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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
2.
3.
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.
The aim of this work is to study the dynamic formation and dissociation of trions and excitons in double barrier resonant tunneling diodes. We propose a system of rate equations that takes into account the formation, dissociation and annihilation of these complexes inside the quantum well. From the solutions of the coupled equations, we are able to study the modulation of excitons and trions formation in the device as a function of the applied bias. The results of our model agree qualitatively with the experiments showing the viability of these rate equations system to study the dynamics of complex systems. 相似文献
5.
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
6.
G. Garcia-Belmonte J. Bisquert L. M. Navarro J. R. Jurado F. M. B. Marques 《Ionics》1995,1(5-6):377-383
In ionic conductors, long range-migrating charges are a main cause of polarization processes. This has complicated, up to
date, the study of ionic thermocurrents (ITC) in solid electrolytes. However, the method is appealing, as it probes directly
charge-formation phenomena that are important both from a scientific point of view and for applications.
This work reports on the observation of ITC in solid electrolytes. Under appropriate experimental conditions, the ITC response
of a zirconia sample electroded with platinum is a reproducible one, thus opening the way to a new characterization method
that may complement other well established methods, such as Impedance Spectroscopy and a number of electrochemical techniques.
The general trends of the response, which is composed of two well resolved ITC peaks, is discussed. One of them, taking place
at higher temperatures, conforms to the standard shape of a first order kinetics depolarization process.
Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995 相似文献
7.
Maria Marques Zhengtian Yu Marvin D. Rausch James C. W. Chien 《Journal of polymer science. Part A, Polymer chemistry》1995,33(16):2787-2793
4-Vinylcyclohexene (VCH) and cyclooctadiene (COD) were investigated as termonomers in EPDM (ethylene/propylene/diene) synthesis by using rac-ethylenebis (1-η5-indenyl) zir-conium dichloride ( 1 ) as a catalyst precursor. Homopolymerizations of VCH, vinylcycloh-exane and cyclohexene were compared. The parameter Kπκp, which is the apparent rate constant for Ziegler-Natta polymerization, is about the same for VCH and vinylcyclohexanebut is 10 times smaller for cyclohexene. Therefore, the linear olefinic double bond is more active than the cyclic internal double bond. VCH reduces ethylene polymerization rate but not propylene polymerization rate in copolymerizations. In terpolymerizations, VCH tends to suppress ethylene incorporation especially at elevated polymerization temperature and Lowers the polymer MW by about two-fold. COD has very low activity as a termonomer. © 1995 John Wiley & Sons, Inc. 相似文献
8.
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
9.
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
10.
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