Search results for "Dynamic"
showing 10 items of 12329 documents
Cyclodextrin/surfactant inclusion complexes: An integrated view of their thermodynamic and structural properties
2021
Cyclodextrins (CDs) play an important role in self-assembly systems of amphiphiles. The structure of CDs provides distinguished physicochemical properties, including the ability to form host-guest complexes. The complexation affects the properties of guest molecules and can produce supramolecular aggregates with desirable characteristics for fundamental and practical applications. Surfactants are particularly attractive host molecules due to their wide variety, availability, responsiveness to different stimuli, and high relevance in different fields, e.g. medical, cosmetic, pharmaceutical, and food industries. The tendency of organization in higher-order supramolecular aggregates arises the…
Pressure dependence in the methyl vinyl ketone + OH and methacrolein + OH oxidation reactions: an electronic structure study.
2005
High-level electronic structure calculations were carried out for the study of the reaction pathways in the OH-initiated oxidations of methyl vinyl ketone (MVK) and methacrolein (MACR). For the two conformers of MVK (called synperiplanar and antiperiplanar), the addition channels of OH to the terminal and central carbon atom of the double bond dominate the overall rate constant, whereas the abstraction of the methyl hydrogen atoms has no significant kinetic role. In the case of MACR, only the antiperiplanar conformer is important in its reactivity. In addition, the lower Gibbs free energy barrier for MACR corresponds to the aldehydic hydrogen abstraction reaction, which will be somewhat mor…
A Novel Gas Chromatographic Method to Measure Sorption of Dense Gases into Polymers
2006
A novel experimental approach to determine the solubility of gaseous compounds inside polymers is here described. The method is based on the gas chromatographic determination of the composition of the fluid phase at equilibrium with the polymer. To take into account the effect of the volume swelling on the measurement a suitable probe, nonabsorbable by the polymer, was added to the fluid phase. Under the adopted configuration the apparatus can operate up to 35 MPa and 80°C. This experimental technique has been used to determine the solubility of carbon dioxide in poly(vinylidene fluoride) using argon as a probe. The latter was chosen because it is negligibly absorbed by the polymer and does…
Studying the role of protein dynamics in an SN2 enzyme reaction using free-energy surfaces and solvent coordinates
2013
Conformational changes are known to be able to drive an enzyme through its catalytic cycle, allowing, for example, substrate binding or product release. However, the influence of protein motions on the chemical step is a controversial issue. One proposal is that the simple equilibrium fluctuations incorporated into transition-state theory are insufficient to account for the catalytic effect of enzymes and that protein motions should be treated dynamically. Here, we propose the use of free-energy surfaces, obtained as a function of both a chemical coordinate and an environmental coordinate, as an efficient way to elucidate the role of protein structure and motions during the reaction. We sho…
Thermodynamically induced shear degradation
1988
The shear degradation of polymers in semiconcentrated solutions is viewed as a function of solvent quality. It is shown that the deterioration of the thermodynamic quality of the solvent leads to a marked flow resistance due to an increasing number of contacts between the chains. This may be probed by viscosimetric measurements as well as by degradation experiments (“thermodynamically induced shear degradation”). For a detailed discussion of this phenomenon the experimental setup for the mechanochemical experiment is outlined first, followed by a survey of the kinetics of chain scission. Finally, experiments mostly obtained on polystyrene in the theta-solvent trans-decalin are discussed. Th…
Behaviour of modified and unmodified polybutadienes in the semidilute regime
1997
Abstract The association behaviour of polybutadiene modified with 4-phenyl-l,2,4-triazoline-3,5-dione was studied in semidilute solution through static (SLS) and dynamic light scattering (DLS). The results were compared with the unmodified polybutadiene, whose behavior in semidilute solution was also studied as function of the molecular weight. At higher concentrations a small-angle excess scattering in SLS and a slow mode motion in DLS were observed both for modified and unmodified polybutadienes suggesting the presence of large clusters. Increasing the polymer concentration, the mass fraction of the slow motion increases up to values near 1, indicating a proximity to the gel point. For po…
Temperature and pressure dependence of phase separation of trans-decahydronaphthalene/polystyrene solution
2004
Abstract The cloud-point temperatures (Tcl’s) of trans-decahydronaphthalene (TD)/polystyrene (PS, Mw=270 kg/mol) solutions were determined by light scattering measurements over a range of temperatures (1–16 °C), pressures (100–900 bar), and compositions (4.2–21.6 vol% polymer). The system phase separates upon cooling and the Tcl was found to increase with the rising pressure for the constant composition. In the absence of special effects this finding indicates positive excess volumes. The special attention was paid to the demixing temperatures as a function of the pressure for the different polymer solutions and the plots in the T-volume fraction plane and P-volume fraction plane. The cloud…
Interactions between proteins and poly(ethylene-glycol) investigated using molecular dynamics simulations
2017
Poly(ethylene-glycol) (PEG) is a polymer used to coat therapeutic preparations, like drugs or drug nanocarriers, and improve their efficacy. This effect is probably due to a reduction of the interactions of the coated species with the host organism. Nevertheless, experiments show that PEGylated materials do interact with the surrounding biological milieu, and in particular with blood proteins. Here, we use atomistic molecular dynamics simulations to characterize the interactions between the polymer and several blood proteins. In these simulations, the proteins are immersed in a mixture of PEG and water molecules. We observe how PEG distributes around the protein surface and measure PEG-prot…
Effects of isotopic substitution on the conformational properties of polymeric aqueous solutions
2000
Abstract This work deals with a side-by-side comparison between the PEO conformational properties in H 2 O and D 2 O. The gyration radius, evaluated by SANS, the hydrodynamic radius, evaluated by PCS, and the Raman D-LAM band analysis furnish valuable information on the structural arrangement of the molecules. The findings clearly show different behavioural properties of the polymer in H 2 O and D 2 O.
Complex Formation of DNA with Oppositely Charged Polyelectrolytes of Different Chain Topology: Cylindrical Brushes and Dendrimers
2007
The complex formation between DNA (pUC19-supercoiled DNA, 2686 base pairs) and some polycations of different chain topologies in aqueous solution was studied by light scattering, gel electrophoresis, and AFM. The investigated polycations comprised cylindrical brush polymers with quaternized poly(vinylpyridine) and polyethylene imine side chains as well as a fifth generation dendrimer thus covering a broad molar mass regime of 3 × 104 g mol-1 < Mw < 1 × 107 g mol-1 and very different chemical charges/molecule, Z+, of 127 < Z+ < 5500. Irrespective of the polycation, the complexes formed in dilute solution exhibited a similar size in terms of the mean square radius of gyration, 〈Rg2〉, i.e., 30…