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2019 | Buch

Topology of Polymers

verfasst von: Dr. Koya Shimokawa, Prof. Kai Ishihara, Yasuyuki Tezuka

Verlag: Springer Japan

Buchreihe : SpringerBriefs in the Mathematics of Materials

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Über dieses Buch

Plastics, films, and synthetic fibers are among typical examples of polymer materials fabricated industrially in massive quantities as the basis of modern social life. By comparison, polymers from biological resources, including proteins, DNAs, and cotton fibers, are essential in various processes in living systems. Such polymers are molecular substances, constituted by the linking of hundreds to tens of thousands of small chemical unit (monomer) components. Thus, the form of polymer molecules is frequently expressed by line geometries, and their linear and non-linear forms are believed to constitute the fundamental basis for their properties and functions. In the field of polymer chemistry and polymer materials science, the choice of macromolecules has continuously been extended from linear or randomly branched forms toward a variety of precisely controlled topologies by the introduction of intriguing synthetic techniques. Moreover, during the first decade of this century, a number of impressive breakthroughs have been achieved to produce an important class of polymers having a variety of cyclic and multicyclic topologies.
These developments now offer unique opportunities in polymer materials design to create unique properties and functions based on the form, i.e., topology, of polymer molecules. The introduction and application of topological geometry (soft geometry) to polymer molecules is a crucial requirement to account for the basic geometrical properties of polymer chains uniquely flexible in nature, in contrast to small chemical compounds conceived upon Euclidian geometry (hard geometry) principles. Topological geometry and graph theory are introduced for the systematic classification and notation of the non-linear constructions of polymer molecules, including not only branched but also single cyclic and multicyclic polymer topologies. On that basis, the geometrical–topological relationship between different polymers having distinctive constructions is discussed. A unique conception of topological isomerism is thus formed, which contrasts with that of conventional constitutional and stereoisomerism occurring in small chemical compounds.
Through the close collaboration of topology experts Shimokawa and Ishihara and the polymer chemist Tezuka, this monograph covers the fundamentals and selected current topics of topology applied in polymers and topological polymer chemistry. In particular, the aim is to provide novel insights jointly revealed through a unique interaction between mathematics (topology) and polymer materials science.

