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Über dieses Buch

This book investigates the latest developments in supramolecular assembly systems for mimicking biological structures and functions. Consisting of 14 chapters, it covers various assembly systems, such as polysaccharides, peptides, proteins, biopolymers, natural materials and various hybrid systems. Further, it focuses on different types of supramolecular systems with particular functions or structures that are relevant to living systems. A number of modern techniques used to study the supramolecular systems, such as total internal reflection fluorescence microscopy (TIRFM) and two-photon confocal microscopy, are also introduced in detail.

Unlike conventional books on supramolecular assemblies, this book highlights the functions of the assembly systems, particularly their biological applications. As such, it offers a valuable resource for experienced researchers, as well as graduate students working in the field of supramolecular chemistry and biomimetic systems.

Inhaltsverzeichnis

Frontmatter

Introduction to Supramolecular Chemistry and Biomimetic Systems

Frontmatter

Chapter 1. Molecular Biomimetics and Molecular Assembly

Abstract
Molecular biomimetics is mimicking the structures and functions of biological systems at the molecular scale via molecular assembly of biomolecules or synthetic components. It not only provides experimental models for guiding researches on biological mutation and evolution in organisms, but also opens up new avenues for the design and fabrication of novel functional materials. In this chapter, main contents of individual chapters are briefly introduced to give readers an overview of this book.
Junbai Li

Chapter 2. Advantages of Self-assembled Supramolecular Polymers Toward Biological Applications

Abstract
Supramolecular self-assembly provides a means of achieving “bottom-up” fabrication of nanoscale materials. Their mechanical properties and functionality arise from the assembly of relatively simple molecular building blocks. These materials have selective affinity to different interfaces, high capacity for interfacial adsorption, nanostructure, and spontaneous formation of unique nano-self-assemblies which exhibit remarkable simplicity and biocompatibility. Due to these attractive features, supramolecular nanostructures, particularly peptide-based, have recently been explored as effective nanomaterials in applications ranging from controlled release and drug delivery, nano-fabrication, skin care, biomineralization, sensing, antimicrobial materials, and tissue engineering. This range of applications is facilitated by the diverse primary sequences of the short peptides, which can be either biomimetic or de novo designed. Thus, their self-assembling mechanistic processes and nanostructures also vary enormously. This chapter highlights recent advances in studying self-assembled peptide systems, focusing on the formation of different nanostructures and their applications in diverse fields.
Michal Halperin-Sternfeld, Moumita Ghosh, Lihi Adler-Abramovich

Biomimetic Membranes

Frontmatter

Chapter 3. Nanoarchitectonics of Biomimetic Membranes

Abstract
Emerging concept, nanoarchitectonics, which is an emerging concept is especially suitable for fabrication of materials systems from organic and biomaterials through self-organization and directed-organization. Nanoarchitectonics tries to control uncontrollable situations through harmonizing various factors and interactions. The most successful example of functional harmony of nanoscale objects can be seen in biological systems and biomimetic systems. In this chapter, we here focus on nanoarchitectonics of biomimetic membranes. This chapter introduces various examples of nanoarchitectonics approaches for bio-related thin films and membranes: (1) two-dimensional biomimetic membrane (molecular recognition, receptor tuning, and nanomaterial film for life control); (2) layer-by-layer biomimetic membrane (bioreactor, hierarchic assembly, and sensing and drug delivery).
Katsuhiko Ariga

Biomolecules Based Molecular Assembly

Frontmatter

Chapter 4. Polysaccharides-Based Microcapsules

Abstract
LbL-assembled microcapsules have gained great interests in diverse fields due to their versatile and engineering properties. In this chapter, we focus on the microcapsules fabricated from biocompatible and biodegradable polysaccharides. Various interactions, including electrostatic interaction, hydrogen bonding, covalent crosslinking, ionic crosslinking, and host–guest interaction are introduced and employed as driving forces to construct polysaccharide microcapsules with specific stimuli-responsivity. The functionalization of polysaccharide microcapsules with bioactive moieties (such as cell surface receptor ligands) is presented and their applications in cancer therapy and blood substitutes are highlighted.
Yi Jia, Xiyun Feng, Junbai Li

Chapter 5. Hemoglobin-Based Molecular Assembly

Abstract
Development of protein-based molecular devices is an active area of research due to their broad applications in biotechnology, biorelated chemistry, bioelectronics, and biomedical engineering. Hemoglobin (Hb) is a physiologically important oxygen-transport metalloprotein present in the red blood cells. In this chapter, we present the recent development in fabrication and tailoring of a variety of hemoglobin protein shells via covalent layer-by-layer (LbL) assembly combined with template technique. Also, the developed strategy is effective and flexible, advantageous for avoiding denaturation of proteins. The as-fabricated Hb shells have better applications in drug delivery and controlled release, biosensors, biocatalysis, and bioreactors due to the enhancement of biological availability. In view of the carrying-oxygen function of Hb protein in blood, we particularly focus on the potential applications of hemoglobin-based nanoarchitectonic assemblies as artificial blood substitutes. These novel oxygen carriers exhibit advantages over traditional carriers and will greatly promote research on reliable and feasible artificial blood substitutes.
Li Duan, Yi Jia, Junbai Li

