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901.
Alexander M. Polozov Alexander V. Khotinen Eugene N. Klimovitskii 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):581-584
Abstract. The X-ray crystal structure of 2-(2′,4′-dioxo-3′-pentyl)-5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinane (2) reveals significant half-chair distortion of the axially oriented cisenol ring. The molecule also undergoes in-plane deformations. R(O...O) = 2.410 Å in the enol moiety indicates a very strong hydrogen bonding. The enol content, δOH and thermodynamic parameters for the axial-equatorial conformational and keto-enol equilibriums were obtained from 1H, 31P NMR and IR measurements in comparison with the planar 4,6-dimethyl isomer (1) containing equatorially oriented enol ring. The X-ray single crystal structure of 5,5-dimethyl-2-(methoxycarbonyl-3′-oxo-2′-butyl)-2-oxo-1,3,2-dioxaphosphorinane (3) reveals the unusual half-chair conformation of the dioxaphosphorinane cycle disposed a trans-enol ring substituent. 1H, 31P NMR and IR solution data support the same structure displays a strong conformational preference while the minor forms are chair conformers with an axial or equatorial cis-enol ring. 相似文献
902.
Mikhael Pudovik Wolf Habicher Irina Nikolaeva Alexander Burilov Vladimir Reznik Alexander Konovalov 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1)
Abstract Reactions of calix[4]resorcinarenes, bearing aliphatic radicals of different length, with P(III)-halides results in the formation of cyclic chlorophosphites and chlorophosphates. 相似文献
903.
Fabian Benz Christoph Roderburg David Vargas Cardenas Mihael Vucur Jérémie Gautheron Alexander Koch Henning Zimmermann J?rn Janssen Lukas Nieuwenhuijsen Mark Luedde Norbert Frey Frank Tacke Christian Trautwein Tom Luedde 《Experimental & molecular medicine》2013,45(9):e42
MicroRNA (miRNA) levels in serum have recently emerged as potential novel biomarkers for various diseases. miRNAs are routinely measured by standard quantitative real-time PCR (qPCR); however, the high sensitivity of qPCR demands appropriate normalization to correct for nonbiological variation. Presently, RNU6B (U6) is used for data normalization of circulating miRNAs in many studies. However, it was suggested that serum levels of U6 themselves might differ between individuals. Therefore, no consensus has been reached on the best normalization strategy in ‘circulating miRNA''. We analyzed U6 levels as well as levels of spiked-in SV40-RNA in sera of 44 healthy volunteers, 203 intensive care unit patients and 64 patients with liver fibrosis. Levels of U6 demonstrated a high variability in sera of healthy donors, patients with critical illness and liver fibrosis. This high variability could also be confirmed in sera of mice after the cecal ligation and puncture procedure. Most importantly, levels of circulating U6 were significantly upregulated in sera of patients with critical illness and sepsis compared with controls and correlated with established markers of inflammation. In patients with liver fibrosis, U6 levels were significantly downregulated. In contrast, levels of spiked-in SV40 displayed a significantly higher stability both in human cohorts (healthy, critical illness, liver fibrosis) and in mice. Thus, we conclude that U6 levels in the serum are dysregulated in a disease-specific manner. Therefore, U6 should not be used for data normalization of circulating miRNAs in inflammatory diseases and previous studies using this approach should be interpreted with caution. Further studies are warranted to identify specific regulatory processes of U6 levels in sepsis and liver fibrosis. 相似文献
904.
Inna P. Tsypysheva Alexander N. Lobov Alena V. Kovalskaya Valentina I. Vinogradova Kyrill Yu. Suponitsky Sergey L. Khursan Marat S. Yunusov 《Tetrahedron: Asymmetry》2013,24(20):1318-1323
The Diels–Alder adducts of the quinolizidine alkaloids N-methylcytisine, (?)-leontidine, and (?)-thermopsine with N-phenylmaleimide have been synthesized. The structures and absolute configurations of the new asymmetric centers of the products were determined by NMR spectroscopy experiments, QC-calculations, and X-ray data. 相似文献
905.
