Supramolecular organization in block copolymers containing a. Presenting the work of pioneering experts in this exciting field of supramolecular polymer chemistry, this monograph covers an extensive range of applications, including drug delivery and catalysis. The material properties of block copolymers can be tuned and potentially improved by introducing noncovalent interactions in place of covalent linkages between polymeric blocks resulting in the formation of supramolecular block copolymers. Selfhealing supramolecular block copolymers request pdf. Elucidating the microstructure of supramolecular copolymers. Such materials combine the microphase separation behavior inherent to block copolymers with the responsiveness of supramolecular materials thereby affording dynamic and reversible materials. Chain architecture can have a profound effect on the appearance of the nmr spectra. In particular, metallosupramolecular block copolymerscopolymers in which the blocks are linked together by a metalligand complexhave seen important progresses, allowing better control over the. Synthesis and characteristics of novel azobased diblock. The book highlights developments in the synthesis of complex structures, chemical des. Some of the possible copolymer architectures are shown in fig.
Conte national center for polymer research 120 governors drive. Pdf supramolecular block copolymers are becoming attractive materials in nascent. Stateoftheart techniques for tapping the vast potential of polymers the use of specific noncovalent interactions to control polymer structure and properties is a rapidly emerging field with applications in diverse disciplines. Supramolecularhybridhydrogelsfromnoncovalentlyfunctionaliz. However, as this work is a numerical analysis, the energy minimum for the system. Supramolecular triblock copolymers through the formation. Supramolecular polymers handbook of metathesis wiley. The most important technical polyesters are presented in detailed chapters, homogeneous polymers as well as copolymers, blends and highperformance reinforced polyester materials are discussed. In this work, we report the synthesis of supramolecular block copolymers ps bbpibps a, where ps is polystyrene and pi is polyisoprene, through the interaction of ps a and ps bbpi linear chains bearing heterocomplementary hydrogen bond forming groups, namely 2,6diaminopurine dap and thymine thy in the first case and hamilton receptor. This is manifested in the area of block copolymer selfassembly where supramolecular systems have displayed remarkable morphologies and properties not attained in classic covalent systems.
In order to do so, their blocks or branches should be different enough and with a real affinity for those phases. Block copolymer templatedirected synthesis of wellordered metallic. May 21, 2014 cocrystallization phase transformations in all. The incorporation of supramolecular chemistry also provides a very. Detailed approach to investigate thermodynamically controlled. It investigates all types of application for block copolymers.
Mainchain supramolecular block copolymers chemical. Fabrication of supramolecular semiconductor block copolymers. In most cases, only short chains of up to about 10 units are created, whereas useful supramolecular polymers. The gelation behavior depended on the structure of the block copolymers. Block copolymers in nanoscience massimo lazzari, guojun. Copolymer sequence is another feature that can have an important impact on the macroscopic behavior of a polymer synthesized from more than a single monomer. Supramolecular block copolymers by seeded living polymerization. Electroactive materials with tunable response based on block. In classical block copolymers, the constituent blocks are linked via a covalent bond.
Monomers within a copolymer may be organized along the backbone in. Future of supramolecular copolymers unveiled by reflecting on. Supramolecular polymer chemistry wiley online library. Part one formation of supramolecular polymers supramolecular polymer chemistry, first edition. It takes into account the supramolecular organisation of the polymer chains as a whole. Synthesis, thermal properties, and morphologies of.
While providing a deeper insight in macromolecular recognition. Mallapragada, department of chemical and biological engineering, iowa state university and ames laboratory. The main aim of this work is to study the respective contribution of the hard and soft blocks of a metalligand containing block copolymer to the selfhealing behavior. For the selfassembly between polymeric constituents, hydrogen bonding interactions should have optimized association constants and directionality to hold individual chains together. The solidstate supramolecular organization of block copolymers containing one pconjugated block and one nonconjugated block is elucidated with a joint experimental and theoretical approach.
