Self-assembling outside equilibrium: emergence of structures mediated by dissipation

2019 ◽  
Vol 21 (32) ◽  
pp. 17475-17493 ◽  
Author(s):  
A. Arango-Restrepo ◽  
D. Barragán ◽  
J. M. Rubi

Self-assembly under non-equilibrium conditions may give rise to the formation of structures not available at equilibrium.

Crystals ◽  
2018 ◽  
Vol 8 (7) ◽  
pp. 300 ◽  
Author(s):  
Munenori Numata ◽  
Chisako Kanzaki

In this study, we investigated a unique aspect of the supramolecular polymerization of tetrakis (4-sulfonatophenyl) porphyrin (TPPS), a self-assembling porphyrin, under non-equilibrium conditions by subtracting the effects of back-pressure on its polymerization. We focused on the enhanced self-assembly abilities of TPPS under a process of rapid proton diffusion in a microflow channel. Rapid protonation caused synchronization of many sets of protonation/deprotonation equilibria on the molecular scale, leading to the production of many sets of growing suparmolecular spices. Pressure effects in the microflow channel, which could potentially promote self-assembly of TPPS, were negligible, becoming predominant only when the system was in the synchronized state.


2012 ◽  
Vol 9 (1) ◽  
pp. 43 ◽  
Author(s):  
Hueyling Tan

Molecular self-assembly is ubiquitous in nature and has emerged as a new approach to produce new materials in chemistry, engineering, nanotechnology, polymer science and materials. Molecular self-assembly has been attracting increasing interest from the scientific community in recent years due to its importance in understanding biology and a variety of diseases at the molecular level. In the last few years, considerable advances have been made in the use ofpeptides as building blocks to produce biological materials for wide range of applications, including fabricating novel supra-molecular structures and scaffolding for tissue repair. The study ofbiological self-assembly systems represents a significant advancement in molecular engineering and is a rapidly growing scientific and engineering field that crosses the boundaries ofexisting disciplines. Many self-assembling systems are rangefrom bi- andtri-block copolymers to DNA structures as well as simple and complex proteins andpeptides. The ultimate goal is to harness molecular self-assembly such that design andcontrol ofbottom-up processes is achieved thereby enabling exploitation of structures developed at the meso- and macro-scopic scale for the purposes oflife and non-life science applications. Such aspirations can be achievedthrough understanding thefundamental principles behind the selforganisation and self-synthesis processes exhibited by biological systems.


2019 ◽  
Author(s):  
Liman Hou ◽  
Marta Dueñas-Diez ◽  
Rohit Srivastava ◽  
Juan Perez-Mercader

<p></p><p>Belousov-Zhabotinsky (B-Z) reaction driven polymerization-induced self-assembly (PISA), or B-Z PISA, is a novel method for the autonomous one-pot synthesis of polymer vesicles from a macroCTA (macro chain transfer agent) and monomer solution (“soup”) containing the above and the BZ reaction components. In it, the polymerization is driven (and controlled) by periodically generated radicals generated in the oscillations of the B-Z reaction. These are inhibitor/activator radicals for the polymerization. Until now B-Z PISA has only been carried out in batch reactors. In this manuscript we present the results of running the system using a continuously stirred tank reactor (CSTR) configuration which offers some interesting advantages.Indeed, by controlling the CSTR parameters we achieve reproducible and simultaneous control of the PISA process and of the properties of the oscillatory cargo encapsulated in the resulting vesicles. Furthermore, the use of flow chemistry enables a more precise morphology control and chemical cargo tuning. Finally, in the context of biomimetic applications a CSTR operation mimics more closely the open non-equilibrium conditions of living systems and their surrounding environments.</p><p></p>


2020 ◽  
Vol 27 (9) ◽  
pp. 923-929
Author(s):  
Gaurav Pandey ◽  
Prem Prakash Das ◽  
Vibin Ramakrishnan

Background: RADA-4 (Ac-RADARADARADARADA-NH2) is the most extensively studied and marketed self-assembling peptide, forming hydrogel, used to create defined threedimensional microenvironments for cell culture applications. Objectives: In this work, we use various biophysical techniques to investigate the length dependency of RADA aggregation and assembly. Methods: We synthesized a series of RADA-N peptides, N ranging from 1 to 4, resulting in four peptides having 4, 8, 12, and 16 amino acids in their sequence. Through a combination of various biophysical methods including thioflavin T fluorescence assay, static right angle light scattering assay, Dynamic Light Scattering (DLS), electron microscopy, CD, and IR spectroscopy, we have examined the role of chain-length on the self-assembly of RADA peptide. Results: Our observations show that the aggregation of ionic, charge-complementary RADA motifcontaining peptides is length-dependent, with N less than 3 are not forming spontaneous selfassemblies. Conclusion: The six biophysical experiments discussed in this paper validate the significance of chain-length on the epitaxial growth of RADA peptide self-assembly.


Soft Matter ◽  
2020 ◽  
Vol 16 (28) ◽  
pp. 6599-6607 ◽  
Author(s):  
Pijush Singh ◽  
Souvik Misra ◽  
Nayim Sepay ◽  
Sanjoy Mondal ◽  
Debes Ray ◽  
...  

The self-assembly and photophysical properties of 4-nitrophenylalanine (4NP) are changed with the alteration of solvent and final self-assembly state of 4NP in competitive solvent mixture and are dictated by the solvent ratio.


2019 ◽  
Vol 4 (1) ◽  
pp. 91-102 ◽  
Author(s):  
Ryan T. Shafranek ◽  
Joel D. Leger ◽  
Song Zhang ◽  
Munira Khalil ◽  
Xiaodan Gu ◽  
...  

Directed self-assembly in polymeric hydrogels allows tunability of thermal response and viscoelastic properties.


2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Jan Ravnik ◽  
Michele Diego ◽  
Yaroslav Gerasimenko ◽  
Yevhenii Vaskivskyi ◽  
Igor Vaskivskyi ◽  
...  

AbstractMetastable self-organized electronic states in quantum materials are of fundamental importance, displaying emergent dynamical properties that may be used in new generations of sensors and memory devices. Such states are typically formed through phase transitions under non-equilibrium conditions and the final state is reached through processes that span a large range of timescales. Conventionally, phase diagrams of materials are thought of as static, without temporal evolution. However, many functional properties of materials arise as a result of complex temporal changes in the material occurring on different timescales. Hitherto, such properties were not considered within the context of a temporally-evolving phase diagram, even though, under non-equilibrium conditions, different phases typically evolve on different timescales. Here, by using time-resolved optical techniques and femtosecond-pulse-excited scanning tunneling microscopy (STM), we track the evolution of the metastable states in a material that has been of wide recent interest, the quasi-two-dimensional dichalcogenide 1T-TaS2. We map out its temporal phase diagram using the photon density and temperature as control parameters on timescales ranging from 10−12 to 103 s. The introduction of a time-domain axis in the phase diagram enables us to follow the evolution of metastable emergent states created by different phase transition mechanisms on different timescales, thus enabling comparison with theoretical predictions of the phase diagram, and opening the way to understanding of the complex ordering processes in metastable materials.


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