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51.
[reaction: see text] We have investigated the olefin metathesis from alkenyl Baylis-Hillman adducts using second-generation Grubbs catalyst. In the experiment, the ring-closing metathesis (RCM) product could not be found, while the cross-metathesis (CM) products were found. The computational studies provided consistent explanations for the experimental result. The most limiting factor for the RCM process using second-generation Grubbs catalyst is caused by the high strain and steric effect in the metallacyclobutane intermediates. 相似文献
52.
Polyacrylamide (PAL) was physically adsorbed onto a hydroxylated silicon surface to form a uniform PAL film and the up-top PAL thin film was treated by nitrogen (N2) plasma for surface modification. The atomic composition of the modified surface of the PAL film adsorbed on silicon substrate was analyzed with Fourier Transform Infrared Spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The surface energy of PAL film was calculated from the data of contact angle of three-probe liquid. The FTIR results show an increase of peak intensity at 1214 cm−1 (NH2 stretch vibration) after the nitrogen plasma treatment, which confirms that the nitrogen was grafted to the PAL surface in the process of N2-plasma treatment. The XPS results show that the ratio of relative intensity of N1s to O1s increases with increasing the plasma treatment time, which further affirms the formation of the amine groups on the PAL surface after the nitrogen plasma treatment. The surface tension increases with increasing the plasma grafting time. However, the surface energy decreases rapidly at the early stage when stored in air and approaches to an equilibrium value. It suggests that some physically-adsorbed ions and alkyl radicals on PAL surface can rapidly lose their activities. The increase of the surface tension of the plasma treated PLA films is due to the amine groups covalently grafted to PAL surface. 相似文献
53.
Petre BA Youhnovski N Lukkari J Weber R Przybylski M 《European journal of mass spectrometry (Chichester, England)》2005,11(5):513-518
Nitration of tyrosine residues in proteins may occur in cells upon oxidative stress and inflammation processes mediated through generation of reactive nitroxyl from peroxynitrite. Tyrosine nitration from oxidative pathways may generate cytotoxic species that cause protein dysfunction and pathogenesis. A number of protein nitrations in vivo have been reported and some specific Tyrosine nitration sites have been recently identified using mass spectrometric methods. High-resolution Fourier transform ion cyclotron resonance mass spectrometry (MALDI) FT-ICR-MS) is shown here to be a highly efficient method in the determination of protein nitrations. Following the identification of nitration of the catalytic site Tyr-430 residue of bovine prostacyclin synthase, we synthesised several model peptides containing both unmodified tyrosine and 3-nitro-tyrosine residues, using solid-phase peptide synthesis (SPPS). The structures of the nitrotyrosine peptides were characterised both by ESI- and by matrix-assisted laser desorption/ionisation (MALDI)-FT-ICR-MS, using a standard ultraviolet (UV) nitrogen nitrogen laser and a 2.97 microm Nd-YAG infrared laser. Using UV-MALDI-MS, 3-nitrotyrosyl-peptides were found to undergo extensive photochemical fragmentation at the nitrophenyl group, which may hamper or prevent the unequivocal identification of Tyr-nitrations in cellular proteins. In contrast, infrared-MALDI-FT-ICR-MS did not produce fragmentation of molecular ions of Tyr-nitrated peptides. 相似文献
54.
Composite of polyacrylamide-bentonite (PAA-B) was prepared by direct polymerisation of PAA in a suspension of bentonite (B). Adsorption and thermodynamic features of phytic acid (Phy) adsorption onto B, PAA and PAA-B, and those of Fe3+, Zn2+, UO2
2+ adsorption onto PAA-B and its modification by Phy (PAA-B-Phy) have been investigated. The reusability, storagability, ion selectivity and recoverability of sorbed ions with 1 M HCl have also been considered.The chemical and physical structure of adsorbents has been characterised by means of FT-IR and XRD. All adsorption isotherms for Phy and the ions were L-type of the Giles classification except, the one which is S type for adsorption of Phy onto PAA. The maximum adsorption capacities for the ions adsorbed were in order of UO2
2+ > Fe3+ > Zn2+ for PAA-B and Zn2+ > Fe3+ > UO2
2+ for PAA-B-Phy. Langmuir equilibrium constants for the adsorption of ions onto PAA-B-Phy were significantly higher than those found for PAA-B; the magnitude of increase for UO2
2+ was about 100. The thermodynamic parameters indicated that adsorption reactions are spontaneous in terms of adsorption free enthalpy.The chemical structure of PAA-B-Phy was not changed at the end of the studies of reusability and storagability. The composite was selective for UO2
2+ of the ions of interest.The composite of PAA-B and its modification by Phy have been used for the first time in this investigation. It is proposed that the composites can be practically used in the investigations and applications of adsorption. 相似文献
55.
