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991.
Achmatowicz M Thiel OR Gorins G Goldstein C Affouard C Jensen R Larsen RD 《The Journal of organic chemistry》2008,73(17):6793-6799
An efficient and scalable three-step one-pot approach to 6-methyl-5-nitroisoquinoline (1) from inexpensive 5-nitroisoquinoline, utilizing the vicarious nucleophilic substitution (VNS) as a key step, is described. The optimized reaction conditions can be applied to a limited number of other aromatic and heteroaromatic nitro compounds. Attempts to understand the observed selectivity in the VNS step led to the discovery of two new reaction pathways under VNS conditions, one leading to an isoxazole and the other resulting in the formal cyclopropanation of an aromatic nitro compound. 相似文献
992.
Homogeneous chitosan films of various thicknesses (10-65 nm) were deposited on thin gold films through spin coating. The resulting interfaces were characterized using surface plasmon resonance (SPR), AFM, profilometry and cyclic voltammetry. The strong chelating properties of chitosan films to Fe(3+) were investigated using cyclic voltammetry. Through SPR measurements, an affinity constant between chitosan and Fe(3+) of 9.49 x 10(5) M(-1) was determined with a detection limit as low as 250 ppb. 相似文献
993.
The single switch trajectory surface hopping algorithm is tested for numerical simulations of a two-state three-mode model for the internal conversion of pyrazine through a conical intersection of potential energy surfaces. The algorithm is compared to two other surface hopping approaches, namely, Tully's method of the fewest switches [J. Chem. Phys. 93, 1061 (1990)] and the method by Voronin et al. [J. Phys. Chem. A 102, 6057 (1998)]. The single switch algorithm achieves the most accurate results. Replacing its deterministic nonadiabatic branching condition by a probabilistic accept-reject criterion, one obtains the method of Voronin et al. without momentum adjustment. This probabilistic version of the single switch approach outperforms the considered algorithms in terms of accuracy, memory requirement, and runtime. 相似文献
994.
Kang C Troyer JL Robertson EM Rothgeb DW Hossain E Wyrwas RB Parmenter CS Jarrold CC 《The Journal of chemical physics》2008,128(10):104309
Anion photoelectron spectra of the O(2)(-) . arene and O(4)(-) . arene complexes with p-xylene and p-difluorobenzene are presented and analyzed with the aid of calculations on the anions and corresponding neutrals. Relative to the adiabatic electron affinity of O(2), the O(2)(-) . arene spectra are blueshifted by 0.75-1 eV. Solvation energy alone does not account for this shift, and it is proposed that a repulsive portion of the neutral potential energy surface is accessed in the detachment, resulting in dissociative photodetachment. O(2)(-) is found to interact more strongly with the p-difluorobenzene than the p-xylene. The binding motif involves the O(2)(-) in plane with the arene, interacting via electron donation along nearby C-H bonds. A peak found at 4.36(2) eV in the photoelectron spectrum of O(2)(-) . p-difluorobenzene (p-DFB) is tentatively attributed to the charge transfer state, O(2)(-) . p-DFB(+). Spectra of O(4)(-) . arene complexes show less blueshift in electron binding energy relative to the spectrum of bare O(4)(-), which itself undergoes dissociative photodetachment. The striking similarity between the profiles of the O(4)(-) . arene complexes with the O(4)(-) spectrum suggests that the O(4)(-) molecule remains intact upon complex formation, and delocalization of the charge across the O(4)(-) molecule results in similar structures for the anion and neutral complexes. 相似文献
995.
Zuyderhoff EM Dekeyser CM Rouxhet PG Dupont-Gillain CC 《Journal of colloid and interface science》2008,319(1):63-71
A series of homopolymer/random copolymer blends was used to produce heterogeneous surfaces by demixing in thin films. The chosen homopolymer is polystyrene (PS) and the random copolymer is poly(methyl methacrylate)-r-poly(methacrylic acid) (PMMA-r-PMAA), whose acidic functions could be used as reactive sites in view of further surface functionalization. The proportion of each polymer at the interface was deduced from X-ray photoelectron spectroscopy (XPS) data using, on the one hand, the O/C ratio, and on the other hand, decomposition of the carbon peak of the blends in two components corresponding to the carbon peaks of PS and PMMA-r-PMAA. Combining the information from XPS with atomic force microscopy (AFM) images, water contact angle measurements and PS selective dissolution, it appears that the surfaces obtained from blends with a high PS content (90/10 to 70/30) display pits with a bottom made of PMMA-r-PMAA, randomly distributed in a PS matrix. On the other hand, the surfaces obtained from blends with a low PS content (30/70 to 10/90) display randomly distributed PS islands surrounded by a PMMA-r-PMAA matrix. The characteristics of the heterogeneous films are thought to be governed by the higher affinity of PMMA-r-PMAA for the solvent (dioxane), which leads to the elevation of the PS phase compared to the PMMA-r-PMAA phase, and to surface enrichment in PMMA-r-PMAA. 相似文献
996.
