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771.
Jan Hegewald Jürgen Pionteck Liane Häußler Hartmut Komber Brigitte Voit 《Journal of polymer science. Part A, Polymer chemistry》2009,47(15):3845-3859
Monoamino‐terminated and monocarboxylic acid‐terminated polystyrenes containing active halogenated end groups were prepared by atom transfer radical polymerization (ATRP) using the so‐called initiator method and protective group chemistry. α‐Chloropropionates were synthesized and utilized as initiators containing the tert‐butoxycarbonyl (t‐BOC)‐protected amino and the tert‐butyl (t‐Bu)‐protected carboxylic acid function, respectively. Optimum polymerization conditions were attained using CuCl/N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine (PMDETA) as catalyst and 10 vol % n‐butanol as homogenizing agent at 110 °C. However, targeting larger quantities an alternative route was established employing 50 vol % N,N‐dimethylformamide (DMF). Subsequent hydrolysis of the ω‐tert‐butoxycarbonyl polystyrenes afforded well‐defined polymers with quantitative deprotection of the functional groups. Comparatively, thermolytic cleavage of the protective sites was studied. 1H NMR verified the quantitative removal of the t‐BOC‐protecting groups. Furthermore, the resulting α‐amino‐ω‐chloro polystyrenes were reacted with Sanger reagent to confirm the existence of the thereby converted primary amino groups. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3845–3859, 2009 相似文献
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773.
Recently, interest in steel alloyed with∼1% Al increased. These materials are expected to show a higher resistance against
oxidation at high temperatures which will improve their performance when used as high-speed-steels. Furthermore, efforts have
been made to combine the advantages of Al-steels with those of powder-metallurgic methods like hotisostatic-pressing (hip).
This should result in a better macro- and microscopic homogeneity of the distribution of all compounds, yielding less waste-production
and a longer life-time of products.
In order to gain deeper insights in the process of “hipping” of the considered material and to see the distribution of both
main as well as trace components, 2D and 3D-SIMS measurements of the material were performed before and after having undergone
the hip process.
The measurements showed enrichments of Na, K, Mg, Ca, and S at the particle boundaries before as well as after the hip-process.
In the hipped material, the enrichments are significantly stronger in the spatial domains in-between larger particles. They
also reveal, that the concentration of C is not equal in all particles and that the particles are covered with an Al2O3-layer which is not dispersed by the hip-process. There were also found small (∼50–100 nm) nitride-precipitates before as
well as after the hip-process. 相似文献
774.
This work deals with the chemical grafting of a styrene maleic anhydride copolymer on the surface of a previously hydrolyzed polyethylene terephthalate (PET) film 12 μm thick via covalent bond. Two different ways are studied. The first one involves an activation of the hydrolyzed PET by the triethylamine before the grafting step. In the second one, the copolymer reacts with the 4-dimethylaminopyridine in order to form maleinyl pyridinium salt which reacts with alcohol function of the hydrolyzed PET. Characterization and quantification of the grafting are performed by Fourier transform infrared spectroscopy. Factorial experiment designs are used to optimize the process and to estimate experimental parameters effects. The opportunity to associate the chemical process to a cold remote nitrogen plasma one is also examined. 相似文献
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778.
Convenient synthesis of multifunctional EDTA-based chiral metal chelates substituted with an S-mesylcysteine 总被引:3,自引:0,他引:3
Leonov A Voigt B Rodriguez-Castañeda F Sakhaii P Griesinger C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(11):3342-3348
We describe the synthetic route to ethylenediaminetetraacetic acid (EDTA) derivatives that can be attached to surface-exposed thiol functional groups of cysteine residues in proteins, via a methylthiosulfonate moiety that is connected in a stereochemically unique way to the C-1 carbon atom of EDTA. Such compounds can be used to align proteins in solution without the need to add liquid crystalline media, and are, therefore, of great interest for the NMR spectroscopic analysis of biomolecules. The binding constant for the paramagnetic tag to lanthanide ions was determined by measuring luminescence. For the Tb(+3)-ligand complex, a K(b) value of 6.5 x 10(17) M(-1) was obtained. This value is in excellent agreement with literature values for the related EDTA compound. In addition, it could be shown that there is no significant reduction in the luminescence intensity upon addition of a 10(4) excess of Ca2+ ions, indicating that this paramagnetic tag is compatible with buffers containing high concentrations of divalent alkaline earth ions. 相似文献
779.
Lars?Einfeldt Wolfgang?Günther Dieter?KlemmEmail author Brigitte?Heublein 《Cellulose (London, England)》2005,12(1):15-24
A homologous series of partially hydrolyzed celluloses (level-off-DP cellulose) with weight-average molecular weight (DPw) < 150 were peracetylated and characterized by 1H-NMR spectroscopy. The results demonstrate the utility of 1H-NMR spectroscopy to assign the chemical shifts of all end groups of the peracetylated cellulose. On the one hand, the chemical shifts of all methine and methylene protons of the non-reducing terminal end group (TEG) as well as the - and -anomer of the reducing end group (REG) could be determined by two-dimensional NMR techniques (COSY-DQF) and by selective excitation of isolated proton signals (1D-TOCSY) of these end groups. On the other hand, the spectral resolution was high enough to determine the number-average molecular weight (DPn) of peracetylated level-off-DP cellulose (LODP cellulose acetates) as shown in comparison with the data of gel permeation chromatography (GPC). This molecular weight determination of cellulose using end group analysis by means of 1H-NMR spectroscopy was demonstrated for the first time. Furthermore, a specific modification of hydroxyls in end groups could be exemplified in case of 1-OH-deacetylation of the REG of peracetylated LODP cellulose. 相似文献
780.