用ICP-AES法测定了东太平洋深海锰结核样品中二十多种主,次及微量元素,结果表明,表面瘤状和表面光滑两种类型锰结核的化学元素含量有较明显的区别,如表面光滑的锰结核TiO2含较高,而表面瘤状的锰结核Mn/Fe之值较高等。 相似文献
56.
Mustafa Şenyel T. Raci Sertbakan Güneş Kürkçüoğ Ergün Kasap Ziya Kantarci 《Journal of inclusion phenomena and macrocyclic chemistry》2001,39(1-2):175-180
Three Hofmann-diaminododecane-type clathrates of the form M(1,12-diaminododecane) Ni(CN)4G (M = Co, Ni or Cd; G = benzene, naphthalene, anthracene, phenanthrene or biphenyl) have been prepared in powder form. The 1,12-diaminododecane molecules in the host lattice permit the inclusion of bulky guest molecules. The spectral features suggest that these compounds are similar in structure to the other Hofmann-diam-type clathrates. 相似文献
57.
H. Güven N. Güngör A. Alemdar C. Ş. Özben 《Journal of Radioanalytical and Nuclear Chemistry》1996,214(4):269-276
Instrumental neutron activation analysis was applied to the determination of trace elements in a Na-bentonitic clay. The irradiation was done in the Triga Mark II type reactor of ITU Nuclear Energy Institute. The sample was irradiated in two steps for short- and long- lived isotopes. After irradiation, spectra were taken using a germanium detector, multichannel analyzer Canberra System 100 and a fitting program called Sampo 90. The spectra of short-lived isotopes were analyzed to determine Al, Mg, Na, K, Ca, Ti elements and Mn, V trace elements. The spectra of long-lived isotopes were analyzed to determine Sc, Br, Sb, Cs, La, Ce, Sm, Yb, Hf, Pa, Np trace elements. 相似文献
58.
N. Ibriş J. Mirza-Rosca A. Santana T. Vişan 《Journal of Solid State Electrochemistry》2002,6(2):119-125
The corrosion and passivation of Zn powder particles dispersed in a paste electrode immersed in 0.5 M Na2SO4 and 5×10–3 M Na2HPO4 solutions were studied mainly by electrochemical impedance spectroscopy. The role played by diffusion in the mechanism of
anodic oxidation of zinc powder particles has been shown. It was demonstrated that the anodic reactionof Zn powder in neutral
or near neutral media involves at least two adsorbed intermediates. By simulating the porous structure of the electrode, some
information about porous nature of zinc electrode could be extracted.
Electronic Publication 相似文献
59.
Manganese in vitamin-minerals tablets was determined by solid sampling electrothermal atomic absorption spectrometry (SS-ETAAS) using three different calibration methods, namely calibration against aqueous standards, standard addition with aqueous standards on solid samples and calibration against solid certified standards. Samples were only finely ground and introduced directly into the furnace by means of solid autosampler system without any dissolving process. Effects of different calibration techniques, temperatures and heating rates of atomization and pyrolysis steps on the accuracy and precision of the analyte elements were investigated. After optimization of the experimental parameters, there is good agreement (at 95% confidence level) between the results obtained by solid sampling and those obtained by acid digestion of samples. 相似文献
60.
Păcurariu C. Lazău R. I. Lazău I. Stoleriu Ş. 《Journal of Thermal Analysis and Calorimetry》2007,88(3):641-645
A kinetic study of the crystallization processes was performed for some decorative ceramic glazes in the PbO-SiO2-Na2O-K2O-CaO(BaO)-Al2O3-B2O3 system with addition of 10% TiO2 and ZnO. The crystallization kinetics has been studied in non-isothermal conditions using DTA technique. The apparent activation
energies of the crystallization processes were calculated using the Kissinger method. The main crystalline phase, which provides
the decorative effect, is rutile. This has been identified by X-ray diffraction and it is clearly visible in the optical microscopy
images taken in transmitted light, as needle-like or even prismatic crystals arranged in radial-fibrous aggregates. 相似文献