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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.
Gustavo A.Carri 《高分子科学》2015,33(4):523-539
We revisit the Simha-Somcynsky model of polymer fluids with the purpose of developing novel theoretical and computational approaches to simplify and speed up its solution as well as the fitting of experimental data, and decrease its level of mathematical complexity. We report a novel method that allows us to solve one of the two equations of the model exactly, thus putting the level of mathematical difficulty on a par with the one of other models for polymer fluids. Moreover, we describe a computational algorithm capable of fitting all five parameters of the model in an unbiased way. The results obtained reproduce literature results and fit experimental pressure-volume-temperature and solubility parameter data for three polymers very accurately. Moreover, the new techniques allow for the investigation of the model at very low temperatures. Unexpectedly, the model predicts behaviors that could be interpreted as a glass transition, as routinely observed in dilatometry and differential scanning calorimetry, and a glass phase. We compared the predicted and experimental T g’s for cis poly(1,4-butadiene) and found an excellent quantitative agreement. 相似文献
3.
Humberto Bustos Rodriguez Dagoberto Oyola Lozano Yebrayl A. Rojas Martínez Germán A. Pérez Alcázar Stefan Flege Adam G. Balogh Louis J. Cabri Michael Tubrett 《Hyperfine Interactions》2007,175(1-3):195-206
X-ray diffraction (XRD), Mössbauer spectrometry (MS), secondary ions mass spectroscopy (SIMS) and laser-ablation microprobe–inductively coupled plasma–mass spectrometry (LAM–ICP–MS) were used to study mineral samples of Colombian auriferous ores collected from the “El Diamante” mine, located in the municipality of Guachavez-Nariño, in Colombia. The samples were prepared as polished thin sections and polished sections. From XRD data, quartz, sphalerite and pyrite were detected and their respective cell parameters were estimated. From MS analyses, pyrite, arsenopyrite and chalcopyrite were identified; their respective hyperfine parameters and respective texture were deduced. Multiple regions of approximately 200 × 200 μm in each sample were analyzed with SIMS; the occurrence of “invisible gold” associated mainly with pyrite and secondarily with arsenopyrite could thus be assigned. It was also found that pyrite is of the arsenious type. Spots from 30 to 40 μm in diameter were analyzed with LAM–ICP–MS for pyrite, arsenopyrite and sphalerite; Au is “homogeneously” distributed inside the structure of the arsenious pyrite and the arsenopyrite (not as inclusions); the chemical composition indicates similarities of this “invisible gold”, forming a solid solution with arsenious pyrite and arsenopyrite. One hundred nineteen and 62 ppm of ‘invisible gold’ was quantified in 21 spots analyzed on pyrite and in 14 spots on arsenopyrite, respectively. 相似文献
4.
The linearized stability of charged thin shell wormholes under spherically symmetric perturbations is analyzed. It is shown that the presence of a large value of charge provides stabilization to the system, in the sense that the constraints onto the equation of state are less severe than for non-charged wormholes. 相似文献
5.
Maximiliano A. Burgos Paci Gustavo A. Argüello Plcido García Helge Willner 《国际化学动力学杂志》2003,35(1):15-19
Thermal decomposition of bis(trifluoromethyl) peroxydicarbonate has been studied. The mechanism of decomposition is a simple bond fission, homogeneous first‐order process when the reaction is carried out in the presence of inert gases such as N2 or CO. An activation energy of 28.5 kcal mol?1 was determined for the temperature range of 50–90°C. Decomposition is accelerated by nitric oxide because of a chemical attack on the peroxide forming substances different from those formed with N2 or CO. An interpretation on the influence of the substituents in different peroxides on the O? O bond is given. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 35: 15–19, 2003 相似文献
6.
7.
