Supramolecular Polymer Assemblies Research Articles

Boron-Nitrogen Lewis Pairs in the Assembly of Supramolecular Macrocycles, Molecular Cages, Polymers, and 3D Materials.

Covering an exceptionally wide range of bond strengths, the dynamic nature and facile tunability of dative B-N bonds is highly attractive when it comes to the assembly of supramolecular polymers and materials. This Minireview offers an overview of advances in the development of functional materials where Lewis pairs (LPs) play a key role in their assembly and critically influence their properties. Specifically, we describe the reversible assembly of linear polymers with interesting optical, electronic and catalytic properties, discrete macrocycles and molecular cages that take up diverse guest molecules and undergo structural changes triggered by external stimuli, covalent organic frameworks (COFs) with intriguing interlocked structures that can embed and separate gases such as CO2 and acetylene, and soft polymer networks that serve as recyclable, self-healing, and responsive thermosets, gels and elastomeric materials.

Boron‐Nitrogen Lewis Pairs in the Assembly of Supramolecular Macrocycles, Molecular Cages, Polymers, and 3D Materials

AbstractCovering an exceptionally wide range of bond strengths, the dynamic nature and facile tunability of dative B−N bonds is highly attractive when it comes to the assembly of supramolecular polymers and materials. This Minireview offers an overview of advances in the development of functional materials where Lewis pairs (LPs) play a key role in their assembly and critically influence their properties. Specifically, we describe the reversible assembly of linear polymers with interesting optical, electronic and catalytic properties, discrete macrocycles and molecular cages that take up diverse guest molecules and undergo structural changes triggered by external stimuli, covalent organic frameworks (COFs) with intriguing interlocked structures that can embed and separate gases such as CO2 and acetylene, and soft polymer networks that serve as recyclable, self‐healing, and responsive thermosets, gels and elastomeric materials.

Simulating Assembly Landscapes for Comprehensive Understanding of Supramolecular Polymer-Solvent Systems.

Complexity in supramolecular polymer systems arises from interactions between different components, including solvent molecules. By varying their concentration or temperature in such multicomponent systems, complex phenomena can occur such as thermally bisignate and dilution-induced assembly of supramolecular polymers. Herein, we demonstrate that both these phenomena emerge from the same underlying interaction mechanism between the components. As a model system, amide-decorated supramolecular polymers of porphyrins were investigated in combination with aliphatic alcohols as hydrogen-bond scavengers, and thermodynamic mass-balance models were applied to map the three-dimensional assembly landscapes. These studies unveiled that the interaction between hydrogen-bond scavengers and monomers is temperature-dependent and becomes dominant at high monomer concentrations. With these insights, we could exploit competitive monomer-alcohol interactions to prompt the dilution-induced assembly of various common monomers as well as bisignate assembly events. Moreover, kinetic insights were obtained by navigating through the assembly landscape. Similar to phase diagrams of covalent polymers, these assembly landscapes provide a comprehensive picture of supramolecular polymerizations, which helps to precisely regulate the system properties. The generality of this approach using assembly landscapes makes it relevant for any supramolecular system, and this enhanced control will open the door to build complex and functional supramolecular polymer systems.

Multistep sequence-controlled supramolecular polymerization by the combination of multiple self-assembly motifs

The precise sequence control of polymer chain is an important research topic of polymer chemistry. Although some methods such as iterative synthesis and supramolecular polymerization have been developed to fabricate sequence-controllable polymer, it is still a great challenge to consecutively prepare multiple supramolecular polymers with different sequence structures. In this work, through the reasonable utilization of assembly motifs, we integrated multiple host-guest recognitions and metal coordination interactions to prepare different sequence-controlled supramolecular polymers by a multistep assembly strategy. This research provides inspiration for the design and preparation of supramolecular polymers with different sequence structures.

Luminescence Sensing of Biomacromolecules Heparin and Protamine in 100% Human Serum and Plasma by Supramolecular Polymeric Assemblies.

Heparin, an anionic biomacromolecule, is routinely used as an anticoagulant during medical surgery to prevent blood clot formation and in the treatment of several heart, lung, and circulatory disorders having a higher risk of blood clotting. We herein report supramolecular polymeric nanoassemblies of cationic pyrene-tagged bis-imidazolium amphiphiles for heparin detection with high sensitivity and selectivity in aqueous buffer, plasma, and serum media. The nano-assemblies exhibited cyan-green excimeric emission in aqueous media, and their multivalent array of positive surface charges allowed them to form co-assemblies with heparin, resulting in significantly enhanced emission. This provided a convenient method for heparin detection in buffer at nanomolar concentrations, and most notably, a ratiometric fluorescence response was obtained even in highly competitive 100% human serum and 100% human plasma in a clinically relevant concentration range. Moreover, using the heparin-based luminescent co-assemblies, protamine sulfate, a clinically administered antidote to heparin, was also detected in 100% human serum and 100% human plasma at sub-micromolar concentrations.

