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Selected AbstractsIsolation and X-Ray Structures of Reactive Intermediates of Organocatalysis with Diphenylprolinol Ethers and with ImidazolidinonesHELVETICA CHIMICA ACTA, Issue 11 20085-Repulsion, A Survey, Comparison with Computed Structures, the Geminal-Diaryl Effect at Work, with 1-Acyl-imidazolidinones: The Abstract Reaction of 2-phenylacetaldehyde with the Me3Si ether of diphenyl-prolinol, with removal of H2O, gives a crystalline enamine (1). The HBF4 salts of the MePh2Si ether of diphenyl-prolinol and of 2-(tert -butyl)-3-methyl- and 5-benzyl-2,2,3-trimethyl-1,3-imidazolidin-4-one react with cinnamaldehyde to give crystalline iminium salts 2, 3, and 4. Single crystals of the enamine and of two iminium salts, 2 and 3, were subjected to X-ray structure analysis (Figs.,1, 2, and 6), and a 2D-NMR spectrum of the third iminium salt was recorded (Fig.,7). The crystal and NMR structures confirm the commonly accepted, general structures of the two types of reactive intermediates in organocatalysis with the five-membered heterocycles, i.e., D, E (Scheme,2). Fine details of the crystal structures are discussed in view of the observed stereoselectivities of the corresponding reactions with electrophiles and nucleophiles. The structures 1 and 2 are compared with those of other diphenyl-prolinol derivatives (from the Cambridge File CSD; Table,1) and discussed in connection with other reagents and ligands, containing geminal diaryl groups and being used in enantioselective synthesis (Fig.,4). The iminium ions 3 and 4 are compared with N -acylated imidazolidinones F and G (Figs.,9, 12, and 13, and Table,3), and common structural aspects such as minimalization of 1,5-repulsion (the ,A1,3 -effect'), are discussed. The crystal structures of the simple diphenyl-prolinol,HBF4 salt (Fig.,3) and of Boc- and benzoyl-(tert -butyl)methyl-imidazolidinone (Boc-BMI and Bz-BMI, resp.; Figs.,10 and 11) are also reported. Finally, the crystal structures are compared with previously published theoretical structures, which were obtained from high-level-of-theory DFT calculations (Figs.,5 and 8, and Table,2). Delicate details including pyramidalization of trigonal N-atoms, distortions around iminium CN bonds, shielding of diastereotopic faces, and the , -interaction between a benzene ring and a Me group match so well with, and were actually predicting the experimental results that the question may seem appropriate, whether one will soon start considering to carry out such calculations before going to the laboratory for experimental optimizations. [source] Atmospheric conditions associated with the exceptional fire season of 2003 in PortugalINTERNATIONAL JOURNAL OF CLIMATOLOGY, Issue 13 2006Ricardo M. Trigo Abstract The summer of 2003 was characterised by exceptional warm weather in Europe, particularly during the first two weeks of August, when a devastating sequence of large fires was observed, reaching an amount of circa 450 000 ha, the largest figure ever recorded in Portugal in modern times. They were concentrated in two relatively confined regions of Portugal and a considerable proportion of burnt area was due to fires started on the 2nd and 3rd of August. It is shown that the 850 hPa temperature values observed over Portugal for the 1st and 2nd of August 2003 were the highest recorded since 1958. Using data from synoptic stations covering the entire Portuguese territory, the event was characterised in fine detail, including the evolution of both maximum and minimum temperatures, surface relative humidity, and wind anomaly fields. The different spatial extent of maximum and minimum temperatures is analysed leading to the new all-time Portuguese records of 47.3 °C for maximum and 30.6 °C for minimum temperatures that were recorded on the 1st of August near the main area of occurrence of the largest fire. Finally, it is shown that the summer of 2003 was preceded by a wet winter followed by a very dry month of May, a precipitation anomalous regime that contributed to a climatic background that favoured the role played by the early August heatwave and the associated meteorological surface conditions. Copyright © 2006 Royal Meteorological Society [source] The effects of plant structure on the spatial and microspatial distribution of a bromeliad-living jumping spider (Salticidae)JOURNAL OF ANIMAL ECOLOGY, Issue 1 2005GUSTAVO Q. ROMERO Summary 1In several regions of South America, the neotropical jumping spider Psecas chapoda inhabits and reproduces strictly on the bromeliad Bromelia balansae. Previous studies reported that this spider is more frequent on bromeliads in grasslands than on those growing in forests, and on larger plants, but only when the bromeliads are without inflorescence. Upon blooming, B. balansae fold their leaves back, thereby changing the plant architecture from a tri-dimensional to a bi-dimensional flattened shape, and our hypothesis is that this alteration affects the spider's habitat-selection decisions. 