Combination of Reaction and Separation in Heterogeneous Catalytic Hydrogenation of Ethylformate

Continuous hydrogenation reaction of ethyl benzoylformate was studied over a (–)‐cinchonidine (CD)‐modified Pt/Al₂O₃ catalyst. The catalyst showed a good stability, and high enantioselectivity was achieved in the fixed‐bed reactor. Chromatographic separation of (R)‐ and (S)‐ethyl mandelate originating from a post‐continuous hydrogenation reaction of ethyl benzoylformate over the (–)‐CD‐modified Pt/Al₂O₃ catalyst was investigated in the same reaction mixture. A commercial column filled with a chiral selector resin was chosen as a perspective preparative‐scale adsorbent. Since adsorption equilibrium isotherms were linear within the entire investigated range of concentrations, they were determined by pulse experiments for the isomers present in a post‐reaction mixture. Breakthrough curves were measured and described successfully by the dispersive plug‐flow model with linear driving force approximation.     

Enantioselective Hydrogenation of Ethyl Benzoylformate,from Mechanism and Kinetics to Continuous Reactor Technology

The enantioselective hydrogenation of ethyl benzoylformate over (?)-cinchonidine (CD)-modified Pt/Al₂O₃ catalyst in semi-batch and continuous fixed bed reactors was studied as a function of the modifier concentration and reaction temperature. The kinetic results from the semibatch reactor showed a higher enantioselectivity and lower initial rate as the amount of modifier was increased. The results from the fixed bed reactor demonstrates that continuous enantioselective hydrogenation is possible and that continuous feeding of (?)-CD is needed to maintain a high steady-state enantioselectivity.     

Kinetics of ion-exchange-induced vitrification of glass-ceramics

Micro-Raman spectroscopy was applied to characterize the ion-exchange-induced vitrification of silicate glass-ceramics with lithium metasilicate crystalline phase. In parallel, the glass-ceramics vitrification was simulated on the base of the theory developed. Comparison of the data obtained with micro-Raman spectroscopy with the results of the simulation allowed revealing the kinetic parameters of vitrification process and evaluating the corresponding activation energies. These experimental approach and theory can be applied to other types of glass-ceramics.     

Inorganic Protection of Polymer Nanocapsules: A Strategy to Improve the Efficiency of Encapsulated Optically Active Molecules

We demonstrate that the efficiency under ambient conditions of optically active molecules encapsulated in polymer nanocapsules can be significantly improved by depositing an inorganic layer onto the polymeric shell. A triplet-triplet annihilation upconversion (TTA-UC) system consisting of a porphyrin derivative and perylene is used as a representative case. Different inorganic materials are deposited on the surface of functionalized polymer nanocapsules synthesized by free-radical polymerization in miniemulsion. First, a silicate clay with formula [Si₈(Mg_5.45Li_0.4)O₂₀(OH)₄]Na_0.7 is deposited on the surface of positively charged polystyrene nanocapsules via layer-by-layer deposition. Second, controlled in situ mineralization of hydroxyapatite and cerium(IV) oxide are carried out on the surface of negatively charged polystyrene nanocapsules. In both cases the inorganic materials on the nanocapsule surface act as a scavenger and avoid the entry of oxygen from the external environment. By avoiding the entry of oxygen, the photo-oxidation process of perylene molecules is avoided within the system, and an increase in the TTA-UC properties occurs.     

Patterning of worm-like soft polydimethylsiloxane structures using a TiO2 nanotubular array

Patterned polydimethylsiloxane (PDMS) is an important structure for soft lithography. Various materials have been deployed as mold for patterning PDMS. Anodized nanotubular array has been sought after as cost-effective alternative for textured silicon. An array of TiO₂ nanotubes with characteristic diameter ≈140 nm and the length of ≈1.5 microns, created by anodic oxidation of a titanium substrate, was used here as a template for soft PDMS molding. The optimal molding process was developed by a combination of silanization, use of solvent, application of a vacuum, and hydraulic pressing. The silanization was confirmed by Fourier transform infrared spectroscopy and contact angle measurements while the PDMS structure was examined by scanning electron microscope and energy dispersive X-ray spectroscopy. Hydraulic pressing significantly improved the infiltration of PDMS into the pores of nanotubular array resulting in formation of PDMS nanobumps after separation of the polymer from the template. Complete infiltration of PDMS precursor into the cavity of nanotubes was observed on the hydraulic-pressed sample without toluene impurities. The hydraulic-pressed samples exhibited higher adhesion strength than nonpressed ones. The adhesive strength was measured by a simple experimental arrangement, in which the PDMS layer was stuck on a vertical glass surface followed by pulling it downwards.     

Evolution of MicroRNA Biogenesis Genes in the Sterlet (Acipenser ruthenus) and Other Polyploid Vertebrates

MicroRNAs play a crucial role in eukaryotic gene regulation. For a long time, only little was known about microRNA-based gene regulatory mechanisms in polyploid animal genomes due to difficulties of polyploid genome assembly. However, in recent years, several polyploid genomes of fish, amphibian, and even invertebrate species have been sequenced and assembled. Here we investigated several key microRNA-associated genes in the recently sequenced sterlet (Acipenser ruthenus) genome, whose lineage has undergone a whole genome duplication around 180 MYA. We show that two paralogs of drosha, dgcr8, xpo1, and xpo5 as well as most ago genes have been retained after the acipenserid-specific whole genome duplication, while ago1 and ago3 genes have lost one paralog. While most diploid vertebrates possess only a single copy of dicer1, we strikingly found four paralogs of this gene in the sterlet genome, derived from a tandem segmental duplication that occurred prior to the last whole genome duplication. ago1,3,4 and exportins1,5 look to be prone to additional segment duplications producing up to four-five paralog copies in ray-finned fishes. We demonstrate for the first time exon microsatellite amplification in the acipenserid drosha2 gene, resulting in a highly variable protein product, which may indicate sub- or neofunctionalization. Paralogous copies of most microRNA metabolism genes exhibit different expression profiles in various tissues and remain functional despite the rediploidization process. Subfunctionalization of microRNA processing gene paralogs may be beneficial for different pathways of microRNA metabolism. Genetic variability of microRNA processing genes may represent a substrate for natural selection, and, by increasing genetic plasticity, could facilitate adaptations to changing environments.