Modelling the effect of hydrogen bonding on elongational flow of supramolecular polymer melts

Hydrogen bonding is the most common noncovalent reversible interaction leading to supramolecular polymeric assemblies. Shabbir et al. (Macromolecules 48:5988–5996, 2015) reported both linear and nonlinear rheological data for a model system consisting of pure poly(n-butyl acrylate) (PnBA) homopolymer and three PnBA-poly(acrylic acid) (PnBA-PAA) copolymers with different numbers of acrylic acid (AA) side groups. Hydrogen bonds between the AA groups not only cause the storage and loss modulus to shift in the direction of a power law scaling of 0.5 in the terminal relaxation regime, but also the elongational viscosity shows increasing strain hardening with a strongly nonlinear dependence on the number of hydrogen bonding groups. Based on the “Sticky Rouse” model and a constitutive equation of the Doi-Edwards type with consideration of chain stretch, we model the effect of hydrogen bonding on the elongational viscosity of the PnBA-AA copolymers. We show that the elongational viscosity data are consistent with a Sticky Rouse relaxation modulus of the AA associations characterized by a constant modulus G_{A} and a constant sticker life time tau_{A}, while the complexity of the hydrogen assemblies as quantified by the Sticky Rouse time increases with the concentration of AA groups from the order of seconds (3% AA) to hours (6%AA) and to 1 day (13%AA), and leads to extreme strain hardening. The elongational stress shows a steady state at large strains and the stretch reaches a limiting value independent of strain rate. At the highest concentration of AA groups investigated (38%AA), the PnBA-AA copolymer is a weak gel fracturing at a critical strain, and the sticker life time loses its significance. The effect of the Sticky Rouse time on self-healing is discussed.

Assembly and functionalization of supramolecular polymers from DNA-conjugated squaraine oligomers.

DNA conjugated oligomers of organic molecules are candidates for applications in the materials and medical sciences, in diagnostics, in optical devices, for delivery or for the design of complex molecular architectures. Herein, we describe the synthesis and properties of DNA-conjugated squaraine (Sq) oligomers. The oligomers self-assemble into supramolecular polymers that are amenable to further functionalization via DNA hybridization, as shown by the attachment of gold nanoparticles (AuNPs).

Visible light mediated BODIPY/Azo/cyclodextrin based supramolecular polymer assemblies in different water content solutions

A novel visible light responsive supramolecular polymer based on oligo(ethylene glycol) modified BODIPY (BDP), tetramethoxyazobenzene (Azo) and dimeric β-cyclodextrin (β-CD-C) was reported.

Tuning the life-time of supramolecular hydrogels using ROS-responsive telechelic peptide-polymer conjugates

The synthesis of multi-stimuli responsive peptide-poly(ethylene glycol) ABA-type conjugates is reported. The β-sheet encoded intramolecular folding and intermolecular self-assembly into 1D nanorods is based on a phenylalanine(F)-methionine(M)-histidine(H) FMHMHF hexapeptide sequence, and the supramolecular nanorods are stabilised by a shielding corona of hydrophilic PEG polymers. Interstrand crosslinking leads to the formation of physical networks and hydrogels at physiological pH and at room temperature. The thioether functional groups integrate oxidation responsive properties in the supramolecular polymer assemblies. We show that the glucose fuelled and glucose oxidase catalysed production of the reactive oxygen species (ROS) leads to transiently stable supramolecular hydrogels that operate in a fully autonomous reaction set-up, with a tuneable gelation life-times of 1–12 h. ROS play an important role in signalling cascades and inflammation processes. We are therefore particularly interested in further developing our strategy for the design of biomaterials for applications in redox microenvironments.

Supramolecular Polymeric Assemblies for the Selective Depletion of Abundant Acidic Proteins in Serum.

The analysis of low-level protein biomarkers in serum is precluded by the presence of other highly abundant serum proteins. Hence, the preliminary removal of serum albumin along with other abundant proteins in serum (i.e., immunoglobulins, transferrin, haptoglobin, α-2-macroglobulin, and apolipoproteins) is often a requirement prior to any biomarker analysis. In this work, we take advantage of the low isoelectric points (pI's) of these highly abundant proteins to selectively deplete them from serum by extraction using functionalized amphiphilic polymeric nanoassemblies. The selectivity of extraction is dependent on the pI of the protein and the extraction pH, which holds true even for extremely complex protein mixtures like serum. High extraction capacity is achieved by optimizing the extraction conditions and is found to be comparable to currently available methods for depletion. Depletion of these abundant acidic proteins allows for the enhanced detection of higher pI proteins and enables a 3 orders of magnitude increase in detection sensitivity for a putative cancer biomarker, demonstrating the utility of these polymeric assemblies for enhancing the analysis of the serum proteome.

Controlled Formation of a Main Chain Supramolecular Polymer Based on Metal-Ligand Interactions and a Thiol-Ene Click Reaction.