Inhaltsverzeichnis

Frontmatter
Chapter 1. Topology meets polymers: Introduction
Abstract
In this chapter, we introduce polymers, long-chain molecules with diverse chemical compositions and structures. Topology can provide fundamental insights into the principle properties of polymers via their segment structures. We also present a brief description of the following chapters with respect to topological geometry and polymer chemistry.
Koya Shimokawa, Kai Ishihara, Yasuyuki Tezuka
Chapter 2. Graph theory analyses of polymers
Abstract
In this chapter, we introduce graph theory for analyzing structures of multicyclic polymers. An essential graph theory reference is [1].
In Section 2.1, we introduce basic concepts of graphs in which we define a polymer graph that represents a polymer structure. In Section 2.2, we introduce a systematic notation of polymer structure by using their graphs. This nomenclature and its application are the main themes of this chapter. In Section 2.3, we enumerate multicyclic polymers using the notation. Figures of graphs with rank 4 at most are discussed here. In Section 2.4, we discuss an application of L. Euler’s solution of the K¨onigsberg bridge problem.We introduce the folding operation and characterize what graph can be obtained from a simple linear graph by folding. As an application, we discuss the characterization of multicyclic polymers obtained from a simple linear graph by folding.
Koya Shimokawa, Kai Ishihara, Yasuyuki Tezuka
Chapter 3. Classification of polymer topologies based on alkane molecular graphs
Abstract
In this chapter, we describe the chemistry-based, hierarchical classification procedure in which a series of nonlinear, cyclic, and branched polymer architectures are classified from the molecular graph presentation of alkanes and cycloalkanes. We also discuss a systematic notation protocol for nonlinear polymer topologies, modified from the previous version ([3]), that is based on classification via the terminus T and junction J values in graph constructions of topological polymers.
Koya Shimokawa, Kai Ishihara, Yasuyuki Tezuka
Chapter 4. Types of graphs
Abstract
As seen in Chapter 2, topology variety increases with increasing multicyclic graphs: e.g., dicyclic, tricyclic, tetracyclic. Multicyclic graphs are classified into spiro, bridge, fused, and hybrid types [1]. In this chapter, we present graph theory definitions of the various multicyclic graphs and characterize each type via construction and decomposition. The characterizations may suggest polymer synthesis procedures. See Chapter 7 for the synthesis of multicyclic polymers.
Koya Shimokawa, Kai Ishihara, Yasuyuki Tezuka
Chapter 5. Knot theory analysis of polymers
Abstract
In this chapter, we discuss topological isomers of multicyclic polymers by using knots, links, and spatial graphs. Essential references on knot theory are [1, 2, 3, 4]. Chemistry applications of knot theory and low-dimensional topology are widely discussed in [5, 6].
Koya Shimokawa, Kai Ishihara, Yasuyuki Tezuka
Chapter 6. Topological operations and chemical isomerism of polymers
Abstract
The control of topological chain properties is essential in biopolymer processes, including DNA transcription and replication promoted by topoisomerase enzymes. Cleavage and re-bonding of DNA chains enables transformation of the chain topologies between a trivial knot (simple ring) and higher knotted constructions, as well as linked counterparts[1, 2]. Recently, topologically remarkable branching/folding structures have been identified in a class of proteins and polypeptides containing S-S bridging of selected cysteine pairs located along the cyclic polypeptide backbone[3, 4]. Their precise spatial 3D structures are crucial for specific biological functions, and enable chemical, thermal, and enzymatic stabilities [3, 4]. Ongoing breakthroughs in synthetic polymer chemistry now allow extensive choices in macromolecular structures beyond linear or randomly branched ones. Synthetic polymer systems with sufficiently long, flexible chains for random coil conformations are compatible with topological geometry conjectures. They are characterized by terminus (chain end) and junction (branching point) numbers as key invariant geometric parameters[5]. In this Chapter, we discuss the geometrical/topological operation of graph-structure polymers, with an emphasis on the relationships between chemical isomerism of topological polymers and geometrical graph transformations. A unique conception of topological isomerism is introduced that contrasts with constitutional and stereoisomerism in small molecules. From these considerations, rational and practical synthetic pathways are discussed for complex polymers having cyclic and multicyclic topologies.
Koya Shimokawa, Kai Ishihara, Yasuyuki Tezuka
Chapter 7. Topological polymer chemistry and graph-structure construction
Abstract
There are abundant examples in which the form of objects dictates their functions and properties at all dimensions and scales. In polymer chemistry and materials science, macromolecular structures have mostly been limited to linear or randomly branched forms. However, a variety of precisely controlled polymer topologies have been synthesized using intriguing techniques[1]. In particular, polymers with cyclic and multicyclic topologies have been made with unprecedented structural precision, and with qualities verified by new spectroscopic and chromatographic techniques[2].
Koya Shimokawa, Kai Ishihara, Yasuyuki Tezuka
Chapter 8. Topology meets polymers: Conclusion and perspectives
Abstract
In this monograph, we discussed and demonstrated ongoing developments in the unique collaboration of topological geometry and polymer chemistry. We described current topological polymer chemistry by highlighting the diverse nature of polymers with respect to both their chemistry and their line constructions. Topological analyses could provide fundamental insights on the principal materials and/or biological properties of polymers based on their segment geometries.
Koya Shimokawa, Kai Ishihara, Yasuyuki Tezuka
Metadaten
Titel
Topology of Polymers
verfasst von
Dr. Koya Shimokawa
Prof. Kai Ishihara
Yasuyuki Tezuka
Copyright-Jahr
2019
Verlag
Springer Japan
Electronic ISBN
978-4-431-56888-9
Print ISBN
978-4-431-56886-5
DOI
https://doi.org/10.1007/978-4-431-56888-9

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