As is well known, liquid-liquid phase separation can occur either upon heating or cooling, corresponding to lower and upper critical solution phase boundaries, respectively. Likewise, self-assembly transitions from a monomeric state to an organized polymeric state can proceed either upon increasing or decreasing temperature, and the concentration dependent ordering temperature is correspondingly called the "floor" or "ceiling" temperature. Motivated by the fact that some phase separating systems exhibit closed loop phase boundaries with two critical points, the present paper analyzes self-assembly analogs of re-entrant phase separation, i.e., re-entrant self-assembly. In particular, re-entrant self-assembly transitions are demonstrated to arise in thermally activated equilibrium self-assembling systems, when thermal activation is more favorable than chain propagation, and in equilibrium self-assembly near an adsorbing boundary where strong competition exists between adsorption and self-assembly. Apparently, the competition between interactions or equilibria generally underlies re-entrant behavior in both liquid-liquid phase separation and self-assembly transitions.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1063/1.3118671 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Complexity in a Simple Self-Assembling System: Lecithin-Water-Ethanol Mixtures Exhibit a Re-Entrant Phase Transition and a Vesicle-Micelle Transition (VMT) on Heating.
Langmuir
August 2024
Department of Chemical & Biomolecular Engineering, University of Maryland, College Park, Maryland 20742, United States.
We report surprising results for the self-assembly of lecithin (a common phospholipid) in water-ethanol mixtures. Lecithin forms vesicles (∼100 nm diameter) in water. These vesicles are transformed into small micelles (∼5 nm diameter) by a variety of destabilizing agents such as single-tailed surfactants and alcohols.
View Article and Find Full Text PDFChemically Fueled Autonomous Sol→Gel→Sol→Gel→Sol Transitions.
Angew Chem Int Ed Engl
June 2023
Institute of Advanced Materials (INAM) and Departament de Química Inorgànica i Orgànica, Universitat Jaume I, Avda Sos Baynat s/n, 12006, Castelló, Spain.
Complex non-equilibrium phase behaviors are a hallmark of natural self-assembling systems. Here we show how intricate phase transitions can be achieved through a chemically fueled reaction cycle to yield autonomous sol→gel→sol→gel→sol transitions. A relay of chemical transformations based on thiazinane metathesis leads to two consecutive transient gelations in a closed system.
View Article and Find Full Text PDFEvaporation-Induced Self-Assembly of Metal Oxide Inverse Opals: From Synthesis to Applications.
Acc Chem Res
July 2022
Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138, United States.
ConspectusInverse opals (IOs) are highly interconnected three-dimensional macroporous structures with applications in a variety of disciplines from optics to catalysis. For instance, when the pore size is on the scale of the wavelength of visible light, IOs exhibit structural color due to diffraction and interference of light rather than due to absorption by pigments, making these structures valuable as nonfading paints and colorants. When IO pores are in an ordered arrangement, the IO is a 3D photonic crystal, a structure with a plethora of interesting optical properties that can be used in a multitude of applications, from sensors to lasers.
View Article and Find Full Text PDFKagome lattice made by impenetrable ellipses with attractive walls.
Soft Matter
May 2022
Institute for Condensed Matter Physics, National Academy of Sciences of Ukraine, 1 Svientsistsky Str., Lviv, UA-79011, Ukraine.
Low-dimensional structures, such as the kagome lattice, are experiencing renewed interest within the physics, chemistry and materials science communities in terms of both basic and applied research. Herein, we show that stable kagome lattices can be made by hard-core ellipses with attractive walls. We study a model in which hard-core ellipse is covered uniformly by an attractive square-well layer.
View Article and Find Full Text PDFColloidal Systems in Concentrated Electrolyte Solutions Exhibit Re-entrant Long-Range Electrostatic Interactions due to Underscreening.
Langmuir
May 2022
Department of Chemical Physics, Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, University of Science and Technology of China, Hefei 230026, P. R. China.
Surface force measurements have revealed that at very high electrolyte concentrations as well as in neat and diluted ionic liquids and deep eutectic solvents, the range of electrostatic interactions is far greater than the Debye length. Here, we explore the consequences of this underscreening for soft-matter and colloidal systems by investigating the stability of nanoparticle dispersions, the self-assembly of ionic surfactants, and the thickness of soap films. In each case, we find clear evidence of re-entrant properties due to underscreening at high salt concentrations.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!