Browsing by Subject "NEUTRON-SCATTERING"

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  • Daub, Christopher D.; Hänninen, Vesa; Halonen, Lauri (2019)
    We present the results of ab initio molecular dynamics simulations of the solution-air interface of aqueous lithium bromide (LiBr). We find that, in agreement with the experimental data and previous simulation results with empirical polarizable force field models, Br- anions prefer to accumulate just below the first molecular water layer near the interface, whereas Li+ cations remain deeply buried several molecular layers from the interface, even at very high concentration. The separation of ions has a profound effect on the average orientation of water molecules in the vicinity of the interface. We also find that the hydration number of Li+ cations in the center of the slab Na-c,Na-Li+-H2O approximate to 4.7 +/- 0.3, regardless of the salt concentration. This estimate is consistent with the recent experimental neutron scattering data, confirming that results from nonpolarizable empirical models, which consistently predict tetrahedral coordination of Li+ to four solvent molecules, are incorrect. Consequently, disruption of the hydrogen bond network caused by Li+ may be overestimated in nonpolarizable empirical models. Overall, our results suggest that empirical models, in particular nonpolarizable models, may not capture all of the properties of the solution-air interface necessary to fully understand the interfacial chemistry.
  • Melcr, Josef; Martinez-Seara, Hector; Nencini, Ricky; Kolafa, Jiri; Jungwirth, Pavel; Ollila, O. H. Samuli (2018)
    Binding affinities and stoichiometries of Na+ and Ca2+ ions to phospholipid bilayers are of paramount significance in the properties and functionality of cellular membranes. Current estimates of binding affinities and stoichiometries of cations are, however, inconsistent due to limitations in the available experimental and computational methods. In this work, we improve the description of the binding details of Na+ and Ca2+ ions to a 1-palmitoyl-2-oleoyl-phosphatidylcholine (POPC) bilayer by implicitly including electronic polarization as a mean field correction, known as the electronic continuum correction (ECC). This is applied by scaling the partial charges of a selected state-of-the-art POPC lipid model for molecular dynamics simulations. Our improved ECC-POPC model reproduces not only the experimentally measured structural parameters for the ion-free membrane, but also the response of lipid headgroup to a strongly bound cationic amphiphile, as well as the binding affinities of Na+ and Ca2+ ions. With our new model, we observe on the one side negligible binding of Na+ ions to POPC bilayer, while on the other side stronger interactions of Ca2+ primarily with phosphate oxygens, which is in agreement with the previous interpretations of the experimental spectroscopic data. The present model results in Ca2+ ions forming complexes with one to three POPC molecules with almost equal probabilities, suggesting more complex binding stoichiometries than those from simple models used to interpret the NMR data previously. The results of this work pave the way to quantitative molecular simulations with realistic electrostatic interactions of complex biochemical systems at cellular membranes.
  • Kondo, Masaaki; Takahashi, Rintaro; Qiu, Xing-Ping; Winnik, Francoise M.; Terao, Ken; Sato, Takahiro (2017)
    Aqueous solutions of the doubly thermosensitive block copolymer poly(2-isopropyl-2-oxazoline)-b-poly(2-ethyl-2-oxazoline) heated to 50 degrees C underwent a macroscopic liquid/liquid phase separation. The small-angle X-ray scattering intensity recorded from the concentrated phase settled on the bottom of a sample indicated that this phase was in the disordered state without any microphase separation, although the block copolymer was amphiphilic in water at 50 degrees C. It was also confirmed that the contribution to the scattering intensities of individual copolymer chains and their aggregates existing in the coexisting concentrated phase was very small, compared with the total scattering intensity of the phase-separated solution, when the concentrated phase was suspended in the form of colloidal droplets in the lean phase.
  • Fowler, Michael; Duhamel, Jean; Qiu, Xing Ping; Korchagina, Evgeniya; Winnik, Francoise M. (2018)
    Aqueous solutions of a series of monodisperse poly(N-isopropylacrylamide)s end-labeled with n-butyl-1-pyrene at one or both chain ends (Py-n-PNIPAMs with n=1 or 2) were studied by turbidimetry, light scattering, and fluorescence. For a given polymer concentration and heating rate, the cloud point (T-c) of an aqueous Py-n-PNIPAM solution, determined by turbidimetry, was found to increase with the number-average molecular weight (M-n) of the polymer. The steady-state fluorescence spectra and time-resolved fluorescence decays of Py-n-PNIPAM aqueous solutions were analyzed and all parameters retrieved from these analyses were found to be affected as the solution temperature passed through T-c, the solution cloud point, and T-m, the temperature where dehydration of PNIPAM occurred. The trends obtained by fluorescence to characterize the aqueous Py-n-PNIPAM solutions as a function of temperature were found to be consistent with the model proposed for telechelic PNIPAM by Koga et al. in 2006. (c) 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 308-318