2In the present study, we examined experimentally the effects of inflorescence, plant size and blockade of the axil of the leaves (spider shelters) of forest bromeliads on the colonization of a bromeliad by P. chapoda. By using sticky traps, we also compared prey availability in grassland and forest. 3Plants with simulated inflorescence were colonized at a lower frequency than those without inflorescence simulation. Grassland bromeliads in which the rosettes were blocked with dry leaves were colonized less frequently than open bromeliads, whereas forest bromeliads from which dry leaves had been removed were not colonized. Spiders generally abandoned bromeliads in which three-quarters of the length of the leaves had been removed, although females with eggsacs remained on these plants. Prey availability (biomass and number) was up to 18 fold higher in the grassland than in the forest. These results suggest that microhabitat structure and prey availability shape the spatial distribution of P. chapoda populations. 4Our findings suggest that Psecas chapoda can evaluate, in fine detail, the physical state of its microhabitat, and this unusual spider,plant association is readily destabilized by changes in the microhabitat (i.e., it is strictly dependent on the size and morphology of the host plant). This study is one of the few to report a strict association between a spider species and its host plant, and also one of the few to examine the effects of habitat and microhabitat structure on the spatial distribution of active hunters on plants. [source] Simple Efficient Contracts in Complex EnvironmentsECONOMETRICA, Issue 3 2008Robert Evans This paper studies a general model of holdup in a setting encompassing the models of Segal (1999) and Che and Hausch (1999) among others. It is shown that if renegotiation is modeled as an infinite-horizon noncooperative bargaining game, then, with a simple initial contract, an efficient equilibrium will generally exist. The contract is robust in the sense that it does not depend on fine details of the model. The contract gives authority to one party to set the terms of trade and gives the other party a nonexpiring option to trade at these terms. The difference from standard results arises because the initial contract ensures that the renegotiation game has multiple equilibria; the multiplicity of continuation equilibria can be used to enforce efficient investment. [source] PERSPECTIVE: SEX, RECOMBINATION, AND THE EFFICACY OF SELECTION,WAS WEISMANN RIGHT?EVOLUTION, Issue 2 2000Austin Burt Abstract., The idea that sex functions to provide variation for natural selection to act upon was first advocated by August Weismann and it has dominated much discussion on the evolution of sex and recombination since then. The goal of this paper is to further extend this hypothesis and to assess its place in a larger body of theory on the evolution of sex and recombination. A simple generic model is developed to show how fitness variation and covariation interact with selection for recombination and illustrate some important implications of the hypothesis: (1) the advantage of sex and recombination can accrue both to reproductively isolated populations and to modifiers segregating within populations, but the former will be much larger than the latter; (2) forces of degradation that are correlated across loci within an individual can reduce or reverse selection for increased recombination; and (3) crossing-over (which can occur at different places in different meioses) will create more variability than having multiple chromosomes and so will have more influence on the efficacy of selection. Several long-term selection experiments support Weismann's hypothesis, including those showing a greater response to selection in populations with higher rates of recombination and higher rates of recombination evolving as a correlated response to selection for some other character. Weismann's hypothesis is also consistent with the sporadic distribution of obligate asexuality, which indicates that clones have a higher rate of extinction than sexuals. Weismann's hypothesis is then discussed