Synthesis of dynamic imine macrocyclic supramolecular polymers via synchronized self-assembly based on dynamic covalent bonds and noncovalent interactions

2020 ◽  
Vol 56 (65) ◽  
pp. 9288-9291 ◽  
Author(s):  
Zhenfeng He ◽  
Yufeng Huo ◽  
Chao Wang ◽  
Duo Pan ◽  
Binbin Dong ◽  
...  

The preparation of host imine macrocycles and the self-assembly aggregation process are merged into one single step for self-assembly to form dynamic imine macrocyclic supramolecular polymers.

MRS Advances ◽  
2020 ◽  
Vol 5 (42) ◽  
pp. 2147-2155
Author(s):  
Sudi Chen ◽  
Xitong Ren ◽  
Shufang Tian ◽  
Jiajie Sun ◽  
Feng Bai

AbstractThe self-assembly of optically active building blocks into functional nanocrystals as high-activity photocatalysts is a key in the field of photocatalysis. Cobalt porphyrin with abundant catalytic properties is extensively studied in photocatalytic water oxidation and CO2 reduction. Here, we present the fabrication of cobalt porphyrin nanocrystals through a surfactant-assisted interfacial self-assembly process using Co-tetra(4-pyridyl) porphyrin as building block. The self-assembly process relies on the combined noncovalent interactions such as π-π stacking and axial Co-N coordination between individual porphyrin molecules within surfactant micelles. Tuning different reaction conditions (temperature, the ratio of co-solvent DMF) and types of surfactant, various nanocrystals with well-defined 1D to 3D morphologies such as nanowires, nanorods and nano hexagonal prism were obtained. Due to the ordered accumulation of molecules, the nanocrystals exhibit the properties of the enhanced capability of visible light capture and can conduce to improve the transport and separation efficiency of the photogenerated carriers, which is important for photocatalysis. Further studies of photocatalytic CO2 reduction are being performed to address the relationship between the size and shape of the nanocrystals with the photocatalytic activity.


2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Oleksandr Shyshov ◽  
Shyamkumar Vadakket Haridas ◽  
Luca Pesce ◽  
Haoyuan Qi ◽  
Andrea Gardin ◽  
...  

AbstractThe development of powerful methods for living covalent polymerization has been a key driver of progress in organic materials science. While there have been remarkable reports on living supramolecular polymerization recently, the scope of monomers is still narrow and a simple solution to the problem is elusive. Here we report a minimalistic molecular platform for living supramolecular polymerization that is based on the unique structure of all-cis 1,2,3,4,5,6-hexafluorocyclohexane, the most polar aliphatic compound reported to date. We use this large dipole moment (6.2 Debye) not only to thermodynamically drive the self-assembly of supramolecular polymers, but also to generate kinetically trapped monomeric states. Upon addition of well-defined seeds, we observed that the dormant monomers engage in a kinetically controlled supramolecular polymerization. The obtained nanofibers have an unusual double helical structure and their length can be controlled by the ratio between seeds and monomers. The successful preparation of supramolecular block copolymers demonstrates the versatility of the approach.


Nanomaterials ◽  
2020 ◽  
Vol 10 (4) ◽  
pp. 651 ◽  
Author(s):  
Huacheng Zhang ◽  
Zhaona Liu ◽  
Hui Fu

Pillararenes trimer with particularly designed structural geometry and excellent capacity of recognizing guest molecules is a very efficient and attractive building block for the fabrication of advanced self-assembled materials. Pillararenes trimers could be prepared via both covalent and noncovalent bonds. The classic organic synthesis reactions such as click reaction, palladium-catalyzed coupling reaction, amidation, esterification, and aminolysis are employed to build covalent bonds and integrate three pieces of pillararenes subunits together into the “star-shaped” trimers and linear foldamers. Alternatively, pillararenes trimers could also be assembled in the form of host-guest inclusions and mechanically interlocked molecules via noncovalent interactions, and during those procedures, pillararenes units contribute the cavity for recognizing guest molecules and act as a “wheel” subunit, respectively. By fully utilizing the driving forces such as host-guest interactions, charge transfer, hydrophobic, hydrogen bonding, and C–H…π and π–π stacking interactions, pillararenes trimers-based supramolecular self-assemblies provide a possibility in the construction of multi-dimensional materials such as vesicular and tubular aggregates, layered networks, as well as frameworks. Interestingly, those assembled materials exhibit interesting external stimuli responsiveness to e.g., variable concentrations, changed pH values, different temperature, as well as the addition/removal of competition guests and ions. Thus, they could further be used for diverse applications such as detection, sorption, and separation of significant multi-analytes including metal cations, anions, and amino acids.


2020 ◽  
Author(s):  
Yufeng Huo ◽  
Zhenfeng He ◽  
Chao Wang ◽  
Lei Zhang ◽  
Qianyu Xuan ◽  
...  

Supramolecular polymers combine the properties of traditional polymers and supramolecules. They are normally formed by the self-assembled polymerization driven via noncovalent interactions (such as hydrogen bonding, π-π stacking, metal coordination,...