Fabian Buffa Gustavo A. Abraham Brian P. Grady Daniel Resasco 《Journal of Polymer Science.Polymer Physics》2007,45(4):490-501
A commercially available aliphatic thermoplastic polyurethane formulated with a methylene bis(cyclohexyl) diisocyanate hard segment and a poly(tetramethylene oxide) soft segment and chain‐extended with 1,4‐butanediol was dissolved in dimethylformamide and mixed with dispersed single‐walled carbon nanotubes. The properties of composites made with unfunctionalized nanotubes were compared with the properties of composites made with nanotubes functionalized to contain hydroxyl groups. Functionalization almost eliminated the conductivity of the tubes according to the conductivity of the composites above the percolation threshold. In most cases, functionalized and unfunctionalized tubes yielded composites with statistically identical mechanical properties. However, composites made with functionalized tubes did have a slightly higher modulus in the rubbery plateau region at higher nanotube fractions. Small‐angle X‐ray scattering patterns indicated that the dispersion reached a plateau in the unfunctionalized composites that was consistent with the plateau in the rubbery plateau region. The room‐temperature modulus and tensile strength increase was proportionally higher than almost all increases seen previously in thermoplastic polyurethanes; however, the increase was still an order of magnitude below what has been reported for the best nanotube–polymer systems. Nanotube addition increased the hard‐segment glass transition temperature slightly, whereas the soft‐segment glass transition was so diffuse that no conclusions could be drawn. Unfunctionalized tubes suppressed the crystallization of the hard segment; whereas functionalized tubes had no effect. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 490–501, 2007 相似文献
8.
Gustavo Portalone Marcello Colapietro 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(11):o650-o654
The asymmetric unit of the amino–oxo tautomer of 5‐formyluracil (systematic name: 2,4‐dioxo‐1,2,3,4‐tetrahydropyrimidine‐5‐carbaldehyde), C5H4N2O3, comprises one planar amino–oxo tautomer, as every atom in the structure lies on a crystallographic mirror plane. At variance with all the previously reported small‐molecule crystal structures containing the 5‐formyluracil residue, the formyl substituent in the title compound exhibits an unusual syn conformation. The molecules are linked into planar sheets parallel to the bc plane by a combination of six N—H...O and C—H...O hydrogen bonds. Four of the hydrogen bonds are utilized to stabilize the formyl group in the syn conformation. 相似文献
9.
R. Arnaldi R. Averbeck K. Banicz J. Castor B. Chaurand C. Cicalo A. Colla P. Cortese S. Damjanovic A. David A. De Falco A. Devaux A. Drees L. Ducroux H. En’yo A. Ferretti M. Floris A. Foerster P. Force N. Guettet A. Guichard H. Gulkanian J. Heuser M. Keil L. Kluberg J. Lozano C. Lourenço F. Manso A. Masoni P. Martins A. Neves H. Ohnishi C. Oppedisano P. Parracho P. Pillot G. Puddu E. Radermacher P. Ramalhete P. Rosinsky E. Scomparin J. Seixas S. Serci R. Shahoyan P. Sonderegger H.J. Specht R. Tieulent G. Usai R. Veenhof H.K. Wöhri 《The European Physical Journal C - Particles and Fields》2007,49(1):235-241
The NA60 experiment at the CERN SPS has studied low-mass muon pairs in 158 A GeV In–In collisions. A strong excess of pairs
is observed above the yield expected from neutral meson decays. The unprecedented sample size close to 400000 events and the
good mass resolution of about 2% made it possible to isolate the excess by subtraction of the decay sources. The shape of
the resulting mass spectrum shows some non-trivial centrality dependence, but is largely consistent with a dominant contribution
from π+π-→ϱ→μ+μ- annihilation. The associated ϱ spectral function exhibits considerable broadening, but essentially no shift in mass. The
pT-differential mass spectra show the excess to be much stronger at low pT than at high pT. The results are compared to theoretical model predictions; they tend to rule out models linking hadron masses directly to
the chiral condensate.
PACS 25.75.-q; 12.38.Mh; 13.85.Qk 相似文献
10.