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Designer supramolecular polymers are a growing field of polymer materials. The designability and flexibility in their structures and functionality have attracted a great deal of attention in polymer science, as well as in supramolecular chemistry. These polymeric structures are formed from one or more molecular components via reversible bonds; therefore, monomeric and polymeric states are in equilibrium on the relevant experimental timescale. The dynamic nature of supramolecular polymers in terms of chain lifetime and conformational flexibility are determined by external conditions. This adaptivity can result in stimuli-responsive structures and properties. This article describes the use of our host–guest structures based on a calix[5]arene, a bisporphyrin, and a self-assembled capsule in the synthesis of supramolecular polymers.
Molecular entanglements (left) divide the crystalline and amorphous phases and are similar to the linked points that cause microphase separation in block copolymer (right). Our melt-drawing technique results in periodic arrangement of these phases and replaces the conventional paradigm of “entanglement exclusion for high performance” with the novel “entanglement utilization for high functionality”. In this review, our recent developments for nanostructured membranes using block copolymers and homopolymers are compared and reviewed based on their structural similarities.
The synthesis of carboxylated IIR was achieved in high yield starting from brominated substrates, which were first converted to azides and used in the copper-catalyzed azide–alkyne Huisgen cycloaddition reaction with acetylenic acids containing different aliphatic spacer lengths. Optimization of the reaction conditions was critical to avoid the formation of gel particles in the reactions and to achieve full conversion of the bromide to carboxylate derivatives.
Poly(methyl methacrylate) smart xerogels (PAsp-xgs) crosslinked by polyaspartate side chains were synthesized and the effects of the polyaspartate helix-sense inversion on their properties were investigated. PAsp-xg was found to irreversibly shrink to a volume ratio of 0.7 when heated to ~393 K. The volume shrinkage was suggested to be induced by the helix-sense inversion of the polyaspartates in the hybrid xerogels.
Ethylene polymerization with bis(diethylamido){di(3-methylindol-2-yl)phenylmethane}titanium (1) was examined using modified methylaluminoxane (MMAO) as an activator. The activity of the 1/MMAO catalyst system was low (16.3 kg of polyethylene (PE)/mol of Ti•h), but pretreatment of 1 with ClSiMe3 followed by activation with MMAO improved the activity up to 154 kg of PE/mol of Ti•h. The obtained PEs are all monomodal by size exclusion chromatography and have linear structures by NMR spectroscopy. The 1/ClSiMe3/MMAO catalyst system was also active for ethylene/1-octene copolymerization (90 kg of copolymer/mol of Ti•h).
Solvent-free base-catalyzed CO2 fixation into polymers having 2-pyridyl group-substituted propargylamine moieties in the main and side chains was achieved under atmospheric CO2 condition. The reactivity of the polymer films was improved by the introduction of pendant tertiary amine moiety.
Epoxy resins, which are obtained by the curing reaction of epoxy- and amine-compounds mixture, have been often utilized in contact with metals. We herein report on the chemical composition of the epoxy resin in close proximity to the copper interface on the basis of a non-destructive method. The concentration of the amine component in the interfacial region was 2-fold higher than that in the bulk, and the interfacial enrichment extended over at least 10 nm.
Irrespective of the degree of polymerization, the molecular mobilities of the 2-hydroxyethyl methacrylate (HEMA) moieties are smaller than those of the 2-methoxyethyl acrylate (MEA) moieties. Preventing the polar functional groups of the foulants and materials from forming a hydrogen-bonding network is important to enhance the mobilities of the molecular chains of non-ionic polymeric materials. We speculate that enhancing the mobilities of the molecular chains is key to improving blood compatibility.