Supramolecular polymers with multiple functionalities and hierarchical structures have received considerable attention and become a hot research topic over the past years. Herein, a main-chain supramolecular polymer has been successfully fabricated by using metal-ligand interactions and a thiol-ene click reaction. 1 H NMR, UV/Vis, DOSY, and viscosity measurements were carried out to investigate the molecular recognition and the process of supramolecular polymerization. From the study, the orthogonality between thiol-ene click reactions and the terpyridine-metal ions complexation behavior was testified, and supramolecular polymeric assemblies could be constructed by a one pot method. In the meantime, due to the incorporation of metal-ligand interactions, the supramolecular polymer shows stimuli-responsive properties toward chemical stimuli. Hence, this work could provide a methodology for developing supramolecular polymers as smart materials.

Formation of Supramolecular Nanotubes by Self-assembly of a Phosphate-linked Dimeric Anthracene in Water.

The assembly of supramolecular polymers from a phosphodiester-linked dimeric anthracene is described. AFM and TEM imaging reveals that the supramolecular polymers self-assemble into nanotubes in water. Subsequent photodimerization experiments indicate that the supramolecular polymerization occurs via end-to-end stacking rather than an interdigitation arrangement of the building blocks.

Smart fluorescent AIEE active supramolecular polymeric assemblies for selective and quantitative detection of fluoride ions in aqueous media

Abstract A fibrous network of AIEE active polyamine derivative 2 has been developed which exhibits living self-assembly in mixed aqueous media accompanied by solvent dependent morphology transformation. Further, the supramolecular assemblies of polyamine derivative 2 in presence of fluoride ions undergo rigidification to generate highly fluorescent supramolecular polyamine ensemble 2:F−. The mechanism of self-aggregation and fluoride induced aggregation is theoretically and experimentally proved. Additionally, electron rich supramolecular polyamine ensemble 2:F− was utilized for the detection of picric acid with detection limit of 15 ppb.

Supramolecular Porphyrin Copolymer Formed Via Competitive Host-Guest Interaction

Polymer properties are directly associated with their primary structures. Control of monomer sequences in polymer sequences is a crucial topic in modern polymer chemistry. Therefore, reorganization of polymer sequences can regulate polymer properties. Sequence reorganization of supramolecular homopolymers to alternating polymers can be realized via competitive guest complexation. We have reported that self-assembly of tetrakisporphyrin 1 produced the supramolecular polymeric assemblies that was dissociated via competitive complexation of trinitrofluorenone (TNF). Employing bis(trinitrofluorenone) 2 instead of TNF as a guest resulted in sequence reorganization of homopolymers (1)n to alternating copolymers (1•2)n. The supramolecular polymerization of (1•2)n was discussed using diffusion-ordered NMR technique, suggesting that large polymeric assemblies were formed with the alternating structures. Solution viscometry of (1)n and (1•2)n demonstrated quite contrastive behaviors. (1•2)n formed entangled solution, whereas (1)n behaved like a rigid rod in solution. Figure 1

Novel rare earth fluorescent supramolecular polymeric assemblies constructed by orthogonal pillar[5]arene-based molecular recognition, Eu(iii)-coordination and π-π donor-acceptor interactions.

Here, a facile strategy is provided to prepare pillar[5]arene-based fluorescent supramolecular polymer assemblies by orthogonal Eu(iii)-coordination and two non-interfering noncovalent interactions.

ChemInform Abstract: Bioinspired Polymer Vesicles and Membranes for Biological and Medical Applications

AbstractReview: 293 refs.

ChemInform Abstract: Supramolecular Polymerization Engineered with Molecular Recognition

AbstractReview: [54 refs.

Supramolecular Polymerization Engineered with Molecular Recognition.

Supramolecular polymeric assemblies represent an emerging, promising class of molecular assemblies with enormous versatility compared with their covalent polymeric counterparts. Although a large number of host-guest motifs have been produced over the history of supramolecular chemistry, only a limited number of recognition motifs have been utilized as supramolecular connections in polymeric assemblies. This account describes the molecular recognition of host molecules based on calix[5]arene and bisporphyrin that demonstrate unique guest encapsulations; subsequently, these host-guest motifs are applied to the synthesis of supramolecular polymers that display polymer-like properties in solution and solid states. In addition, new bisresorcinarenes are developed to form supramolecular polymers that are connected via a rim-to-rim hydrogen-bonded dimeric structure, which is composed of two resorcinarene moieties.

Formation of fluorescent supramolecular polymeric assemblies via orthogonal pillar[5]arene-based molecular recognition and metal ion coordination.

A fluorescent supramolecular polymer was efficiently constructed by pillar[5]arene-based host-guest molecular recognition and zinc ion coordination.

Molecular design of a discrete chain-folding polyimide for controlled inkjet deposition of supramolecular polymers

Herein we describe the generation of a well-defined polyimide to afford coloured supramolecular polymer assemblies with electronically complementary pyrenyl terminated polymers which can be inkjet printed.