Metal Nanoparticles on Stainless Steel Surfaces as Novel Heterogeneous Catalysts

The goal of this work was the development of a novel type of heterogeneous catalyst, consisting of bare metal nanoparticles on stainless steel foils, which can be shaped to any kind of architecture and, if necessary, heated electrically. Solutions of pre-prepared, ligand protected and monodispersed gold, palladium, platinum and rhodium nanoparticles were sprayed onto stainless steel foils, followed by the careful removal of the ligand molecules by an oxygen plasma treatment. Due to this, bare particles become irreversibly fixed on the steel support. It could be shown that the original particle sizes do not change during the plasma treatment. Foils, densely coated with the nanoparticles, were used for gas phase catalyses in a self-made reactor at room temperature or at 60 °C. Hydrogenation of 1,3-butadiene at 15 nm Pd and 2 nm Pt, CO oxidation at 16 nm, 8 nm and 1.4 nm gold and NO reduction with NH₃ at 2 nm Rh particles were performed, indicating that the novel catalysts might in principle be applicable in technical processes if the experimental conditions like form and temperature would be optimized. Dedicated to Professor Dieter Fenske on the occassion of his 65th birthday.     

Chemical constituents from the roots of <Emphasis Type="Italic">Polygonum bistorta</Emphasis>

Investigation of the roots of Polygonum bistorta L. afforded seven compounds including five triterpenoids, a coumarin, and a steroid, the structures of which were identified by EIMS, ¹H NMR, ¹³C NMR, DEPT, and HMBC experiments. All the compounds have been isolated from Polygonum genus for the first time. Published in Khimiya Prirodnykh Soedinenii, No. 5, pp. 463–465, September–October, 2007.     

Immunoassay of P-glycoprotein on single cell by capillary electrophoresis with laser induced fluorescence detection

The cellular mechanism based on P-glycoprotein (PGP) for its drug pump function has become very important in multidrug resistance (MDR) research. A method has been established to characterize PGP on single K562 cell by coupling capillary electrophoresis with laser induced fluorescence detection. A permeable intact cell after the immunoassay binding with fluorescence labeling antibody was injected into the capillary and directly separated without lysis. It was found that once 5-10 optional cells were detected in batch, the PGP amount on this cell line could be outlined and calculated clearly. The PGP amount on K562 MDR cell line is 3.88 times higher than that on K562 sensitive cell line. These two cell lines with immunoassay binding were also analyzed by injection of multi-cells in order to improve the throughput. A resistance factor so called multidrug resistance multiple (MRM) was introduced to evaluate the MDR difference between cell lines. The MRM values of the cell line K562 measured by single cell analysis are well correlated with those by flow cytometry, which also prove the validity of our method in single cell analysis for the possibility of cancer diagnosis, pharmacokinetics and drug screening in future.     

Synthesis and characterization of cobalt(II), nickel(II), copper(II), palladium(II) and dioxouranium(VI) complexes of the antipyrine Schiff base of 3-formylsalicylic acid

A new Schiff base has been synthesized from 4-aminoantipyrine and 3-formylsalicylic acid. The ligand has a dianionic tetradentate compartmental OONO donor system. The cobalt(II), nickel(II), copper(II) and dioxouranium(VI) complexes exist in phenolato-bridged dinuclear species, while palladium(II) gives a mononuclear complex with free –COOH groups. The complexes have been characterized by elemental analyses, i.r., u.v.-vis, thermal and magnetic measurements.     

Carboxylic Acids from <Emphasis Type="Italic">Phyllanthus urinaria</Emphasis>

Five compounds, terephthalic acid mono-[2-(4-carboxy-phenoxycarbonyl)-vinyl] ester (1), (E)-3-(5′-hydroperoxy-2,2′-dihydroxy[1,1′-biphenyl]-4-yl)-2-propenoic acid (2), 3,4,5-trihydroxybenzoic acid (3), succinic acid (or butanedioic acid) (4), and 2,3,4,5,6-pentahydroxybenzoic acid (5), were isolated from Phyllanthus urinaria. The structures of these compounds were elucidated by means of spectral techniques including IR, MS, and 1D/2D NMR. 1 and 2 are new compounds.__________Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 14–17, January–February, 2005.     

The separation of hypericin's enantiomers and their photophysics in chiral environments

We report the first separation of the enantiomers of hypericin. Their steady-state optical spectra and ultrafast primary photoprocesses are investigated in chiral environments. Within experimental error, there is no difference between the two enantiomers in any of the systems considered. This is consistent with the emerging picture that the rich and extended absorption spectrum of hypericin is not a result of ground-state heterogeneity. It is also consistent with the observation that the spectra and photophysics of hypericin are generally insensitive to environments in which it does not aggregate.     

