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91.
5'-O-DMT-deoxyribonucleoside-3'-O-(2-selena-4,4-pentamethylene-1,3,2-oxathiaphospholane) monomers, derivatives of dA, dC, dG, and T, can be resolved into pure P-diastereomers by silica gel column chromatography. They have been used for DBU-promoted, either solution- or solid-phase synthesis of P-stereodefined phosphoroselenoate analogues of oligodeoxyribonucleotides. Fast- and slow-eluting monomers are precursors of phosphoroselenoate internucleotide linkage of R(P) and S(P) absolute configuration, respectively. [reaction: see text] 相似文献
92.
Ricardo H. M. Godoi Ana F. L. Godoi Anna Worobiec Sandro J. Andrade Johan de Hoog Mary R. Santiago-Silva Rene Van Grieken 《Mikrochimica acta》2004,145(1-4):53-56
Biomass burning is an important primary and secondary source of aerosol particles. The presence of carbonaceous particles in the respirable size range makes the study of this fraction important in view of possible health and climatic effects. The annual burning of sugar cane plantations causes emission of huge amounts of pyrogenic particles. Aerosol samples were collected in Araraquara city, São Paulo state, Brazil, during the harvest season for fine and coarse particles and bulk; they were analysed by electron-probe microanalysis, including facilities for low-Z element determination (low-Z EPMA) and by energy-dispersive X-ray fluorescence (EDXRF), in order to investigate the elemental composition of individual particles and bulk samples, respectively. Numerical analysis of the EPMA results by hierarchical clustering shows high contributions of carbonaceous particles that can be distinguished mainly in two different types: biogenic and carbon-rich. Additionally, two significant contributions of aluminosilicate particles were identified: as rather pure aluminosilicates or mixed with carbonaceous species. The EDXRF results are compatible with those of aerosol particles in Amazon, which is nowadays one of the main sources of biogenic particles in the world. 相似文献
93.
The modern theory of polarization in extended insulators is applied to one-dimensional models for conjugated polymers and charge transfer salts. Closed expressions for the dependence of the polarization on the site and bond energy alternations are presented for uncorrelated models, and results from exact real-space diagonalization are obtained for correlated models. Changes in polarization induced by lattice phonons or molecular vibrations are directly related to the intensity of infrared bands in the far and mid-IR, respectively. We model intensities by introducing linear electron-vibration coupling and show that coupling to delocalized electrons generates a combination band consisting of a lattice phonon and a molecular vibration. The displaced dipole operator is defined on a real-space basis allowing for the finite field calculation of linear polarizability in finite size systems with periodic boundary conditions. Size-consistency arguments are used to demonstrate that the resulting polarizability becomes exact in the thermodynamic limit, and numerical calculations demonstrate that this approach leads to reliable results that converge rapidly to the thermodynamic limit. 相似文献
94.
Piatek AM Bomble YJ Wiskur SL Anslyn EV 《Journal of the American Chemical Society》2004,126(19):6072-6077
The mathematics for modeling indicator-displacement assay isotherms is presented and contrasted to the classical host-guest binding isotherm. It is shown that the signal response can be tuned to occur closer to 1 equiv of guest relative to a standard binding algorithm. This delay in response leads to a better triggering protocol for threshold detection schemes. The determination of malate in Pinot Noir must was calculated using this new mathematical model, which demonstrates how a color change can be tuned to occur near a desired concentration of analyte. 相似文献
95.
Gy. Marosi R. Lágner Gy. Bertalan P. Anna A. Tohl 《Journal of Thermal Analysis and Calorimetry》1996,47(4):1155-1161
Nucleating and transcrystallization behaviour of additives in engineering PP composites and the effect of modified interfacial structure is the subject of this series of papers. The first part concentrates on polypropylene/liquid crystalline polyester blends. Increased crystallisation temperature and degree of crystallinity of polypropylene is characteristic to the blends containing different amount of LCP additive. Transcrystallization process governs the formation of crystalline structure in these systems in course of isothermal crystallisation at 132C. The nucleating effect of LCP gives rise to more uniform crystalline structure in the polypropylene phase.The financial support of the OTKA 014194 is acknowledged with gratitude. 相似文献
96.
Giampaolo Giacomelli Anna Maria Caporusso Luciano Lardicci 《Tetrahedron letters》1981,22(37):3663-3666
The reduction of a series of α,β-unsaturated ketones has been studied under various experimental conditions, by using β-branched trialkylalanes. Asymmetric induction phenomena are observed when optically active trialkylalanes are used. 相似文献
97.
Anna Bernardi Silvia Cardani Cesare Gennari Giovanni Poli Carlo Scolastico 《Tetrahedron letters》1985,26(52):6509-6512
MgBr2 mediated addition of Methyl α-methylthio propionate silylketene acetal to α and α,β-alkoxy aldehydes is highly 3,4 -selective (18:1). -α- methylene-β- hydroxy-?-alkoxy esters (6) and (8) are synthesized. 相似文献
98.