Chapter 6. Photosystem II Based Multilayers

Abstract
During billions of years of evolution and development, photosynthesis has formed an effective mechanism for solar energy fixation and conversion. The unique property of photosystem II (PSII) to split water in ambient condition makes it the key role in the process of photosynthesis. Assembly of PSII-based multilayers toward the construction of water splitting systems has attracted more and more attention. As a means to study PSII, it might lead to quicker solutions to understand the electron transfer mechanism in such hybrid systems and how activities of PSII can be affected by different physicochemical or environmental factors. Such systems might also provide guidelines for the design and fabrication of artificial photosynthetic energy conversion systems. In this chapter, we concentrate on the design and development of PSII-based water splitting systems, in which photoelectrochemical (PEC) cells utilizing PSII will be discussed in detail.
Peng Cai, Guangle Li, Jiao Li, Yi Jia, Zhongfeng Zhang, Junbai Li

Chapter 7. Peptide-Based Supramolecular Chemistry

Abstract
Supramolecular chemistry of highly important biomolecules and bioinspired molecules has attracted tremendous interest due to its acknowledged importance in construction of novel functional materials and in revealing the mechanisms of formation and evolution of natural living organisms. As one kind of representative biomolecules, peptides are among the most appealing programmable building blocks for supramolecular self-assembly. In this chapter, we present recent progresses in supramolecular chemistry of self-assembling aromatic dipeptides, including self-assembly of aromatic dipeptides and co-assembly of aromatic dipeptides with various functional molecular motifs, such as porphyrins, azobenzenes, photosensitizers, polyoxometalates, quantum dots, and glutaraldehyde. Particularly, hierarchical self-assembly of peptides and structural transition of the self-assembled peptide architectures are in-depth discussed in controllable fabrication of peptide materials along with revealing the non-covalent interactions that determine the self-assembly and the structure–property relationships of the formed peptide materials. Also, the applications of peptide-based supramolecular materials as optical waveguiding materials, biomimetic energy materials, and biomaterials are highlighted, providing an increased understanding of the role of peptide-based supramolecular chemistry in construction of novel functional materials.
Qianli Zou, Kai Liu, Manzar Abbas, Xuehai Yan

Chapter 8. Functional Nanomaterials Via Self-assembly Based Modification of Natural Cellulosic Substances

Abstract
Natural cellulose substances possess inherent sophisticated hierarchical structures and morphologies which are impossible to be created by artificial methods at the present time. Precise surface modification of cellulose matters with specific guest substances at the molecular and nanometer scales provides a facile shortcut to combine the unique physical properties of cellulose materials and specifically designed chemical functionalities to give a large variety of new nanomaterials for various practical applications.
Shun Li, Yuanqing Gu, Jianguo Huang

Molecular Assembly of Motor Proteins and Artificial Micro-/Nanomotors

Frontmatter

Chapter 9. Directional Transportation of Assembled Molecular Linear Motors

Abstract
The transport and localization of organelles within a eukaryotic cell are dependent on a complex network of protein filaments called the cytoskeleton and the associated proteins, including actin filaments and myosins. Myosin is a molecular motor which has ATPase activity and is able to convert the energy from ATP into mechanical movement along actin filaments. To transport cargo efficiently and to prevent the futile hydrolysis of ATP, the motor activity of myosin must be tightly regulated. In the past two decades, considerable progress has been achieved in understanding new myosins and regulatory mechanism of myosin motors. This chapter will present a general view of myosin family and focus on the structure, function, and regulation of three myosins, i.e., smooth muscle myosin-2, myosin-5, and myosin-19.
Ning Zhang, Xiang-Dong Li

Chapter 10. Reconstitution of Motor Protein ATPase

Abstract
Molecular motor proteins are amazing biological units that are responsible for the transformation of the chemical or biological components into mechanical works. These molecular machines express stronger energy conversion than man-made systems, which inspired scientists to pursue the target of improved performance of current synthetic devices. Thus, it is significant to explore interesting features of biomolecular motors, and design the novel intelligent platforms that mixed motor proteins with synthetic materials. Biomimetic molecular assembly enables the possibility for the in vitro reconstruction of biomolecular motors, further provides a variety of functionalized strategies. In this chapter, we gave a detailed introduction for one of the most familiar biomolecular motors, adenosine triphosphatase (ATPase), and deepen the understanding of their working mechanism and clarified how to conjugate ATPase with the artificially synthetic materials. In addition, some promising examples and significant comments were highlighted to display reconstructed performance of ATPase during this exploring voyage.
Mingjun Xuan, Yi Jia, Junbai Li

Chapter 11. Controlled Molecular Assembly Toward Self-propelled Micro-/Nanomotors