Supramolecular selfassembly of multiblock copolymers in aqueous solution michael d. In particular, metallo supramolecular block copolymers copolymers in which the blocks are linked together by a metalligand complexhave seen important progresses, allowing better control over the. In a dispersed system, the graft andor block copolymers selforganize at interface and modify to a great extent interfacial properties, thus enhancing phase compatibility. The aim of the thesis was the noncovalent synthesis of highly desirable supramolecular block copolymers by the approach of living seeded supramolecular polymerization and to study the impact of. Supramolecular conjugated block copolymers macromolecules. This approach combines atomic force microscopy afm measurements on thin polymer deposits, which reveal the typical microscopic morphologies, and molecular. For example, two main mechanisms have been distinguished.
This contribution introduces mainchain supramolecular abc and abb. Hydrogen bonding in supramolecular polymer networks. This is manifested in the area of block copolymer selfassembly where supramolecular and dynamic covalent polymers. Pdf supramolecular block copolymers under thermodynamic. The main property, which has to be highlighted, is the reversibility of the supramolecular binding units which are located in the main chain. Phase separation of supramolecular and dynamic block. Mainchain supramolecular block copolymers have received significant attention for their regulable and processable material properties. Here we report the formation of supramolecular block copolymers by. The combination of controlled anionic polymerization and subsequent introduction of hydrogen bonding groups was established to form thermoreversible, supramolecular networks. Supramolecular interactions between certain molecules have long been recognized. Complementary quadruple hydrogen bonding in supramolecular copolymers. Complementary quadruple hydrogen bonding in supramolecular. Hierarchical structure formation in supramolecular combshaped block copolymers anton h.
With different block ratio of p2vp to p3ht, the block copolymers exhibit sphere, cylinder, lamellae, and nanofiber nanostructures. Part of the advances in polymer science book series polymer, volume 268. While providing a deeper insight in macromolecular recognition and the. Synthesis, thermal properties, and morphologies of amphiphilic brush block copolymers with tacticitycontrolled polyether main chain. In addition, block copolymers bcs having the interplay between the microphase separation and the elastic deformation of liquid crystal ordering which is defined as supramolecular cooperative motion smcm, exhibit more hierarchical structures with photoresponsive features. Supramolecular block copolymers are becoming attractive materials in nascent. Until recently, these metal complexes have been used to prepare mainly micelle type structures. Supramolecular block copolymers under thermodynamic control. Block copolymers containing polysilane blocks are unique in that the polysilane components possess electroactive properties and are readily photodegradable. Supramolecular chemistryconcepts and applications ajay kumar manna ramananda college, department of chemistry, bishnupur, bankura, west bengal, 722122, india abstract. The selforganisation of polysilane block copolymers. Study of supramolecular sidechain copolymers containing lightemitting hacceptors and electrontransporting dendritic hdonors pojen yang, chungwen wu, duryodhan sahu, and hongcheu lin department of materials science and engineering, national chiao tung university, hsinchu, taiwan, roc.
The selected examples provide an overview about the various possibilities, which this special polymer class offers. The synthesis, selfassembly and selforganisation of. While these studies yield synthetic foldamers, multiple directional and orthogonal interactions must be. Pdmabpnipam, we successfully prepared block copolymer grafted graphene sheets via inclusion complexation for the. Two polymer chains, each carrying a complementary multiple hydrogenbonding site at the center, led to supramolecular block copolymers where two segments are connected in an xshaped configuration. Nmr spectroscopy are the primary tools for microstructural. Supramolecular organization in block copolymers containing. In supramolecular copolymers, this connection is replaced by a more labile, in some cases reversible, one hydrogen bonding, hostguest interaction, and metaltoligand complexation represent the most prominent and versatile examples in this respect. Introduction to polymer science and technology download. The book covers current knowledge on all aspects of polyester synthesis, structure, properties chemical, physical and application relevant and recycling.