Carlo Carlini Marco Di Girolamo Alessandro Macinai Mario Marchionna Marilena Noviello Anna Maria Raspolli Galletti Glauco Sbrana 《Journal of molecular catalysis. A, Chemical》2003,200(1-2):137-146
The synthesis of isobutanol via the Guerbet condensation between methanol and ethanol was studied by using sodium methoxide (MeONa) as soluble basic component and copper-based catalysts as heterogeneous dehydrogenating/hydrogenating metal species. The effect of the nature of the catalyst and the relative amount of its individual components with respect to the reacting alcohols as well as of temperature on productivity and selectivity of the process was investigated. The collected data indicated that the copper chromite/MeONa was more active than Cu-Raney/MeONa system. The reaction was shown to proceed with the formation only of n-propanol and isobutanol. Ethanol conversion up to 61% with selectivity to isobutanol up to 98.4% was obtained. The same catalytic systems were also employed in the reaction of the methanol/ethanol/n-propanol ternary mixture. Again copper chromite/MeONa resulted more active than the Cu-Raney/MeONa system. Finally, experiments were carried out on methanol/n-propanol mixtures in the presence of the copper chromite/MeONa catalytic system by recycling both the recovered solid copper component and the liquid reaction mixture for evidencing eventual copper leaching by MeONa. On the basis of the obtained results it was concluded that in the Guerbet reaction copper chromite works as heterogeneous catalyst. 相似文献
99.
Zusammenfassung Tabakmosaikvirus hoher spezifischer Aktivität, das am Phosphor und/oder Kohlenstoff markiert war, wurde biosynthetisch hergestellt. Damit wurde jeweils ein Blatt einer Pflanze von Nicotiana tabacum infiziert und der etwaige Transport von intaktem Virus durch das Leitungssystem der Pflanzen dadurch weitgehend unterbunden, daß die Leitgefäße des behandelten Blattes durchtrennt wurden.Das aus den unbehandelten Blättern der Pflanze nach 17 1/2, 48 und 72 Stdn. isolierte Virus wies im Vergleich zum eingesetzten TMV einen viel geringeren Anteil an Gesamtradiokohlenstoff im Protein auf. Dies deutet darauf hin, daß das Virus der unbehandelten Blätter höchstens zu einem sehr geringen Teil aus intakt transportiertem TMV bestehen könnte.Die nicht im TMV enthaltenen Polynukleotide der unbehandelten Blätter enthalten 7 Stdn. nach der Infektion verhältnismäßig viel32P, doch tritt derselbe innerhalb 70 Stdn. zum allergrößten Teil in niedermolekulare Verbindungen über.Die in Puffer unlöslichen Polynukleotide der unbehandelten Blätter (Blattnukleinsäure) weisen ein mit der Zeit abnehmendes Verhältnis von32P/14C auf. Auch innerhalb der Nukleinsäure (NS) des TMV dieser Blätter nimmt dieses Verhältnis zunächst ab, steigt aber später wieder an.Die angeführten Ergebnisse stehen mit der Vorstellung im Einklang, daß das Virus NS abspaltet und sowohl die systemische Infektion der Pflanze wie auch die Virusvermehrung mindestens zum Teil durch diese freie NS bewirkt wird. Die aus dem Virus stammende freie NS unterliegt zum großen Teil lebhaftem Abbau, wobei ihre Komponenten wahrscheinlich dem Aufbau normaler Blattbestandteile dienen.Mit 3 Abbildungen 相似文献
100.
Gioacchini AM Menotta M Bertini L Rossi I Zeppa S Zambonelli A Piccoli G Stocchi V 《Rapid communications in mass spectrometry : RCM》2005,19(17):2365-2370
This study describes a rapid method to identify different truffle species by analysis of their volatile compound fraction using static headspace solid-phase microextraction gas chromatography/mass spectrometry. The volatile organic compounds (VOCs) were extracted using a new 2-cm 50/30 microm DVB/CAR/PDMS fiber placed for 10 min in the headspace of the truffle sample with the vial maintained at 20 degrees C (in a thermostatically controlled analysis room). The mass spectra of the VOC chromatograms were represented as 'fingerprints' of the analysed samples. Next, stepwise factorial discriminant analysis afforded a limited number of characteristic fragment ions that allowed a classification of the truffle species studied. This new method provides an effective approach to rapid quality control and identification of truffle species by analysis of their volatile fraction. Moreover, this method offers the advantage of minimizing thermal, mechanical, and chemical modifications of the truffles, thereby reducing the risk of analytical artifacts. 相似文献