scholarly journals Towards Building Blocks for Supramolecular Architectures Based on Azacryptates

Molecules ◽  
2020 ◽  
Vol 25 (7) ◽  
pp. 1733 ◽  
Author(s):  
Ana Miljkovic ◽  
Sonia La Cognata ◽  
Greta Bergamaschi ◽  
Mauro Freccero ◽  
Antonio Poggi ◽  
...  

In this work, we report the synthesis of a new bis(tris(2-aminoethyl)amine) azacryptand L with triphenyl spacers. The binding properties of its dicopper complex for aromatic dicarboxylate anions (as TBA salts) were investigated, with the aim to obtain potential building blocks for supramolecular structures like rotaxanes and pseudo-rotaxanes. As expected, UV-Vis and emission studies of [Cu2L]4+ in water/acetonitrile mixture (pH = 7) showed a high affinity for biphenyl-4,4′-dicarboxylate (dfc2−), with a binding constant of 5.46 log units, due to the best match of the anion bite with the Cu(II)-Cu(II) distance in the cage’s cavity. Compared to other similar bistren cages, the difference of the affinity of [Cu2L]4+ for the tested anions was not so pronounced: conformational changes of L seem to promote a good interaction with both long (e.g., dfc2−) and short anions (e.g., terephthalate). The good affinity of [Cu2L]4+ for these dicarboxylates, together with hydrophobic interactions within the cage’s cavity, may promote the self-assembly of a stable 1:1 complex in water mixture. These results represent a good starting point for the application of these molecular systems as building units for the design of new supramolecular architectures based on non-covalent interactions, which could be of interest in all fields related to supramolecular devices.

2008 ◽  
Vol 80 (3) ◽  
pp. 639-658 ◽  
Author(s):  
Jing Lv ◽  
Huibiao Liu ◽  
Yuliang Li

Building supramolecular architectures with well-defined shapes and functions is of great importance in materials science, nanochemistry, and biomimetic chemistry. In recent years, we have devoted much effort to the construction of well-defined supramolecular structures through noncovalent forces such as hydrogen bonding, π-stacking, metal-ligand bonds, and hydrophilic and hydrophobic interactions, with the aid of functional building blocks. The morphologies and their physical properties were studied, and new methods for the construction of one-dimensional nanoscale structures have been developed. In this review, we summarize our recent studies on the design and synthesis of the supramolecular systems, as well as the physical properties of nanoscale structures.


2007 ◽  
Vol 19 (1) ◽  
pp. 219-230 ◽  
Author(s):  
María del Carmen Barral ◽  
Rodrigo González-Prieto ◽  
Santiago Herrero ◽  
Reyes Jiménez-Aparicio ◽  
José Luis Priego ◽  
...  

2011 ◽  
Vol 1299 ◽  
Author(s):  
M. R. Gullo ◽  
L. Jacot-Descombes ◽  
L. Aeschimann ◽  
J. Brugger

ABSTRACTThis paper presents the experimental and numerical study of hydrophobic interaction forces at nanometer scale in the scope of engineering micron-sized building blocks for self-assembly in liquid. The hydrophobic force distance relation of carbon, Teflon and dodeca-thiols immersed in degassed and deionized water has been measured by atomic force microscopy. Carbon and dodeca-thiols showed comparable attractive and binding forces in the rage of pN/nm2. Teflon showed the weakest binding and no attractive force. Molecular dynamic simulations were performed to correlate the molecular arrangement of water molecules and the hydrophobic interactions measured by atomic force microscopy. The simulations showed a depletion zone of 2Å followed by a layered region of 8Å in the axis perpendicular to the hydrophobic surface.


