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101.
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103.
Ligia Frunza Stefan Frunza Irina Zgura Traian Beica Nicoleta Gheorghe Paul Ganea Daniel Stoenescu Adrian Dinescu Andreas Schönhals 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2010,75(4):1228-1235
Composites prepared from aerosil A380 and liquid crystals (LCs) of 4-n-alkyl-4′-cyanophenyl benzoate type, with four to six carbon atoms in the alkyl chain were investigated by infrared spectroscopy. Their high silica content (of 2–7 g aerosil/1 g of LC) was given by thermogravimetric investigations and allows the observation of a rather thin LC layer on the silica particles. Several surface species onto the external surface of the grains were demonstrated. Arguments are given that monomer and dimer species are present in the bulk cyanophenyl benzoate materials while bulk-like species along with hydrogen-bonded ones coexist in the so-called surface layer of the composites. The main interaction of LC molecules with the aerosil surface is by hydrogen bonding taking place with the involvement of the cyan group. There is a contribution of ester carbonyl group to these surface interactions but this cannot be well quantified. 相似文献
104.
Oleg V. Shishkin Irina V. Omelchenko Andrei L. Kalyuzhny Boris V. Paponov 《Structural chemistry》2010,21(5):1005-1011
Results of X-ray diffraction study and quantum-chemical calculations revealed that molecular conformation of thioindirubin
molecule creates suitable conditions for formation of intramolecular C–H···O and S···O interactions. Analysis of molecular
electrostatic potential (MEP) demonstrates existence of two areas of positive MEP (σ-holes) in the outermost part of the sulfur
atom on the continuation of the lines of the C–S bonds. One of these σ-holes is oriented toward region of negative MEP around
the oxygen atom of carbonyl group. Such situation corresponds to formation of σ-hole or chalcogen bond. Existence of both
types of bonding interactions is confirmed by topological analysis of electron density distribution using “Atoms in Molecules”
(AIM) theory. Energies of the C–H···O hydrogen bond and the S···O σ-hole bond derived from AIM and NBO theories are very close. 相似文献
105.
Sergei V. Kostjuk Alexei Yu. Dubovik Irina V. Vasilenko Alexander N. Frolov Fyodor N. Kaputsky 《European Polymer Journal》2007,43(3):968-979
The cationic polymerization of styrene with the 2-phenyl-2-propanol (CumOH)/AlCl3 · OBu2 initiating system at various dibutyl ether concentrations in a mixture of 1,2-dichloroethane and n-hexane (55:45 v/v) at −15 °C was investigated. The experimental results showed that an increase in dibutyl ether concentration leads to a noticeable decrease in the polymerization rate as well as to the more controlled polymerization in terms of molecular weight (Mn) and molecular weight distribution (MWD) evolutions. The kinetic investigation revealed that the polymerization proceeds in two stages. The first stage is characterized by high polymerization rate and slow initiation relative to propagation. During this stage molecular weight decreases or does not change and MWD increases with conversion. In the second stage considerably slower quasiliving polymerization of styrene occurs. The quasiliving nature of the styrene polymerization by the CumOH/AlCl3 · OBu2 system is proved and mechanistic scheme of the polymerization is proposed. 相似文献
106.
As a popular tool in exploring free energy landscapes, the metadynamics method has been widely applied to elucidate various chemical or biochemical processes. As deeply discussed by Laio et al. [J. Phys. Chem. B 109, 6714 (2005)], the size of the updating Gaussian function is pivotal to the free energy convergence toward the target free energy surface. For instance, a greater Gaussian height can facilitate the quick visit of a conformation region of interest; however, it may lead to a larger error of the calculated free energy surface. In contrast, a lower Gaussian height can guarantee a better resolution of the calculated free energy surface; however, it will take longer time for such a simulation to navigate through the defined conformational region. In order to reconcile such confliction, the authors present a method by implementing the Wang-Landau recursion scheme in the metadynamics simulations to adaptively update the height of the unit Gaussian function. As demonstrated in their model studies on both a toy system, and a realistic molecular system treated with the hybrid quantum mechanical and molecular mechanical (QMMM) potential, the present approach can quickly result in more decently converged free energy surfaces, compared with the classical metadynamics simulations employing the fixed Gaussian heights. 相似文献
107.
