An efficient modification of ellipticine synthesis and preparation of 13-hydroxyellipticine

A simple modification of a previously published ellipticine synthesis is reported, which decreases the reaction time and increases the yield and purity of the product. Benzylic oxidations of 1,4-dimethylcarbazole and ellipticine derivatives were studied and 13-hydroxyellipticine was prepared.     

An investigation into the initial degradation steps of four major dye chromophores: study of their one-electron oxidation and reduction by EPR, ENDOR, cyclic voltammetry, and theoretical calculations

The degradation of dyes is frequently initiated by one-electron oxidation or reduction; however, relatively little is known about the initially formed radicals. Acid Green 25 (AG25), Crystal Violet (CVI), Methylene Blue (MB), and Acid Orange 7 (AO7), representing paradigms of four types of commercial organic dyes, were therefore investigated in terms of their redox behavior. Their redox potentials in MeCN and buffered aqueous solutions were determined by cyclic voltammetry. The structures of the one-electron reduced and oxidized dyes were established by EPR spectroscopy and by theoretical calculations on the density functional level of theory.     

Biosynthesis of Quantum Dots (CdTe) and its Effect on Eisenia fetida and Escherichia coli

Biosynthesis belongs to one of the new possibilities of nanoparticles preparation, whereas its main advantage is biocompatibility. In addition, the ability of obtaining the raw material for such synthesis from the soil environment is beneficial and could be useful for remediation. However, the knowledge of mechanisms that are necessary for the biosynthesis or effect on the bio-synthesizing organisms is still insufficient. In this study, we attempted to evaluate the effect of quantum dots (QDs) not only on a model organism of collembolans, but also on another soil organism—earthworm Eisenia fetida—and in also one widespread microorganism such as Escherichia coli. Primarily, we determined 28EC₅₀ as 72.4 μmol L⁻¹ for CdTe QDs in collembolans. Further, we studied the effect of QDs biosynthesis in E. fetida and E. coli. Using determination of QDs, low-molecular thiols and antioxidant activities, we found differences between both organisms and also between ways how they behave in the presence of Cd and/or Cd and Te. The biosynthesis in earthworms can be considered as its own protective mechanism; however, in E. coli, it is probably a by-product of protective mechanisms.

     

A mesoscopic thermomechanically coupled model for thin-film shape-memory alloys by dimension reduction and scale transition

We design a new mesoscopic thin-film model for shape-memory materials which takes into account thermomechanical effects. Starting from a microscopic thermodynamical bulk model, we guide the reader through a suitable dimension reduction procedure followed by a scale transition valid for specimen large in area up to a limiting model which describes microstructure by means of parametrized measures. All our models obey the second law of thermodynamics and possess suitable weak solutions. This is shown for the resulting thin-film models by making the procedure described above mathematically rigorous. The main emphasis is, thus, put on modeling and mathematical treatment of joint interactions of mechanical and thermal effects accompanying phase transitions and on reduction in specimen dimensions and transition of material scales.     

Sorption of iron(III)–alginate complexes on cellulose fibres

Multivalent ions take a significant role in the sorption of soluble polysaccharides on solid cellulose substrates and thus demonstrate an important principle in structural polysaccharide organisation. Sorption of Fe(III)–alginate complexes on lyocell fibres as model for the insoluble cellulose matrix has been studied between pH 3–13, at 30 and 60 °C. Sorption maximum of the Fe(III)–alginate complex was observed at pH 3 where the sorbed amounts of alginate and iron were 6,600 and 85 mg iron per kg cellulose respectively. Under the experimental conditions used, a concentration of 0.05 mM Fe(III) is sufficient to achieve surface sorption of Fe(III)–alginate complex. The alginate sorption exhibited minor dependence on molar ratio of Fe(III) to alginate. In environmental scanning electron microscopy no deposition of Fe-hydroxides on the fiber surface was detected. The thickness of the adsorbed Fe(III)–alginate layer on the fiber surface was estimated with 12–22 nm. Tensile strength and abrasion resistance of Fe(III)–alginate treated fibers were not reduced through the sorption treatment. Alginate modified cellulose is of interest as material for medical application, as sorbent and textile finish.     

Biosynthesis of Quantum Dots (CdTe) and its Effect on Eisenia fetida and Escherichia coli

Biosynthesis belongs to one of the new possibilities of nanoparticles preparation, whereas its main advantage is biocompatibility. In addition, the ability of obtaining the raw material for such synthesis from the soil environment is beneficial and could be useful for remediation. However, the knowledge of mechanisms that are necessary for the biosynthesis or effect on the bio-synthesizing organisms is still insufficient. In this study, we attempted to evaluate the effect of quantum dots (QDs) not only on a model organism of collembolans, but also on another soil organism—earthworm Eisenia fetida—and in also one widespread microorganism such as Escherichia coli. Primarily, we determined 28EC₅₀ as 72.4 μmol L^?1 for CdTe QDs in collembolans. Further, we studied the effect of QDs biosynthesis in E. fetida and E. coli. Using determination of QDs, low-molecular thiols and antioxidant activities, we found differences between both organisms and also between ways how they behave in the presence of Cd and/or Cd and Te. The biosynthesis in earthworms can be considered as its own protective mechanism; however, in E. coli, it is probably a by-product of protective mechanisms.     