Abstract
Micro-/nanomotors (MNMs) are able to propel themselves in fluids through converting different energies from environment into kinetic energy. Recently, layer-by-layer (LbL) assembly, a versatile assembly approach, has been employed to access MNMs with advantages such as regulated motion, stimuli-response properties, and multifunctionality. In this chapter, we review the recent progress on controlled fabrication, motion control, and biomedical applications of MNMs based on controlled molecular assembly. Through integrating diverse functional building blocks such as nanoparticles, enzymes, and metal shells, MNMs with various structures (e.g., hollow capsules and nanotubes) have been prepared, and the control over the on/off state of the MNM motion has been realized. In addition, we also discuss a special type of MNMs which is derived from the combination of as-assembled biological aggregates and artificial nanostructures. These MNMs can be driven by bubble recoil, irradiation by near-infrared light, and ultrasonic fields. We have also demonstrated the potential applications of these assembled MNMs in biomedical fields such as targeted drug delivery, photothermal therapy, and detoxification.
Xiankun Lin, Zhiguang Wu, Qiang He

Hierarchical Dendrimer, Polyoxometalates Complexes and Inorganic-Organic Hybrid Systems

Frontmatter

Chapter 12. Functional Dendrimer-Based Vectors for Gene Delivery Applications

Abstract
Poly (amidoamine) (PAMAM) dendrimers are a class of highly branched, monodispersed, synthetic macromolecules with abundant terminal functional groups, and have significant advantages over other cationic polymers as gene delivery vectors due to their well-defined structure, the possibility of facile surface modification, and capacity of carrying large gene segments. The surface amine groups of dendrimers can be conjugated with functional molecules (e.g., hydrophobic moieties, β-cyclodextrin, polyethylene glycol, etc.), and targeting ligands (e.g., folic acid, arginine-glycine-aspartic peptide), while the unique interior of dendrimers affords their uses to form dendrimer-entrapped gold nanoparticles. These modifications render the dendrimer-based vectors with an ability for targeted and enhanced gene delivery, including pDNA and siRNA delivery. In this chapter, we review some recent advances made in multifunctional poly(amidoamine) dendrimer-based nanoparticles for gene delivery applications.
Lingdan Kong, Xiangyang Shi

Chapter 13. Polyoxometalates and Their Complexes Toward Biological Application

Abstract
Polyoxometalates (POMs) are a type of inorganic polyanionic clusters bearing well-defined topologic architecture consisted of transition oxo-metalates. Due to their negatively charged features, various dimensions, acidity, and so forth, POMs also show specific functions in biological system. To understand the activity at molecular level, we start the discussion from the basic binding modes of POMs with biomolecules to the expression of the binding diversity on the crystallography, inhibition and hydrolysis of biomolecules. Moreover, the selective inhibition of POMs for biomolecules displays the potential roles in antitumor, antiviral, and antimicrobial activities. In the chapter, recent achievements concerning the applications of POMs on biological-related systems are summarized. The discussion involves the interaction of POMs with amino acids, peptides, and proteins, the co-crystallization of proteins with the help of POMs, the inhibitory effect of POMs on enzymes and some diseases, the mimetic enzyme functions of POMs for hydrolysis of peptides and proteins, the antiviral, antibacterial, and antitumoral activity of POMs, and their bio-imaging features.
Lixin Wu, Jing Liang

Chapter 14. Inorganic-Organic Hybrid Materials Based on Nanopolyoxometalates

Abstract
Various types of nano-scale polyoxometalates (POMs) with beautiful topologies has been synthesized successfully by destroying the hydration shell of the anions caused by the extremely hydrophilic surface. Their magnetic, electronic, and photoluminescent properties and valuable applications in catalysis, medicine, and material science are discussed. Meanwhile, the last ten years have witnessed a remarkable development in terms of preformed organic-inorganic POM-based hybrid systems for the rational design of functional architectures, assemblies and materials. Hydrophilic POMs of different sizes and shapes can interact with hydrophobic cationic surfactants, the resulting materials show amphiphilic properties with electrostatic interactions between the hydrophilic and hydrophobic components, called Surfactant-Encapsulated Clusters (SECs) or Surfactant-Encapsulated-POMs (SEPs). This hydrophobic surfactant-encapsulated clusters (HSECs) can fabricated through covalent or non-covalent interaction, which can construct ordered self-assembly, e.g. robust onionlike structures, honeycomb films or giant vesicle. Moreover, This ordered giant vesicle acts as building block to fabricate three dimensional structures. In addition, SECs can further self-assemble to give a variety of nanostructures on various surfaces/interfaces, among them, the most representative nanostructures discussed below is ordered honeycomb films, which is carried out by a simple solvent-evaporation method. It is reasonable to assume that the condensed water microdroplets induced by the quick evaporation of solvents play an important role as template for the formation of pores. Various factors are being investigated to construct thin films with different morphologies. We hope the inorganic-organic hybrid functional materials based on POMs will bridge polyoxometalate chemistry and material chemistry, which can be further explored application in many fields.
Yitong Wang, Jingcheng Hao
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