scholarly journals Bifurcation of self-assembly pathways to sheet or cage controlled by kinetic template effect

2019 ◽  
Vol 2 (1) ◽  
Author(s):  
Leonardo Hayato Foianesi-Takeshige ◽  
Satoshi Takahashi ◽  
Tomoki Tateishi ◽  
Ryosuke Sekine ◽  
Atsushi Okazawa ◽  
...  

Abstract The template effect is a key feature to control the arrangement of building blocks in assemblies, but its kinetic nature remains elusive compared to the thermodynamic aspects, with the exception of very simple reactions. Here we report a kinetic template effect in a self-assembled cage composed of flexible ditopic ligands and Pd(II) ions. Without template anion, a micrometer-sized sheet is kinetically trapped (off-pathway), which is converted into the thermodynamically most stable cage by the template anion. When the template anion is present from the start, the cage is selectively produced by the preferential cyclization of a dinuclear intermediate (on-pathway). Quantitative and numerical analyses of the self-assembly of the cage on the on-pathway revealed that the accelerating effect of the template is stronger for the early stage reactions of the self-assembly than for the final cage formation step itself, indicating the kinetic template effect.

Soft Matter ◽  
2021 ◽  
Author(s):  
Jiawei Lu ◽  
Xiangyu Bu ◽  
Xinghua Zhang ◽  
Bing Liu

The shapes of colloidal particles are crucial to the self-assembled superstructures. Understanding the relationship between the shapes of building blocks and the resulting crystal structures is an important fundamental question....


1997 ◽  
Vol 488 ◽  
Author(s):  
DeQuan Li ◽  
M. Lütt ◽  
Xiaobo Shi ◽  
M. R. Fitzsimmons

AbstractThe layer-by-layer growth of film structures consisting of sequential depositions of oppositely charged polymers and macrocycles (ring-shaped molecules) have been constructed using molecular self-assembly techniques. These self-assembled thin films were characterized with X-ray reflectometry, which yielded (1) the average electron density, (2) the average thicknesses, and (3) the roughness of the growth surface of the self-assembled multilayer of macrocycles and polymers. These observations suggest that inorganic-organic interactions play an important role during the initial stages of thin-film growth, but less so as the thin film becomes thicker. Optical absorption techniques were also used to characterize the self-assembled multilayers. Phorphyrin and phthalocyanine derivatives were chosen as the building blocks of the self-assembled multilayers because of their interesting optical properties.


Polymers ◽  
2021 ◽  
Vol 13 (7) ◽  
pp. 1114
Author(s):  
Petra Bačová ◽  
Dimitris G. Mintis ◽  
Eirini Gkolfi ◽  
Vagelis Harmandaris

We present an atomistic molecular dynamics study of self-assembled mikto-arm stars, which resemble patchy-like particles. By increasing the number of stars in the system, we propose a systematic way of examining the mutual orientation of these fully penetrable patchy-like objects. The individual stars maintain their patchy-like morphology when creating a mesoscopic (macromolecular) self-assembled object of more than three stars. The self-assembly of mikto-arm stars does not lead to a deformation of the stars, and their shape remains spherical. We identified characteristic sub-units in the self-assembled structure, differing by the mutual orientation of the nearest neighbor stars. The current work aims to elucidate the possible arrangements of the realistic, fully penetrable patchy particles in polymer matrix and to serve as a model system for further studies of nanostructured materials or all-polymer nanocomposites using the mikto-arm stars as building blocks.


Molecules ◽  
2020 ◽  
Vol 25 (17) ◽  
pp. 4033
Author(s):  
Enrique Folgado ◽  
Matthias Mayor ◽  
Vincent Ladmiral ◽  
Mona Semsarilar

To date, amphiphilic block copolymers (BCPs) containing poly(vinylidene fluoride-co-hexafluoropropene) (P(VDF-co-HFP)) copolymers are rare. At moderate content of HFP, this fluorocopolymer remains semicrystalline and is able to crystallize. Amphiphilic BCPs, containing a P(VDF-co-HFP) segment could, thus be appealing for the preparation of self-assembled block copolymer morphologies through crystallization-driven self-assembly (CDSA) in selective solvents. Here the synthesis, characterization by 1H and 19F NMR spectroscopies, GPC, TGA, DSC, and XRD; and the self-assembly behavior of a P(VDF-co-HFP)-b-PEG-b-P(VDF-co-HFP) triblock copolymer were studied. The well-defined ABA amphiphilic fluorinated triblock copolymer was self-assembled into nano-objects by varying a series of key parameters such as the solvent and the non -solvent, the self-assembly protocols, and the temperature. A large range of morphologies such as spherical, square, rectangular, fiber-like, and platelet structures with sizes ranging from a few nanometers to micrometers was obtained depending on the self-assembly protocols and solvents systems used. The temperature-induced crystallization-driven self-assembly (TI-CDSA) protocol allowed some control over the shape and size of some of the morphologies.