906.
907.
Zhai HJ Yang X Wang XB Wang LS Elliott B Boldyrev AI 《Journal of the American Chemical Society》2002,124(23):6742-6750
Although neutral and ionic O4(0/-/+) species have been observed experimentally and considered for energetic materials, O4(2-) and O5(2-) dianions have not yet been explored. O4(2-) is valent isoelectronic to the well-known ClO3- and SO3(2-) anions, and O5(2-) is valent isoelectronic to ClO4- and SO4(2-). All are stable, common anions in solutions and inorganic salts. In this article, we explore the possibility of making covalently bound O4(2-) and O5(2-) species stabilized in the forms of M+O4(2-) and M+O5(2-) (M = Li, Na, K, Cs) in the gas phase. Laser vaporization experiments using M-containing targets and an O2-seeded carrier gas yielded very intense mass peaks corresponding to MO4- and MO5-. To elucidate the structure and bonding of the newly observed MO4- and MO5- species, we measured their photoelectron spectra and then compared them with ab initio calculations and the spectra of ClO3-, Na+SO3(2-), ClO4-, and Na+SO4(2-). Careful analyses of the experimental and ab initio results showed, however, that the observed species are of the forms, O2-M+O2- and O2-M+O3-. The more interesting M+O4(2-) and M+O5(2-) species were found to be higher-energy isomers, but they are true minima on the potential energy surfaces, which suggests that it might be possible to synthesize bulk materials containing covalently bound tetra- and pentatomic oxygen building blocks. 相似文献
908.
Victor A. Kabanov Alexander B. Zezin Valentina B. Rogacheva Yulia V. Khandurina Olga A. Novoskoltseva 《Macromolecular Symposia》1998,126(1):79-94
Slightly cross-linked polyelectrolytes absorb oppositely charged surfactants in aqueous media. Transfer of amphiphilic ions from solution into the swollen network proceeds as a frontal heterogeneous cooperative reaction causing a collapse of the original polyelectrolyte gel. Small and wide angle X-ray diffraction data show that electrostatic complex formed as a result of the reaction consists of lamellar type surfactant micelles embedded in a polyelectrolyte network. It is also shown that such complexes contain equimolar amount of surfactant ions and ionized polyelectrolyte units paired with amphiphil head groups. In other words a charged network is not able to bind surplus oppositely charged surfactant ions. However, it is still able to solubilize a substantial amount of a nonionized surfactant. Chemical structure of surfactants strongly affect internal structure of lamellae and stability of the complexes. 相似文献
909.
Oxidation of 1,4-hydroquinones to 1,4-benzoquinones by mercuric oxide or mercuric trifluoroacetate in methanol has recently been described, and required reaction times of 1–12 hours.1 We now report that use of bromomercury(II) species as oxidants under alkaline conditions greatly reduces the reaction time. This oxidation system has recently been used for conversion of aromatic aldehydes into carboxylic acids.2 相似文献
910.
Lin Y Böker A Skaff H Cookson D Dinsmore AD Emrick T Russell TP 《Langmuir : the ACS journal of surfaces and colloids》2005,21(1):191-194
The self-assembly of nanoparticles at fluid interfaces, driven by the reduction in interfacial energy, was investigated. With spherical, tri-n-octyl-phosphine-oxide covered cadmium selenide (CdSe) nanoparticles (1-8 nm), thermal fluctuations compete with the interfacial segregation giving rise to a size-dependent self-assembly of the particles. The structure of the nanoparticle assembly was studied using electron microscopy, atomic force microscopy, and X-ray scattering in situ, which indicate that the particles form a densely packed monolayer. The energetics of the adsorption of nanoparticles onto the interface was revealed by time-dependent fluorescence studies on a mixture of two different sized nanoparticles at the interface. The dynamics of the nanoparticles at the fluid interface, probed using fluorescence photobleaching methods, suggests a liquid-like behavior. The results have implications in the design of hierarchical self-assemblies of nanoparticles for the one-step fabrication of devices on multiple length scales. 相似文献