973 resultados para Stereogenic quaternary center


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Historical flood events produced lakes in the Mojave River watershed in southeastern California and represent climatic conditions similar to those in the late Quaternary when perennial lakes formed in the Mojave Desert. Historical lakes are related to tropical and subtropical sources of moisture and an extreme southward shift of storm tracks. It is suggested that this atmospheric pattern occurred frequently during earlier periods with perennial lakes in the Mojave River drainage basin.

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EXTRACT (SEE PDF FOR FULL ABSTRACT): Laminated sediments are preserved in upper Pleistocene sections of cores collected on the continental slope at water depths within the present oxygen-minimum zone from at least as far north as the Klamath River and as far south as Point Sur. Comparison of sediment components in the laminae with those delivered to sediment traps as pelagic marine "snow" show the dark/light lamination couplets are indeed annual (varves). ... The presence of carbon-, sulfur-, and metal-rich sediments, as well as lack of bioturbation, all support the theory that the oxygen-minimum zone in the northeastern Pacific Ocean was more intense - in fact, anoxic - during the late Pleistocene in response to greater coastal upwelling and higher organic productivity.

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EXTRACT (SEE PDF FOR FULL ABSTRACT): Analyses of the modern summer synoptic climatology of Beringia illustrate that the region cannot be treated as a homogenous climatic unit as a result of different circulation controls that operate over the region. GCM (general circulation model) simulations and information from the modern synoptic climatology were used to infer the summer paleosynoptic climatology of the region since the last glacial maximum. ... Variations in these climatic controls offer important implications in assessing the vegetation histories of western Beringia versus eastern Beringia.

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When ε-nitro-a,β-unsaturated esters are added to conjugated cyanosulfones in the presence of a bifunctional thiourea catalyst, a highly stereoselective domino reaction occurs to generate complex cyclohexanes with up to four stereogenic centers, one of which is quaternary in nature. Therefore, it is demonstrated that, like nitro compounds, sulfones can undergo an asymmetric intramolecular conjugate addition to r,β- unsaturated esters in the presence of a bifunctional organocatalyst.

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N-metallo ketene imines are attractive for the preparation of a wide range of organic compounds. Our research group has been engaged in the preparation and application of the N-metallo imines (SKIs). In this frame we have studied the uncatalyzed reaction of SKIs with isocyanates to give the corresponding malonamides with good yields. It has been demonstrated that the use of SKIs, instead of simple lithium anion of nitriles, is essential for the success of the reaction. A possible explanation assumes that this new reaction proceeds via a silatropism. In the course of our studies, reported in this thesis, the synthesis and the reactivity of N-silyl ketene imines in the preparation of 2,2-diaryl-3,4- dihydroxy- alcanonitrile in an uncatalyzed adol-type reaction has been performed. Our conception has been to use a chiral aldehyde to introduce asymmetric induction at the β-position and at the α-quaternary stereogenic center in the new forming diols. To achieve this goal, we used diarylacetonitrile as the substrate to form the corresponding N-trimethylsylilketene-imines to be reacted with (S)–lactic aldehyde with different protecting groups on the hydroxyl functionality. A number of 2,2-diaryl-3,4-dihydroxy-pentanenitrile were prepared with good to excellent stereo-control and satisfactory yields. Extension of this protocol to other metallo-ketene imines was performed. Accordingly, the preparation of tin ketene imines was attempted in analogy of the corresponding silyl ketene imine. The reaction of tin ketene imines with aldehydes was tested as a new tool for the synthesis of beta-hydroxynitriles starting from carbonyl compounds (aldehydes and/or ketones). Dialkyl(aryl)silyl nitriles and dialkyl(aryl)tin nitriles presents different reactivity. Finally, N-aluminium-ketene imines, as nucleophilic partner in the opening reaction of epoxides were studied. Preliminary positive results foster us to continue our studies in enlightening the scope and the limitations of this new reaction.

