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961.
Lehenmeier MW Bruckmeier C Klaus S Dengler JE Deglmann P Ott AK Rieger B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(32):8858-8869
The homogeneous dinuclear zinc catalyst going back to the work of Williams et al. is to date the most active catalyst for the copolymerisation of cyclohexene oxide and CO2 at one atmosphere of carbon dioxide. However, this catalyst shows no copolymer formation in the copolymerisation reaction of propylene oxide and carbon dioxide, instead only cyclic carbonate is found. This behaviour is known for many zinc‐based catalysts, although the reasons are still unidentified. Within our studies, we focus on the parameters that are responsible for this typical behaviour. A deactivation of the catalyst due to a reaction with propylene oxide turns out to be negligible. Furthermore, the catalyst still shows poly(cyclohexene carbonate) formation in the presence of cyclic propylene carbonate, but the catalyst activity is dramatically reduced. In terpolymerisation reactions of CO2 with different ratios of cyclohexene oxide to propylene oxide, no incorporation of propylene oxide can be detected, which can only be explained by a very fast back‐biting reaction. Kinetic investigations indicate a complex reaction network, which can be manifested by theoretical investigations. DFT calculations show that the ring strains of both epoxides are comparable and the kinetic barriers for the chain propagation even favour the poly(propylene carbonate) over the poly(cyclohexene carbonate) formation. Therefore, the crucial step in the copolymerisation of propylene oxide and carbon dioxide is the back‐biting reaction in the case of the studied zinc catalyst. The depolymerisation is several orders of magnitude faster for poly(propylene carbonate) than for poly(cyclohexene carbonate). 相似文献
962.
Fu Y Habtemariam A Basri AM Braddick D Clarkson GJ Sadler PJ 《Dalton transactions (Cambridge, England : 2003)》2011,40(40):10553-10562
We report the synthesis and characterisation of 32 half sandwich phenylazopyridine Os(II) arene complexes [Os(η(6)-arene)(phenylazopyridine)X](+) in which X is chloride or iodide, the arene is p-cymene or biphenyl and the pyridine and phenyl rings contain a variety of substituents (F, Cl, Br, I, CF(3), OH or NO(2)). Ten X-ray crystal structures have been determined. Cytotoxicity towards A2780 human ovarian cancer cells ranges from high potency at nanomolar concentrations to inactivity. In general the introduction of an electron-withdrawing group (e.g. F, Cl, Br or I) at specific positions on the pyridine ring significantly increases cytotoxic activity and aqueous solubility. Changing the arene from p-cymene to biphenyl and the monodentate ligand X from chloride to iodide also increases the activity significantly. Activation by hydrolysis and DNA binding appears not to be the major mechanism of action since both the highly active complex [Os(η(6)-bip)(2-F-azpy)I]PF(6) (9) and the moderately active complex [Os(η(6)-bip)(3-Cl-azpy)I]PF(6) (23) are very stable and inert towards aquation. Studies of octanol-water partition coefficients (log P) and subcellular distributions of osmium in A2780 human ovarian cancer cells suggested that cell uptake and targeting to cellular organelles play important roles in determining activity. Although complex 9 induced the production of reactive oxygen species (ROS) in A2780 cells, the ROS level did not appear to play a role in the mechanism of anticancer activity. This class of organometallic osmium complexes has new and unusual features worthy of further exploration for the design of novel anticancer drugs. 相似文献
963.
There are particular benefits in spectrum simulation for the interpretation of characteristic X-ray peaks below about 2 keV
in energy, where peak overlaps, a sloping background and changing detector efficiency make it difficult to measure true peak
intensities. Despite these difficulties, we have shown that a useful accuracy of simulation is possible without major revision
of the existing theory, allowing the electron microprobe user to compare on-line a measured spectrum with one synthesised
from an assumed sample composition.
As part of a wider study, we have used a database of X-ray spectra from 150 samples of known composition to confirm the accuracy
of simulation over the energy range from 0.28–1.9 keV, finding an RMS error of better than 8%. The database included 181 Kα,
Lα and Mα peaks from elements of atomic number 6–77, excited by beam voltages from 5–30 kV. Central to the method is the use
of the ratio of (Peak Intensity)/(Total Background Intensity), which allows spectra to be compared from instruments of differing
collection efficiency, thereby easing the collection of data over a wide range of conditions.
