Using classical density functional theory(DFT), we calculate the density profile ρ(𝐫) and local compressibility χ(𝐫) of a simple liquidsolvent in which a pair of blocks with (microscopic) rectangular cross section are immersed. We consider blocks that are solvophobic, solvophilic and also ones that have both solvophobic and solvophilic patches. Large values of χ(𝐫) correspond to regions in space where the liquid density is fluctuating most strongly. We seek to elucidate how enhanced density fluctuations correlate with the solvent mediated force between the blocks, as the distance between the blocks and the chemical potential of the liquid reservoir vary. For sufficiently solvophobic blocks, at small block separations and small deviations from bulk gas-liquid coexistence, we observe a strongly attractive (near constant) force, stemming from capillary evaporation to form a low density gas-like intrusion between the blocks. The accompanying χ(𝐫) exhibits a structure which reflects the incipient gas-liquid interfaces that develop. We argue that our model system provides a means to understanding the basic physics of solvent mediated interactions between nanostructures, and between objects such as proteins in water that possess hydrophobic and hydrophilic patches.
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http://dx.doi.org/10.1063/1.4978352 | DOI Listing |
J Chem Phys
January 2025
Department of Materials Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8552, Japan.
The liquid/liquid interfaces of room-temperature ionic liquids (RTILs) play a pivotal role in chemical reactions owing to their characteristic microscopic structure, yet the structure of hydrophobic liquid/RTIL interfaces remains unclear. We studied the structure at the liquid/liquid interfaces of carbon tetrachloride (CCl4) and 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([Cnmim][TFSA]; n = 4 and 8) RTILs using infrared-visible sum frequency generation (SFG) vibrational spectroscopy. A comparison of the SFG spectra of the CCl4/RTIL and air/RTIL interfaces revealed that the solvation of the alkyl chains of the [Cnmim]+ cations by CCl4 reduces the number of gauche defects in the alkyl chain and the interface number density of the cation at the CCl4 interface.
View Article and Find Full Text PDFJ Colloid Interface Sci
February 2025
Faculty of Physics, Lomonosov Moscow State University, 119991 Moscow, Russia; Semenov Federal Research Center for Chemical Physics, 119991 Moscow, Russia. Electronic address:
Hypothesis: Micelles formed by copolymers with mixed solvophobic blocks have attracted much attention lately. It is expected that changing the mixed blocks sequence can be used as a tool to influence the micellization behavior in a way that is not equivalent to simply varying the incompatibility parameter for pure diblock-copolymers. Simulations: By using coarse-grained simulations, the micellization behavior of copolymers with twelve types of solvophobic blocks, which differed in the fraction f as well as the sequence of solvophilic units in the solvophobic blocks, was studied.
View Article and Find Full Text PDFACS Appl Mater Interfaces
September 2024
School of Polymer Science and Polymer Engineering, The University of Akron, Akron, Ohio 44325, United States.
J Chem Phys
June 2024
Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08544, USA.
Histogram-reweighting grand canonical Monte Carlo simulations are used to obtain the critical properties of lattice chains composed of solvophilic and solvophobic monomers. The model is a modification of one proposed by Larson et al. [J.
View Article and Find Full Text PDFJ Am Chem Soc
May 2024
Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea.
Depolymerization breaks down polymer chains into monomers like unthreading beads, attracting more attention from a sustainability standpoint. When polymerization reaches equilibrium, polymerization and depolymerization can reversibly proceed by decreasing and increasing the temperature. Here, we demonstrate that such dynamic control of a growing polymer chain in a selective solvent can spontaneously modulate the self-assembly of block copolymer micellar nano-objects.
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