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2022 | Buch

Supramolecular Assemblies Based on Electrostatic Interactions

herausgegeben von: Dr. M. Ali Aboudzadeh, Prof. Antonio Frontera

Verlag: Springer International Publishing

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Über dieses Buch

This volume presents recent advances and current knowledge in the field of supramolecular assemblies based on electrostatic interactions. The flexibility and simplicity of constructing assemblies is explained via several examples, illustrations, figures, case studies, and historical perspectives. Moreover, as there is an increasing demand for the use of theoretical and computational models of the interaction strengths for assisting with the experimental studies, one chapter specifically focuses on the "modelling'' of supramolecular assemblies. Finally, various aspects of the recent advances of the field as well as potential future opportunities are discussed, with the goal being to stimulate critical discussions among the community and to encourage further discovery. This volume aims to inspire and guide fellow scientists and students working in this field and thus it provides a great tool for all researchers, graduates and professionals specializing on the topic.

Inhaltsverzeichnis

Frontmatter
Chapter 1. Supramolecular Ionic Networks: Design and Synthesis
Abstract
Supramolecular polymer networks are chains of low molecular mass monomers held together by reversible non-covalent interactions, such as hydrogen bonds, metal–ligand bonds, hydrophobic or π−π  stacking interactions. The reversibility and low energy bonding bring about additional features compared to conventional covalent polymers, which potentially lead to new properties such as improved processing, self-healing behavior, and stimuli-responsiveness. Whereas the use of (multiple) hydrogen bonds is leading the discoveries in this area, the emerging ionic chemistry has also been translated to the development of supramolecular assemblies based on ionic interactions. This approach provides exciting opportunities for synthesizing new supramolecular materials via manipulation of the type and strength of the ion pair as well as the number of interactions. In this chapter, the most relevant advances and current knowledge in design and synthesis of supramolecular ionic networks, including those prepared from low molecular weight molecules, polymers, or a combination of the two are briefly reviewed. Their flexible and simple construction is depicted via several examples and case studies. Finally, the important concerns and possible opportunities are explained to inspire critical discussions and boost further findings.
M. Ali Aboudzadeh
Chapter 2. Supramolecular Ionic Networks: Properties
Abstract
Non-covalent ionic interactions are present in all elements of nature and can be used adequately to generate a wide variety of supramolecular assemblies. In recent years, a lot of scientists have been studying and exploring the ability to utilize ionic interactions to build controlled polymeric networks and to tailor desirable properties. The reversibility and low energy bonding of these interactions bring about additional features compared to conventional covalent polymers, which potentially lead to new properties such as improved processing, self-healing behaviour and stimuli responsiveness. In spite of these advantages, a basic physical–chemical characterization of supramolecular ionic networks is still far from complete. This is because obtaining an overall picture of the structure, the dynamics, and the properties of these networks is a key step to their use as high-performance materials. This chapter summarizes the current knowledge on different characterizations (e.g. morphology, thermal, electrical, rheological, and self-healing) of supramolecular ionic networks and attempts to derive consistent relations between their structure, dynamics, and properties. Various case studies are discussed in this chapter, using them as examples in order to elucidate their structure–property relation.
M. Ali Aboudzadeh, Shaghayegh Hamzehlou
Chapter 3. The Role of Electrostatic Interaction in the Self-assembly of Macroions
Abstract
With sizes (1–5 nm) between simple ions and large colloids, solution behaviors of macroions cannot be described either by Debye-Hückel limiting theory or DLVO theory. In addition, the large size disparity between macroions and small counterions makes their self-assembly process even more complicated. With charges carried by macroions, electrostatic interaction usually plays a critical role during self-assembly. A well-known feature of these structurally well-defined macroions with moderate charges is the spontaneous formation of hollow, spherical, single-layered blackberry structures, whose size can be accurately controlled via pH, solvent polarity, and salt concentration, based on counterion-mediated attraction. These blackberry structures show some unique properties, e.g., unique kinetic properties similar to the virus capsid formation, self-recognition, chiral-recognition, and permeation of small counterions through their membranes. Based on the complex structures of macroions, various interactions, such as hydrophobic interaction, van der Waals forces, hydrogen bonding, and cation-π interactions, can be involved to compete or cooperate with electrostatic interaction to tune their self-assembly behaviors.