in light of other patterns in the distribution of sexuality versus asexuality. To account for variation in the frequency of obligate asexuality in different taxa, a simple model is developed in which this frequency is a function of three parameters: the rate of clonal origin, the initial fitness of clones when they arise, and the rate at which that fitness declines over time. Variation in all three parameters is likely to be important in explaining the distribution of obligate asexuality. Facultative asexuality also exists, and for this to be stable it seems there must be ecological differences between the sexual and asexual propagules as well as genetic differences. Finally, the timing of sex in cyclical parthenogens is most likely set to minimize the opportunity costs of sex. None of these patterns contradict Weismann's hypothesis, but they do show that many additional principles unrelated to the function of sex are required to fully explain its distribution. Weismann's hypothesis is also consistent with what we know about the mechanics and molecular genetics of recombination, in particular the tendency for chromatids to recombine with a homolog rather than a sister chromatid at meiosis, which is opposite to what they do during mitosis. However, molecular genetic studies have shown that cis -acting sites at which recombination is initiated are lost by gene conversion as a result, a factor that can be expected to affect many fine details in the evolution of recombination. In summary, although Weismann's hypothesis must be considered the leading candidate for the function of sex and recombination, nevertheless, many additional principles are needed to fully account for their evolution. [source] Newborns' Mooney-Face PerceptionINFANCY, Issue 6 2009Irene Leo The aim of this study is to investigate whether newborns detect a face on the basis of a Gestalt representation based on first-order relational information (i.e., the basic arrangement of face features) by using Mooney stimuli. The incomplete 2-tone Mooney stimuli were used because they preclude focusing both on the local features (i.e., the fine details of the individual features) and on the second-order relational information (i.e., the distance between the internal elements); therefore, face detection can rely only on a Gestalt representation of a face. Two experiments were carried out by using a preferential looking procedure. Experiment 1 demonstrated that newborns prefer upright Mooney faces to inverted Mooney faces (180° rotated). Experiment 2 showed that newborns prefer a Mooney face as compared to a Mooney-like object equated for the number of elements in the upper part. Overall, the results indicate that newborns bind and organize the fragmentary parts of the Mooneized face stimulus into a whole and detect the first-order relations of a face on the basis of holistic processing. [source] Nanocrystalline domain size distributions from powder diffraction dataJOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 4 2004Matteo Leoni The need for an a priori domain size distribution is one of the main limitations of existing line profile analysis methodologies. A numerical modification of the whole-powder-pattern modelling algorithm is proposed, to allow the refinement of a general domain size distribution from powder diffraction data. The shape of domains has to be inferred for the specimen under study. The algorithm is robust enough to unveil fine details in the refined distribution, as witnessed by the results of tests performed both on simulated and on real patterns of nanocrystalline ceria. [source] Three-dimensional reconstruction and neural map of the serotonergic brain of Asplanchna brightwellii (Rotifera, Monogononta)JOURNAL OF MORPHOLOGY, Issue 4 2009Rick Hochberg Abstract The basic organization of the rotifer brain has been known for nearly a century; yet, fine details on its structure and organization remain limited despite the importance of rotifers in studies of evolution and population biology. To gain insight into the structure of the rotifer brain, and provide a foundation for future neurophysiologic and neurophylogenetic research, the brain of Asplanchna brightwellii was studied with immunohistochemistry, confocal laser scanning microscopy, and computer modeling. A three-dimensional map of serotonergic connections reveals a complex network of approximately 28 mostly unipolar, cerebral perikarya and associated neurites. Cells and their projections display symmetry in quantity, size, connections, and pathways between cerebral hemispheres within