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A means of analyzing protein quaternary structure using matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI MS) and chemical crosslinking was evaluated. Proteins of known oligomeric structure, as well as monomeric proteins, were analyzed to evaluate the method. The quaternary structure of proteins of unknown or uncertain structure was investigated using this technique. The stoichiometry of recombinant E. coli carbamoyl phosphate synthetase and recombinant human farnesyl protein transferase were determined to be heterodimers using glutaraldehyde crosslinking, agreeing with the stoichiometry found for the wild type proteins. The stoichiometry of the gamma subunit of E. coli DNA polymerase III holoenzyme was determined in solution without the presence of other subunits to be a homotetramer using glutaraldehyde crosslinking and MALDI MS analysis. Chi and psi subunits of E. coli DNA polymerase III subunits appeared to form a heterodimer when crosslinked with heterobifunctional photoreactive crosslinkers.^ Comparison of relative % peak areas obtained from MALDI MS analysis of crosslinked proteins and densitometric scanning of silver stained sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) gels showed excellent qualitative agreement for the two techniques, but the quantitative analyses differed, sometimes significantly. This difference in quantitation could be due to SDS-PAGE conditions (differential staining, loss of sample) or to MALDI MS conditions (differences in ionization and/or detection). Investigation of pre-purified crosslinked monomers and dimers recombined in a specific ratio revealed the presence of mass discrimination in the MALDI MS process. The calculation of mass discrimination for two different MALDI time-of-flight instruments showed the loss of a factor of approximately 2.6 in relative peak area as the m/z value doubles over the m/z range from 30,000 to 145,000 daltons.^ Indirect symmetry was determined for tetramers using glutaraldehyde crosslinking with MALDI MS analysis. Mathematical modelling and simple graphing allowed the determination of the symmetry for several tetramers known to possess isologous D2 symmetry. These methods also distinguished tetramers that did not fit D2 symmetry such as apo-avidin. The gamma tetramer of E. coli DNA polymerase III appears to have isologous D2 symmetry. ^

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The Alps and the Alpine foreland have been shaped by repeated glaciations during Quaternary glacial-interglacial cycles. Extent, timing and impact on landscape evolution of these glaciations are, however, poorly constrained due to the fragmentary character of terrestrial archives. In this context, the sedimentary infills of subglacially eroded, ‘overdeepened’, basins may serve as important archives to complement the Quaternary stratigraphy over several glacial-interglacial cycles. In this thesis, the infills of deep subglacial basins in the Lower Glatt valley (N Switzerland) are explored to better constrain the Middle- to Late Pleistocene environmental change. Five drill cores gave direct insight into to the up to ~200 m thick valley fill at the study site and allowed for detailed analysis of sedimentary facies, age and architecture of the basin fills. A first focus is set on the sedimentology of coarse-grained diamicts with sorted interbeds overlying bedrock in the trough center, which mark the onset of deposition in many glacial bedrock troughs. Evidence from macro- and microsedimentology suggests that these sediments are emplaced subglacially and reflect deposition, reworking and deformation in response to repeated coupling and decoupling of the ice-bed interface promoted by high basal water pressures. Overlying these subglacial sediments, large volumes of sandy glacio-deltaic, fine-grained glacio-lacustrine and lacustrine sediments document sedimentation during glacier retreat from the basins. On these thick valley fill sequences the applicability and reliability of luminescence dating is investigated in a second step on the basis of experiments with several different luminescence signals, protocols and experiments to assess the signal stability. The valley fill of the Lower Glatt valley is then grouped into nine depositional cycles (Formations A-I), which are related to the Birrfeld Glaciation (~MIS2), the Beringen Glaciation (~MIS6), and up to three earlier Middle Pleistocene glaciations, tentatively correlated to the Hagenholz, Habsburg, and Möhlin Glaciations, according to the regional glaciation history. The complex bedrock geometry and valley fill architecture are shown to be the result of multiple erosion and infilling cycles and reflect the interplay of subglacial erosion, glacial to lacustrine infilling of overdeepened basins, and fluvial down-cutting and aggradation in the non-overdeepened valley fill. Evidence suggests that in the study area deep bedrock incision, and/or partial re-excavation, occurred mainly during the Beringen and Hagenholz Glaciation, while older structures may have existed. Together with the observation of minor, ‘inlaid’ glacial basins, dynamic changes in the magnitude and focus of subglacial erosion over time are documented.

