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41.
Luc Martinon Stéphane Azoulay E. Peter Kündig 《Journal of organometallic chemistry》2004,689(23):3831-3836
A Pd-catalyzed three-component assembling of highly functionalized 4-benzyl-(and allyl-)pyrrolidines was achieved based on a combination of allyl amines, gem-diactivated alkenes, and unsaturated halides (or triflate). 相似文献
42.
Leif Schrder Christian Schmitz Peter Bachert 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,171(2):87
Proton NMR resonances of the endogenous metabolites creatine and phosphocreatine ((P)Cr), taurine (Tau), and carnosine (Cs, β-alanyl-l-histidine) were studied with regard to residual dipolar couplings and molecular mobility. We present an analysis of the direct 1H–1H interaction that provides information on motional reorientation of subgroups in these molecules in vivo. For this purpose, localized 1H NMR experiments were performed on m. gastrocnemius of healthy volunteers using a 1.5-T clinical whole-body MR scanner. We evaluated the observable dipolar coupling strength SD0 (S = order parameter) of the (P)Cr-methyl triplet and the Tau-methylene doublet by means of the apparent line splitting. These were compared to the dipolar coupling strength of the (P)Cr-methylene doublet. In contrast to the aliphatic protons of (P)Cr and Tau, the aromatic H2 (δ = 8 ppm) and H4 (δ = 7 ppm) protons of the imidazole ring of Cs exhibit second-order spectra at 1.5 T. This effect is the consequence of incomplete transition from Zeeman to Paschen-Back regime and allows a determination of SD0 from H2 and H4 of Cs as an alternative to evaluating the multiplet splitting which can be measured directly in high-resolution 1H NMR spectra. Experimental data showed striking differences in the mobility of the metabolites when the dipolar coupling constant D0 (calculated with the internuclear distance known from molecular geometry in the case of complete absence of molecular dynamics and motion) is used for comparison. The aliphatic signals involve very small order parameters S ≈ (1.4 − 3) × 10−4 indicating rapid reorientation of the corresponding subgroups in these metabolites. In contrast, analysis of the Cs resonances yielded S ≈ (113 − 137) × 10−4. Thus, the immobilization of the Cs imidazole ring owing to an anisotropic cellular substructure in human m. gastrocnemius is much more effective than for (P)Cr and Tau subgroups. Furthermore, 1H NMR experiments on aqueous model solutions of histidine and N-acetyl-l-aspartate (NAA) enabled the assignment of an additional signal component at δ = 8 ppm of Cs in vivo to the amide group at the peptide bond. The visibility of this proton could result from hydrogen bonding which would agree with the anticipated stronger motional restriction of Cs. Referring to the observation that all dipolar-coupled multiplets resolved in localized in vivo 1H NMR spectra of human m. gastrocnemius collapse simultaneously when the fibre structure is tilted towards the magic angle (θ ≈ 55°), a common model for molecular confinement in muscle tissue is proposed on the basis of an interaction of the studied metabolites with myocellular membrane phospholipids. 相似文献
43.
Peter Nesvadba Lucienne Bugnon Rosemarie Sift 《Journal of polymer science. Part A, Polymer chemistry》2004,42(13):3332-3341
The synthesis of new 7‐membered diazepanone alkoxyamines [2,2,7,7‐tetramethyl‐1‐(1‐phenyl‐ethoxy)‐[1,4]diazepan‐5‐one ( 3 ) and 2,7‐diethyl‐2,3,7‐trimethyl‐1‐(1‐phenyl‐ethoxy)‐[1,4]diazepan‐5‐one ( 8 )] through the Beckmann rearrangement of piperidin‐4‐one alkoxyamines was developed. Both 3 and 8 were evaluated as initiators and regulators for the nitroxide‐mediated radical polymerization of styrene and n‐butyl acrylate. 8 , a sterically highly hindered alkoxyamine readily available as a crystalline solid, allowed the fast and controlled polymerization and preparation of polymers with low polydispersity indices (1.2–1.4) up to a degree of polymerization of about 100. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3332–3341, 2004 相似文献
44.
45.