2020 ◽  
Vol 21 (22) ◽  
pp. 8431
Author(s):  
Qinsi Xiong ◽  
Ziye Liu ◽  
Wei Han

The molecular design of short peptides to achieve a tailor-made functional architecture has attracted attention during the past decade but remains challenging as a result of insufficient understanding of the relationship between peptide sequence and assembled supramolecular structures. We report a hybrid-resolution model to computationally explore the sequence–structure relationship of self-assembly for tripeptides containing only phenylalanine and isoleucine. We found that all these tripeptides have a tendency to assemble into nanofibers composed of laterally associated filaments. Molecular arrangements within the assemblies are diverse and vary depending on the sequences. This structural diversity originates from (1) distinct conformations of peptide building blocks that lead to different surface geometries of the filaments and (2) unique sidechain arrangements at the filament interfaces for each sequence. Many conformations are available for tripeptides in solution, but only an extended β-strand and another resembling a right-handed turn are observed in assemblies. It was found that the sequence dependence of these conformations and the packing of resulting filaments are determined by multiple competing noncovalent forces, with hydrophobic interactions involving Phe being particularly important. The sequence pattern for each type of assembly conformation and packing has been identified. These results highlight the importance of the interplay between conformation, molecular packing, and sequences for determining detailed nanostructures of peptides and provide a detailed insight to support a more precise design of peptide-based nanomaterials.


2018 ◽  
Vol 22 (4) ◽  
pp. 1659-1664 ◽  
Author(s):  
Dan Tian ◽  
Xiaoxia Li ◽  
Ji-Huan He

Many nature materials have hierarchical structure, and its last cascade is always on a molecule scale, e. g., double-stranded DNA, making the hierarchy effective with minimal building blocks. Now artificial hierarchy can begin with a nanoscale level to embody the material with remarkable and fascinating properties which can be never achieved using non-hierarchical structure. A strong desire to fabricate some biomimicking hierarchies from a molecule level has been stimulating scientists. Herein we show that molecular structure can be easily controlled by a long and narrow tube, and self-assembly of macromolecules can be achieved to improve its crystallinity with plenty of excellent properties. We anticipate this paper to be a starting point for more sophisticated fabrication of fibers with self-assembly of macromolecules.


2020 ◽  
Vol 27 (8) ◽  
pp. 688-697
Author(s):  
Yu Chen ◽  
Kai Tao ◽  
Wei Ji ◽  
Pandeeswar Makam ◽  
Sigal Rencus-Lazar ◽  
...  

Supramolecular self-assembled functional materials comprised of cyclic dipeptide building blocks have excellent prospects for biotechnology applications due to their exceptional structural rigidity, morphological flexibility, ease of preparation and modification. Although the pharmacological uses of many natural cyclic dipeptides have been studied in detail, relatively little is reported on the engineering of these supramolecular architectures for the fabrication of functional materials. In this review, we discuss the progress in the design, synthesis, and characterization of cyclic dipeptide supramolecular nanomaterials over the past few decades, highlighting applications in biotechnology and optoelectronics engineering.


2019 ◽  
Vol 10 ◽  
pp. 494-499
Author(s):  
Achintya Jana ◽  
Puneet Mishra ◽  
Neeladri Das

Exploring the surface self-assembly of small molecules that act as building blocks (tectons) for complex supramolecular structures is crucial for realizing surface-supported functional molecular devices. Here, we report on the synthesis and surface self-assembly of a new pyrazine-derived molecule with pyridine pendants. Ambient scanning tunneling microscopy investigation at the solution–solid interface reveals polymorphic self-assembly of these molecules on a HOPG substrate. Two different molecular packing structures with equal distribution are observed. Detailed analysis of the STM images emphasizes the crucial role of weak intermolecular hydrogen bonding, and molecule–substrate interactions in the formation of the observed polymorphs. Such weak hydrogen bonding interactions are highly desirable for the formation of modular supramolecular architectures since they can provide sufficiently robust molecular structures and also facilitate error correction.


2019 ◽  
Vol 17 (28) ◽  
pp. 6719-6734 ◽  
Author(s):  
Ronja Otter ◽  
Pol Besenius

The following review gives an overview about synthetic peptide–polymer conjugates as macromolecular building blocks and their self-assembly into a variety of supramolecular architectures, from supramolecular polymer chains, to anisotropic 1D arrays, 2D layers, and more complex 3D networks.


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