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1.
The influence of different referencing methods on the accuracy of δ13C value measurement of ethanol fuel by gas chromatography/combustion/isotope ratio mass spectrometry 下载免费PDF全文
2.
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 下载免费PDF全文
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
3.
4.
Vito Gigante Laura Aliotta Maria Beatrice Coltelli Patrizia Cinelli Luigi Botta Francesco Paolo La Mantia Andrea Lazzeri 《Journal of polymer science. Part A, Polymer chemistry》2020,58(23):3264-3282
The development of biodegradable materials for tailored applications, particularly in the field of polymeric films and sheets, is a challenging technological goal as well as a contribution to help protect the environment. Poly(lactic) acid (PLA) is a promising substitute for several oil-based polymers; however, to overcome its thermal and mechanical drawbacks, researchers have developed solutions such as blending PLA with polybutylene adipate terephthalate (PBAT), which is capable of increasing the ductility of the final material. In this study, PLA/PBAT binary blends, with minimum possible content of nonrenewable materials, were examined from processing, thermal, morphological, and rheological perspective. An optimized PLA/PBAT ratio was chosen as the polymeric basis to obtain a biodegradable formulation by adding a biobased plasticizer and appropriate fillers to produce a micrometer film with tailored flexibility and tear resistance. The processing technology involved flat-die extrusion, followed by calendering. The tearing resistance of the produced film was investigated, and the results were compared with literature data. A study on the essential work of fracture was implemented to explore the mode III out-of-plane fracture resistance starting from a trouser tear test. 相似文献
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6.
A set of exact conditions is compiled for the purpose of developing and testing approximations for the exchange-correlation energy as a functional of the electron density. Special emphasis is placed upon recently developed density-scaling relationships. Commonly used generalized gradient approximations are compared against several of these conditions. A direct tabular comparison of these functionals (not of calculated properties) with one another is also made. © 1994 John Wiley & Sons, Inc. 相似文献
7.
M. Castagnino R. Id Betan R. Laura 《International Journal of Theoretical Physics》2003,42(10):2423-2439
By extending the notion of mixed states to functionals acting on the space of observables with diagonal singularity we obtain a well-defined complex spectral decomposition of the time evolution for a quantum decaying system. In this formalism, generalized Gamow states are obtained with well-defined physical properties. 相似文献
8.
We study the expected delay in cyclic polling models with general ‘branching-type’ service disciplines. For this class of
models, which contains models with exhaustive and gated service as special cases, we obtain closed-form expressions for the
expected delay under standard heavy-traffic scalings. We identify a single parameter associated with the service discipline
at each queue, which we call the ‘exhaustiveness’. We show that the scaled expected delay figures depend on the service policies
at the queues only through the exhaustiveness of each of the service disciplines. This implies that the influence of different
service disciplines, but with the same exhaustiveness, on the expected delays at the queues becomes the same when the system
reaches saturation. This observation leads to a new classification of the service disciplines. In addition, we show monotonicity
of the scaled expected delays with respect to the exhaustiveness of the service disciplines. This induces a complete ordering
in terms of efficiency of the service disciplines. The results also lead to new rules for optimization of the system performance
with respect to the service disciplines at the queues. Further, the exact asymptotic results suggest simple expected waiting-time
approximations for polling models in heavy traffic. Numerical experiments show that the accuracy of the approximations is
excellent for practical heavy-traffic scenarios.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
9.
Modulated
DSC for gas hydrates analysis 总被引:1,自引:0,他引:1
C. Giavarini F. Maccioni Maria Laura Santarelli 《Journal of Thermal Analysis and Calorimetry》2006,84(2):419-424
Modulated DSC has been applied to the study of methane,
ethane and propane hydrates at different hydrate and ice concentrations. The
reversing component of the TMDSC curves, makes it possible to characterize
such hydrates.
Methane and ethane hydrates show the melting-decomposition
peak at a temperatures higher than the ice contained in the sample, while
propane hydrate melts and decomposes at lower temperature than the ice present
in the sample. The hydrate peaks tend to disappear if the hydrate is stored
at atmospheric pressure. Guest size and cavity occupation fix the heat of
dissociation and stability of the hydrates, as confirmed by parallel tests
on tetrahydrofurane hydrates. 相似文献
10.
Let G be a finite group. A complete Sylow product of G is a product of Sylow subgroups of G, one for each prime divisor of |G|. We shall call G a Sylow factorizable group if it is equal to at least one of its complete Sylow products. We prove that if G is a Sylow factorizable group then the
intersection of all complete Sylow products of G is equal to the solvable radical of G. We generalize the concepts and the result to Sylow products which involve an arbitrary subset of the prime divisors of |G|.
Received: 26 January 2005 相似文献