Yuqing Yang, Ehsan Raee, Yifan Zhou, Tianbo Liu
Chapter 4. Ionic Self-Assembly of Dendrimers
Abstract
Dendrimers are highly branched macromolecules that possess a large number of functional groups at the periphery. Among the different types of dendrimers, those bearing charged sites in their structure, namely ionic dendrimers, attract increasing attention due to their exceptional self-assembling properties. These charged sites stimulate a cooperative binding mechanism that extends toward the formation of nanostructures both in bulk and in solution. Specifically, ionic dendrimers self-assemble in the solid state forming liquid crystal phases, even without being functionalized with liquid crystal units. Ionic dendrimers also self-assemble in solution leading to a wide variety of nanostructures, such as micelles or vesicles. The self-assembly of ionic dendrimers is a hot topic in materials science, and they have found several potential applications in ion conductive materials, optoelectronics, drug delivery, or gene transfection. The main objective of this chapter is to give a comprehensive overview of the functions, structures, and properties of these self-assembling ionic dendrimers.
Alberto Concellón, Verónica Iguarbe
Chapter 5. Nano-Objects by Spontaneous Electrostatic Self-Assembly in Aqueous Solution
Abstract
Electrostatic self-assembly for the formation of well-defined nano-objects in solution represents an emerging field. The key is to use building blocks with a certain geometry and/or a combination of noncovalent interaction types. Polyelectrolytes providing both stability and designability are especially valuable. Central for a targeted design is the fundamental understanding of structure-directing effects. This chapter addresses both an introduction to the field of spontaneous electrostatic self-assembly as well as the state of the art of its understanding. It commences from the special effects of polyelectrolytes, shortly pictures the established areas of polyelectrolyte complexes and block polyelectrolyte micelles, before focusing on novel approaches: Besides discussing the interplay of ionic and π-π interaction in a dendrimer-dye model system, we elucidate how thermodynamics encodes the nanoscale structure: the free energy determines the aggregation number but the entropy/enthalpy ratio the nano-object’s shape. The approach’s versatility applicable for building blocks from linear or cylindrical brush polyelectrolytes, proteins, DNA, polyoxometalate clusters to micelles is demonstrated. We provide examples of photocatalytic activity and triggering of the nano-objects’ size, shape, or function (e.g., enzyme activity) by addressing multiple stimuli such as pH and light. This includes the novel use of photoacids as interconnecting counterions with light-switchable valency.
Alexander Zika, Anja Krieger, Franziska Gröhn
Chapter 6. Electrostatic Layer-by-Layer Self-Assembly Method: A Physico-Chemical Perspective
Abstract
The use of the Layer-by-Layer (LbL) method for the fabrication of structural and functional materials through the alternate deposition of polyelectrolyte bearing opposite charges has undergone a spectacular development due to the numerous avenues that offer for controlling the assembly process by simply tuning some operational parameters or characteristic of the layering molecules. This is only possible by a careful examination of the physicochemical bases underlying the assembly process. This chapter tries to provide a broad physicochemical perspective trying to disentangle some of the most fundamental aspects underlying the exploitation of the LbL electrostatic self-assembly for opening new avenues in the design of novel nanomaterials.
Eduardo Guzmán, Ana Mateos-Maroto, Francisco Ortega, Ramón G. Rubio
Chapter 7. Supramolecular Assemblies Based on σ-hole Interactions
Abstract
Elements belonging to Groups 14–17 and Periods 3–6 frequently act as Lewis acids which are able to establish directional noncovalent interactions (NCI) with a variety of Lewis bases (lone pair donors), π-systems (aromatic rings, triple and double bonds) and non-nucleophilic anions (BF4, PF6, ClO4, etc.). These promising NCIs are named in general as σ-hole interactions that are subdivided as tetrel bonds for elements belonging to group 14, pnictogen bonding for group 15, chalcogen bonding for group 16, and halogen bonding for group 17. In general, σ-hole interactions offer differentiating features when moving down in the same group (larger and more positive σ-holes) or moving left in the same row (number of available σ-holes and directionality) of the periodic table. This chapter shows that Molecular Electrostatic Potential (MEP) surface calculation is a powerful tool to explain the solid-state architecture of many X-ray structures. This is exemplified by using many examples retrieved from the Cambridge Structural Database (CSD), especially focused on σ-hole interactions.
Antonio Bauzá, Antonio Frontera
Chapter 8. Regium Bonds: A Bridge Between Coordination and Supramolecular Chemistry
Abstract