Generation of a main chain supramolecular polymer by. It focuses on new structures and phenomena of cyclodextrinbased supramolecular polymers and many other compound classes. Supramolecular polymer chemistry has emerged as a major research focus. Block copolymers in nanoscience massimo lazzari, guojun liu. The strength of the forces responsible for spatial organization of the system range from weak intermolecular forces, electrostatic charge, or hydrogen bonding to strong covalent bonding, provided that the electronic coupling strength remains small relative to the energy. Foldamerbased chiral supramolecular alternate block copolymers tuned by ionpair binding. Controlled polymerization techniques in combination with supramolecular assembly are used to engineer hetero. A block copolymers sustained by orthogonal metal coordination and hydrogen bonding between telechelic polymers that feature distinct secondary structure motifs.
Our mainchain orthogonal assembly approach allows the engineering of multiblock copolymer scaffolds featuring diverse secondary structures via the directional assembly of telechelic building blocks. Nature utilizes hydrogen bonding to guide the supramolecular assembly of lipids. The noncovalent staining, typical of ipaint, allows the investigation of supramolecular polymers structure in situ without any chemical modification. Pdf research on block copolymers bcps has played a critical role in the. Monomers within a copolymer may be organized along the backbone in a variety of ways.
This first book to take a detailed look at one of the key focal points where nanotechnology and polymers meet provides both an introductory view for beginners as well as indepth knowledge for specialists in the various research areas involved. Generation of a main chain supramolecular polymer by oxidative covalent polymerization of a ditopic supramolecular building block nabarun roy, eric buhler and jeanmarie lehn supporting information electronic supplementary material esi for polymer chemistry. Linear copolymers consist of a single main chain, and include alternating copolymers. Block and graft copolymers act as oil in oil emulsifiers. In supramolecular polymer chemistry, hydrogen bonding has been used widely for creating welldefined supramolecular block copolymers via mainchain selfassembly of telechelic polymers containing terminal recognition units. Supramolecular polymers 2nd edition alberto ciferri. Molecular recognition and polymers covers the fundamental aspects and applications of molecular recognitionin the creation of novel polymeric materials for use in. The optical properties are examined, whereby individual ppvs exhibit similar properties regardless of the nature of the end group. This book is geared toward current supramolecular polymer researchers as well. Painting supramolecular polymers in organic solvents by super.
Supramolecular polymers elizabeth elacqua new york university, molecular design institute and department of chemistry, 100 washington square east, new york, ny 3. Despite the rapid development of complex functional supramolecular systems, visualization of these architectures under native conditions at high resolution has remained a challenging endeavor. Each of the applications mentioned above will be elaborated on in the main text. Polymer chain ends equipped with an alkyl halide enables atrp to prepare bcps through. A copolymer is a polymer derived from more than one species of monomer. Blockionomer for fuel cell application in block copolymers in nanoscience lazzari, liu and lecommendoux ed. This contribution introduces main chain supramolecular abc and abb. Click download or read online button to get introduction to polymer science and technology book now. P3htp2vp block copolymers were synthesized using anionic macroinitiation of a vinyl endfunctionalized p3ht.
Molecularrecognitiondirected formation of supramolecular polymers. The past few decades have seen a significant growth in the field of supramolecular polymerizations, in which reversible noncovalent interactions e. Supramolecular multiblock copolymers featuring complex. For the precision synthesis of the pairing precursor polymers, a set of bifunctional initiators were designed, xdadx and yaday, that consist of three hydrogen bondforming sites in series dad. Mainchain supramolecular block copolymers chemical society. Block copolymers in nanoscience massimo lazzari, guojun liu, sebastien lecommandoux this first book to take a detailed look at one of the key focal points where nanotechnology and polymers meet provides both an introductory view for beginners as well as indepth knowledge for specialists in the various research areas involved. Stuparu mc, khan a, hawker cj 2012 phase separation of supramolecular and dynamic block. Novel supramolecular block copolymer of isotactic polypropylene and ethylenecopropylene connected by complementary quadruple hydrogen bonding system.