2007 ◽  
Vol 129 (46) ◽  
pp. 14187-14189 ◽  
Author(s):  
Hai-Bo Yang ◽  
Koushik Ghosh ◽  
Brian H. Northrop ◽  
Yao-Rong Zheng ◽  
Matthew M. Lyndon ◽  
...  

2006 ◽  
Vol 25 (22) ◽  
pp. 5276-5285 ◽  
Author(s):  
Seung Uk Son ◽  
Jeffrey A. Reingold ◽  
Gene B. Carpenter ◽  
Paul T. Czech ◽  
Dwight A. Sweigart

2014 ◽  
Vol 50 (59) ◽  
pp. 7982-7985 ◽  
Author(s):  
Feng Lin ◽  
Tian-Guang Zhan ◽  
Tian-You Zhou ◽  
Kang-Da Zhang ◽  
Guang-Yu Li ◽  
...  

Two types of stick-like supramolecular polymers possessing rigid backbones have been fabricated through the self-assembly of rod-like monomers and cucurbit[8]uril in water.


2019 ◽  
Author(s):  
Piero Gasparotto ◽  
Davide Bochicchio ◽  
Michele Ceriotti ◽  
Giovanni M. Pavan

A central paradigm of self-assembly is to create ordered structures starting from molecular<br>monomers that spontaneously recognize and interact with each other via noncovalent interactions.<br>In the recent years, great efforts have been directed toward reaching the perfection in the<br>design of a variety of supramolecular polymers and materials with different architectures. The<br>resulting structures are often thought of as ideally perfect, defect-free supramolecular fibers,<br>micelles, vesicles, etc., having an intrinsic dynamic character, which are typically studied at the<br>level of statistical ensembles to assess their average properties. However, molecular simulations<br>recently demonstrated that local defects that may be present or may form in these assemblies, and which are poorly captured by conventional approaches, are key to controlling their dynamic<br>behavior and properties. The study of these defects poses considerable challenges, as the<br>flexible/dynamic nature of these soft systems makes it difficult to identify what effectively constitutes<br>a defect, and to characterize its stability and evolution. Here, we demonstrate the power<br>of unsupervised machine learning techniques to systematically identify and compare defects in<br>supramolecular polymer variants in different conditions, using as a benchmark 5°A-resolution<br>coarse-grained molecular simulations of a family of supramolecular polymers. We shot that this<br>approach allows a complete data-driven characterization of the internal structure and dynamics<br>of these complex assemblies and of the dynamic pathways for defects formation and resorption.<br>This provides a useful, generally applicable approach to unambiguously identify defects in<br>these dynamic self-assembled materials and to classify them based on their structure, stability<br>and dynamics.<br>


Author(s):  
Huacheng Zhang

Pillararenes trimer with particularly designed structural geometry and excellent capacity of recognizing guest molecules is a very efficient and attractive building block for the fabrication of advanced self-assembled materials. Pillararenes trimers could be prepared via both covalent and noncovalent bonds. The classic organic synthesis reactions such as click reaction, Palladium-catalyzed coupling reaction, amidation, esterification and aminolysis are employed to build covalent bonds and integrate three pieces of pillararenes subunits together into the &ldquo;star-shaped&rdquo; trimers and linear foldamers. Alternatively, pillararenes trimers could also be assembled in the form of host-guest inclusions and mechanically interlocked molecules via noncovalent interactions, and during those procedures, pillararenes units contribute the cavity for recognizing guest molecules and act as a &ldquo;wheel&rdquo; subunit, respectively. By fully utilizing the driving forces such as host-guest interactions, charge transfer, hydrophobic, hydrogen bonding, C&mdash;H&hellip;&pi; and &pi;&mdash;&pi; stacking interactions, pillararenes trimers-based supramolecular self-assemblies provide a possibility in the construction of multi-dimensional materials such as vesicular and tubular aggregates, layered networks, as well as frameworks. Interestingly, those assembled materials exhibit interesting external stimuli responsiveness to e.g., variable concentrations, changed pH values, different temperature, as well as the addition/removal of competition guests and ions. Thus, they could further be used for diverse applications such as detection, sorption and separation of significant multi-analytes including metal cations, anions and amino acids.


2021 ◽  
Vol 8 ◽  
Author(s):  
Peter Faller ◽  
Christelle Hureau

The self-assembly of peptides and proteins into amyloid fibrils and other aggregates are linked to several diseases. One of the most studied cases is the peptide amyloid-β (Aβ), found self-assembled in Alzheimer's disease patients' brains. In test tubes, assays with chemically synthesized or recombinant Aβ are widely investigated to understand the aggregation process and to find modulators, which could be of therapeutic interest. Experience over more than a decade in our laboratory through discussions with colleagues, expertly studying the literature, and as reviewers revealed to us the widely encountered difficulty to control the aggregation and obtain reproducible results in the test tube. However, this issue is scarcely reported and discussed in the publications, which we think hampers strongly the progress in this field and can deceive newcomers. Here, we describe the difficulty and potential reasons to obtain reproducible aggregation data and propose some guidelines for working with it.


Sign in / Sign up

Export Citation Format

Share Document