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161.
Benchmarking of ruthenium initiators for the ROMP of a norbornenedicarboxylic acid ester 总被引:1,自引:0,他引:1
Sandra Demel Wolfgang Schoefberger Christian Slugovc Franz Stelzer 《Journal of molecular catalysis. A, Chemical》2003,200(1-2):11-19
The kinetic study of ring-opening metathesis polymerization (ROMP) of a diester functionalised norbornene derivative, (±)-exo,endo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid diethyl ester, with a series of ruthenium benzylidene complexes revealed the applicability of these initiators for well defined polymerization reactions. Values for the rate of initiation as well as the rate of propagation of the initiators were determined and correlated to the molecular weight and polydispersity of the isolated polymers. As the only initiator providing an entry to virtually monodisperse polymers the classical “first generation Grubbs-catalyst” was identified, while N-heterocyclic carbene based initiators polymerized with a rate of propagation much higher than the rate of initiation yielding polymers with a broader molecular weight distribution. 相似文献
162.
Crystal Structures of KNdTe4, RbPrTe4, and RbNdTe4 — Investigations concerning the Thermal Stability of KNdTe4 as well as some Remarks concerning Additional Representatives of the Composition ALnTe4 (A = K, Rb, Cs and Ln = Rare Earth Metal) Of the compounds ALnQ4 (A = Na, K, Rb, Cs; Ln = Lanthanoid; Q = S, Se and Te) the crystal structures of the three new tellurides KNdTe4, RbPrTe4 and RbNdTe4 were determined by X‐ray single‐crystal structure analysis and of the three additional new ones KCeTe4, KPrTe4 and CsNdTe4 by X‐ray powder diffraction experiments. All six new compounds are isotypic with KCeSe4. Characteristic for the crystal structure of the compounds mentioned above are layers built from (Q2)2— dumbbells in form of 4.32.4.3 nets with embedded cations A+ and Ln3+ between them, which are coordinated eightfold in form of square‐shaped antiprisms by Q ions. The distances Te‐Te within the dumbbells were found to be 277.8(2) pm for all investigated tellurides. By combination of X‐ray diffraction and DTA measurements it was shown that the compound KNdTe4 is metastable at ambient temperature with a limited existence range between the temperatures 260 and 498 °C. 相似文献
163.
In this article, we describe the unique fragmentations of oligodeoxynucleotides (ODNs) whose phosphate groups are completely depleted of protons and replaced with metal ions. The production of the ubiquitous [a(n) - base] ions still occurs, but no longer by transfer of an acidic phosphate proton to an adjoining 3' base. Nor is the extent of the reaction determined by the proton affinity of that base. Rather, the reaction now occurs via a cleavage 3' to both pyrimidines and purines; cleavage 3' to pyrimidine is more favorable than that 3' to purine. We also demonstrate that an ODN is more stable in the gas phase when its phosphate groups are bound to metal ions than when its phosphate groups are attached to hydrogens. This study also provides further evidence for the ODN fragmentation mechanism that involves H transfer to a nucleobase. To establish the structural utility of this new fragmentation, we applied it to distinguishing small ODNs containing a photomodified cis,syn-cyclobutane pyrimidine dimer from the parent ODNs, a system that cannot be distinguished by collisional activation of precursor species that do not contain metal ions. 相似文献
164.
Depecker G Patino N Di Giorgio C Terreux R Cabrol-Bass D Bailly C Aubertin AM Condom R 《Organic & biomolecular chemistry》2004,2(1):74-79
A cyclic molecule including a hexameric PNA sequence has been designed and synthesized in order to target the TAR RNA loop of HIV-1 through the formation of a "kissing complex". For comparison, its linear analogue has also been investigated. The synthesis of the cyclic and linear PNA has been accomplished following a liquid-phase strategy using mixed PNA and fully N-protected (aminoethylglycinamide) fragments. The interactions of this cyclic PNA and its linear analogue with TAR RNA have been studied and the results indicate clearly that no interaction occurs between the cyclic antisense PNA and TAR RNA, whereas a tenuous interaction has been detected with its linear PNA analogue. 相似文献
165.
Hubertus Appler Lutz W. Gross Bernd Mayer Wilhelm P. Neumann 《Journal of organometallic chemistry》1985,291(1):9-23
Factors governing the ease and mechanism of 7-silabicyclo[2.2.1]heptadienes thermolysis in order to generate free silylenes and the corresponding benzene derivatives are investigated. For this purpose, 29 new compounds of the types VII–X have been prepared. No indications for a polar mechanism or an intermediate biradical could be found. The degradation is exactly of first order in all cases investigated sofar, and is enhanced by phenyl groups at the bridgehead C atoms, if a conformation coplanar with the basic ring is allowed by the neighbouring substituents, but is not enhanced by phenyl groups at the Si. The X-ray structure of two typical derivatives is discussed with this respect. A special mechanism is operating in the easy thermolysis of carbomethoxy-substituted compounds leading to cyclic sila enolether intermediates. 相似文献
166.
