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151.
152.
Edgar Marquez Alexis Maldonado Felix Rosas Beatriz Ramirez Gabriel Chuchani 《Molecular physics》2014,112(3-4):462-473
The kinetics and mechanisms of thermal decomposition of phenyl acetate and p-tolyl acetate in the gas phase were studied by means of electronic structure calculations using density functional theory methods: B3LYP/6-31G(d,p), B3LYP/6-31++G(d,p), B3PW91/6-31G(d,p), B3PW91/6-31++G(d,p), MPW1PW91/6-31G(d,p), MPW1PW91/6-31++G(d,p), PBE/6-31G(d,p) and PBE/6-31++G(d,p). Two possible mechanisms have been considered: mechanism A is a stepwise process involving electrocyclic [1,5] hydrogen shift to eliminate ketene through concerted six-membered cyclic transition-state structure, followed by tautomerisation of cyclohexadienone or by 4-methyl cyclohexadienone intermediate to give the corresponding phenol. Mechanism B is a one-step concerted [1,3] hydrogen shift through a four-membered cyclic transition-state geometry, to produce ketene and phenol or p-cresol. Theoretical calculations showed reasonable agreement with experimental activation parameters when using the Perdew, Burke and Ernserhof (PBE)functional, through the stepwise [1,5] hydrogen-shift mechanism. For mechanism B, large deviation for the entropy of activation was observed. No experimental data were available for p-tolyl acetate; however, theoretical calculations showed similar results to phenyl acetate, thus supporting the stepwise mechanism for both phenyl acetate and p-tolyl acetate. 相似文献
153.
Ademar B. Lugao Lucia Noda Elisabeth. C. L. Cardoso Beatriz Hustzler Shinichi Tokumoto Ana Nery F. Mendes 《Radiation Physics and Chemistry》2002,63(3-6):509-512
It is well known that polypropylene undergoes simultaneous crosslinking and degradation under irradiation. However, there are speculations regarding the formation of branching under special conditions. It is also well known that the melt-strength property of a polymer increases with molecular weight and with long-chain branching due to the increase in the entanglement level. This study was a contribution to the understanding of the following points: the role of molecular weight, the role of structural modifications on nucleation properties; the structural changes on polypropylene.
The results showed that degradation was the major reaction in the initial step of irradiation, however, the largely modified molecules concentrated in the high molecular weight fraction. The results also confirm that the branching formation is likely to occur. 相似文献
154.
Beatriz Pérez-Artacho Visitación Gallardo M. Adolfina Ruiz José L. Arias 《Journal of nanoparticle research》2012,14(4):768
A reproducible methodology is described for the synthesis, by following the double emulsion/solvent evaporation technique,
of magnetic nanocomposites (average diameter ≈ 135 nm) consisting of maghemite nuclei and a biodegradable poly(d,l-lactide-co-glycolide) matrix. The heterogeneous structure of the nanoparticles can confer them the responsiveness to magnetic gradients,
giving both the possibility of their use as a drug delivery system and adequate heating characteristics for a hyperthermia
effect. The physical chemistry of the nanocomposites was extensively characterized, this establishing that their surface properties
were similar to that of pure poly(d,l-lactide-co-glycolide). From an electrokinetic point of view, zeta potential determinations (as a function of the ionic strength, and
pH) pointed out that the nanocomposites were almost indistinguishable from the copolymer. The surface thermodynamic analysis
agreed with the electrophoretic one in suggesting that the coverage of the magnetic nuclei was complete, since the hydrophilic
nature of maghemite was modified and the nanoparticles turned into hydrophobic, just like the copolymer, when they were embedded
into poly(d,l-lactide-co-glycolide). The magnetic behaviours of the composite nanoparticles were also checked. Their heating properties were studied
in vitro in a high-frequency alternating gradient of magnetic field: a stable maximum temperature of 47 °C was satisfactorily
achieved within 45 min. Blood compatibility of the nanocomposites was also defined in vitro. To our knowledge, this is the
first time that such kind of magnetic-sensitive nanoformulation with very promising characteristics (e.g. blood compatibility,
magnetic drug targeting capabilities, and hyperthermia) has been developed for therapeutic purposes. 相似文献
155.
