Search results for "Thermodynamics"
showing 10 items of 2774 documents
Optical tweezing electrophoresis of isolated, highly charged colloidal spheres
2001
Abstract We report on a novel optical tweezing experiment measuring the electrophoretic mobility μ of highly charged spherical particles suspended in water at volume fractions Φ≤2×10 −7 . At deionised conditions μ =2.5×10 −8 m 2 V −1 s −1 , it decreases further upon increasing the salt concentration c . We compare our data to measurements at larger Φ, where generally much larger μ and a qualitatively different dependence on the salt concentration are observed. To characterise the dependence on Φ we performed measurements at no added salt. There the mobility increases in the unordered state but stays constant at μ =6.8×10 −8 m 2 V −1 s −1 as the system develops fluid order. In the ordered re…
On what terms and why the thermodynamic properties of polymer solutions depend on chain length up to the melt
2003
Theoretical considerations based on chain connectivity and conformational variability of polymers have lead to an uncomplicated relation for the dependence of the Flory-Huggins interaction parameter, chi, on the volume fraction of the polymer, phi, and on its number of segments, N. The validity of this expression is being tested extensively by means of vapor pressure measurements and inverse gas chromatography (complemented by osmotic and light scattering data from literature) for solutions of poly(dimethylsiloxane) in the thermodynamically vastly different solvents n-octane (n-C8), toluene (TL), and methylethylketone (MEK) over the entire range of composition for at least six different mol…
Analysis of amino acids using serially coupled columns.
2017
Single conventional columns in reversed-phase LC are insufficient for analysing the isoindoles of primary amino acids, due to their limited functionality. An interesting possibility for increasing the separation power is the combination of several columns of different nature, where the length is modified by coupling small segments. This approach may require a considerable investment to have multiple lengths for each stationary phase. However, the combination of only two columns of fixed length can be enough to resolve satisfactorily relatively complex mixtures, provided that an optimised gradient program is applied. In this work, a mixture of 19 primary amino acid isoindoles found in protei…
Effective pair potential between charged nanoparticles at high volume fractions
2017
Simulations of charged colloidal dispersions are technically challenging. One possible workaround consists in reducing the system to the colloids only, whose interactions are described through an effective pair potential, wf. Still, the determination of wf is difficult mainly because it depends on the colloidal density, ϕ. Here we propose to calculate wf from simulations of a pair of colloids placed in a cubic box with periodic boundary conditions. The variation in ϕ is mimicked by an appropriate change in the concentration of counterions neutralized by an homogeneous background charge. The method is tested at the level of the primitive model. A good description of the structure of the coll…
Volume and heat capacity studies to evidence interactions between cyclodextrins and nicotinic acid in water
2008
Density and heat capacity of the water+cyclodextrin (CD), water+nicotinic acid (NA) and water+CD+NA mixtures were determined at 298.15 K. CDs with different cavity size and alkylation were selected. From the experimental data the apparent molar properties were calculated. Assuming the formation of inclusion complexes of 1:1 stoichiometry, these properties were modeled and provided the stability constants of CD/NA inclusion complexes and the corresponding property change. The binding of NA with the smallest sized alpha-cyclodextrin (alpha-CD) generates more stable complexes accompanied by the lower volume and the heat capacity changes. These results are in agreement with earlier proposed bin…
Thermodynamics of cyclodextrin-star copolymer threading-dethreading process
2015
We investigated the interactions of a star-like copolymer with cyclodextrins (CD) with different cavity size. Direct measurements of thermodynamic properties were done, and the application of proper molecular models was useful for the interpretation of the involved phenomena. The CD–copolymer inclusion complexes were characterized by isothermal titration calorimetry. The copolymer aggregation induced by temperature was investigated by differential scanning calorimetry, volume and compressibility measurements. The behavior of the ternary T1107/CD/water mixture was interpreted considering competing equilibria. The investigated systems showed an interesting temperature responsive behavior so t…
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…