Supramolecular assembly of functional peptide–polymer conjugates

2019 ◽  
Vol 17 (28) ◽  
pp. 6719-6734 ◽  
Author(s):  
Ronja Otter ◽  
Pol Besenius
Keyword(s):  
Self Assembly ◽  
Synthetic Peptide ◽  
Supramolecular Assembly ◽  
Building Blocks ◽  
Polymer Chains ◽  
Supramolecular Polymer ◽  
Polymer Conjugates ◽  
Supramolecular Architectures ◽  
Functional Peptide ◽  
3D Networks

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.

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 ◽  
...  
Keyword(s):  
Conformational Changes ◽  
Self Assembly ◽  
Hydrophobic Interactions ◽  
Building Blocks ◽  
Water Mixture ◽  
Molecular Systems ◽  
Supramolecular Architectures ◽  
Starting Point ◽  
The Difference ◽  
Supramolecular Devices

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.

Self-Assembly of Supramolecular Architectures Using Chlorotetra(Pyrrole-2-Carboxylato)Diruthenium Molecules as Building Blocks

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

scholarly journals α-Cyclodextrin-Based Polypseudorotaxane Hydrogels

Materials ◽  
2019 ◽  
Vol 13 (1) ◽  
pp. 133 ◽  
Author(s):  
Adrian Domiński ◽  
Tomasz Konieczny ◽  
Piotr Kurcok
Keyword(s):  
Self Assembly ◽  
Polymeric Nanoparticles ◽  
Functional Materials ◽  
Building Blocks ◽  
Polymer Chains ◽  
Physical Interaction ◽  
Wide Range ◽  
Potential Applications ◽  
Noncovalent Bonds ◽  
Significant Attention

Supramolecular hydrogels that are based on inclusion complexes between α-cyclodextrin and (co)polymers have gained significant attention over the last decade. They are formed via dynamic noncovalent bonds, such as host–guest interactions and hydrogen bonds, between various building blocks. In contrast to typical chemical crosslinking (covalent linkages), supramolecular crosslinking is a type of physical interaction that is characterized by great flexibility and it can be used with ease to create a variety of “smart” hydrogels. Supramolecular hydrogels based on the self-assembly of polypseudorotaxanes formed by a polymer chain “guest” and α-cyclodextrin “host” are promising materials for a wide range of applications. α-cyclodextrin-based polypseudorotaxane hydrogels are an attractive platform for engineering novel functional materials due to their excellent biocompatibility, thixotropic nature, and reversible and stimuli-responsiveness properties. The aim of this review is to provide an overview of the current progress in the chemistry and methods of designing and creating α-cyclodextrin-based supramolecular polypseudorotaxane hydrogels. In the described systems, the guests are (co)polymer chains with various architectures or polymeric nanoparticles. The potential applications of such supramolecular hydrogels are also described.

Self-Assembly of Cyclic Dipeptides: Platforms for Functional Materials

2020 ◽  
Vol 27 (8) ◽  
pp. 688-697
Author(s):  
Yu Chen ◽  
Kai Tao ◽  
Wei Ji ◽  
Pandeeswar Makam ◽  
Sigal Rencus-Lazar ◽  
...  
Keyword(s):  
Self Assembly ◽  
Functional Materials ◽  
Building Blocks ◽  
Cyclic Dipeptide ◽  
Design Synthesis ◽  
Cyclic Dipeptides ◽  
The Past ◽  
Supramolecular Architectures ◽  
Structural Rigidity

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.

scholarly journals Polymorphic self-assembly of pyrazine-based tectons at the solution–solid interface

2019 ◽  
Vol 10 ◽  
pp. 494-499
Author(s):  
Achintya Jana ◽  
Puneet Mishra ◽  
Neeladri Das
Keyword(s):  
Hydrogen Bonding ◽  
Self Assembly ◽  
Building Blocks ◽  
Molecular Structures ◽  
Scanning Tunneling ◽  
Tunneling Microscopy ◽  
Equal Distribution ◽  
Solid Interface ◽  
Supramolecular Architectures ◽  
Microscopy Investigation

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.

