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101.
Benaskar F Engels V Rebrov EV Patil NG Meuldijk J Thüne PC Magusin PC Mezari B Hessel V Hulshof LA Hensen EJ Wheatley AE Schouten JC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(6):1800-1810
New routes for the preparation of highly active TiO(2)-supported Cu and CuZn catalysts have been developed for C-O coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles, synthesized using a reduction by solvent method, were deposited onto calcined films to obtain a Cu loading of 2 wt%. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, temperature-programmed oxidation/reduction (TPO/TPR) techniques, (63)Cu nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (S/TEM-EDX) and X-ray photo-electron spectroscopy (XPS). The activity and stability of the catalysts obtained have been studied in the C-O Ullmann coupling of 4-chloropyridine and potassium phenolate. The titania-supported nanoparticles retained catalyst activity for up to 12 h. However, catalyst deactivation was observed for longer operation times due to oxidation of the Cu nanoparticles. The oxidation rate could be significantly reduced over the CuZn/TiO(2) catalytic films due to the presence of Zn. The 4-phenoxypyridine yield was 64% on the Cu/nonporous TiO(2) at 120 °C. The highest product yield of 84% was obtained on the Cu/mesoporous TiO(2) at 140 °C, corresponding to an initial reaction rate of 104 mmol g(cat) (-1) s(-1). The activation energy on the Cu/mesoporous TiO(2) catalyst was found to be (144±5) kJ mol(-1), which is close to the value obtained for the reaction over unsupported CuZn nanoparticles (123±3 kJ mol(-1)) and almost twice the value observed over the catalysts deposited onto the non-porous TiO(2) support (75±2 kJ mol(-1)). 相似文献
102.
Denysenko D Werner T Grzywa M Puls A Hagen V Eickerling G Jelic J Reuter K Volkmer D 《Chemical communications (Cambridge, England)》2012,48(9):1236-1238
Postsynthetic metal ion exchange in a benzotriazolate-based MFU-4l(arge) framework leads to a Co(II)-containing framework with open metal sites showing reversible gas-phase oxidation properties. 相似文献
103.
104.
Kirsten Werner Volker Steinert Steffi Reinhardt 《Macromolecular rapid communications》1995,16(9):673-678
The polarographic behaviour of hydrolyzed propene-maleic anhydride copolymers in the interval pH 2.0–11.0 has been investigated by differential pulse polarography in aqueous lithium chloride solution at 25°C. In dependence on the pH-value, one, two or three signals, belonging to the acid groups in the copolymer, appear in the polarograms. Three apparent polarographic acid constants have been determined graphically from the changes in the half-wave potential of the separate peaks in correlation with pH. 相似文献
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108.
Herzog G Abul Kashem MM Benecke G Buffet A Gehrke R Perlich J Schwartzkopf M Körstgens V Meier R Niedermeier MA Rawolle M Ruderer MA Müller-Buschbaum P Wurth W Roth SV 《Langmuir : the ACS journal of surfaces and colloids》2012,28(21):8230-8237
The installation of large scale colloidal nanoparticle thin films is of great interest in sensor technology or data storage. Often, such devices are operated at elevated temperatures. In the present study, we investigate the effect of heat treatment on the structure of colloidal thin films of polystyrene (PS) nanoparticles in situ by using the combination of grazing incidence small-angle X-ray scattering (GISAXS) and optical ellipsometry. In addition, the samples are investigated with optical microscopy, atomic force microscopy (AFM), and field emission scanning electron microscopy (FESEM). To install large scale coatings on silicon wafers, spin-coating of colloidal pure PS nanoparticles and carboxylated PS nanoparticles is used. Our results indicate that thermal annealing in the vicinity of the glass transition temperature T(g) of pure PS leads to a rapid loss in the ordering of the nanoparticles in spin-coated films. For carboxylated particles, this loss of order is shifted to a higher temperature, which can be useful for applications at elevated temperatures. Our model assumes a softening of the boundaries between the individual colloidal spheres, leading to strong changes in the nanostructure morphology. While the nanostructure changes drastically, the macroscopic morphology remains unaffected by annealing near T(g). 相似文献
109.
Graf C Gao Q Schütz I Noufele CN Ruan W Posselt U Korotianskiy E Nordmeyer D Rancan F Hadam S Vogt A Lademann J Haucke V Rühl E 《Langmuir : the ACS journal of surfaces and colloids》2012,28(20):7598-7613
The influence of the surface functionalization of silica particles on their colloidal stability in physiological media is studied and correlated with their uptake in cells. The surface of 55 ± 2 nm diameter silica particles is functionalized by amino acids or amino- or poly(ethylene glycol) (PEG)-terminated alkoxysilanes to adjust the zeta potential from highly negative to positive values in ethanol. A transfer of the particles into water, physiological buffers, and cell culture media reduces the absolute value of the zeta potential and changes the colloidal stability. Particles stabilized by L-arginine, L-lysine, and amino silanes with short alkyl chains are only moderately stable in water and partially in PBS or TRIS buffer, but aggregate in cell culture media. Nonfunctionalized, N-(6-aminohexyl)-3-aminopropyltrimethoxy silane (AHAPS), and PEG-functionalized particles are stable in all media under study. The high colloidal stability of positively charged AHAPS-functionalized particles scales with the ionic strength of the media, indicating a mainly electrostatical stabilization. PEG-functionalized particles show, independently from the ionic strength, no or only minor aggregation due to additional steric stabilization. AHAPS stabilized particles are readily taken up by HeLa cells, likely as the positive zeta potential enhances the association with the negatively charged cell membrane. Positively charged particles stabilized by short alkyl chain aminosilanes adsorb on the cell membrane, but are weakly taken up, since aggregation inhibits their transport. Nonfunctionalized particles are barely taken up and PEG-stabilized particles are not taken up at all into HeLa cells, despite their high colloidal stability. The results indicate that a high colloidal stability of nanoparticles combined with an initial charge-driven adsorption on the cell membrane is essential for efficient cellular uptake. 相似文献
110.
Acrylamide complexes of metal nitrates: [M(O‐OC(NH2)CHCH2)n(H2O)m][NO3]2 (M = Co( 1 ), Ni( 2 ) (n = 6 and m = 0) and Zn( 3 ) (n = 4 and m = 2)) have been determined by using single crystal X‐ray diffraction analysis. All complexes crystallize in the triclinic space group . The structures of 1 and 2 represent octahedral species [M(AAm)6]2+ (AAm = O‐OC(NH2)CHCH2 and M = Co or Ni) and uncoordinated nitrate ions. The structure of 3 involves the octahedral cation [Zn(AAm)4(H2O)2]2+ in which the Zn2+ environment includes oxygen atoms of four acrylamide and two water molecules that are stabilized using ionic nitrate ions. The observations of the solid‐state IR spectroscopic vibrational frequencies of these acrylamide complexes are in agreement with the crystal structures. 相似文献