During the past century, the coordination chemistry of coinage metals (elements of Group 11) has been extensively studied owing to their strong implications in crystal engineering, protein-drug chemistry, or catalysis. Very recently, their role has been expanded to the “noncovalent realm” by providing evidence of their ability to behave as Lewis acids and undergo noncovalent binding. More precisely, Cu, Ag, and Au are able to undertake noncovalent interactions (NCI) involving Lewis bases of different nature (e.g., lone pair donors, π-systems) or even small charged anions (e.g., Cl). This has been mainly attributed to presence of positive (σ-hole) and negative (σ-lump) electrostatic potential regions, which mimic in some way the electrophilic (σ-hole) and nucleophilic (belt) regions present in aerogens (Group 18), halogens (Group 17), chalcogens (Group 16) and pnictogens (Group 15). Group 11 noncovalent bonds have been named “regium bonds (RgB)” owing to the noble metal character of Cu, Ag, and Au elements. This chapter encompasses a series of both theoretical and experimental examples of RgBs to provide a general picture of the promising features of the interaction in crystal engineering, biological systems, and surface absorption processes as well as interplay and cooperativity between RgBs and other noncovalent forces.
Antonio Frontera, Antonio Bauzá
Chapter 9. Aqueous Supramolecular Assemblies of Photocontrolled Molecular Amphiphiles
Abstract
Amphiphilic molecules, are composed of hydrophobic and hydrophilic parts and the intrinsic tendence to assemble in aqueous conditions, producing numerous supramolecular assembled structures and functional systems. Some of the recent challenges in the design of adaptive, responsive, far-from-equilibrium functional systems in aqueous environments, the proper design of photo-controlled moieties in intrinsic charged amphiphilic molecular structures offers fruitful opportunities to create supramolecular assembly systems, based on electrostatic interaction, with response to light in aqueous environment. In this chapter, we discuss the design strategy of photo-controlled molecular amphiphiles, the supramolecular assembled structures in aqueous environment and at air–water interfaces, as well as different strategies for producing dynamic functions in both isotropic and anisotropic supramolecular assembled materials. The motions at air–water interface, foam formation, reversible supramolecular assembly at nanometer length-scale, and life-like artificial muscle function are discussed. Manipulating the molecular structural design, supramolecular assembling conditions, and external stimulation, the photo-controlled molecular amphiphiles open directions toward applications ranging from controlled bio-target delivery to soft robotic.
Franco King-Chi Leung
Chapter 10. Organic Salts as Tectons for Self-assembly Processes in Solution
Abstract
The literature, covering the last decade, about the self-assembly processes of organic salts in conventional solvents was analyzed. In particular, data reported about imidazolium and ammonium salts have been considered. The analysis shows that these processes are highly determined by structural features of the salts. Indeed, besides the nature of the cationic head, features of the alkyl chain borne on the cation structure and its possible functionalization, as well as the nature of the anion play a pivotal role. These factors determine not only the nature of the solvent in which the process occurs but also the nature of the self-assembly mechanism. Consequently, the structure tunability of the salts affects the characteristics of the aggregates and, in turn, their possible applications. To this aim, some interesting applications in the biomedical field are reviewed and discussed.
Salvatore Marullo, Carla Rizzo, Francesca D’Anna
Chapter 11. Computational Modelling of Supramolecular Polymers
Abstract
Supramolecular polymers are a type of polymers where the monomeric units are held together via non-covalent interactions and, thus, exhibit a dynamic character similar to that found in biological systems (e.g., proteins). Over the last years, supramolecular polymers have received a deal of attention due to their potential as functional materials. Nevertheless, the characterization of the final supramolecular polymeric architectures at atomistic resolution (i.e., dominant interactions, polymerization mechanism, transfer and amplification of chirality) is quite challenging for the current experimental techniques but accessible by computational modelling. In this chapter, we highlight, by a selection of research examples, that computational chemistry methods (at quantum and classical level) can be seen as powerful techniques to gain insights not only into the structure of the final supramolecular assemblies but also into the nature of the key intermolecular interactions and the mechanism that control the supramolecular polymerization growth as well as the chiral response. The computational tools discussed in this chapter can be also applied to the theoretical characterization of other supramolecular systems; for instance, those mainly governed by intermolecular electrostatic interactions.
Azahara Doncel-Giménez, Joaquín Calbo, Enrique Ortí, Juan Aragó
Backmatter
Metadaten
Titel
Supramolecular Assemblies Based on Electrostatic Interactions
herausgegeben von
Dr. M. Ali Aboudzadeh
Prof. Antonio Frontera
Copyright-Jahr
2022
Electronic ISBN
978-3-031-00657-9
Print ISBN
978-3-031-00656-2
DOI
https://doi.org/10.1007/978-3-031-00657-9

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