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141.
142.
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
143.
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
144.
Beatriz Martín‐García Prof. M. Mercedes Velázquez Dr. Francesco Rossella Prof. Vittorio Bellani Prof. Enrique Diez Prof. Jose Luis García Fierro Jose Antonio Pérez‐Hernández Juan Hernández‐Toro Sergi Claramunt Prof. Albert Cirera 《Chemphyschem》2012,13(16):3682-3690
Films of a few layers in thickness of reduced graphite oxide (RGO) sheets functionalized by the zwitterionic surfactant N‐dodecyl‐N,N‐dimethyl‐3‐ammonio‐1‐propanesulfonate (DDPS) are obtained by using the Langmuir–Blodgett method. The quality of the RGO sheets is checked by analyzing the degrees of reduction and defect repair by means of X‐ray photoelectron spectroscopy, atomic force microscopy (AFM), field‐emission scanning electron microscopy (SEM), micro‐Raman spectroscopy, and electrical conductivity measurements. A modified Hummers method is used to obtain highly oxidized graphite oxide (GO) together with a centrifugation‐based method to improve the quality of GO. The GO samples are reduced by hydrazine or vitamin C. Functionalization of RGO with the zwitterionic surfactant improves the degrees of reduction and defect repair of the two reducing agents and significantly increases the electrical conductivity of paperlike films compared with those prepared from unfunctionalized RGO. 相似文献
145.
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
146.
Christian Carrot Jean-Charles Majesté Beatriz Olalla René Fulchiron 《Rheologica Acta》2010,49(5):513-527
The purpose of the presented work was to test the capability of the model proposed by Leonov (J Rheol 34:1039–1068, 1990) for the prediction of secondary plateaus on the storage and loss moduli during small-amplitude oscillatory shear flow experiments
on filled or heterogeneous polymer melts. Though the occurrence of a plateau on the storage modulus can be well explained
in the frame of a filler network, a plateau on the loss modulus can hardly be described with the classical models. In the
Leonov model, the continuum of dissipative processes is attributed to the rupture of flocs of particles. Experiments with
polyolefins filled with magnesium hydroxide show that there is a clear connection between the amount of agglomerates and the
occurrence of a plateau on the loss modulus. However, the value of the critical strain for floc rupture that can be calculated
from the experiment shows that the processes responsible for the low-frequency dissipation are rather changes of configuration
within the agglomerates than floc rupture. These processes are not described by the Leonov model, and the predicted strain
dependence of the plateau is not observed experimentally. 相似文献
147.
Díaz MC Illescas BM Martín N Viruela R Viruela PM Ortí E Brede O Zilbermann I Guldi DM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(8):2067-2077
A new class of pi-extended TTF-type electron donors (11 a-c) has been synthesized by Wittig-Horner olefination of bianthrone (9) with 1,3-dithiole phosphonate esters (10 a-c). In cyclic voltammetry experiments, donors 11 a-c reveal a single, electrochemically irreversible oxidation-yielding the corresponding dicationic products-at relatively low oxidation potentials (approximately 0.7-0.8 V). Theoretical calculations, performed at the DFT level (B3 P86/6-31 G*), predict a highly-folded C(2h) structure for 11 a. In the ground state, the molecule adopts a double saddle-like conformation to compensate the steric hindrance. The calculations suggest that the intramolecular charge transfer associated with the HOMO-->LUMO transition is responsible for an absorption band observed above 400 nm. While the radical cation 11 a*+ retains the folded C(2h) structure predicted for the neutral molecule as the most stable conformation, the dication 11 a(2+) has a fully aromatic D(2) structure, formed by an orthogonal 9,9'-bianthryl central unit to which two singly-charged dithiole rings are attached. The drastic conformational changes that compounds 11 undergo upon oxidation account for their electrochemical properties. By means of pulse radiolysis measurements, radical-induced one-electron oxidation of 11 a-c was shown to lead to the radical cation species (11 a-c*+), which were found to disproportionate with generation of the respective dication species (11 a-c(2+)) and the neutral molecules (11 a-c). 相似文献
148.
149.
A reverse flow injection spectrophotometric enzymatic method is proposed to quantify total phenols in urine samples. The polyphenol oxidase (PPO; EC 1.14.18.1) obtained as a crude extract from sweet potato root (Ipomoea batatas) was used as enzymatic catalyze. The detection limit, the sample throughput and relative standard deviation were 7.7 mg l−1 of total phenols, 49 h−1 and 0.9%, respectively. The method was applied to real samples and a recovery study was carried out in order to its validation. 相似文献
150.
Basic Physicochemical Properties of Polyethylene Glycol Coated Gold Nanoparticles that Determine Their Interaction with Cells
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Dr. Pablo del Pino Fang Yang Dr. Beatriz Pelaz Dr. Qian Zhang Karsten Kantner Raimo Hartmann Dr. Natalia Martinez de Baroja Marta Gallego Marco Möller Dr. Bella B. Manshian Dr. Stefaan J. Soenen René Riedel Prof. Dr. Norbert Hampp Prof. Dr. Wolfgang J. Parak 《Angewandte Chemie (International ed. in English)》2016,55(18):5483-5487
A homologous nanoparticle library was synthesized in which gold nanoparticles were coated with polyethylene glycol, whereby the diameter of the gold cores, as well as the thickness of the shell of polyethylene glycol, was varied. Basic physicochemical parameters of this two‐dimensional nanoparticle library, such as size, ζ‐potential, hydrophilicity, elasticity, and catalytic activity ,were determined. Cell uptake of selected nanoparticles with equal size yet varying thickness of the polymer shell and their effect on basic structural and functional cell parameters was determined. Data indicates that thinner, more hydrophilic coatings, combined with the partial functionalization with quaternary ammonium cations, result in a more efficient uptake, which relates to significant effects on structural and functional cell parameters. 相似文献