Structural water as an essential comonomer in supramolecular polymerization.
ABSTRACT: Although the concept of structural water that is bound inside hydrophobic pockets and helps to stabilize protein structures is well established, water has rarely found a similar role in supramolecular polymers. Water is often used as a solvent for supramolecular polymerization, however without taking the role of a comonomer for the supramolecular polymer structure. We report a low-molecular weight monomer whose supramolecular polymerization is triggered by the incorporation of water. The presence of water molecules as comonomers is essential to the polymerization process. The supramolecular polymeric material exhibits strong adhesion to surfaces, such as glass and paper. It can be used as a water-activated glue, which can be released at higher temperatures and reused many times without losing its performance.
Project description:A new method of supramolecular polymerization at the water-oil interface is developed. As a demonstration, an oil-soluble supramonomer containing two thiol end groups linked by two ureidopyrimidinone units and a water-soluble monomer bearing two maleimide end groups are employed. Supramolecular interfacial polymerization can be implemented by a thiol-maleimide click reaction at the water-chloroform interface to obtain supramolecular polymeric films. The glass transition temperature of such supramolecular polymers can be well-tuned by simply changing the polymerization time and temperature. It is highly anticipated that this work will provide a facile and general approach to realize control over supramolecular polymerization by transferring the preparation of supramolecular polymers from solutions to water-oil interfaces and construct supramolecular materials with well-defined properties.
Project description:Multicomponent supramolecular polymers are a versatile platform to prepare functional architectures, but a few studies have been devoted to investigate their noncovalent synthesis. Here, we study supramolecular copolymerizations by examining the mechanism and time scales associated with the incorporation of new monomers in benzene-1,3,5-tricarboxamide (BTA)-based supramolecular polymers. The BTA molecules in this study all contain three tetra(ethylene glycol) chains at the periphery for water solubility but differ in their alkyl chains that feature either 10, 12 or 13 methylene units. C10BTA does not form ordered supramolecular assemblies, whereas C12BTA and C13BTA both form high aspect ratio supramolecular polymers. First, we illustrate that C10BTA can mix into the supramolecular polymers based on either C12BTA or C13BTA by comparing the temperature response of the equilibrated mixtures to the temperature response of the individual components in water. Subsequently, we mix C10BTA with the polymers and follow the copolymerization over time with UV spectroscopy and hydrogen/deuterium exchange mass spectrometry experiments. Interestingly, the time scales obtained in both experiments reveal significant differences in the rates of copolymerization. Coarse-grained simulations are used to study the incorporation pathway and kinetics of the C10BTA monomers into the different polymers. The results demonstrate that the kinetic stability of the host supramolecular polymer controls the rate at which new monomers can enter the existing supramolecular polymers.
Project description:Considerable progress in platinum metallacycle-based supramolecular polymerization has promoted the fabrication and application of supramolecular materials. However, despite recent advances, supramolecular polymers constructed through platinum metallacycle-based host-guest complexation remain rare because of the dynamics of platinum metallacycles. Here, we achieve linear supramolecular polymerization via platinum metallacycle-based host-guest complexation by following the design rule of suppressing the dynamics of the metallacycles. The establishment of the platinum metallacycle-based host-guest system and the realization of this type of supramolecular polymerization are expected to open opportunities for platinum metallacycle-based functional materials.
Project description:In recent years, the development of sophisticated analytical tools, kinetic models and sample preparation methods has significantly advanced the field of supramolecular polymerization, where the competition of kinetic vs. thermodynamic processes has become commonplace for a wide range of building blocks. Typically, the kinetic pathways are identified in thermally controlled assembly experiments before they ultimately evolve to the thermodynamic minimum. However, there might be cases where the identification and thus the assessment of the influence of kinetic aggregates is not trivial, making the analysis of the self-assembly processes a hard task. Herein, we demonstrate that "hidden" kinetic pathways can have drastic consequences on supramolecular polymerization processes, to the point that they can even overrule thermodynamic implications. To this end, we analyzed in detail the supramolecular polymerization of a chiral PdII complex 1 that forms two competing aggregates (Agg I and Agg II) of which kinetic Agg II is formed through a "hidden" pathway, i.e. this pathway is not accessible by common thermal polymerization protocols. The hidden pathway exhibits two consecutive steps: first, Agg II is formed in a cooperative process, which subsequently evolves to clustered superstructures driven by rapid kinetics. At standard conditions, Agg II displays an extraordinary kinetic stability (>6 months), which could be correlated to its cooperative mechanism suppressing nucleation of thermodynamic Agg I. Furthermore, the fast kinetics of cluster formation sequester monomers from the equilibria in solution and prevents the system from relaxing into the thermodynamic minimum, thus highlighting the key implications of hidden pathways in governing supramolecular polymerization processes.