Block copolymers are key building blocks for a variety of applications ranging from electronic devices to drug delivery. The creation of this book has been accomplished with the help of many other. The growing synergy between supramolecular chemistry and polymer synthesis is driven by the realization that the dynamic nature of noncovalent interactions may bring new properties and material performance to the field of polymer science. Hofman, gerrit ten brinke, katja loos polymer, volume 107, 19 december 2016, pages 343356. Supramolecular triblock copolymers through the formation of. The targeted assemblies, a mix of sequencedefined helixsheetcoil and helixsheethelix architectures. This site is like a library, use search box in the widget to get ebook that you want. Superresolution microscopy was recently proposed as an effective tool to unveil onedimensional nanoscale structures in aqueous media upon chemical functionalization with suitable fluorescent probes. Supramolecular xshaped homopolymers and block polymers by.
The defects formed via the growth of amorphous polymer chains hinder the alignment of the dipoles, resulting in antiferroelectriclike behavior. Painting supramolecular polymers in organic solvents by. Supramolecular selfassembly of multiblock copolymers in. Generation of a main chain supramolecular polymer by oxidative covalent polymerization of a ditopic supramolecular building block nabarun roy, eric buhler and jeanmarie lehn. The material properties of block copolymers can be tuned and potentially improved by introducing noncovalent interactions in place of covalent linkages between polymeric blocks re. Facile synthesis of welldefined block copolymers containing. Supramolecular helixhelix block copolymers macromolecules. Department of polymer science and engineering university of massachusetts amherst silvio o.
Controlled polymerization techniques in combination with supramolecular assembly are used to engineer heterotelechelic. Supramolecular polymer chemistry supramolecular chemistry. Chapter 2 block copolymers in this thesis, the lamellar orientation in thin lms of a symmetric diblock copolymer polystyrenepolymethylmethacylate psbmma under competing e ects of surface interactions and an electric eld applied perpendicular to the surfaces will be studied. The optical properties are examined, whereby individual ppvs exhibit similar. You are advised to consult the publishers version publishers pdf if you wish to. Publishers pdf, also known as version of record includes final page, issue and volume numbers. Supramolecular polymer an overview sciencedirect topics. The quasipermanent adsorption of the dye to the polymer is exploited to identify blocklike arrangements within supramolecular fibers, which were obtained upon mixing homopolymers that w. Hierarchical structure formation in supramolecular comb. Study of supramolecular sidechain copolymers containing.
Supramolecular polymers, second edition details assembly processes and structurefunction correlation in natural and synthetic selfassembling materials, focusing on developments occurred over the past five years. Lee yh1, chen wc, yang yl, chiang cj, yokozawa t, dai ca. Supramolecular networks from block copolymers based on. Um ihnen ein besseres nutzererlebnis zu bieten, verwenden wir cookies. Study of supramolecular side chain copolymers containing lightemitting hacceptors and electrontransporting dendritic hdonors pojen yang, chungwen wu, duryodhan sahu, and hongcheu lin department of materials science and engineering, national chiao tung university, hsinchu, taiwan, roc. Odians classic textbook principles of polymerization.
However, as this work is a numerical analysis, the energy minimum for the system is not found, as a result, the finer details of the selfassociation of the polymer remain unclear. Graft or grafted copolymers contain side chains or branches whose repeat units have a different composition or configuration than the main chain. Tremendous efforts have been devoted to developing novel ligands to minimize. We have recently introduced welldefined secondary structures in main chain supramolecular block copolymers and observed that the secondary structures remain intact and localized upon assembly both in solution and in the solid state. Many research groups have explored the properties and solution self. Supramolecularhybridhydrogelsfromnoncovalentlyfunctionalized. The branches are added on to a preformed main chain macromolecule. The resultant hybrid graphene inclusion complex hgic turned into supramolecular polymeric hydrogels upon heating. Supramolecular polymerizations and mainchain supramolecular.
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