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A series of 7 cerium double-decker complexes with various tetrapyrrole ligands including porphyrinates, phthalocyaninates, and 2,3-naphthalocyaninates have been prepared by previously described methodologies and characterized with elemental analysis and a range of spectroscopic methods. The molecular structures of two heteroleptic \[(na)phthalocyaninato](porphyrinato) complexes have also been determined by X-ray diffraction analysis which exhibit a slightly distorted square antiprismatic geometry with two domed ligands. Having a range of tetrapyrrole ligands with very different electronic properties, these compounds have been systematically investigated for the effects of ligands on the valence of the cerium center. On the basis of the spectroscopic (UV−vis, near-IR, IR, and Raman), electrochemical, and structural data of these compounds and compared with those of the other rare earth(III) counterparts reported earlier, it has been found that the cerium center adopts an intermediate valence in these complexes. It assumes a virtually trivalent state in cerium bis(tetra-tert-butylnaphthalocyaninate) as a result of the two electron rich naphthalocyaninato ligands, which facilitate the delocalization of electron from the ligands to the metal center. For the rest of the cerium double-deckers, the cerium center is predominantly tetravalent. The valences (3.59−3.68) have been quantified according to their LIII-edge X-ray absorption near-edge structure (XANES) profiles.

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Visiting a modern shopping center is becoming vital in our society nowadays. The fast growth of shopping center, transportation system, and modern vehicles has given more choices for consumers in shopping. Although there are many reasons for the consumers in visiting the shopping center, the influence of travel time and size of shopping center are important things to be considered towards the frequencies of visiting customers in shopping centers. A survey to the customers of three major shopping centers in Surabaya has been conducted to evaluate the Ellwood’s model and Huff’s model. A new exponent value N of 0.48 and n of 0.50 has been found from the Ellwood’s model, while a coefficient of 0.267 and an add value of 0.245 have been found from the Huff’s model.

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The Granadilla eruption at 600 ka was one of the largest phonolitic explosive eruptions from the Las Cañadas volcano on Tenerife, producing a classical plinian eruptive sequence of a widespread pumice fall deposit overlain by an ignimbrite. The eruption resulted in a major phase of caldera collapse that probably destroyed the shallow-level magma chamber system. Granadilla pumices contain a diverse phenocryst assemblage of alkali feldspar + biotite + sodian diopside to aegirine–augite + titanomagnetite + ilmenite + nosean/haüyne + titanite + apatite; alkali feldspar is the dominant phenocryst and biotite is the main ferromagnesian phase. Kaersutite and partially resorbed plagioclase (oligoclase to sodic andesine) are present in some eruptive units, particularly in pumice erupted during the early plinian phase, and in the Granadilla ignimbrite at the top of the sequence. Associated with the kaersutite and plagioclase are small clots of microlitic plagioclase and kaersutite interpreted as quenched blebs of tephriphonolitic magma within the phonolite pumice. The Granadilla Member has previously been recognized as an example of reverse-then-normal compositional zonation, where the zonation is primarily expressed in terms of substantial variations in trace element abundances with limited major element variation (cryptic zonation). Evidence for cryptic zonation is also provided by the chemistry of the phenocryst phases, and corresponding changes in intensive parameters (e.g. T, f O2, f  H2O). Geothermometry estimates indicate that the main body of phonolite magma had a temperature gradient from 860 °C to ∼790 °C, with hotter magma (≥900 °C) tapped at the onset and terminal phases of the eruption. The reverse-then-normal chemical and thermal zonation reflects the initial tapping of a partially hybridized magma (mixing of phonolite and tephriphonolite), followed by the more sequential tapping of a zoned and relatively large body of highly evolved phonolite at a new vent and during the main plinian phase. This suggests that the different magma types within the main holding chamber could have been laterally juxtaposed, as well as in a density-stratified arrangement. Correlations between the presence of mixed phenocryst populations (i.e. presence of plagioclase and kaersutite) and coarser pumice fall layers suggest that increased eruption vigour led to the tapping of hybridized and/or less evolved magma probably from greater depths in the chamber. New oxygen isotope data for glass and mineral separates preclude syn-eruptive interaction between the vesiculating magma and hydrothermal fluids as the cause of the Sr isotope disequilibrium identified previously for the deposit. Enrichment in radiogenic Sr in the pumice glass has more likely been due to low-temperature exchange with meteoric water that was enriched in 87Sr by sea spray, which may be a common process affecting porous and glassy pyroclastic deposits on oceanic islands.