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1.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis
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Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
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Teresa uczak Radosaw Pankiewicz Bogusawa ska Grzegorz Schroeder Maria Betowska-Brzezinska Bogumil Brzezinski 《Journal of Molecular Structure》2006,800(1-3):140-145
Novel self-assembled monolayers were obtained on silver using 4,7-diazaheptyl-trimethoxy-silane (SiN) and vinyl-trialkoxy-silane (SiVA, where the alkyl group is 3,6,9,12,15,18,21,24,27,30,33,36,39,42,45,48,51,54,57,60-eicozaoxa- hexaheptaconan). It was shown that thus modified metal surface was protected against electrooxidation. A densely packed monolayer remained stable and did not desorb from the Ag electrode on the potential cycling. The structure of SiN and SiVA as well as their complexes with Li+ cations were calculated and visualised by the AM1d and PM5 semi-empirical methods. 相似文献
4.
Biosorption of Chromium(III) by Biomass of Seaweed Sargassum sp. in a Fixed-Bed Column 总被引:2,自引:0,他引:2
Eneida Sala Cossich Edson Antonio da Silva Célia Regina Granhen Tavares Lúcio Cardozo Filho Teresa Massako Kakuta Ravagnani 《Adsorption》2004,10(2):129-138
This work aimed at modeling chromium biosorption using the biomass of seaweed Sargassum sp. in a fixed-bed column. The mathematical model used was obtained from the mass balance of the component in the liquid phase and in the biosorbent material. The effects of both axial dispersion in the column and the resistance to mass transfer in the solid were considered for the solution of the partial differential equations of the model, using the Galerkin method on finite elements. To represent the equilibrium data of the batch system the Langmuir isotherm were used. The chromium ion adsorption capacity of the seaweed Sargassum sp., at a temperature of 30°C and pH 3.5, was 2.61 mmol/g. The model performance was evaluated from experimental data obtained at 30°C for flow rates of 2, 6 and 8 mL/min. The parameters of the model, mass transfer and axial dispersion coefficients, were adjusted from these experimental data. The model proved adequate to describe chromium biosorption dynamics in fixed-bed columns. 相似文献
5.
Sajewicz Mieczysław Hauck Heinz-E. Drabik Gabriela Namysło Ewa Głód Bronisław Kowalska Teresa 《平面色谱法杂志一现代薄层色谱法》2006,19(4):278-281
JPC – Journal of Planar Chromatography – Modern TLC - We have previously described unexpected two-dimensionality in the thin-layer chromatographic separation of pairs of enantiomers of... 相似文献
6.
Luis Anchordoqui María Teresa Dova Thomas McCauley Stephen Reucroft 《Annals of Physics》2004,314(1):145-207
The properties of cosmic rays with energies above 106 GeV have to be deduced from the spacetime structure and particle content of the air showers which they initiate. In this review we summarize the phenomenology of these giant air showers. We describe the hadronic interaction models used to extrapolate results from collider data to ultra high energies, and discuss the prospects for insights into forward physics at the LHC. We also describe the main electromagnetic processes that govern the longitudinal shower evolution, as well as the lateral spread of particles. Armed with these two principal shower ingredients and motivation from the underlying physics, we provide an overview of some of the different methods proposed to distinguish primary species. The properties of neutrino interactions and the potential of forthcoming experiments to isolate deeply penetrating showers from baryonic cascades are also discussed. We finally venture into a terra incognita endowed with TeV-scale gravity and explore anomalous neutrino-induced showers. 相似文献
7.
Gabriela Jeronimo Teresa Krick Juan Sabia Martín Sombra 《Foundations of Computational Mathematics》2004,4(1):41-117
We present a bounded probability algorithm for the computation of the
Chowforms of the equidimensional components of an algebraic variety. In particular,
this gives an alternative procedure for the effective equidimensional decomposition
of the variety, since each equidimensional component is characterized by its Chow
form.
The expected complexity of the algorithm is polynomial in the size and the geometric
degree of the input equation system defining the variety. Hence it improves (or
meets in some special cases) the complexity of all previous algorithms for computing Chow forms. In addition to this, we clarify the probability and uniformity aspects,
which constitutes a further contribution of the paper.
The algorithm is based on elimination theory techniques, in line with the geometric
resolution algorithm due to M. Giusti, J. Heintz, L. M. Pardo, and their collaborators.
In fact, ours can be considered as an extension of their algorithm for zero-dimensional
systems to the case of positive-dimensional varieties. The key element for dealing
with positive-dimensional varieties is a new Poisson-type product formula. This
formula allows us to compute the Chow form of an equidimensional variety from a
suitable zero-dimensional fiber.
As an application, we obtain an algorithm to compute a subclass of sparse resultants,
whose complexity is polynomial in the dimension and the volume of the input
set of exponents. As another application, we derive an algorithm for the computation
of the (unique) solution of a generic overdetermined polynomial equation system. 相似文献
8.
José A. Anquela Teresa Cortés Miguel Gómez-Lozano Mercedes Siles-Molina 《Acta Mathematica Hungarica》2004,103(3):177-196
We investigate the basic properties of the different socles that can be considered in not necessarily semiprime associative
systems. Among other things, we show that the socle defined as the sum of minimal (or minimal and trivial) inner ideals is
always an ideal. When trivial inner ideals are included, this inner socle contains the socles defined in terms of minimal
left or right ideals.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
9.
Educators involved in the current reform movement in mathematics education recommend that students be actively involved in constructing their own knowledge and developing powerful mathematical concepts. This study suggests how ideas based on constructivist learning theory can be put into practice in a preservice mathematics education class. 相似文献
10.
Extension of a combined analytical/numerical initial value problem solver for unsteady periodic flow
Here we describe analytical and numerical modifications that extend the Differential Reduced Ejector/ mixer Analysis (DREA), a combined analytical/numerical, multiple species ejector/mixing code developed for preliminary design applications, to apply to periodic unsteady flow. An unsteady periodic flow modelling capability opens a range of pertinent simulation problems including pulse detonation engines (PDE), internal combustion engine ICE applications, mixing enhancement and more fundamental fluid dynamic unsteadiness, e.g. fan instability/vortex shedding problems. Although mapping between steady and periodic forms for a scalar equation is a classical problem in applied mathematics, we will show that extension to systems of equations and, moreover, problems with complex initial conditions are more challenging. Additionally, the inherent large gradient initial condition singularities that are characteristic of mixing flows and that have greatly influenced the DREA code formulation, place considerable limitations on the use of numerical solution methods. Fortunately, using the combined analytical–numerical form of the DREA formulation, a successful formulation is developed and described. Comparison of this method with experimental measurements for jet flows with excitation shows reasonable agreement with the simulation. Other flow fields are presented to demonstrate the capabilities of the model. As such, we demonstrate that unsteady periodic effects can be included within the simple, efficient, coarse grid DREA implementation that has been the original intent of the DREA development effort, namely, to provide a viable tool where more complex and expensive models are inappropriate. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献