Sándor G?r?g 《Analytical sciences》2004,20(5):767-782
The development during the last 15 years and the state-of-the-art in the analysis of bulk steroid hormone drugs and hormone-like structures and pharmaceutical formulations made thereof are summarized. Other steroids (sterols, bile acids, cardiac glycosides, vitamins D) as well as biological-clinical aspects and pharmacokinetic and metabolic studies are excluded from this review. The state-of-the-art is summarized based on comparisons of monographs in the latest editions of the European Pharmacopoeia, United States Pharmacopoeia and the Japanese Pharmacopoeia. This is followed by sections dealing with new developments in the methodology for the fields of spectroscopic and spectrophotometric, chromatographic, electrophoretic and hyphenated techniques as well electroanalytical methods. The review is terminated by two problem-oriented sections: examples on impurity and degradation profiling as well as enantiomeric analysis. 相似文献
46.
The electrochemical reduction of 1-([(4-halophenyl)imino]methyl)-2-naphthols on graphite electrodes was studied using cyclic voltammetry, chronoamperometry, constant-potential coulometry and preparative constant-potential electrolysis techniques. The data revealed that the reduction on graphite was irreversible and followed an EC mechanism. The diffusion coefficients and the number of electrons transferred were determined using the chronoamperometric Cottrell slope and the ultramicro disc Pt-electrode steady-state current. The number of electrons was also determined by bulk electrolysis. The compounds were subjected to constant-potential preparative electrolysis and the electrolysis products were purified and identified by spectroscopic methods. Based on these findings, a mechanism for the electro-reduction process is proposed. 相似文献
47.
Hans‐Peter Brack Denise Ruegg Heinrich Bührer Michal Slaski Selmiye Alkan Günther G. Scherer 《Journal of Polymer Science.Polymer Physics》2004,42(13):2612-2624
The influence of irradiation and grafting on the crystallinity of three base polymers has been investigated with differential scanning calorimetry. Grafting has the largest effect on the base polymer crystallinity and results in a reduction of the crystallinity. The thermal degradation of the base polymers and grafted films has been investigated with thermogravimetric analysis. The extent of the fluorination of the base polymer, the irradiation method, and the graft level all influence the thermal degradation and its activation energy. It is proposed that the variation of the chain lengths of the grafted polystyrene chains is actually a primary underlying factor responsible for the influence of these various parameters on the degradation process. The first results of a comparative thermal analysis of some fuel‐cell membranes are also presented, and the promise and shortcomings of this method are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2612–2624, 2004 相似文献
48.
Ionel Rosenthal Joe Z. Sostaric Peter Riesz 《Research on Chemical Intermediates》2004,30(7-8):685-701
Sonochemistry and photochemistry are initiated by high-energy transient species, which may be prone to mutual interaction. Electronic excitation of solutes by energy transfer from high energy species generated in collapsing bubbles is already supported by experimental evidence. The rates of photochemical reactions can be affected by ultrasound-induced mixing of liquids caused by microstreaming near pulsating cavitation bubbles and shockwaves due to bubble collapse. This may not only improve light absorption but also modify the pathway of reaction by increasing the contact between reagents. Finally, one may speculate about a potentially new chemistry of photoexcited solutes under the extreme conditions inside cavitation microreactors. This work reviews research on the excitation of solutes by sonoluminescence, the combined effects of ultrasound and light on liquid systems and the effect of ultrasound on photocatalytic reactions. 相似文献
49.
We study a combinatorially defined double complex structure on the ordered chains of any simplicial complex. Its columns are related to the cell complex Kn whose face poset is isomorphic to the subword ordering on words without repetition from an alphabet of size n. This complex is shellable and as an application we give a representation theoretic interpretation for derangement numbers and a related symmetric function considered by Désarménien and Wachs [11].
We analyze the two spectral sequences arising from the double complex in the case of the bar resolution for a group. This spectral sequence converges to the cohomology of the group and provides a method for computing group cohomology in terms of the cohomology of subgroups. Its behavior is influenced by the complex of oriented chains of the simplicial complex of finite subsets of the group, and we examine the Ext class of this complex. 相似文献
50.