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41.
Serge Schubert Philippe Renaud Pierre-Alain Carrupt Kurt Schenk 《Helvetica chimica acta》1993,76(7):2473-2489
Radical addition to enamines using Bu3SnH as reducing agent are reported (Schemes 2 and 4). The diastereoselectivity of these reactions was examined in different systems (Tables 1 and 2). Enamines derived from cyclic ketones such as cyclohexanone were alkylated with high diastereoselectivity with preferential formation of the cis-disubstituted cycloalkanes. In acyclic systems such as enamines derived from propiophenone and diethyl ketone, moderate to high stereoselectivities were observed in the H-abstraction step. A model based principally on minimization of allylic 1,3-strain (A1,3 strain) was deduced from the experimental results and semi-empirical (AM1) calculations. 相似文献
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Gohy JF Lohmeijer BG Schubert US 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(15):3472-3479
The formation of asymmetric bis-complexes, based on terpyridine ligands and ruthenium ions, is described as a powerful tool for the self-assembly of polymer blocks end-functionalized with terpyridine units. This is illustrated in this contribution for the synthesis of amphiphilic metallo-supramolecular block copolymers, which are further used to produce aqueous micelles. Finally, the reversibility of the supramolecular bond opens new avenues for the preparation and manipulation of these nano-objects. 相似文献
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A series of epoxy resins has been formulated on the basis of obtaining low water sorption, low water vapor permeability, retention of electrical properties, and resistance to biodegradation by the body. These resins have been tested for these properties both by accelerated aging in 100°C water and in vivo studies. A literature survey was conducted on the biodegradation of surgical plastics with the findings that nylon lost 80% of its tensile strength after 3 years implantation while Orlon and Dacron deteriorated considerably less in a 2-year period. Teflon, Mastic, and Mylar showed almost no loss in tensile strength after 17 to 22 months. The epoxies tested on this program showed no loss in strength after 6 months in vivo. It appears that materials whose chemical structure contain bonds similar to those found in the body (such as amide groups) are susceptible to biodegradation whereas those such as Teflon which contain only C-C bonds or C-F bonds are not. Two general types of biodegradation can occur on polymers: Attack starting at the end of a polymer chain and proceeding along the chain to produce monomeric fragments (as in polypropylene), and attack at regular intervals along a polymer chain where susceptible cross-linking groups are present to produce macromolecular fragments. It has been postulated that attack on polymers takes place in the amorphous areas (if they are present) to leave the more crystalline areas of the material intact. Thus, with implantation, these types of materials become brittle. Histology on the developed epoxies indicated that epoxies containing nonreactive hydrophobic diluents showed a greater foreign body reaction than normal epoxies without such diluents. 相似文献
47.
Sarah Crotty Felix H. Schacher Ulrich S. Schubert 《Journal of polymer science. Part A, Polymer chemistry》2012,50(23):4958-4965
We report the synthesis and characterization of well‐defined homo‐ and diblock copolymers containing poly(furfuryl glycidyl ether) (PFGE) via living anionic ring‐opening polymerization using different initiators. The obtained materials were characterized by SEC, MALDI‐TOF MS, and 1H NMR spectroscopy and molar masses of up to 9400 g/mol were obtained for PFGE homopolymers. If the amphiphilic diblock copolymer PEG‐block‐PFGE was dissolved in water, micelles with a PFGE core and a PEG corona were formed. Hereby, the hydrophobic PFGE core domains were used for the incorporation of a suitable bismaleimide and heating to 60 °C induced the crosslinking of the micellar core via Diels‐Alder chemistry. This process was further shown to be reversible. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
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Georgy M. Pavlov Anke Teichler Stephanie Höppener Christine Weber Jürgen Nowotny Lars Blankenburg Jürgen Popp Martin D. Hager Benjamin Dietzek Ulrich S. Schubert 《Journal of polymer science. Part A, Polymer chemistry》2012,50(15):3192-3205
In order to form suitable systems designed for resonance energy transfer, a series of monodisperse methacrylate‐based monomers containing rigid π‐conjugated oligo(phenylene ethynylenes) with different sizes of the conjugated systems ( M1 – M3 ), and therefore different optoelectronic properties, were synthesized and subsequently polymerized using the reversible addition–fragmentation chain transfer polymerization technique ( P1 – P3 ). In addition, these oligomers were also copolymerized with methyl methacrylate. The obtained polymers were characterized by 1H NMR spectroscopy, size exclusion chromatography, and analytical ultracentrifugation. The photophysical properties of the polymers were studied by UV–vis absorption and emission spectroscopy in diluted solutions as well as in thin films and compared to the photophysics of the corresponding monomers. Thereby, changes going from monomeric to polymeric systems could be detected in fluorescence quantum yields and lifetimes pointing to energy trapping, e.g., energy transfer. Donor–acceptor copolymers containing different numbers of monomeric units within the side chain exhibit differences in the emission spectra, indicating that energy trapping in polymers is very sensitive to structural properties such as the chain length. UV–vis absorption spectroscopy as well as time‐resolved lifetime studies indicate intrapolymer and interpolymer energy transfer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
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Intra‐ and inter‐supramolecular complexation of poly(butyl methacrylate)‐co‐2‐(1,2,3‐triazol‐4‐yl)pyridine copolymers induced by CoII,FeII, and EuIII ions monitored by molecular hydrodynamics methods 下载免费PDF全文
Georges M. Pavlov Igor Perevyazko Bobby Happ Ulrich S. Schubert 《Journal of polymer science. Part A, Polymer chemistry》2016,54(16):2632-2639
Poly(butyl methacrylate) copolymers embedding bidentate 2‐(1,2,3‐triazol‐4‐yl)pyridine (trzpy) chelating units as comonomer in the side chains were synthesized by controlled radical addition‐fragmentation transfer (RAFT) polymerization. Intracomplexation and intercomplexation of the macromolecules of the poly(butyl methacrylate) copolymers containing 20 % mol of trzpy units induced by CoII, FeII, and EuIII ions were studied in the solutions by macromolecular hydrodynamics methods. The sedimentation velocity of extremely diluted copolymer solutions and the dynamic viscosity of moderately diluted solutions were studied in a wide range of the salts concentrations. Differences were observed with respect to the copolymer behavior in the presence of the Co2+, Fe2+, Eu3+ ions. These differences are namely due to the differences in the number of coordination bonds required for complex formation and not explicitly to the nature of the corresponding anions. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2632–2639 相似文献
50.
Christian Martschitsch Ulrich Schubert 《Monatshefte für Chemie / Chemical Monthly》2014,145(4):577-584