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11.
C. D. Eisenbach A. Göldel M. Terskan-Reinold U. S. Schubert 《Colloid and polymer science》1998,276(9):780-785
Transmission electron microscopy (TEM) studies on bipyridine (bpy) containing block copolymer systems showed the formation
of nanoscopic polymer–ion complexes through complexation with copper(I) ions which segregated to highly ordered columnar domains
of mesoscopic dimensions. The domains, i.e. stacks of [(bpy)2Cu(I)] complex moieties could be visualized by complementary TEM techniques. First, electron energy loss spectra (EELS) showed
the absorption edges of copper and nitrogen, which are specific for the bipyridine copper complexes. The element spectroscopic
imaging (ESI) technique allowed the imaging of the net copper and net nitrogen distribution, and the coinciding pictures exhibited
a microphase separated system in the case of a 3-block copolymer with complexed end segments. High resolution elastic bright
field images showed interference lines with a line to line distance of about 8 A which could be related to the Cu–Cu distance
in staggered Cu(I)–bipyridine complexes.
Received: 6 August 1997 Accepted: 28 April 1998 相似文献
12.
Albrecht H Binder U Harder G Lembke-Koppitz I Philipp A Schmidt-Parzefall W Schröder H Schulz HD Wurth R Donker JP Drescher A Matthiesen U Scheck H Spaan B Spengler J Wegener aD Gabriel JC Schubert KR Stiewe J Waldi R Weseler S Brown NN Edwards KW Frisken WR Fukunaga C Gilkinson DJ Gingrich DM Goddard M Kapitza H Kim PC Kutschke R MacFarlane DB McKenna JA McLean KW Nilsson AW Orr RS Padley P Patel PM Prentice JD Seywerd HC Stacey BJ Yoon T Yun JC Ammar R Coppage D Davis R Kanekal S Kwak N 《Physical review letters》1986,56(6):549-552
13.
Ulrich Schubert 《Journal of Sol-Gel Science and Technology》2003,26(1-3):47-55
Organically substituted metal alkoxides can be prepared by reaction of the parent alkoxides with complexing organic compounds. The chemical and structural consequences of such substitutions are discussed in this article. Examples are given showing how functional organic moieties, such as polymerizable groups, can be incorporated into sol-gel materials via the complexing ligands. Major structural differences between silica-based and metal-based hybrid materials originate from the different charge/coordination number ratios of silicon and most metals. This results in a high tendency for the molecular building blocks to aggregate. In many cases, metal oxide clusters are formed which are capped by the organic ligands. Such surface-modified clusters are themselves very valuable condensed matter units for materials syntheses. 相似文献
14.
Meier MA de Gans BJ van den Berg AM Schubert US 《Rapid communications in mass spectrometry : RCM》2003,17(20):2349-2353
Recently, a new multiple-layer matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) sample spotting technique for poly(ethylene glycol), offering improved analysis possibilities, was described. In this contribution the application of ink-jet printing to automated, multiple-layer MALDI-TOFMS sample preparation of synthetic polymers is presented, allowing accurate deposition of matrix, additive and analyte solutions. The new sample preparation technique was evaluated for poly(ethylene glycol) as well as poly(methyl methacrylate) standards, and optimized settings for both synthetic polymers have been obtained. 相似文献
15.
The hydrogenation of unsaturated organic substrates such as olefins and ketones is usually effected by homogeneous or heterogeneous transition-metal catalysts. On the other hand, a single case of a transition-metal-free and purely base-catalyzed hydrogenation of ketones was reported by Walling and Bollyky some 40 years ago. Unfortunately, the harsh reaction conditions (ca. 200 degrees C, >100 bar H(2), potassium tert-butoxide as base) limit the substrate spectrum of this reaction to robust, nonenolizable ketones such as benzophenone. We herein present a mechanistic study of this process as a basis for future rational improvement. The base-catalyzed hydrogenation of ketones was found to be irreversible, and it shows first-order kinetics with respect to the substrate ketone, hydrogen, and catalytic base. The rate of the reaction depends on the type of alkali ion present (Cs > Rb - K > Na > Li). Using D(2) instead of H(2) revealed a rapid base-catalyzed isotope exchange/equilibration between the gas phase and the solvent as a concomitant reaction. The degree of deuteration of the product alcohols did not indicate a significant kinetic isotope effect. It is proposed that both ketone reduction and isotope exchange proceed via similar six-membered cyclic transition states involving the H(2)(D(2))-molecule, the alkoxide base, and the ketone (solvent alcohol in the case of isotope exchange). Mechanistic analogies are pointed out which apparently exist between the base-catalyzed hydrogenation of ketones studied here and the Ru-catalyzed asymmetric ketone hydrogenation developed by Noyori. In both cases, heterolysis of the hydrogen molecule appears to be assisted by a Br?nsted-base (i.e., alkoxide), the latter being bound to the substrate ketone or the catalyst ligand, respectively, by a bridging Lewis-acidic alkali ion. 相似文献
16.