Temperature‐programmed capillary high‐performance liquid chromatography with atmospheric pressure chemical ionization mass spectrometry for analysis of fatty acid methyl esters

A new capillary high‐performance liquid chromatography method with atmospheric pressure chemical ionization mass spectrometry was developed for the analysis of fatty acid methyl esters and long‐chain alcohols. The chromatographic separation was achieved using a Zorbax SB‐C18 HPLC column (0.3 × 150 mm, 3.5 μm) with a mobile phase composed of acetonitrile and formic acid and delivered isocratically at a flow rate of 10 μL/min. The column temperature was programmed simply, using a common column oven. Good reproducibility of the temperature profile and retention times were achieved. The temperature programming during the isocratic high‐performance liquid chromatography run had a similar effect as a solvent gradient; it reduced retention times of later eluting analytes and improved their detection limits. Two atmospheric pressure chemical ionization sources of the mass spectrometry detector were compared: an enclosed conventional ion source and an in‐house made ion source with a glass microchip nebulizer. The enclosed source provided better detectability of saturated fatty acid methyl esters and made it possible to determine the double bond positions using acetonitrile‐related adducts, while the open chip‐based source provided better analytical figures of merit for unsaturated fatty acid methyl esters. Temperature‐programmed capillary high‐performance liquid chromatography is a promising method for analyzing neutral lipids in lipidomics and other applications.     

Effect of Low Temperature Air Plasma Treatment on Wetting and Flow Properties of Kaolinite Powders

It was found in this study that the air plasma treatment of particular kaolinite has led to the change of its wettability, which was reflected in the decreased values of water contact angles of wetting from 88.7° for virgin kaolinite to 86.3° for 30?min air plasma treated one. Plasma treated samples show higher average surface energies in the wide range of coverage regimes in comparison to the virgin samples as determined by inverse gas chromatography. Results of these measurements confirmed our assumption, that air plasma treatment activates surface energy of the crystal planes of the kaolinite as reflected in the broadened dispersive surface energy distribution after 10?min treatment time. However with prolonged 30?min treatment time the dispersive surface energy distribution profile was decreased. We assume, that the latter decrease reflects the distorsion of the crystal lattice of the kaolinite as confirmed by FTIR analysis as reflected in changes of Si?CO?CSi and Al₂O?CH characteristic absorption bands. Calculated dispersive surface free energy for 24?% surface coverage was increased from original 35?mJ/m² to 40.3 and 40.8?mJ/m² for 10 and 30?min treatment times. There were determined yield locus and flow function dependencies at different stress levels for virgin and different time plasma treated samples (flow index??ff _c , effective angle of internal friction???? _e , unconfined yield strength???? _c ). It was found that by plasma treatment the character of the flow was shifting from region of very cohesive (ff _c ?=?2.39) to the cohesive (ff _c ?=?3.19). For untreated samples effective angle of internal friction was decreased with increasing applied consolidation stress, while for plasma treated kaolinite it was increased.     

Voltage enhancement in dye-sensitized solar cell using (001)-oriented anatase TiO2 nanosheets

A nanocrystalline TiO₂ (anatase) nanosheet exposing mainly the (001) crystal faces was tested as photoanode material in dye-sensitized solar cells. The nanosheets were prepared by hydrothermal growth in HF medium. Good-quality thin films were deposited on F-doped SnO₂ support from the TiO₂ suspension in ethanolic or aqueous media. The anatase (001) face adsorbs a smaller amount of the used dye sensitizer (C101) per unit area than the (101) face which was tested as a reference. The corresponding solar cell with sensitized (001)-nanosheet photoanode exhibits a larger open-circuit voltage than the reference cell with (101)-terminated anatase nanocrystals. The voltage enhancement is attributed to the negative shift of flatband potential for the (001) face. This conclusion rationalizes earlier works on similar systems, and it indicates that careful control of experimental conditions is needed to extract the effect of band energetic on the current/voltage characteristics of dye-sensitized solar cell.     

Mixed‐Metal MIL‐100(Sc,M) (M=Al,Cr, Fe) for Lewis Acid Catalysis and Tandem CC Bond Formation and Alcohol Oxidation

The trivalent metal cations Al³⁺, Cr³⁺, and Fe³⁺ were each introduced, together with Sc³⁺, into MIL‐100(Sc,M) solid solutions (M=Al, Cr, Fe) by direct synthesis. The substitution has been confirmed by powder X‐ray diffraction (PXRD) and solid‐state NMR, UV/Vis, and X‐ray absorption (XAS) spectroscopy. Mixed Sc/Fe MIL‐100 samples were prepared in which part of the Fe is present as α‐Fe₂O₃ nanoparticles within the mesoporous cages of the MOF, as shown by XAS, TGA, and PXRD. The catalytic activity of the mixed‐metal catalysts in Lewis acid catalysed Friedel–Crafts additions increases with the amount of Sc present, with the attenuating effect of the second metal decreasing in the order Al>Fe>Cr. Mixed‐metal Sc,Fe materials give acceptable activity: 40 % Fe incorporation only results in a 20 % decrease in activity over the same reaction time and pure product can still be obtained and filtered off after extended reaction times. Supported α‐Fe₂O₃ nanoparticles were also active Lewis acid species, although less active than Sc³⁺ in trimer sites. The incorporation of Fe³⁺ into MIL‐100(Sc) imparts activity for oxidation catalysis and tandem catalytic processes (Lewis acid+oxidation) that make use of both catalytically active framework Sc³⁺ and Fe³⁺. A procedure for using these mixed‐metal heterogeneous catalysts has been developed for making ketones from (hetero)aromatics and a hemiacetal.