and among individuals. Most immunopositive cells are distributed close to the brain midline. Three pairs of neurites form decussations at the brain midline and may innervate sensory receptors in the corona. A single neuronal pathway appears to connect both the lateral horns and dorsolateral apical receptors, suggesting that convergence of synaptic connections may be common in the afferent sensory systems of rotifers. Results show that the neural map of A. brightwellii is much more intricate than that of other monogonont rotifers; nevertheless, the consistency in neural circuits provides opportunities to identify homologous neurons, distinguish functional regions based on neurotransmitter phenotype, and explore new avenues of neurophylogeny in Rotifera. J. Morphol. 2009. © 2008 Wiley-Liss, Inc. [source] Space-demanding intramolecular isomerizations in the solid stateJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 3 2002G. Kaupp Abstract The thermal isomerizations of meso - and rac -3,4-dibromo-1,6-diphenyl-1,6-bis(p -tolyl)-1,2,4,5-hexatetraene (1) to give stereospecifically the 3,4-bis(phenyl- p -tolylmethylene)-1,2-dibromocyclobutenes 3 and 5,+,6 were studied in the solid state using atomic force microscopy (AFM) and interpreted on the basis of known crystal structural data. These isomerizations run to completion in the bulk and include highly space-demanding internal rotations around the central bond. Far-reaching anisotropic molecular movements are detected on the major faces that align the surface features along cleavage planes in the initial phase rebuilding stage. Only one of three identified cleavage planes of meso - 1 is successful, owing to closer interactions of the bromine substituents in the non-used cleavage planes. Thus, very fine details can be correlated and predicted for the occurrence of internal rotations and molecular movements in the crystal lattice. The second stage in these intramolecular isomerizations, the phase transformation, produces very high features up to 100,nm and still parallel to the preferred cleavage plane of meso - 1 but in the,µm range without relation to the initial crystal structure in the case of rac - 1. Copyright © 2002 John Wiley & Sons, Ltd. [source] Performance and numerical behavior of the second-order scheme of precise time-step integration for transient dynamic analysisNUMERICAL METHODS FOR PARTIAL DIFFERENTIAL EQUATIONS, Issue 6 2007Hang Ma Abstract Spurious high-frequency responses resulting from spatial discretization in time-step algorithms for structural dynamic analysis have long been an issue of concern in the framework of traditional finite difference methods. Such algorithms should be not only numerically dissipative in a controllable manner, but also unconditionally stable so that the time-step size can be governed solely by the accuracy requirement. In this article, the issue is considered in the framework of the second-order scheme of the precise integration method (PIM). Taking the Newmark-, method as a reference, the performance and numerical behavior of the second-order PIM for elasto-dynamic impact-response problems are studied in detail. In this analysis, the differential quadrature method is used for spatial discretization. The effects of spatial discretization, numerical damping, and time step on solution accuracy are explored by analyzing longitudinal vibrations of a shock-excited rod with rectangular, half-triangular, and Heaviside step impact. Both the analysis and numerical tests show that under the framework of the PIM, the spatial discretization used here can provide a reasonable number of model types for any given error tolerance. In the analysis of dynamic response, an appropriate spatial discretization scheme for a given structure is usually required in order to obtain an accurate and meaningful numerical solution, especially for describing the fine details of traction responses with sharp changes. Under the framework of the PIM, the numerical damping that is often required in traditional integration schemes is found to be unnecessary, and there is no restriction on the size of time steps, because the PIM can usually produce results with machine-like precision and is an unconditionally stable explicit method. © 2007 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2007 [source] Processing of CFTR: Traversing the cellular maze,How much CFTR needs to go through to avoid cystic fibrosis?PEDIATRIC PULMONOLOGY, Issue 6 2005Margarida D. Amaral PhD Abstract Biosynthesis of the cystic fibrosis transmembrane conductance regulator (CFTR), like