Acrylic esters, thioesters and N-acryloyl pyrrole have been identified as effective electrophiles in the enantioselective Michael addition reaction with beta-keto ester pro-nucleophiles catalysed by a cinchona alkaloid derived bifunctional organocatalyst; enantiomeric excesses of up to 98% and yields of up to 96% can be obtained for a range of Michael acceptors and pro-nucleophiles. 相似文献
997.
Dynamic and controlled rate thermal analysis of attapulgite 总被引:2,自引:0,他引:2
Veronika Vágvölgyi Lisa M. Daniel Caroline Pinto J. Kristóf R. L. Frost Erzsébet Horváth 《Journal of Thermal Analysis and Calorimetry》2008,92(2):589-594
We have investigated the effect of magnesium chloride hexahydrate [MgCl2·H2O] as a nondurable finish on the flammability of 100% woven cotton fabric, (plain construction, with a density of 144 g m−2, the number of yarns 21/10 mm). The laundered bone-dried, massed fabrics were impregnated with suitable concentrations of
aqueous solution of the above-mentioned salt, by means of squeeze rolls. They were then dried horizontally in an oven at 110°C
for 30 min. The optimum add-on value after the fulfillment of vertical flame spread test to donate flame-retardancy onto cotton
fabric was obtained to be in the range of 6.73–8.30 g of the salt per 100 g fabric. Thermogravimetry (TG) of pure cotton,
treated cotton and the salt was accomplished, and their TG curves were compared and commented. The results obtained are in
favor of the ‘gas dilution theory’, chemical action theory and also in compliance with the ‘free radical theory’. The formation
of sal ammoniac was proven by sprinkling concentrated ammonia upon the inflamed treated specimen. 相似文献
998.
Donohoe TJ Thomas RE Cheeseman MD Rigby CL Bhalay G Linney ID 《Organic letters》2008,10(16):3615-3618
A general strategy for the production of pyrrolizidine alkaloids is described, starting from intermediate (+)-9. The key features are diastereoselective dihydroxylation, inversion at the ring junction by hydroboration of an enamine, and ring closure to form the bicyclo ring system. This route is attractive because of its brevity and versatility; four natural products were prepared with differing stereochemistry and substitution patterns. Finally, this work allowed assignment of the absolute stereochemistry of 2,3,7-triepiaustraline and hyacinthacine A 7. 相似文献
999.
Silyl-protected benzyl alcohol derivatives and the salt 1 are used to form ortho-substituted C12 electrophilic organoiron building blocks which are converted into a spirocyclic cyclohexenone to complete a formal total synthesis of (+/-)-maritidine (5). The choice of TBDPS protection was shown to be better than TIPS and compatible with ipso nucleophile addition to form a quaternary center. The reaction sequence is the first example of a successful application in the synthesis of an arylcyclohexadienyliron complex with an ortho-carbon substituent in the position required for Amaryllidaceae alkaloids of this type. 相似文献
1000.
Gurcel C Vercoutter-Edouart AS Fonbonne C Mortuaire M Salvador A Michalski JC Lemoine J 《Analytical and bioanalytical chemistry》2008,390(8):2089-2097
The O-linked β-N-acetylglucosamine (O-GlcNAc) modification is an abundant post-translational modification in eukaryotic cells. This dynamic glycosylation plays
a fundamental role in the activity of many nuclear and cytoplasmic proteins and is associated with pathologies like type II
diabetes, Alzheimer’s disease or some cancers. However the exact link between O-GlcNAc-modified proteins and their function in cells is largely undefined for most cases. Here we report a strategy based
on the 1,3-dipolar cycloaddition, called click chemistry, between unnatural N-acetylglucosamine (GlcNAc) analogues (substituted with an azido or alkyne group) and the corresponding biotinylated probe
to specifically detect, enrich and identify O-GlcNAc-modified proteins. This bio-orthogonal conjugation confirms that only azido analogue of GlcNAc is metabolized by the
cell. Thanks to the biotin probe, affinity purification on streptavidin beads allowed us to identify 32 O-GlcNAc-azido-tagged proteins by LC-MS/MS analysis in an MCF-7 cellular model, 14 of which were previously unreported. This
work illustrates the use of the click-chemistry-based strategy combined with a proteomic approach to get further insight into
the pattern of O-GlcNAc-modified proteins and the biological significance of this post-translational modification.
Figure Detection of biotinylated O-GlcNAz proteins in MCF-7 cells
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.
Caroline Gurcel and Anne-Sophie Vercoutter-Edouart contributed equally to this work. 相似文献