scholarly journals Supramolecular Modification of ABC Triblock Terpolymers in Confinement Assembly

Nanomaterials ◽  
2018 ◽  
Vol 8 (12) ◽  
pp. 1029 ◽  
Author(s):  
Giada Quintieri ◽  
Marco Saccone ◽  
Matthias Spengler ◽  
Michael Giese ◽  
André H. Gröschel

The self-assembly of AB diblock copolymers in three-dimensional (3D) soft confinement of nanoemulsions has recently become an attractive bottom up route to prepare colloids with controlled inner morphologies. In that regard, ABC triblock terpolymers show a more complex morphological behavior and could thus give access to extensive libraries of multicompartment microparticles. However, knowledge about their self-assembly in confinement is very limited thus far. Here, we investigated the confinement assembly of polystyrene-block-poly(4-vinylpyridine)-block-poly(tert-butyl methacrylate) (PS-b-P4VP-b-PT or SVT) triblock terpolymers in nanoemulsion droplets. Depending on the block weight fractions, we found spherical microparticles with concentric lamella–sphere (ls) morphology, i.e., PS/PT lamella intercalated with P4VP spheres, or unusual conic microparticles with concentric lamella–cylinder (lc) morphology. We further described how these morphologies can be modified through supramolecular additives, such as hydrogen bond (HB) and halogen bond (XB) donors. We bound donors to the 4VP units and analyzed changes in the morphology depending on the binding strength and the length of the alkyl tail. The interaction with the weaker donors resulted in an increase in volume of the P4VP domains, which depends upon the molar fraction of the added donor. For donors with a high tendency of intermolecular packing, a visible change in the morphology was observed. This ultimately caused a shape change in the microparticle. Knowledge about how to control inner morphologies of multicompartment microparticles could lead to novel carbon supports for catalysis, nanoparticles with unprecedented topologies, and potentially, reversible shape changes by light actuation.

2020 ◽  
Author(s):  
lingying shi ◽  
Sangho Lee ◽  
Qingyang Du ◽  
rong ran ◽  
Runze Liu ◽  
...  

Abstract The formation of zig-zags, chevrons, Y-junctions and line segments is demonstrated in thin films formed from cylindrical morphology Si-containing rod-coil diblock copolymers and triblock terpolymers under solvent annealing. Directed self-assembly of the block copolymers within trenches yields well-ordered cylindrical microdomains oriented either parallel or transverse to the sidewalls depending on the chemical functionalization of the sidewalls, and the location and structure of concentric bends in the cylinders is determined by the shape of the trenches. The innate etching contrast, the spontaneous sharp bends and junctions, and the range of demonstrated periodicity and line/space ratios make these conformationally asymmetric rod-coil polymers attractive for nanoscale pattern generation.


2012 ◽  
Vol 1450 ◽  
Author(s):  
Biswajit Sannigrahi ◽  
Juana Mendenhall ◽  
Ishrat M Khan

ABSTRACTBottom-up design of materials via self-assembly with appropriate building blocks offers the possibility of developing innovative three-dimensional all synthetic materials with new functionalities. Helical optically active poly(3-methyl-4-vinylpyridine)/(R) and (S) mandelic acid and helical optically active poly(3-methyl-4-vinylpyridine) (P3M4VP)/ D- and L- amino acid complexes have been prepared. A diblock copolymer of helical poly[(3-methyl-4-vinylprydine)/mandelic acid complex]-block-poly(styrene) has been processed into smectic layer-like helical-bundle structures on silicon wafer. Additionally, optically active helical poly(2-methoxystyrene) (P2PMS) has been synthesized and the surfaces of the chiral helical P2MS have been shown to be effective as supports for mouse and human osteoblast cells. The cell attachment and growth data demonstrate that the chiral P2MS surfaces were better supports compared to achiral P2MS surfaces.


2020 ◽  
Vol 6 (42) ◽  
pp. eabc3644
Author(s):  
Hsiao-Fang Wang ◽  
Po-Ting Chiu ◽  
Chih-Ying Yang ◽  
Zhi-Hong Xie ◽  
Yu-Chueh Hung ◽  
...  