Beatriz Veleirinho Manuel F. Rei J. A. Lopes‐DA‐Silva 《Journal of Polymer Science.Polymer Physics》2008,46(5):460-471
This study describes the preparation and characterization of nanofibrous mats obtained by electrospinning poly(ethylene terephthalate) (PET) solutions in trifluoroacetic acid/dichloromethane (TFA/DCM). Special attention was paid to the effect of polymer concentration and solvent properties on the morphology, structure, and mechanical and thermal properties of the electrospun nonwovens. The results show that the spinnable concentration of PET solution in TFA/DCM solvents is above 10 wt %. Mats have nanofibrous morphology with fibers having an average diameter in the range of 200–700 nm (depending on polymer concentration and solvent composition) and an interconnected pore structure. Higher solution concentration favors the formation of uniform fibers without beads and with higher diameter. Morphology and fiber assembly changed with the solvent properties. Solvent mixtures rich in TFA, i.e., those with higher dielectric constant and lower surface tension, originated fibers with small diameter. However, due to the lower volatility, those solvent mixtures also produced more branched and crosslinking fibers, with less morphologic uniformity. Mechanical properties (Young's modulus, ultimate strength, and elongation at break) and thermal properties (glass transition, crystallization, and melting) have been studied for the PET electrospun nanomats and compared with those of the original polymer. Solvent effect on fiber crystallinity was not significant, but a complex effect was observed on the mechanical properties of the electrospun mats, as a consequence of the different structural organization of the fibers within the mat network. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 460–471, 2008 相似文献
156.
Semicarbazide: occurrence in food products and state-of-the-art in analytical methods used for its determination 总被引:2,自引:0,他引:2
This review provides an overview of the information currently available about the presence of semicarbazide (SEM) in food. Likely sources of SEM in food matrices are summarised and discussed. Detailed information is given about the analytical methods used to determine SEM; features and drawbacks associated with them are carefully evaluated. Performance criteria characterising the analytical methods discussed are also given. 相似文献
157.
Modulating the Folding Landscape of Superoxide Dismutase 1 with Targeted Molecular Binders 下载免费PDF全文
Dr. David N. Bunck Beatriz Atsavapranee Dr. Anna K. Museth Dr. David VanderVelde Prof. James R. Heath 《Angewandte Chemie (International ed. in English)》2018,57(21):6212-6215
Amyotrophic lateral sclerosis, or Lou Gehrig's disease, is characterized by motor neuron death, with average survival times of two to five years. One cause of this disease is the misfolding of superoxide dismutase 1 (SOD1), a phenomenon influenced by point mutations spanning the protein. Herein, we used an epitope‐specific high‐throughput screen to identify a peptide ligand that stabilizes the SOD1 native conformation and accelerates its folding by a factor of 2.5. This strategy may be useful for fundamental studies of protein energy landscapes as well as designing new classes of therapeutics. 相似文献
158.
María S. Di Nezio Marcelo F. Pistonesi Wallace D. Fragoso Mrcio J.C. Pontes Hctor C. Goicoechea Mrio C.U. Araujo e Beatriz S. Fernndez Band 《Microchemical Journal》2007,85(2):194-200
This paper proposes an analytical method to determine directly and simultaneously five phenolic compounds (4-nitrophenol, 2-nitrophenol, phenol, 2,4,6-trichlorophenol and 4-chlorophenol) in sea water (Ria de Bahía Blanca, Argentine). The advantages of this method is that only requires spectrophotometric measurements (separation steps and derivatization reagents are avoided) and chemometric modelling (PLS and MLR–SPA).The statistical comparison between PLS — a well established multivariate method — and MLR–SPA — a recently presented chemometric modelling — demonstrated better analytical performance for the later one. This fact is indicative of the potentiality of MLR–SPA for solving complex analytical problems. 相似文献
159.
del Amo V Siracusa L Markidis T Baragaña B Bhattarai KM Galobardes M Naredo G Pérez-Payán MN Davis AP 《Organic & biomolecular chemistry》2004,2(22):3320-3328
Cholic acid 2a has been converted into two new orthogonally-protected triamino scaffolds, 13 and 14. The synthesis proceeds via the bis-Boc-NH-substituted azide 10, for which an improved preparation is described. After removal of the Boc groups, the two axial amines are differentiated through a novel monoprotection employing 1-(2-nitrobenzenesulfonyloxy)-benzotriazole 29. Regioselectivity of > or 50 : 1 is achieved, presumably reflecting an exceptional sensitivity to steric hindrance. Protection of the remaining amino group as Boc or Alloc gives the scaffolds in approximately 40% overall yield from cholic acid. Scaffold 13 has been sequentially deprotected and derivatised with N-carbamoyl amino acids, to give a model for tripodal peptide libraries. 相似文献
160.
Treatment of 5-vinylpyranosides with Et2Zn and catalytic Pd(0), in the presence of ZnCl2, results in the formation of 5-membered carbocyclic products. This carbohydrate ring-contraction features an intramolecular allylation of a ring-opened carbohydrate aldehyde by an in situ-generated nucleophilic allylzinc species. The stereoselectivity about vinyl and free hydroxyl groups at the newly created stereogenic centers varies from low to moderate while both its extent and sense are found to depend on particular structural features (e.g. the configuration of the starting carbohydrate). 相似文献