Polymers ◽  
2021 ◽  
Vol 13 (18) ◽  
pp. 3131
Author(s):  
Naisheng Jiang ◽  
Donghui Zhang

Polypeptoids, a class of synthetic peptidomimetic polymers, have attracted increasing attention due to their potential for biotechnological applications, such as drug/gene delivery, sensing and molecular recognition. Recent investigations on the solution self-assembly of amphiphilic block copolypeptoids highlighted their capability to form a variety of nanostructures with tailorable morphologies and functionalities. Here, we review our recent findings on the solutions self-assembly of coil-crystalline diblock copolypeptoids bearing alkyl side chains. We highlight the solution self-assembly pathways of these polypeptoid block copolymers and show how molecular packing and crystallization of these building blocks affect the self-assembly behavior, resulting in one-dimensional (1D), two-dimensional (2D) and multidimensional hierarchical polymeric nanostructures in solution.


2021 ◽  
Vol 12 ◽  
pp. 1140-1150
Author(s):  
Huan Ren ◽  
Lifang Wu ◽  
Lina Tan ◽  
Yanni Bao ◽  
Yuchen Ma ◽  
...  

Biomolecules, such as proteins and peptides, can be self-assembled. They are widely distributed, easy to obtain, and biocompatible. However, the self-assembly of proteins and peptides has disadvantages, such as difficulty in obtaining high quantities of materials, high cost, polydispersity, and purification limitations. The difficulties in using proteins and peptides as functional materials make it more complicate to arrange assembled nanostructures at both microscopic and macroscopic scales. Amino acids, as the smallest constituent of proteins and the smallest constituent in the bottom-up approach, are the smallest building blocks that can be self-assembled. The self-assembly of single amino acids has the advantages of low synthesis cost, simple modeling, excellent biocompatibility and biodegradability in vivo. In addition, amino acids can be assembled with other components to meet multiple scientific needs. However, using these simple building blocks to design attractive materials remains a challenge due to the simplicity of the amino acids. Most of the review articles about self-assembly focus on large molecules, such as peptides and proteins. The preparation of complicated materials by self-assembly of amino acids has not yet been evaluated. Therefore, it is of great significance to systematically summarize the literature of amino acid self-assembly. This article reviews the recent advances in amino acid self-assembly regarding amino acid self-assembly, functional amino acid self-assembly, amino acid coordination self-assembly, and amino acid regulatory functional molecule self-assembly.


Molecules ◽  
2020 ◽  
Vol 25 (2) ◽  
pp. 402
Author(s):  
Changjun Park ◽  
Jinhee Lee ◽  
Taehyoung Kim ◽  
Jaechang Lim ◽  
Jeyoung Park ◽  
...  

Here, we report the formation of homochiral supramolecular thin film from achiral molecules, by using circularly polarized light (CPL) only as a chiral source, on the condition that irradiation of CPL does not induce a photochemical change of the achiral molecules. Thin films of self-assembled structures consisting of chiral supramolecular fibrils was obtained from the triarylamine derivatives through evaporation of the self-assembled triarylamine solution. The homochiral supramolecular helices with the desired handedness was achieved by irradiation of circularly polarized visible light during the self-assembly process, and the chiral stability of supramolecular self-assembled product was achieved by photopolymerization of the diacetylene moieties at side chains of the building blocks, with irradiation of circularly polarized ultraviolet light. This work provides a novel methodology for the generation of homochiral supramolecular thin film from the corresponding achiral molecules.


2016 ◽  
Vol 52 (28) ◽  
pp. 5023-5026 ◽  
Author(s):  
Lin-Xiu Dai ◽  
Xin-Yu Wang ◽  
Xiao-Yu Zheng ◽  
Ya-Wen Zhang

N,N-Dimethylformamide (DMF) serves as the facet-specific agent for the formation of a cubic shape and the structure-directing agent for the self-assembly of Pt and Pt–Rh building blocks of the supercrystals.


MRS Advances ◽  
2020 ◽  
Vol 5 (64) ◽  
pp. 3507-3520
Author(s):  
Chunhui Dai ◽  
Kriti Agarwal ◽  
Jeong-Hyun Cho

AbstractNanoscale self-assembly, as a technique to transform two-dimensional (2D) planar patterns into three-dimensional (3D) nanoscale architectures, has achieved tremendous success in the past decade. However, an assembly process at nanoscale is easily affected by small unavoidable variations in sample conditions and reaction environment, resulting in a low yield. Recently, in-situ monitored self-assembly based on ion and electron irradiation has stood out as a promising candidate to overcome this limitation. The usage of ion and electron beam allows stress generation and real-time observation simultaneously, which significantly enhances the controllability of self-assembly. This enables the realization of various complex 3D nanostructures with a high yield. The additional dimension of the self-assembled 3D nanostructures opens the possibility to explore novel properties that cannot be demonstrated in 2D planar patterns. Here, we present a rapid review on the recent achievements and challenges in nanoscale self-assembly using electron and ion beam techniques, followed by a discussion of the novel optical properties achieved in the self-assembled 3D nanostructures.


Soft Matter ◽  
2021 ◽  
Author(s):  
Meng Sun ◽  
Qintang Li ◽  
Xiao Chen

Luminescent gels have been successfully fabricated through the self-assembly of sodium cholate and a europium ion in choline chloride-based deep eutectic solvents.


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