Manning, and marcus weck macromolecules 2016 49 19, 71177128. Controlled polymerization techniques in combination with supramolecular assembly are used to engineer heterotelechelic. In particular, metallosupramolecular block copolymerscopolymers in which the blocks are linked together by a metalligand complexhave seen important progresses, allowing better control over. Supramolecular micellization of diblock copolymer mixtures. Lee yh1, chen wc, yang yl, chiang cj, yokozawa t, dai ca. Synthesis and characteristics of novel azobased diblock.
Block copolymers, which are the main subject of this paper, could be incorporated into a large range. 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. Supramolecular assemblies of block copolymers in aqueous. The optical properties are examined, whereby individual ppvs exhibit similar properties regardless of the nature of the end group. Encyclopedia of supramolecular chemistry twovolume set. Thus we have developed a ph temperaturedependent, reversible hierarchically selfassembling block copolymer system with structures spanning nano to microscale dimensions. Supramolecular alternating block copolymers via metal. Structure and composition revealed by theoretical modeling. Hydrosilylation of vinylbenzyl chloride at the two corners of a doubledecker silsesquioxane. Main chaintype block copolymers through atom transfer. This book focuses on the area of metalcontaining polymers which, based on the. Part one formation of supramolecular polymers supramolecular polymer chemistry, first edition.
Nanostructured supramolecular block copolymers based on polydimethylsiloxane and polylactide. Mainchain supramolecular block copolymers have received significant attention for their regulable and processable material properties. 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. This contribution introduces main chain supramolecular abc and abb.
Supramolecularhybridhydrogelsfromnoncovalentlyfunctionaliz. Mallapragada, department of chemical and biological engineering, iowa state university and ames laboratory. Chain architecture can have a profound effect on the appearance of the. Supramolecular alternating block copolymers via metal coordination. Phase separation of supramolecular and dynamic block. 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. Supramolecular multiblock copolymers featuring complex. 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 the book highlights developments in the synthesis of complex structures, chemical design principles, and theoretical models of growth. Polymer chain ends equipped with an alkyl halide enables atrp to prepare bcps. Supramolecular selfassembly of multiblock copolymers in.
Booth c, yu ge, nace vm 2000 block copolymers of ethylene oxide and 1,2butylene oxide. In this study, we synthesized two main chaintype block copolymers. Various kinds of amphiphilic blockcopolymers composed of a variety of hydrophilic and hydrophobic segments have so far been synthesized, and their selfassembly. Due to the extraordinary range of properties accessible, polymers have come to play an essential and ubiquitous role in everyday life from plastics and elastomers on the one hand to.
Inspired by the twodimensionality and surface chemistry of red blood cells and blood. Users may download and print one copy of any publication from the public portal for the purpose of private study or research. One of the most important technical applications of bcps is as. The solventfree microparticles contain an inner structure that corresponds to. Download citation mainchain supramolecular block copolymers block copolymers are key building blocks for a variety of applications ranging from electronic devices to drug delivery.
Mainchain supramolecular block copolymers chemical society. Massimo lazzari received his phd in macromolecular chemistry at the university of torino italy under the supervision of prof. Transcension of this structural paradigm via the formation of main chain zwitterionic supramolecular polymers could lead to readily processable, as well as selfhealing andor degradable. His main interest focuses on studying the mechanisms of supramolecular polymerizations, using chiral amplification as a tool for studying twocomponent systems. 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. Lightresponsive selfassembled materials by supramolecular postfunctionalization via hydrogen bonding of amphiphilic block copolymers. Molecularrecognitiondirected formation of supramolecular polymers. Despite this success, most polyzwitterions have nondegradable polyolefin backbones with pendant zwitterionic groups. Selfassembly of amphiphilic block copolymers in selective. Supramolecular polymer interactions based on the alternating copolymer of styrene and maleimide citation for published version apa. Block copolymers are key building blocks for a variety of applications ranging from electronic devices to drug delivery. This contribution introduces mainchain supramolecular abc and abb. Supramolecular selfassembly of multiblock copolymers. Covering features of the chemistry and physics of block copolymers that are not found in comparable texts, block copolymers illustrates the structureactivity relationship of block copolymers and offers suggestions for the design of specific applications.
Pdf research on block copolymers bcps has played a critical role in. Some of the possible copolymer architectures are shown in fig. 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. The supporting information is available free of charge on the acs. Mainchain supramolecular block copolymers researchgate. Type block copolymers through atom transfer radical. Viewing from the material design perspective, the sophistication of nature in generating materials with great precision provides opportunities to learn from in order to achieve the controlled generation of functional materials with welldefined architectures, ordered periodicity, and stability. Here we report the formation of supramolecular block copolymers by. Supramolecular block copolymers for the synthesis of higher order nanostructured assemblies.
Macro and microphase separation in block copolymer supramolecular assemblies induced by solvent annealing. Supramolecular triblock copolymers through the formation. This approach creates block copolymoc bcpmoc materials whose microscopic structures and mechanical properties are readily tunable by adjusting the size and geometry of the mocs and the composition of the bcps. Abstract the synthesis of complex architectures, namely block copolymers with tailored enduse properties, is currently an important research area in academia and industry. The aim of the thesis was the noncovalent synthesis of highly desirable supramolecular block copolymers by the approach of.