Examples are given to illustrate the use of the simulator in helping to choose the best conditions for analysis, and as an
aid in interpreting the spectra so obtained. Both modes of operation are iterative in nature and require a fast and accurate
simulator that is easy to use. Further development will be guided by experience in its use. 相似文献
964.
Monochrome coloured glass beads of the Merovingians (5th–7th cent. AD) have been examined by different analytical methods. The elemental composition of a large number of mostly unprepared
beads have been measured non-destructively by X-ray fluorescence analysis. After subtracting the content of the colouring
oxides of the glass beads and normalising the residual values to 100% an identical soda-lime-glass matrix was obtained. X-ray
diffraction was used for the identification of the crystalline colouring and opacifying pigments (SnO2, Cu, Cu2O, PbSnO3), and scanning electron microscopy as well as electron probe microanalysis were applied to study the microstructure and the
composition of white, brown, green, orange and yellow coloured glass beads. Oxidised metals, alloys (lead, copper, bronze,
brass and mixtures of them) and iron smelting slag have been identified as raw materials to colour the soda-lime-glass. 相似文献
965.
Leva S Lichte A Burmeister J Muhn P Jahnke B Fesser D Erfurth J Burgstaller P Klussmann S 《Chemistry & biology》2002,9(3):351-359
Mirror-image oligonucleotide ligands (Spiegelmers) that bind to the pharmacologically relevant target gonadotropin-releasing hormone I (GnRH) with high affinity and high specificity have been identified using the Spiegelmer technology. GnRH is a decapeptide that plays an important role in mammalian reproduction and sexual maturation and is associated with several benign and malignant diseases. First, aptamers that bind to D-GnRH with dissociation constants of 50-100 nM were isolated out of RNA and DNA libraries. The respective enantiomers of the DNA and RNA aptamers were synthesized, and their binding to L-GnRH was shown. These Spiegelmers bind to L-GnRH with similar affinity to that of the corresponding aptamers that bind to D-GnRH. We further demonstrated dose-dependent inhibition of GnRH-induced Ca(2+) release in Chinese hamster ovary cells that were stably transfected with the human GnRH receptor. 相似文献
966.
Graham DL Lowe PN Grime GW Marsh M Rittinger K Smerdon SJ Gamblin SJ Eccleston JF 《Chemistry & biology》2002,9(3):375-381
The formation of complexes between small G proteins and certain of their effectors can be facilitated by aluminum fluorides. Solution studies suggest that magnesium may be able to replace aluminum in such complexes. We have determined the crystal structure of RhoA.GDP bound to RhoGAP in the presence of Mg(2+) and F(-) but without Al(3+). The metallofluoride adopts a trigonal planar arrangement instead of the square planar structure of AlF(4)(-). We have confirmed that these crystals contain magnesium and not aluminum by proton-induced X-ray emission spectroscopy. The structure adopted by GDP.MgF(-) possesses the stereochemistry and approximate charge expected for the transition state. We suggest that MgF3(-) may be the reagent of choice for studying phosphoryl transfer reactions. 相似文献
967.
Kang YK Rubtsov IV Iovine PM Chen J Therien MJ 《Journal of the American Chemical Society》2002,124(28):8275-8279
The electron-transfer (ET) dynamics of a series of unusually rigid pi-stacked porphyrin-quinone (P-Q) systems, in which sub-van der Waals interplanar distances separate juxtaposed porphyryl, aromatic bridge, and quinonyl components of these assemblies, are reported. The photoinduced charge separation (CS) and thermal charge recombination (CR) ET reactions of [5-[8'-(2',5'-benzoquinonyl)-1'-naphthyl]-10,20-diphenylporphinato]zinc(II) (1a-Zn), [5-[8'-(4'-[8'"-(2'"',5'"'-benzoquinonyl)-1'"-naphthyl]-1'-phenyl)-1'-naphthyl]-10,20-diphenylporphinato]zinc(II) (2a-Zn), and [5-(8'-[4'-(8'"-[4'"'-(8'"-[2'"',5'"'-benzoquinonyl]-1'"-naphthyl)-1'"'-phenyl]-1'"-naphthyl)-1'-phenyl]-1'-naphthyl)-10,20-diphenylporphinato]zinc(II) (3a-Zn) in CH(2)Cl(2) were investigated by pump-probe transient absorption spectroscopy. Analyses of these data show that the phenomenological ET distance dependence (beta) for both the CS and CR reactions in these systems is soft (beta(CS) = 0.43 A(-1); beta(CR) = 0.35 +/- 0.16 A(-1)). This work demonstrates that simple aromatic building blocks such as benzene, which are characterized by highly stabilized filled molecular orbitals and large HOMO-LUMO gaps, can provide substantial D-A electronic coupling when organized within a pi-stacked structural motif that features a modest degree of arene-arene interplanar compression. 相似文献
968.
