbon nitride (h-BCN), and graphitic carbon nitride (g-C3N4)) in liquids leads to the breakdown of the 3D graphitic structure into a 2D structure; the efficiency of this process is highly dependent upon the physical effects of the ultrasound. Atomic force microscopy (AFM), transmission electron microscopy (TEM), and selected area electron diffraction (SAED) were employed to verify the quality of the exfoliation. Herein, this new method of exfoliation with ultrasound assistance for application to mono- and bilayered materials in hydrophobic and hydrophilic environments is presented.

Doping of TiO2-GO and TiO2-rGO with noble metals: synthesis, characterization and photocatalytic performance for azo dye discoloration.

The nanocomposites of titania coupled with graphene oxide (GO) and reduced graphene oxide (rGO), respectively, were prepared by homogeneous hydrolysis with urea. Graphene was obtained by effect of high-intensity cavitation field on natural graphite in the presence of strong aprotic solvents in pressurized ultrasonic reactor. The morphology of TiO2-GO and TiO2-rGO composites was assessed by scanning electron microscopy and atomic force microscopy. The nitrogen adsorption-desorption was used for determination of surface area (BET) and porosity. Raman and IR spectroscopy were used for qualitative analysis and diffuse reflectance spectroscopy was employed to estimate band-gap energies. Further enhancement of the photocatalytic activity was attained by codoping of composites with noble metals--Au, Pd and Pt. The photocatalytic activity of TiO2-GO and TiO2-rGO were assessed by photocatalytic decomposition of Orange II dye in an aqueous slurry under UV and visible light irradiation. The photocatalytic activity of noble metals codoped samples was determined with decomposition of Reactive Black 5 azo dye.