One of the most intensively studied topics in the developing field of selfassembled block copolymers is the polymeric micelles formed in aqueous media from amphiphilic block copolymers. Todemonstratethis,wesynthesized pbabps diblock copolymers endfunctionalized with a welldefined quadruple hbonding motif, 2ureido4pyrimidinone upy. Supramolecular helixhelix block copolymers anna croom, kylie b. Supramolecular interactions between certain molecules have long been recognized. Supramolecular block copolymers are becoming attractive materials in nascent.
Oh end groups were converted to moieties able to form complementary hydrogen bonds including 2,6diaminopurine, dap, thymine, thy. Block copolymer bcp selfassembly is one of the most versatile concepts for the. Polymers are huge macromolecules composed of repeating structural units. We report a stepwise assembly strategy for the integration of metalorganic cages mocs into block copolymers bcps. 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. Supramolecular block copolymers by seeded living polymerization. Userfriendly and highquality articles parse the latest supramolecular advancements and methods in the areas of chemistry, biochemistry, biology, environmental and materials science and engineering, physics, computer. In most cases, only short chains of up to about 10 units are created, whereas useful supramolecular polymers. Pmma, or pba segments using sequential free radical polymerization and atrp 30. Block copolymers containing polysilane blocks are unique in that the polysilane components possess electroactive properties and are readily photodegradable. While polymer in popular usage suggests plastic, the term actually refers to a large class of natural and synthetic materials.
Polyzwitterions have found extensive applications in biological and materials sciences. Block copolymocs by stepwise selfassembly journal of. Photoresponsive liquid crystalline block copolymers. Study of supramolecular sidechain copolymers containing. Supramolecular organization in block copolymers containing. Summary the twovolume encyclopedia of supramolecular chemistry offers authoritative, centralized information on a rapidly expanding interdisciplinary field. Complementary quadruple hydrogen bonding in supramolecular.
This first part covers newer developments in polymer synthesis, including living radical polymerization, catalytic chain transfer and freeradical ringopening polymerization, along with strategies for the synthesis of conducting polymers, dendrimers, hyperbranched polymers and block copolymers. Gebel, blockionomer for fuel cell application in block copolymers in nanoscience lazzari, liu and lecommendoux ed. 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. Alexandridis p, lindman b eds amphiphilic block copolymers. The supramolecular polymerization of macromolecular repeating units affords a novel class of materials that not only maintains attractive features. Main chaintype block copolymers through atom transfer radical polymerization from doubledeckershaped polyhedral oligomeric silsesquioxane. In the past 60 years, polymers have revolutionized.
The synthesis, selfassembly and selforganisation of. Anionic polymerization techniques were employed for the synthesis of linear polystyrene ps and block copolymer of ps and polyisoprene pi psbpi bearing end hydroxyl groups. Controlling the morphology of side chain liquid crystalline block copolymer thin films through variations in liquid crystalline content. Mainchain supramolecular block copolymers chemical. This is manifested in the area of block copolymer selfassembly where supramolecular and dynamic covalent polymers. Mainchain zwitterionic supramolecular polymers derived. Many research groups have explored the properties and solution self. Due to their broad range of properties, both synthetic and natural polymers play essential and ubiquitous roles in everyday life.
Supramolecular polymers 2nd edition alberto ciferri. Supramolecular chemistry is the domain of chemistry concerning chemical systems composed of a discrete number of molecules. The full text of this article hosted at is unavailable due to technical difficulties. Polymers range from familiar synthetic plastics such as polystyrene to natural biopolymers such as dna. Polymers free fulltext main chaintype block copolymers. Supramolecular selfassembly of multiblock copolymers in aqueous solution michael d. Pdmabpnipam, we successfully prepared block copolymer grafted graphene sheets via inclusion complexation for the. A block copolymers sustained by orthogonal metal coordination and hydrogen bonding between telechelic polymers that feature distinct secondary structure motifs.
Divided into five sectionsblock copolymers includes chapters on. Supramolecular block copolymers under thermodynamic control. Complementary quadruple hydrogen bonding in supramolecular copolymers. Selfassembly of block copolymers into internally ordered. Selfassembly supramolecular structures of block copolymer hybrid complexes.
Biography martin wolffs third from right received his m. The incorporation of supramolecular chemistry also provides a very. Hacceptor copolymers p3 and p4 were complexed with different generations of dendritic hdonors g1coohg3cooh bearing 1,3,4oxadiazole oxd dendrons and terminal benzoic acids via hbonded selfassembly to form supramolecular sidechain copolymers i. Hatada at the osaka university japan, where he learned the secrets of anionic polymerisation, in 1998 he became assistant professor at the university of torino, working on the.
Controlled polymerization techniques in combination with supramolecular assembly are used to engineer hetero. The gelation behavior depended on the structure of the block copolymers. Supramolecular organization in block copolymers containing a conjugated segment. Supramolecular conjugated block copolymers macromolecules. Overview on an open zeroemission car nissan and a schematic view of a single h2fuel cell extracted from a stack.
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