Nanonetwork-structured materials can be found in nature and synthetic materials. A double gyroid (DG) with a pair of chiral networks but opposite chirality can be formed from the self-assembly of diblock copolymers. For triblock terpolymers, an alternating gyroid (GA) with two chiral networks from distinct end blocks can be formed; however, the network chirality could be positive or negative arbitrarily, giving an achiral phase. Here, by taking advantage of chirality transfer at different length scales, GA with controlled chirality can be achieved through the self-assembly of a chiral triblock terpolymer. With the homochiral evolution from monomer to multichain domain morphology through self-assembly, the triblock terpolymer composed of a chiral end block with a single-handed helical polymer chain gives the chiral network from the chiral end block having a particular handed network. Our real-space analyses reveal the preferred chiral sense of the network in the GA, leading to a chiral phase.


2013 ◽  
Vol 815 ◽  
pp. 512-515
Author(s):  
Yu Xin Zuo ◽  
Guo Qing Wang ◽  
Ying Yu ◽  
Chun Cheng Zuo ◽  
Yi Rui Wang

Self-assembly of symmetric diblock copolymers (DCP) confined in multiwalled carbon nanotubes (MWCNTs) is studied using coarse-grained molecular dynamic (MD) simulations. The dependence of the self-assembled morphologies on the strength of the surface interactions is examined systematically. A rich variety of novel morphologies under the three-dimensional confinement have been revealed. The adsorption energy and cohesive energy have been discussed qualitatively and used to account for the appearance of the complex morphological transition.


Author(s):  
D. Reis ◽  
B. Vian ◽  
J. C. Roland

Wall morphogenesis in higher plants is a problem still open to controversy. Until now the possibility of a transmembrane control and the involvement of microtubules were mostly envisaged. Self-assembly processes have been observed in the case of walls of Chlamydomonas and bacteria. Spontaneous gelling interactions between xanthan and galactomannan from Ceratonia have been analyzed very recently. The present work provides indications that some processes of spontaneous aggregation could occur in higher plants during the formation and expansion of cell wall.Observations were performed on hypocotyl of mung bean (Phaseolus aureus) for which growth characteristics and wall composition have been previously defined.In situ, the walls of actively growing cells (primary walls) show an ordered three-dimensional organization (fig. 1). The wall is typically polylamellate with multifibrillar layers alternately transverse and longitudinal. Between these layers intermediate strata exist in which the orientation of microfibrils progressively rotates. Thus a progressive change in the morphogenetic activity occurs.


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.


2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Chaojian Chen ◽  
Manjesh Kumar Singh ◽  
Katrin Wunderlich ◽  
Sean Harvey ◽  
Colette J. Whitfield ◽  
...  

AbstractThe creation of synthetic polymer nanoobjects with well-defined hierarchical structures is important for a wide range of applications such as nanomaterial synthesis, catalysis, and therapeutics. Inspired by the programmability and precise three-dimensional architectures of biomolecules, here we demonstrate the strategy of fabricating controlled hierarchical structures through self-assembly of folded synthetic polymers. Linear poly(2-hydroxyethyl methacrylate) of different lengths are folded into cyclic polymers and their self-assembly into hierarchical structures is elucidated by various experimental techniques and molecular dynamics simulations. Based on their structural similarity, macrocyclic brush polymers with amphiphilic block side chains are synthesized, which can self-assemble into wormlike and higher-ordered structures. Our work points out the vital role of polymer folding in macromolecular self-assembly and establishes a versatile approach for constructing biomimetic hierarchical assemblies.


Micromachines ◽  
2019 ◽  
Vol 11 (1) ◽  
pp. 13 ◽  
Author(s):  
Bin Zhang ◽  
Jaehyun Lee ◽  
Mincheol Kim ◽  
Naeeung Lee ◽  
Hyungdong Lee ◽  
...  

The macroscopic assembly of two-dimensional materials into a laminar structure has received considerable attention because it improves both the mechanical and chemical properties of the original materials. However, conventional manufacturing methods have certain limitations in that they require a high temperature process, use toxic solvents, and are considerably time consuming. Here, we present a new system for the self-assembly of layer-by-layer (LBL) graphene oxide (GO) via an electrohydrodynamic (EHD) jet printing technique. During printing, the orientation of GO flakes can be controlled by the velocity distribution of liquid jet and electric field-induced alignment spontaneously. Closely-packed GO patterns with an ordered laminar structure can be rapidly realized using an interfacial assembly process on the substrates. The surface roughness and electrical conductivity of the LBL structure were significantly improved compared with conventional dispensing methods. We further applied this technique to fabricate a reduced graphene oxide (r-GO)-based supercapacitor and a three-dimensional (3D) metallic grid hybrid ammonia sensor. We present the EHD-assisted assembly of laminar r-GO structures as a new platform for preparing high-performance energy storage devices and sensors.


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