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81.
Zou Y Wang D Wurst K Kühnel C Reinhardt I Decker U Gurram V Camadanli S Buchmeiser MR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(49):13832-13846
Two novel Zr(IV)- and Hf(IV)-based bisamido complexes bearing the 6-[2-(diethylboryl)phenyl]pyrid-2-yl motif, that is, [ZrCl(2){Me(2)Si(DbppN)(2)}(thf)] (9) and [HfCl(2){Me(2)Si(DbppN)(2)}(thf)(2)] (10) (DbppN=6-[2-(diethylboryl)phenyl]pyridine-2-amido) have been prepared. Their reactivities have been compared with that of a model precatalyst that does not bear the aminoborane motif. Upon activation with methylalumoxane, precatalysts 9 and 10 are active in the homopolymerization of ethylene (E) yielding high-density polyethylene (HDPE). In the copolymerization of E with cyclopentene (CPE), for example by the action of 9, the presence of CPE resulted in a dramatic increase in the polymerization activity of E, while CPE incorporation remained close to or at zero. In the vinyl-insertion copolymerization of norborn-2-ene (NBE) with E by the action of 9, statistical cyclic olefin copolymers of these two monomers were obtained. At higher NBE concentrations, however, 9 gave rise to reversible ring-opening metathesis (ROMP)/vinyl-insertion polymerization (VIP) of NBE with E, resulting in the formation of multi-block copolymers of the general formula poly(NBE)(ROMP)-co-poly(NBE)(VIP)-co-poly(E). This particular feature of precatalyst 9, that is, the ability to induce a reversible α-H elimination/α-H addition reaction, is attributed to the unique role of the 6-[2-(diethylboryl)phenyl]pyrid-2-yl ligand. Accordingly, a model precatalyst lacking this ligand does not have the ability to induce α-H elimination/α-H addition reactions. The different (11)B NMR shifts of various diethylborylphenylpyrid-2-ylamines and -amides permit a ranking of the strengths of the B-N bonds in these compounds. This strength of the B-N bond is correlated with the propensity of 9/MAO to produce poly(NBE)(ROMP)-co-poly(NBE)(VIP)-co-poly(E) at different temperatures. 相似文献
82.
Tietze LF Schmuck K Schuster HJ Müller M Schuberth I 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(6):1922-1929
Chemotherapy of malign tumors is usually associated with serious side effects as common anticancer drugs lack selectivity. An approach to deal with this problem is the antibody-directed enzyme prodrug therapy (ADEPT) and the prodrug monotherapy (PMT). Herein, the synthesis and biological evaluation of new glycosidic prodrugs suitable for both concepts are described. All prodrugs but one are stable in human serum and show QIC(50) values (IC(50) of prodrug/IC(50) of prodrug in the presence of the appropriate glycohydrolase) of up to 6500. This is the best value found so far for compounds interacting with DNA. 相似文献
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Monzote Fidalgo L Sariego Ramos I García Parra M Cuesta-Rubio O Márquez Hernández I Campo Fernández M Piccinelli AL Rastrelli L 《Natural product communications》2011,6(7):973-976
In this paper we analyzed the antiprotozoal effects of eighteen Cuban propolis extracts (brown, red and yellow type) collected in different geographic areas, using Leishmania amazonensis (as a model of intracellular protozoa) and Trichomonas vaginalis (as a model of extracellular protozoa). All evaluated propolis extracts caused inhibitory effect on intracellular amastigotes of L. amazonensis. However, cytotoxicity on peritoneal macrophages from BALB/c mice was observed. Only five samples decreased the viability of T. vaginalis trophozoites at concentrations lower than 10 microg/mL. No correlation between the type of propolis and antiprotozoal activity was found. Cuban propolis extracts demonstrated activity against both intracellular and extracellular protozoa model, as well as the potentialities of propolis as a natural source to obtain new antiprotozoal agents. 相似文献
86.
Summary A series of apomorphine congeners has been studied with respect to their ability to mimic the structural requirements of the dopamine pharmacophore in the potent and stereoselective dopamine receptor agonist (R)-apomorphine. Conformational energies of the mimicking structures calculated by molecular mechanics (MMP2) correlate well with the observed biological activities. 相似文献
87.
Ingrid Rotter 《Czechoslovak Journal of Physics》2005,55(9):1167-1172
Avoided crossings of discrete states as well as of resonance states are traced back to the existence of branch points (BPs)
which are singular points in the complex energy plane. They cannot be identified with exceptional points. At a BP width bifurcation
occurs, different Riemann sheets evolve and the levels do not cross anymore when the system is still further opened. The BPs
are physically meaningful: they influence the dynamics of open as well as of closed quantum systems. The geometric phase that
arises by encircling a BP, is different from the phase that appears by encircling a diabolic point. This is found to be true
even for the two BPs into which the diabolic point is unfolded by opening the system.
Presented at the 3rd International Workshop “Pseudo-Hermitian Hamiltonians in Quantum Physics”, Istanbul, Turkey, June 20–22,
2005. 相似文献
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