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71.
Bendiak B 《Journal of the American Chemical Society》2002,124(50):14862-14863
Through-space residual dipolar correlations in NMR spectra can be measured between nuclei of small organic molecules by partially aligning them with respect to the magnetic field in a pure deuterated liquid solvent, 4-pentyl-4'-cyanobiphenyl. A simple temperature change of this liquid phase enables spectra to be compared between samples under isotropic tumbling conditions and weakly oriented anisotropic states. This should provide access of a number of small nonpolar molecules to more sensitive through-space nuclear correlations than possible through NOE experiments, depending on the net orientation of specific nuclear pairs with respect to the magnetic field and the specific coherence transfers employed. 相似文献
72.
Super-hydrophobic tin oxide nanoflowers 总被引:4,自引:0,他引:4
Super-hydrophobic 3D SnO(2) flowers with nanoporous petals were produced from the 3D Sn nanoflowers using a controlled shape-preserving thermal oxidation process. 相似文献
73.
A new one-pot synthesis of allyldiphenyl-phosphine oxide has been developed using a tandem Sn2′ / Michaelis-Arbuzov sequence. The application of microwave heating lowers the reaction time significantly. 相似文献
74.
Sinu C. Rajappan Brad J. Davis Travis L. Thornell Yoan C. Simon 《Journal of polymer science. Part A, Polymer chemistry》2021,59(22):2742-2753
A better understanding of polymer degradation and post-degradation processes are essential for the development of novel degradable polymers. Herein, we present the synthesis of a new aliphatic azo-containing polyurethane and its degradation behavior toward external stimuli like heat and UV light. A relatively stable radical forming azo-monomer present in the current polyurethane is readily undergoing thermal degradation, whereas the azo-group is less susceptible to optical degradation. A comparison of the stimuli-responsive properties of the new azo-polymer with a previously known, relatively active radical forming monomer incorporated azo-polymer reveals the dependencies of the monomer and radical stability in the controlled degradation process. Our results point toward the importance of radical activity in azo-containing polymers. 相似文献
75.
Heinrich Kipphardt Ralf Matschat Jochen Vogl Tamara Gusarova Michael Czerwensky Hans-Joachim Heinrich Akiharu Hioki Leonid A. Konopelko Brad Methven Tsutomu Miura Ole Petersen Gundel Riebe Ralph Sturgeon Gregory C. Turk Lee L. Yu 《Accreditation and quality assurance》2010,15(1):29-37
Within the National Metrology Institutes (NMIs) and designated laboratories, an interlaboratory comparison, CCQM-P107, was conducted to verify the degree of international comparability concerning the results of purity analysis. The mass fractions of Ag, Bi, Cd, Cr, Ni, Tl at the lower mg/kg-level in a high purity zinc material were determined, but the real measurand in metrological sense was the sum of the six mass fractions. Homogeneity was investigated by glow discharge mass spectrometry, reference values were obtained using isotope dilution mass spectrometry. Six NMIs participated, contributing eight independent data sets. The agreement amongst the results of the participants, their median and the agreement with the reference values were usually excellent and in almost all cases below the target uncertainty of 30% relative. In this manner, the accuracy of results and the comparability between the participants was demonstrated to be established. 相似文献
76.
An enantioselective synthetic route to the enediyne antibiotic N1999A2 (1) is described, proceeding in 21 steps (0.4% yield, 77% average yield per step) from (R)-(+)-glycidol. The route involves the convergent assembly of three components: a (1-iodovinyl) stannane (2), a 1,5-hexadiyne-3,4-diol derivative (3), and a substituted naphthoic acid (4). Important transformations in the synthetic sequence include the palladium-catalyzed coupling of 2 and 3, an intramolecular oxidative cyclization of a terminal bisacetylene, and a transannular anionic (bi)cyclization of a cyclic bromoenetriyne. The careful selection and manipulation of protective groups throughout the sequence proved to be critical to the development of the synthetic route, where all late-stage intermediates were unstable and could not be concentrated. In the final step of the sequence, three protective groups were removed in a single operation, providing synthetic N1999A2 (1) in 76% yield. Conditions were found that, for the first time, led to the precipitation of 1 as a solid. 相似文献
77.
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79.
Basuli F Bailey BC Brown D Tomaszewski J Huffman JC Baik MH Mindiola DJ 《Journal of the American Chemical Society》2004,126(34):10506-10507
Four-coordinate vanadium complexes containing a terminal neopentylidyne functionality have been prepared by two consecutive alpha-hydrogen abstraction reactions both of which were induced by one-electron oxidations. Among these vanadium-alkylidyne complexes are the neutral and the cation (Nacnac)VCtBu(OTf) and [(Nacnac)VCtBu(THF)]+, respectively (Nacnac- = [Ar]NC(CH3)CHC(CH3)N[Ar], Ar = 2,6-(CHMe2)2C6H3). The vanadium-alkylidynes have been characterized by 1H, 13C, 51V NMR spectroscopy and single-crystal X-ray diffraction and are consistent with a short VC bond. These alkylidynes were found to transform to azametalacyclohexatriene systems via an intramolecular cross-metathesis reaction. Kinetic studies of the transformation of (Nacnac)VCtBu(OTf) in C7D8 reveal the formation of the azametalacyclohexatriene to be independent of solvent (toluene vs THF) and the reaction to be first order in vanadium (k = 3.30(5) x 10-5 s-1 at 80 degrees C, with activation parameters DeltaH= 25.4(3) kcal/mol, DeltaS = -6(3) cal/molK). High-level DFT calculations on the full model suggest an intramolecular mechanism invoking only one transition state. The overall thermodynamic driving force for the reaction (DeltaG) in solution phase was estimated to be -21.3 kcal/mol. 相似文献
80.
Novel flame photometric detector for gas chromatography based on counter-current gas flows 总被引:1,自引:0,他引:1
A novel analytical device has been developed for gas chromatography. It is based on optical emission from a counter-current (i.e. counter-flowing) air or oxygen flame, which burns in an opposing stream of hydrogen and column effluent. The flame is typically positioned "upside down" on the upper (air) jet, which faces the lower (hydrogen + effluent) jet. It can also be positioned on the lower jet, be connected to both jets, or be suspended in the gap between them. Excellent stability can be obtained in any of these modes. Overall, this new "counter-current flame photometric detector" (ccFPD) responds to analytes in the manner of a conventional flame photometric detector (FPD); however, it can be operated over a much wider range of gas flows. For instance, the same physical ccFPD burner easily supports stable flames of air flows between 5 and 200 ml/min and corresponding hydrogen flows between 5 and 10,000 ml/min. Visual observation of the counter-current flame, in the presence of sulfur and phosphorus as test analytes, reveals intense, steady luminescence under a wide variety of conditions. Additionally, and in contrast to the commercial FPD, flame conductivity signals can be obtained that are similar in quality to those produced by a conventional flame ionization detector (FID). Thus the ccFPD is a flexible, easily optimized photometric detector. The exceptional flow stability of the ccFPD was used to explore the earlier reported phenomenon of strong signal/noise (S/N) ratios, which had been obtained for hetero-elements of the iron group from a conventional FPD with a small, stoichiometric flame. Results using the ccFPD, which also exhibits this unusual response, indicate that these high S/N ratios are only partly due to the predictable decrease in flame noise with decreasing flame size. Contrary to expectations, the absolute analyte signal often increases as the flame size decreases to the point of extinction. The signal intensity and the magnitude of the observed changes depend to some degree on the flame composition (H2/O2 ratio). 相似文献