Role of Anion–π Interactions in the Supramolecular Assembly of Salts Containing Asymmetrical Bis(pyridyl) Cations

2014 ◽  
Vol 67 (10) ◽  
pp. 1504
Author(s):  
Zhu-Yan Zhang ◽  
Zhao-Peng Deng ◽  
Li-Hua Huo ◽  
Shu-E Zhang ◽  
Hui Zhao ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Self Assembly ◽  
Supramolecular Assembly ◽  
Interpenetrating Networks ◽  
Π Interactions ◽  
Supramolecular Architectures ◽  
Left Handed ◽  
Inorganic Acids ◽  
Thermal Stability Of

Self-assembly of three flexible bis(pyridyl) molecules with different inorganic acids (HPF6, HClO4, and HNO3) leads to the formation of eight salts, which exhibit diverse architectures involving hydrogen bonding and anion–π interactions. The three types of inorganic anions in these salts formed anion–π interactions with HM+ and H2M2+ except for 2, in which the six F atoms were involved in hydrogen bonds. Anion–π interactions produced diverse motifs of one (anion)-to-one (cation) in 1, 3, 4, and 6, two (anion)-to-one (cation) in 5 and 7, and (4,4) layer in 8. Hydrogen bonds resulted in interesting supramolecular architectures, such as right- and left-handed helical chains in 3, 2-fold interpenetrating networks in 5, and 3-fold interpenetrating networks in 8. Structural analyses indicated that the conformations of the three flexible asymmetrical bis(pyridyl) molecules and the non-covalent bonding interactions, such as hydrogen bonds and anion···π interactions, play crucial roles in the final architectures of these salts. Thermogravimetric analyses indicated that the thermal stability of the eight salts decreased in the order of perchlorates, hexafluorophosphates, and nitrates. The emission intensity of the perchlorates is much stronger than that of the hexafluorophosphates, nitrates, and their corresponding organic molecules in the solid state at room temperature.

scholarly journals Multiswitchable photoacid–hydroxyflavylium–polyelectrolyte nano-assemblies

2021 ◽  
Vol 17 ◽  
pp. 166-185
Author(s):  
Alexander Zika ◽  
Franziska Gröhn
Keyword(s):  
Self Assembly ◽  
Supramolecular Assembly ◽  
Building Blocks ◽  
Titration Calorimetry ◽  
Ph Responsive ◽  
Interaction Forces ◽  
Vis Spectroscopy ◽  
The Stability ◽  
State Dissociation ◽  
Naphthol Derivatives

Light- and pH-responsive nano-assemblies with switchable size and structure are formed by the association of a photoacid, anthocyanidin, and a linear polyelectrolyte in aqueous solution. Specifically, anionic disulfonated naphthol derivatives, neutral hydroxyflavylium, and cationic poly(allylamine) are used as building blocks for the ternary electrostatic self-assembly, forming well-defined supramolecular assemblies with tunable sizes of 50 to 500 nm. Due to the network of possible chemical reactions for the anthocyanidin and the excited-state dissociation of the photoacid upon irradiation, different ways to alter the ternary system through external triggering are accessible. The structure and trigger effects can be controlled through the component ratios of the samples. Dynamic and static light scattering (DLS, SLS) and ζ-potential measurements were applied to study the size and the stability of the particles, and information on the molecular structure was gained by UV–vis spectroscopy. Isothermal titration calorimetry (ITC) provided information on the thermodynamics and interaction forces in the supramolecular assembly formation.

A regular thymine tetrad and a peculiar supramolecular assembly in the first crystal structure of an all-LNA G-quadruplex

2014 ◽  
Vol 70 (2) ◽  
pp. 362-370 ◽  
Author(s):  
Irene Russo Krauss ◽  
Gary Nigel Parkinson ◽  
Antonello Merlino ◽  
Carlo Andrea Mattia ◽  
Antonio Randazzo ◽  
...  
Keyword(s):  
Self Assembly ◽  
Supramolecular Assembly ◽  
Building Blocks ◽  
Crystallographic Analysis ◽  
Order Structure ◽  
Promising Tool ◽  
G Quadruplex ◽  
Nuclease Resistance ◽  
Diagnostic Applications ◽  
Structural Descriptions

Locked nucleic acids (LNAs) are formed by bicyclic ribonucleotides where the O2′ and C4′ atoms are linked through a methylene bridge and the sugar is blocked in a 3′-endoconformation. They represent a promising tool for therapeutic and diagnostic applications and are characterized by higher thermal stability and nuclease resistance with respect to their natural counterparts. However, structural descriptions of LNA-containing quadruplexes are rather limited, since few NMR models have been reported in the literature. Here, the first crystallographically derived model of an all-LNA-substituted quadruplex-forming sequence 5′-TGGGT-3′ is presented refined at 1.7 Å resolution. This high-resolution crystallographic analysis reveals a regular parallel G-quadruplex arrangement terminating in a well defined thymine tetrad at the 3′-end. The detailed picture of the hydration pattern reveals LNA-specific features in the solvent distribution. Interestingly, two closely packed quadruplexes are present in the asymmetric unit. They face one another with their 3′-ends giving rise to a compact higher-order structure. This new assembly suggests a possible way in which sequential quadruplexes can be disposed in the crowded cell environment. Furthermore, as the formation of ordered structures by molecular self-assembly is an effective strategy to obtain nanostructures, this study could open the way to the design of a new class of LNA-based building blocks for nanotechnology.

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