Amphiphiles self-assemble into a variety of bicontinuous mesophases whose equilibrium structures take the form of high-symmetry cubic networks. Here, we show that the symmetry-breaking distortions in these systems give rise to anomalously large, nonaffine collective deformations, which we argue to be a generic consequence of "mass equilibration" within deformed networks. We propose and study a minimal "liquid network" model of bicontinuous networks, in which acubic distortions are modeled by the relaxation of residually stressed mechanical networks with constant-tension bonds. We show that nonaffinity is strongly dependent on the valency of the network as well as the degree of strain-softening or strain-stiffening tension in the bonds. Taking diblock copolymer melts as a model system, liquid network theory captures quantitative features of two bicontinuous phases based on comparison with self-consistent field theory predictions and direct experimental characterization of acubic distortions, which are likely to be pronounced in soft amphiphilic systems more generally.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1103/PhysRevLett.132.218201 | DOI Listing |
Molecules
November 2024
Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, AB T2N 1N4, Canada.
This study explores the liquid crystalline properties of novel amphiphilic β-cyclodextrin derivatives functionalized with seven oligoethylene glycol chains at the primary face, terminated with either an O-methyl or an O-cyanoethyl group, and fourteen hydrophobic aliphatic chains (elaidic or oleic acids) at the secondary face. These derivatives were designed to study the impact of chain conformation and terminal group polarity on their mesomorphic behavior. Thermal, microscopic, and X-ray diffraction studies revealed that the elaidic derivatives form columnar hexagonal mesophases, with the O-cyanoethyl derivative undergoing a slow, temperature-dependent transition to a bicontinuous cubic phase.
View Article and Find Full Text PDFJ Colloid Interface Sci
December 2024
Department of Pharmacy, Faculty of Health and Medical Sciences, University of Copenhagen, Copenhagen 2100, Denmark; Drug Delivery, Disposition and Dynamics, Monash Institute of Pharmaceutical Sciences, Parkville 3052, VIC Australia. Electronic address:
Hypothesis: Low-frequency Raman (LFR) spectroscopy is proposed as a novel non-destructive methodology to probe pH-related phase transitions in self-assembled lipid particles. In this case, dispersed lipid mesophases were composed of ionisable oleic acid (OA) or nicergoline (NG) in monoolein (MO). The sensitivity of LFR spectroscopy to low-energy intermolecular vibrations was hypothesised to be due to structural transformation in ionisable dispersed mesophases upon changes in pH.
View Article and Find Full Text PDFJ Colloid Interface Sci
February 2025
Interfaces, Confinement, Matériaux et Nanostructures (ICMN), CNRS-Université d'Orléans, UMR 7374, 1b rue de la Férollerie, CS 40059, 45071 Orléans Cedex 2, France.
Hypothesis: Mesophase dispersions are promising colloids for removing micropollutants from water. We hypothesized that the complex internal nanostructure and tunable lipid/water interface amounts play a crucial role in absorbed quantities. Modifications in interfacial organization within the particles while trapping the micropollutant is assumed.
View Article and Find Full Text PDFChemistry
December 2024
Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, AB, T2N 1N4, Canada.
Amphiphilic supramolecular materials based on biodegradable cyclodextrins (CDs) have been known to self-assemble into different types of thermotropic liquid crystals, including smectic and hexagonal columnar mesophases. Previous studies on amphiphilic CDs bearing 14 aliphatic chains at the secondary face and 7 oligoethylene glycol (OEG) chains at the primary face showed that the stability of the mesophase can be rationally tuned through implementation of terminal functional groups to the OEG chains. Here, we report the syntheses of first examples of crown ether-functionalized amphiphilic cyclodextrins that unexpectedly form thermotropic bicontinuous cubic phases.
View Article and Find Full Text PDFPhys Rev Lett
May 2024
Department of Polymer Science and Engineering, University of Massachusetts, Amherst, Massachusetts 01003, USA.
Amphiphiles self-assemble into a variety of bicontinuous mesophases whose equilibrium structures take the form of high-symmetry cubic networks. Here, we show that the symmetry-breaking distortions in these systems give rise to anomalously large, nonaffine collective deformations, which we argue to be a generic consequence of "mass equilibration" within deformed networks. We propose and study a minimal "liquid network" model of bicontinuous networks, in which acubic distortions are modeled by the relaxation of residually stressed mechanical networks with constant-tension bonds.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!