The collision-induced dissociation (CID) spectra of five alkylmethyleneimmonium ions (H2C-N+R1R2, (a) R1 = R2 = C2H5, (b) R1 = n-C3H7, R2 = H, (c) R1 = n-C3H7, R2 = CH3, (d) R1 = n-C3H7, R2 = C2H5, (e) R1 = R2 = n-C3H7) are reported and discussed in terms of the mechanism of alkane loss. The most abundant alkane losses result from 2-azaallylic bond cleavages within R1 and R2 leading to daughter ions of m/z 84. Ion d (R1 = n-C3H7, R2 = C2H5) was chosen for a deuterium-labelling study because it exhibited methane loss nearly free from interferences with other fragmentations. The methane lost consists to a great extent (95%) of the methyl moiety of R2. Whereas the methyl moiety obviously stays intact during the fragmentation process, the hydrogen additionally needed originates from all positions of R1 and the double-bonded methylene in an approximately random distribution, suggesting extensive hydrogen migrations preceding the transfer step. 相似文献
167.
Ur?ka L. ?tangar Urh ?ernigoj Polonca Treb?e Ksenija Maver Silvia Gross 《Monatshefte für Chemie / Chemical Monthly》2006,1(6):647-655
Transparent TiO2 films with a high photodegradation activity towards an azo dye in aqueous solution were prepared by sol–gel processing. Films
on soda–lime glass supports protected with a thin silica barrier layer exhibited better crystallization and monodisperse nanoparticles,
higher absorption of light below 370 nm, and higher photocatalytic activity than those films deposited on bare glass supports
proving the detrimental effect of interdiffused sodium ions on the development of the anatase nanostructure. The effect of
substrate was more pronounced in thinner films (300 nm) than in thicker ones (1200 nm), which were achieved by adding a template
(i.e. Pluronic F127) to the sol. 相似文献
168.
We report the first six-dimensional quantum dynamical study of the dissociative adsorption of H(2) on a (110) surface. We have performed quantum coupled-channel calculations for the system H(2)/Pd(110) based on a potential energy surface (PES) that was derived from ab initio electronic structure calculations. In particular, we have focused on the effects of the corrugation and anisotropy of the PES on the H(2) dissociation probability. Our results agree well with the available experimental data for the sticking probability as a function of the initial kinetic energy and the angle of incidence. Because of the coupling between the anisotropy and corrugation of the potential energy surface our calculations predict an unusual rotational heating and a rather small rotational alignment in desorption. 相似文献
169.
Christophe Vande Velde Evi Bultinck Karla Tersago Christian Van Alsenoy Frank Blockhuys 《International journal of quantum chemistry》2007,107(3):670-679
Unhindered ortho‐dimethoxy‐substituted phenyl rings often display a coplanar conformation. A theoretical study of a series of methoxybenzenes consisting of methoxybenzene (anisole), the three dimethoxybenzenes, and 1,2,4,5‐tetramethoxybenzene, at the DFT/B3LYP/6‐311++G** level of theory, allows us to identify the factors influencing the conformational preference and attribute the coplanarity of such methoxy groups to mesomeric effects. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
170.
QI Qu Edward Tucker Sherril D. Christian 《Journal of inclusion phenomena and macrocyclic chemistry》2002,43(3-4):213-222
A series of sulfoalkyl ether -cyclodextrin derivatives, including sulfoethyl, sulfopropyl and sulfobutyl ethyl -cyclodextrins, have been synthesized and characterized. Each sulfoalkyl ether -cyclodextrin is a mixture of various degrees of substitution and different positional isotherms. Elemental analysis, 1H NMR, MS, and Differential Scanning Calorimetry analysis were used to determine the average degree of substitution for each -cyclodextrin derivative. The average degrees of substitution are 3.4, 1.6 and 2.5 for sulfoethyl, sulfopropyl and sulfobutyl ether -cyclodextrin, respectively. The water solubility of these derivatives is substantially higher than that of -cyclodextrin. 1H NMR indicates thatsulfoethyl ether -cyclodextrin may have major substitution on the secondaryhydroxyl group while the major substitution in sulfopropyl and sulfobutyl ether-cyclodextrin could be on the primary hydroxyl group. MS spectra showthat no more than one substitution occurred on a single glucose unit. 相似文献