Project description:The "comonomer effect" is an intriguing kinetic phenomenon in olefin copolymerization that still remains without a detailed explanation. It typically relates to the rate of enhancement undergone in ethylene and propene catalytic polymerization just by adding small fractions of an alpha-olefin. The difficulty lies in the fact that changes caused by the presence of the comonomer in reaction parameters are so conspicuous that it is really difficult to pin down which of them is the primary cause and which ones are side factors with marginal contribution to the phenomenon. Recent investigations point to the modification of the catalyst active sites as the main driving factor. In this work, the comonomer effect in the metallocene copolymerization of propene and 1-nonene is analysed and correlated to the comonomer role in the termination of the chain-growing process. The associated termination mechanisms involved furnish most of chain-free active sites, in which the selective interaction of the comonomer was proposed to trigger the insertion of monomers. A thorough characterisation of chain-end groups by means of the 1H NMR technique allows for detailing of specific transfer processes, ascribed to comonomer insertions, as well as evidencing the influence of the growing chain's microstructure over the different termination processes available.
Project description:Although living supramolecular polymerization (LSP) has recently been realized, the scope of the monomer structures applicable to the existing methods is still limited. For instance, a monomer that spontaneously nucleates itself cannot be processed in a manner consistent with LSP. Herein, we report a new method for such a "reactive" monomer. We use a 'dummy' monomer which has a similar structure to the reactive monomer but is incapable of one-dimensional supramolecular polymerization. We show that in the presence of the dummy monomer, the reactive monomer is kinetically trapped in the dormant state. In this way, spontaneous nucleation of the reactive monomer is retarded; yet, addition of seeds of a supramolecular polymer can initiate the supramolecular polymerization in a chain growth manner. As a result, we obtain the supramolecular polymer of the reactive monomer with a controlled length, which is otherwise thermodynamically inaccessible. We believe that this concept will expand the scope of LSP for the synthesis of other functional supramolecular polymers, and thus lead to a variety of applications.
Project description:A carboxylic acid appended naphthalene-diimide (NDI) derivative spontaneously aggregates in decane to generate a kinetically controlled product with irregular fibrillar morphology. By fine-tuning the sample preparation conditions, the carboxylic acid group can be trapped by intra-molecular H-bonds with the adjacent imide carbonyl, which retards the spontaneous aggregation. In the presence of a catalytic amount of a non-nucleophilic organic base (DBU or DMAP), the meta-stable monomer exhibits supramolecular polymerization through a thermodynamically controlled pathway involving simultaneous H-bonding and π-stacking and generates ultra-thin 2D nano-sheets. DMAP/DBU helps in ring-opening of the intra-molecularly H-bonded monomer and in situ breeds the free acid, which, beyond a critical concentration, initiates controlled supramolecular ring opening polymerization (SROP) via the chain-growth mechanism. The 2D polymer acts as a macro-initiator for subsequent two cycles of SROP and produces laterally extended ultra-thin nano-sheets.
Project description:The synthesis and supramolecular polymerization of a ureidopyrimidinone-based Sauvage-type catenane is reported. The monomer synthesis explores many routes using the elegant metathesis catalysts of Bob Grubbs, yielding a catenane with one ureidopyrimidinone in each cycle. The supramolecular polymer obtained features both mechanical bonds and quadruple hydrogen bonding connections.
Project description:Surface-initiated controlled radical polymerization is a popular technique for the modification of biomaterials with, for example, antifouling polymers. Here, we report on the functionalization of a supramolecular biomaterial with zwitterionic poly(sulfobetaine methacrylate) via atom transfer radical polymerization from a macroinitiator additive, which is embedded in the hard phase of the ureido-pyrimidinone-based material. Poly(sulfobetaine methacrylate) was successfully polymerized from these surfaces, and the polymerized sulfobetaine content, with corresponding antifouling properties, depended on both the macroinitiator additive concentration and polymerization time. Furthermore, the polymerization from the macroinitiator additive was successfully translated to functional electrospun scaffolds, showing the potential for this functionalization strategy in supramolecular material systems.
Project description:A versatile, bottom-up approach allows the controlled fabrication of polydopamine (PD) nanostructures on DNA origami. PD is a biosynthetic polymer that has been investigated as an adhesive and promising surface coating material. However, the control of dopamine polymerization is challenged by the multistage-mediated reaction mechanism and diverse chemical structures in PD. DNA origami decorated with multiple horseradish peroxidase-mimicking DNAzyme motifs was used to control the shape and size of PD formation with nanometer resolution. These fabricated PD nanostructures can serve as "supramolecular glue" for controlling DNA origami conformations. Facile liberation of the PD nanostructures from the DNA origami templates has been achieved in acidic medium. This presented DNA origami-controlled polymerization of a highly crosslinked polymer provides a unique access towards anisotropic PD architectures with distinct shapes that were retained even in the absence of the DNA origami template.