108.
Bezsonova I Evanics F Marsh JA Forman-Kay JD Prosser RS 《Journal of the American Chemical Society》2007,129(6):1826-1835
The N-terminal SH3 domain of the Drosophila modular protein Drk undergoes slow exchange between a folded (Fexch) and highly populated unfolded (Uexch) state under nondenaturing buffer conditions, enabling both Fexch and Uexch states to be simultaneously monitored. The addition of dissolved oxygen, equilibrated to a partial pressure of either 30 atm or 60 atm, provides the means to study solvent exposure with atomic resolution via 13C NMR paramagnetic shifts in 1H,13C HSQC (heteronuclear single quantum coherence) spectra. Absolute differences in these paramagnetic shifts between the Fexch and Uexch states allow the discrimination of regions of the protein which undergo change in solvent exposure upon unfolding. Contact with dissolved oxygen for both the Fexch and Uexch states could also be assessed through 13C paramagnetic shifts which were normalized based on the corresponding paramagnetic shifts seen in the free amino acids. In the Fexch state, the 13C nuclei belonging to the hydrophobic core of the protein exhibited very weak normalized paramagnetic shifts while those with greater solvent accessible surface area exhibited significantly larger normalized shifts. The Uexch state displayed less varied 13C paramagnetic shifts although distinct regions of protection from solvent exposure could be identified by a lack of such shifts. These regions, which included Phe9, Thr12, Ala13, Lys21, Thr22, Ile24, Ile27, and Arg38, overlapped with those found to have residual nativelike and non-native structures in previous studies and in some cases provided novel information. Thus, the paramagnetic shifts from dissolved oxygen are highly useful in the study of a transient structure or clustering in disordered systems, where conventional NMR measurements (couplings, chemical shift deviations from random coil values, and NOEs) may give little information. 相似文献
109.
Irina Odinets Tamás Körtvélyesi Tamás Kégl László Kollár György Keglevich 《Transition Metal Chemistry》2007,32(3):299-303
In the series of 1-(2,4,6-trialkylphenyl-)3-methyl-1H-phospholes (1a–c) that are to a certain extent of aromaticity, only the isopropyl substituted one (1a) entered into reaction with dimeric (pentamethylcyclopentadienyl)rhodium dichloride to afford Rh(III) complex (2a) in a reversible manner. After a careful workup, (2a) could be prepared and characterized whose stereostructure was elucidated by B3LYP/3–21G*, B3LYP/6–31G* and LANL2DZ calculations.
Complex (2a) as a preformed catalyst, as well as the Rh(acac)(CO)2 + 2(1a) in situ catalytic system were useful in the hydroformylation of styrene and gave the branched aldehyde in regioselectivities of 65–96%. 相似文献
110.
Irina F. Catta Preta Solange K. Sakata G. Garcia J. P. Zimmermann F. Galembeck Claudia Giovedi 《Journal of Thermal Analysis and Calorimetry》2007,87(3):657-659
Polyacrylonitrile
(PAN) polymers are used as precursors for carbon fiber production. This process
requires an oxidative stabilization step, which can be studied by differential
scanning calorimetry (DSC). In this sense, thermal behavior of PAN based terpolymers
by different polymerization processes, compositions and itaconic acid concentrations
in the reaction media were investigated. The obtained results showed that
the addition of itaconic acid and methyl acrylate as comonomers resulted a
lower heat flow during the process comparing to the PAN homopolymer. It suggested
that these comonomers aid the oxidative stabilization stage for all studied
process. The redox system polymerization at 40°C resulted in a lower heat
flow. Itaconic acid decreases slightly initial and peak temperatures of the
terpolymer and heat flow until concentration of 3y. The cyclization temperature
decreases when MAis incorporated into the terpolymer compared to the MMA terpolymer
and increases when MAA is the acidic monomer. Among terpolymers the AN/MA/AA
polymer showed the best thermal behavior for carbon fiber producing. 相似文献