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11.
The photopolymerization of methylmethacrylate in solution or in bulk, initiated by DMPA (2,2-dimethoxy-2-phenylacetophenone) and BP (benzophenone), has been investigated in the presence of ZnCI2 as a complexing agent. We have studied the steady state polymerization (measurement of R, and OT) and the behaviour of the excited states by laser spectroscopy. We have shown the following points: Rp and DP increase with [ZnCI2]; the rate constant for propagation increases with [ZnC12]; the rate of initiation remains constant in presence of BP-ZnCl2 but increases with DMPA-ZnCl2. The results are accounted for by the results of laser spectroscopy. 相似文献
12.
Alternating adsorption of poly(acrylic acid) and a polyethylenimine-Pd(II) complex on alumina and subsequent reduction of Pd(II) by NaBH4 yield catalytic Pd nanoparticles embedded in multilayer polyelectrolyte films. The polyelectrolytes limit aggregation of the particles and impart catalytic selectivity in the hydrogenation of alpha-substituted unsaturated alcohols by restricting access to catalytic sites. Hydrogenation of allyl alcohol by encapsulated Pd(0) nanoparticles can occur as much as 24-fold faster than hydrogenation of 3-methyl-1-penten-3-ol. Additionally, the nanoparticle/polyelectrolyte system suppresses unwanted substrate isomerization, when compared to a commercial palladium catalyst. Selective diffusion through poly(acrylic acid)/polyethlyenimine membranes suggests that hydrogenation selectivities are due to different rates of diffusion to nanoparticle catalysts. First-order kinetics are also consistent with a diffusion-limited mechanism. Further exploitation of the versatility of polyelectrolyte films should increase selectivity in hydrogenation as well as other reactions. 相似文献
13.
Merlin Rosales Janeth Navarro Ligbel Sánchez Angel González Ysaías Alvarado Raúl Rubio Carlos De La Cruz Tamara Rajmankina 《Transition Metal Chemistry》1996,21(1):11-15
Summary The complex [RuH(CO)(NCMe)2(PPh3)2]BF4 (1) is an efficient and regioselective catalyst precursor for the hydrogenation of polyaromatic nitrogen compounds such as quinoline (Q), isoquinoline (iQ), indole (ln), 5,6- and 7,8-benzoquinoline (BQ) and acridine (A) under relatively mild reaction conditions (125 °C, 4 atm H2). The order of individual initial rates was: A > Q > 5,6-BQ > 7,8-BQ > ln > iQ, reflecting both steric and electronic effects. For the regioselective homogeneous hydrogenation of A to 9,10-dihydroacridine (DHA) catalysed by complex (1), a kinetic study was carried out; the experimentally determined rate law was r = k
1 [Ru] [H2]. These findings are consistent with a mechanism involving the hydrogenation of [RuH(CO)(A)(NCMe)(PPh3)2]BF4 to yield DHA and the unsaturated species [RuH(CO)(NCMe)(PPh3)2]BF4 in the rate-determining step. 相似文献
14.
15.
Merlin A. Fox Fang-Jie Zhao Steve P. McGrath 《International journal of environmental analytical chemistry》2013,93(5):323-329
A new method for the determination of the 34S/32S ratio of water-extractable sulphate in soil is described. Soils are extracted directly with deionized water, which is evaporated down. The remaining residue is then rehydrated and transferred to tin cups containing an adsorbent and mixed with an oxygen donor (V2O5). Samples are then analysed using a continuous flow isotope ratio mass spectrometer. The new method requires around 10?g soil per determination, compared to much larger amounts (up to kilograms) of soil required for the previous methods. Sample preparation and subsequent analysis is quick and efficient. The method is demonstrated using a number of soils collected from around the world to provide a range of determined δ34S values. The δ34S values of water-extractable sulphur were broadly similar to those of the soil total sulphur. 相似文献
16.
Mathematische Semesterberichte - We describe in the form of a dialogue a development of various reflections on the combinatorics of set partitions; among the topics we pursue are... 相似文献
17.
Merlin Heß Dr. Ivo Krummenacher Dr. Theresa Dellermann Prof. Dr. Holger Braunschweig 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(37):9503-9507
A series of highly substituted 1,2-azaborinines, including a phenylene-bridged bis-1,2-azaborinine, was synthesized from the reaction of 1,2-azaborete rhodium complexes with variously substituted alkynes. 1-Rhoda-3,2-azaborole complexes, which are accessible by phosphine addition to the corresponding 1,2-azaborete complexes, were also found to be suitable precursors for the synthesis of 1,2-azaborinines and readily reacted with alkynyl-substituted 1,2-azaborinines to generate new regioisomers of bi-1,2-azaborinines, which feature directly connected aromatic rings. Their molecular structures, which can be viewed as boron-nitrogen isosteres of biphenyls, show nearly perpendicular 1,2-azaborinine rings. The new method using rhodacycles instead of 1,2-azaborete complexes as precursors is shown to be more effective, allowing the synthesis of a wider range of 1,2-azaborinines. 相似文献
18.
Vrielynck L Wallet JC Merlin JC 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2000,(12):2439-2450
The FT-infrared and Raman microscopy spectra of the 2',6'-dimethoxyflavone and its 1:1 complex with formic acid in solid state have been recorded and analysed. Some vibrational components appear as specific to the cis-rotamer of formic acid in the crystalline sample, especially the CH group stretching vibration feature. The broad and intense infrared absorption observed in the range 3400-1900 cm(-1) and assigned to the hydrogen bonded OH group stretching vibration exhibits the characteristic ABC structure of strong hydrogen bonded complexes. This ABC pattern corroborates previous X-ray crystallographic data showing that cis-formic acid is strongly hydrogen bonded to the flavonic compound. The inclusion complex is quite unstable and the infrared spectrum clearly shows that formic acid disappears after a period of a few months. In order to get some information on the stability criterions of the intermolecular hydrogen bonded complex, semiempirical AM1 calculations have been investigated. The comparison of the calculated heats of complexation (deltacH) for chelates involving the cis- and trans-conformers of formic acid suggests that the reaction of hydrogen bonding complexation with the cis-rotamer is surely favoured. 相似文献
19.
Photocurable finishes should be extensively used for industrial wood joinery in the near future even if some technical problems
have still to be solved and if the durability of the finishing system has to be enhanced. In a previous work, we studied the
curing reaction of acrylic resins containing some particular photoinitiators by photocalorimetry and showed that curing can
be achieved under daylight with these compounds (i.e. solving the problem of restoration on site). The aim of this work is
to enhance the durability of these systems by incorporating UV absorbers into the formulations. The consequences of such an
addition onto the curing kinetics are again investigated by photocalorimetry. 相似文献
20.
Light-weight robots are advantageous considering the low energy consumption and the low material cost. However, in light-weight structures significant oscillations can occur which make the control very challenging. Objective of this research is end-effector trajectory tracking of a parallel manipulator with flexible links. Hereby, only the manipulator's drives are used, and no additional actuation on the flexible bodies is considered. For accurate trajectory tracking, feedforward control of the manipulator is used based on inverse dynamics and servo-constraints, combined with feedback control of the drive positions. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献