Sol–gel preparation and properties of hydroxypropylcellulose–titania hybrid thin films

Hydroxypropylcellulose (HPC)–titania hybrid thin films were prepared by sol–gel method where titanium tetraisopropoxide Ti(OC₃H₇ ⁱ )₄ was hydrolyzed under acidic conditions in the presence of HPC, followed by dip-coating and drying at 120 °C for 24 h. The viscosity average molecular weight of HPC was 55,000–70,000 or 110,000–150,000, and the TiO₂/(HPC + TiO₂) mass ratio ranged from 0 to 1, which was calculated on the assumption that all Ti(OC₃H₇ ⁱ )₄ is converted into TiO₂. The films were 0.35–1.0 μm thick, transparent in visible region and opaque in ultraviolet (UV) region, where the optical absorption coefficient in UV region increased with increasing titania content. The refractive index increased with increasing titania content, ranging from 1.6 to 1.8 for the hybrid thin films. The pencil hardness increased from 6B to 5H, the durability in hot water significantly increased and the contact angle of water on films increased from 35° to 89° with increasing titania content. Crack-free films could be deposited on organic polymer substrates irrespective of titania or HPC contents, where cracking did not occur at higher HPC contents even when the substrate was bent.     

Influence of the cathodic polarization on the stability of Ti surface in concentrated KOH solutions

The stability of spontaneous thin layers and thin layers formed upon cathodical polarization of Ti in KOH solutions have been studied by potentiostatic and ellipsometric methods. At open circuit potential (OCP) the strongly adherent films, whose thickness depends on the concentration of the KOH solution, were formed. During the cathodic polarization the transformation of these films to weakly adsorbed precipitated layers on the electrode surface was observed. Comparing the theoretically computed curves with the experimental Ψ vs Δ loci measured ellipsometrically, the complex indices of refraction and the thickness of the generated films, from 3.6 to 60 nm in 1 M KOH and from 36 to 105 nm in 5 M KOH (adherent to the electrode surface), were determined. At OCP the rate of film growth increases with increasing the concentration of KOH solution. Cathodic polarizations change the chemical composition and retard the rate of film growth. Based on the ellipsometric and electrochemical data the chemical compositions of the formed films consisted of TiO₂, Ti₂O₃, TiO₂·H₂O, Ti(OH)₃ and TiOOH·nH₂O.     

Fuzzy Symmetries for Linear Molecules and their Molecular Orbitals

In this paper, the fuzzy symmetry of some prototypical linear molecules has been analyzed. The results show that some molecular orbitals (MOs) are less symmetrical but some others are more symmetrical than the molecular skeleton, which the MOs correspond to. The membership functions of space inversion for MOs are closely related to the chemical characteristics of the MOs. Sometimes, although the symmetry of a molecular skeleton is not obvious, however that of some MO is quite obvious. The membership functions of the fuzzy inversion symmetry depend on the choice of the position of the center of inversion. As compared to those of diatomic molecules and linear tri-atomic molecules, the linear polyatomic molecules in which a distinctive fuzzy symmetry of space translation may exist, and thus a significant effect on their properties can be expected.     

Synthesis and characterization of microencapsulated dicyclopentadiene with melamine–formaldehyde resins

Microcapsules containing healing agents have been used to develop the self-healing polymeric composites. These microcapsules must possess special properties such as appropriate strength and stability in surrounding medium. A new series of microcapsules containing dicyclopentadiene (DCPD) with melamine–formaldehyde (MF) resin as shell material were synthesized by in situ polymerization technology. These microcapsules may satisfy the requirements for self-healing polymeric composites. The chemical structure of microcapsule was identified by using Fourier transform infrared (FTIR) spectrometer. The morphology of microcapsule was observed by using optical microscope (OM) and scanning electron microscope. Size distribution and mean diameter of microcapsules were determined with OM. The thermal properties of microcapsules were investigated by using thermogravimetric analysis and differential scanning calorimetry. Additionally, the self-healing efficiency was evaluated. The results indicate that the poly(melamine–formaldehyde) (PMF) microcapsules containing DCPD have been synthesized successfully, and their mean diameters fall in the range of 65.2∼202.0 μm when the adjusting agitation rate varies from 150 to 500 rpm. Increasing the surfactant concentration can decrease the diameters of microcapsules. The prepared microcapsules are thermally stable up to 69 °C. The PMF microcapsules containing DCPD can be applied to polymeric composites to fabricate the self-healing composites.