Meier MS Bergosh RG Gallagher ME Spielmann HP Wang Z 《The Journal of organic chemistry》2002,67(17):5946-5952
The fulleride dianions C(60)(2-) and C(70)(2-) were generated by deprotonation of the corresponding hydrogenated fullerenes, 1,2-C(60)H(2) and 1,2-C(70)H(2). These anions were prepared in the presence of a variety of alkylating agents, and mono- or dialkylated products were obtained. Alkylation was not successful with sulfonate ester alkylating agents. Deprotonation of monoalkylated compounds, followed by second alkylation with a different alkylating agent, produced heterodialkylated compounds. The monoalkyated material was invariably the 1,2-isomers, while the dialkylated materials were generally 1,4-isomers, although some 1,2-isomer was observed in the C(70) context. The major product from alkylation of C(70)(2-) was the 7,23-isomer 13a, a structure where the alkylation took place near the equator of the fullerene cage, rather than at the more strained carbons near the poles. 相似文献
969.
Eldrup AB Christensen C Haaima G Nielsen PE 《Journal of the American Chemical Society》2002,124(13):3254-3262
The synthesis and evaluation of a series of novel nucleobases based on substituted 1,8-naphthyridin-2(1H)-ones are reported. The nucleobases were designed to meet the requirements for incorporation into peptide nucleic acids (PNAs) and were evaluated as part of PNA duplex and triplex nucleic acid recognition systems. Of the various nucleobases tested, only the 7-chloro-1,8-naphthyridin-2(1H)-one (7-Cl-bT) nucleobase led to consistently increased affinity in all recognition systems, duplex (Watson-Crick) as well as triplex (Hoogsteen). For multiply modified systems, the increase in thermal stability per modification was dependent on the sequence context, ranging from 2.0 degrees C (in separate positions) to 3.5 degrees C (in adjacent positions) in PNA-DNA duplexes and from 1.2 degrees C (in separate positions) to 3.2 degrees C (in adjacent positions) in PNA-RNA duplexes. Singly mismatched oligonucleotide targets were employed to demonstrate uncompromised sequence discrimination. When part of multiply modified triplex (Hoogsteen) recognition systems, the 7-Cl-bT unit gave rise to increases in the thermal stability ranging from 2.7 to 3.5 degrees C when incorporated into separated and adjacent positions, respectively. Our results furthermore indicate that the duplex stabilization is predominantly enthalpic and therefore most likely not a consequence of single-strand preorganization. Finally, and most surprisingly, we find no direct correlation between the end-stacking efficiency of this type of nucleobase and its helix stabilization when involved in Watson-Crick base pairing within a helix. 相似文献
970.
Stahl F Moran D von Ragué Schleyer P Prall M Schreiner PR 《The Journal of organic chemistry》2002,67(5):1453-1461
Aromaticity criteria (magnetic susceptibility exaltations, nucleus independent chemical shifts (NICS), and aromatic stabilization energy (ASE) evaluations) for enediyne and enyne-allene cyclizations evaluated at (UBS)-BLYP/6-31G* all agree that the degrees of cyclic electron delocalization of the benzenoid systems formed by the Bergman (3) and Myers-Saito reactions (5) are comparable to benzene. The reaction enthalpy differences between the parent cyclizations and their benzannelated analogues are not entirely due to disparities in gained ASE during the reactions. The alternative formation of fulvene biradicals is not accompanied by favorable aromatic effects. 相似文献