other proteins aimed at the cell surface, involves transport through a series of membranous compartments, the first of which is the endoplasmic reticulum (ER), where CFTR encounters the appropriate environment for folding, oligomerization, maturation, and export from the ER. After exiting the ER, CFTR has to traffic through complex pathways until it reaches the cell surface. Although not yet fully understood, the fine details of these pathways are starting to emerge, partially through identification of an increasing number of CFTR-interacting proteins (CIPs) and the clarification of their roles in CFTR trafficking and function. These aspects of CFTR biogenesis/degradation and by membrane traffic and CIPs are discussed in this review. Following this description of complex pathways and multiple checkpoints to which CFTR is subjected in the cell, the basic question remains of how much CFTR has to overcome these barriers and be functionally expressed at the plasma membrane to avoid CF. This question is also discussed here. Pediatr Pulmonol. © 2005 Wiley-Liss, Inc. [source] Photo-CIDNP Study of the Interaction of Tyrosine with Nifedipine.PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 3 2004An Attempt to Model the Binding Between Calcium Receptor, Calcium Antagonist Nifedipine This article proposes a new approach to the modeling of the molecular-level mechanism of ligand-receptor interaction for Ca2+ receptor binding site. Chemically induced dynamic nuclear polarization (CIDNP) technique has been used to unravel fine details of the reaction in the model system composed of one of the known Ca2+ antagonist drugs, nifedipine (NF), and isolated amino acid residuals (e.g. tyrosine [Tyr]) of Ca2+ receptor binding site. It has been conclusively demonstrated that the reaction between NF and Tyr resulting in the oxidation product,nitroso form of NF,obeys the radical mechanism. CIDNP data in combination with the results of mathematical modeling of the structures of ligandreceptor complexes have allowed to propose the mechanism of the interaction of NF with Ca2+ receptor binding site. [source] Renin: from ,pro' to promoterBIOESSAYS, Issue 5 2003Brian J. Morris Renin is the rate-limiting enzyme in a cascade that leads to production of angiotensin II, which is perhaps our most important regulator of salt and water balance and blood pressure. In this personal perspective, I describe how I entered the renin field 33 years ago by discovering that proteases increased the level of renin activity in biological fluids, so revealing the existence of a ,pro' form of the molecule. This led me on a journey that encapsulated all of the major milestones in molecular discovery for renin. These included (1) the elucidation of the steps in renin biosynthesis, (2) the cloning of renin cDNA and its gene, (3) demonstration of the structure of the renin protein, (4) using the renin gene in the first genetic studies in hypertension, (5) finding the mechanism by which the major controller, cyclic AMP, regulates the promoter, (6) showing that a strong enhancer and its weak promoter control this physiologically regulatable gene in accord with the variegation (on/off switching) model, and (7) being the first to identify molecules involved in posttranscriptional control. The renin molecule, its gene and molecular control are now very well understood, but more fine details on the topic of renin continue to emerge to delight ,reninologists' and others. BioEssays 25:520,527, 2003. © 2003 Wiley Periodicals, Inc. [source] Genomic Analyses and the Origin of the EukaryotesCHEMISTRY & BIODIVERSITY, Issue 11 2007Maria Abstract The availability of whole-genome data has created the extraordinary opportunity to reconstruct in fine details the ,tree of life'. The application of such comprehensive effort promises to unravel the enigmatic evolutionary relationships between prokaryotes and eukaryotes. Traditionally, biologists have represented the evolutionary relationships of all organisms by a bifurcating phylogenetic tree. But recent analyses of completely sequenced genomes using conditioned reconstruction (CR), a newly developed gene-content algorithm, suggest that a cycle graph or ,ring' rather than a ,tree' is a better representation of the evolutionary relationships between prokaryotes and eukaryotes. CR is the first phylogenetic-reconstruction method to provide precise evidence about the origin of the eukaryotes. This review summarizes how the CR analyses of complete genomes provide evidence for a fusion origin of the eukaryotes. [source] | ||||||||||||||||