52 research outputs found
Quasi-chemical theory with a soft cutoff
In view of the wide success of molecular quasi-chemical theory of liquids,
this paper develops the soft-cutoff version of that theory. This development
has important practical consequences in the common cases that the packing
contribution dominates the solvation free energy of realistically-modeled
molecules because treatment of hard-core interactions usually requires special
purpose simulation methods. In contrast, treatment of smooth repulsive
interactions is typically straightforward on the basis of widely available
software. This development also shows how fluids composed of molecules with
smooth repulsive interactions can be treated analogously to the molecular-field
theory of the hard-sphere fluid. In the treatment of liquid water,
quasi-chemical theory with soft-cutoff conditioning doesn't change the
fundamental convergence characteristics of the theory using hard-cutoff
conditioning. In fact, hard cutoffs are found here to work better than softer
ones.Comment: 5 pages, 2 figure
Molecular Dynamics Simulation Study of T Cell Receptor Molecular Recognition of Peptide-Major Histocompatibility Complexes
Direct observation of a hydrophobic bond in loop-closure of a capped (-OCH2CH2-)n oligomer in water
The small r variation of the probability density P(r) for end-to-end
separations of a -CH2CH3 capped (-OCH2CH2-)n oligomer in water is computed to
be closely similar to the CH4 ... CH4 potential of mean force under the same
circumstances. Since the aqueous solution CH4 ... CH4 potential of mean force
is the natural physical definition of a primitive hydrophobic bond, the present
result identifies an experimentally accessible circumstance for direct
observation of a hydrophobic bond which has not been observed previously
because of the low solubility of CH4 in water. The physical picture is that the
soluble chain molecule carries the capping groups into aqueous solution, and
permits them to find one another with reasonable frequency. Comparison with the
corresponding results without the solvent shows that hydration of the solute
oxygen atoms swells the chain molecule globule. This supports the view that the
chain molecule globule might have a secondary effect on the hydrophobic
interaction which is of first interest here. The volume of the chain molecule
globule is important for comparing the probabilities with and without solvent
because it characterizes the local concentration of capping groups. Study of
other capping groups to enable X-ray and neutron diffraction measurements of
P(r) is discussed.Comment: 4 pages, 3 figure
Surfactant-based critical phenomena in microgravity
The objective of this research project is to characterize by experiment and theoretically both the kinetics of phase separation and the metastable structures produced during phase separation in a microgravity environment. The particular systems we are currently studying are mixtures of water, nonionic surfactants, and compressible supercritical fluids at temperatures and pressures where the coexisting liquid phases have equal densities (isopycnic phases). In this report, we describe experiments to locate equilibrium isopycnic phases and to determine the 'local' phase behavior and critical phenomena at nearby conditions of temperature, pressure, and composition. In addition, we report the results of preliminary small angle neutron scattering (SANS) experiments to characterize microstructures that exist in these mixtures at different fluid densities
Isopycnic Phases and Structures in H2O/CO2/Ethoxylated Alcohol Surfactant Mixtures
Ternary mixtures of H2O and CO2 with ethoxylated alcohol (C(i)E(j)) surfactants can form three coexisting liquid phases at conditions where two of the phases have the same density (isopycnic phases). Isopycnic phase behavior has been observed for mixtures containing the surfactants C8E5, C10E6, and C12E6, but not for those mixtures containing either C4E1 or CgE3. Pressure-temperature (PT) projections for this isopycnic three-phase equilibrium were determined for H2O/CO2/C8E5 and H2O/CO2/C10E6 mixtures at temperatures from approximately 25 to 33 C and pressures between 90 and 350 bar. As a preliminary to measuring the microstructure in isopycnic three component mixtures, phase behavior and small angle neutron scattering (SANS) experiments were performed on mixtures of D2O/CO2/ n-hexaethyleneglycol monododecyl ether (C12E6) as a function of temperature (25-31 C), pressure (63.1-90.7 bar), and CO2 composition (0-3.9 wt%). Parameters extracted from model fits of the SANS spectra indicate that, while micellar structure remains essentially unchanged, critical concentration fluctuations increase as the phase boundary and plait point are approached
Origin of entropy convergence in hydrophobic hydration and protein folding
An information theory model is used to construct a molecular explanation why
hydrophobic solvation entropies measured in calorimetry of protein unfolding
converge at a common temperature. The entropy convergence follows from the weak
temperature dependence of occupancy fluctuations for molecular-scale volumes in
water. The macroscopic expression of the contrasting entropic behavior between
water and common organic solvents is the relative temperature insensitivity of
the water isothermal compressibility. The information theory model provides a
quantitative description of small molecule hydration and predicts a negative
entropy at convergence. Interpretations of entropic contributions to protein
folding should account for this result.Comment: Phys. Rev. Letts. (in press 1996), 3 pages, 3 figure
Identification of Conserved and HLA Promiscuous DENV3 T-Cell Epitopes
Anti-dengue T-cell responses have been implicated in both protection and immunopathology. However, most of the T-cell studies for dengue include few epitopes, with limited knowledge of their inter-serotype variation and the breadth of their human leukocyte antigen (HLA) affinity. In order to expand our knowledge of HLA-restricted dengue epitopes, we screened T-cell responses against 477 overlapping peptides derived from structural and non-structural proteins of the dengue virus serotype 3 (DENV3) by use of HLA class I and II transgenic mice (TgM): A2, A24, B7, DR2, DR3 and DR4. TgM were inoculated with peptides pools and the T-cell immunogenic peptides were identified by ELISPOT. Nine HLA class I and 97 HLA class II novel DENV3 epitopes were identified based on immunogenicity in TgM and their HLA affinity was further confirmed by binding assays analysis. A subset of these epitopes activated memory T-cells from DENV3 immune volunteers and was also capable of priming naïve T-cells, ex vivo, from dengue IgG negative individuals. Analysis of inter- and intra-serotype variation of such an epitope (A02-restricted) allowed us to identify altered peptide ligands not only in DENV3 but also in other DENV serotypes. These studies also characterized the HLA promiscuity of 23 HLA class II epitopes bearing highly conserved sequences, six of which could bind to more than 10 different HLA molecules representing a large percentage of the global population. These epitope data are invaluable to investigate the role of T-cells in dengue immunity/pathogenesis and vaccine design. © 2013 Nascimento et al
Molecular Thermodynamics and Knudsen Cell - Mass Spectrometer Studies of Liquid Metal Mixtures
188 p.Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1976.U of I OnlyRestricted to the U of I community idenfinitely during batch ingest of legacy ETD
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