On Chalcogenolates. 159. Reaction of 1,2-Ethanedithiolates with Carbon Disulfide. 1. Synthesis and Characterization of 1,2-Ethane-bis(trithiocarbonates) The reaction of 1,2-ethanedithiolates with carbon disulfide forms the corresponding 1,2-ethane-bis(trithiocarbonates). The compounds M2[S2C? SCH2CH2S? CS2] with M = Li, Na, K, Rb, Cs, NH4, Tl have been characterized with chemical methods as well as by means of electron absorption, infrared, nuclear magnetic resonance (1H and 13C), and mass spectra. 相似文献
17.
Reinhard Schubert Achim Ansmann Paul Bleckmann Bernhard Schrader 《Journal of Molecular Structure》1975,26(2):429-438
By using the values of the vibrational frequencies of normal and deuterated cyclopropenone (II-d0 , II-d2 ) and 16 O-and 18 O-substituted dimethylcyclopropenone (III) as -well as the infrared and Raman intensities of II a consistent set of force constants has been derived for the cyclopropenone skeleton. The derived values show that the zwitterionic form makes a substantial contribution to the electronic ground state of the molecule. The combined frequency and intensity calculation - simulation of the infrared and the Raman spectrum - is shown to be a good method for making a proper assignment of calculated and observed vibrations and deriving realistic sets of force constants. 相似文献
18.
Preparation of Acetatolead(1V) and Acetatotin(1V) Manganese Pentacarbonyls by Acidolysis of (C6H5)4?n M[Mn(CO)5]n (M ? Sn, Pb; n = 1, 2) with Acetic Acid By acidolysis of (C6H5)4?nM[Mn(CO)5]n (M ? Sn, Pb; n = 1, 2) with acetic acid no M? Mn bonds are broken, but M? C bonds. In this reaction (CH3COO)2M[Mn(CO)5]2 is formed from (C6H5)2M[Mn(CO)5]2, and (CH3COO)3SnMn(CO)5 and (CH3COO)2C6H5PbMn(CO)5 from (C6H5)3MMn-(CO)5. (CH3COO)2C6H5SnMn(CO)5 is prepared from Cl2C6H5SnMn(CO)5 and AgCH3COO. According to IR spectroscopic data the acetato ligands of the diacetato complexes are bidentate, while in (CH3COO)3SnMn(CO)5 bi- and monodentate carboxylate groups are present. For the central atoms Sn and Pb octahedral coordination is proposed. 相似文献
19.
An optical biosensor for the determination of hydrogen peroxide based on immobilized horseradish peroxidase is described. The fluorescence of the dimeric product of the enzyme catalysed oxidation of homovanillic acid is utilized to determine the concentration of H2O2. The membrane-bound enzyme is attached to a bifurcated fibre bundle permitting excitation and detection of the fluorescence by a fluorometer. The response of the sensor is linear from 1 to 130 M hydrogen peroxide; the coefficient of variation is 3%. The sensor is stable for more than 10 weeks. The operating pH for maximal sensor response is 8.15. This allows the sensor to be used in combination with oxidase reactions producing hydrogen peroxide, as is demonstrated with a co-immobilized lactate oxidase-horseradish peroxidase optode for the determination of L-lactate. The fluorescence intensity of this sensor depends linearly on the concentration of lactate between 3 and 200 M and a throughput of 10 samples per hour is possible. The precision is in the same range as that of the monoenzyme optode. The lifetime of the bienzyme sensor for lactate is considerably shorter than that of the peroxidase sensor; it is limited by the stability of the immobilized lactate oxidase enzyme. The sensor has been applied to the determination of lactate in control serum. 相似文献
20.
The loss of substituents X from molecular ions of ortho substituted 2-benzoyl pyridines has been investigated as a function of the dissociation energy of the C? X bond. Comparison of unimolecular and collisional induced decompositions of the resulting [M ? X]+ ions and reference ions arising from 3-hydroxypyrido[1,2-α]indole shows that cyclic fragment ions are formed in every case by an intramolecular substitution reaction with the exception of the parent compound (X = H), which gives rise to a mixture of [M ? H]+ ions with different structures. The heat of formation of the cyclic ion has been estimated experimentally and by calculation using thermochemical data, and from this value and the appearance energies, the activation energies of the reverse reactions have been evaluated for the different reaction systems. Measurement of the kinetic energy release during the substitution reactions shows that only part of the reverse activation energy is released as kinetic energy. The energy partitioning quotient varies from 0.37 to 0.08 depending on the dissociation energy of the C? X bond or the reaction enthalpy. A sudden change in the energy partitioning quotient is observed with increasing exothermicity of the reaction, paralleling the behaviour of similar reaction systems. These results are interpreted as a demonstration of the influence of the variation of transition state position on the energy partitioning quotient. 相似文献