Hydrogen-bonded Supramolecular Polymers Research Articles

Visible-Light Driven Control Over Triply and Quadruply Hydrogen-Bonded Supramolecular Assemblies.

Supramolecular polymers offer tremendous potential to produce new "smart" materials, however, there remains a need to develop systems that are responsive to external stimuli. In this work, visible-light responsive hydrogen-bonded supramolecular polymers comprising photoresponsive supramolecular synthons (I-III) consisting of two hydrogen bonding motifs (HBMs) connected by a central ortho-tetrafluorinated azobenzene have been characterized by DOSY NMR and viscometry. Comparison of different hydrogen-bonding motifs reveals that assembly in the low and high concentration regimes is strongly influenced by the strength of association between the HBMs. I, Incorporating a triply hydrogen-bonded heterodimer, was found to exhibit concentration dependent switching between a monomeric pseudo-cycle and supramolecular oligomer through intermolecular hydrogen bonding interactions between the HBMs. II, Based on the same photoresponsive scaffold, and incorporating a quadruply hydrogen-bonded homodimer was found to form a supramolecular polymer which was dependent upon the ring-chain equilibrium and thus dependent upon both concentration and photochemical stimulus. Finally, III, incorporating a quadruply hydrogen-bonded heterodimer represents the first photoswitchable AB type hydrogen-bonded supramolecular polymer. Depending on the concentration and photostationary state, four different assemblies dominate for both monomers II and III, demonstrating the ability to control supramolecular assembly and physical properties triggered by light.

Chalcogen Atom Size Dictates Stability of Benzene-1,3,5-triamide Polymers: Overlooked Role of Geometrical Fit for Enhanced Hydrogen Bonding.

Our quantum chemical analyses elucidated how the replacement of O in the amide bonds of benzene-1,3-5-tricarboxamides (OBTAs) with the larger chalcogens S and Se enhances the intermolecular interactions and thereby the stability of the obtained hydrogen-bonded supramolecular polymers due to two unexpected reasons: i) the SBTA and SeBTA monomers have a better geometry for self-assembly and ii) induce stronger covalent (hydrogen-bond) interactions besides enhanced dispersion interactions. In addition, it is shown that the cooperativity in benzene-1,3,5-triamide (BTA) self-assembly is caused by charge separation in the σ-electronic system following the covalency in the hydrogen bonds.

Conductive Supramolecular Polymer Nanocomposites with Tunable Properties to Manipulate Cell Growth and Functions.

Synthetic bioactive nanocomposites show great promise in biomedicine for use in tissue growth, wound healing and the potential for bioengineered skin substitutes. Hydrogen-bonded supramolecular polymers (3A-PCL) can be combined with graphite crystals to form graphite/3A-PCL composites with tunable physical properties. When used as a bioactive substrate for cell culture, graphite/3A-PCL composites have an extremely low cytotoxic activity on normal cells and a high structural stability in a medium with red blood cells. A series of in vitro studies demonstrated that the resulting composite substrates can efficiently interact with cell surfaces to promote the adhesion, migration, and proliferation of adherent cells, as well as rapid wound healing ability at the damaged cellular surface. Importantly, placing these substrates under an indirect current electric field at only 0.1 V leads to a marked acceleration in cell growth, a significant increase in total cell numbers, and a remarkable alteration in cell morphology. These results reveal a newly created system with great potential to provide an efficient route for the development of multifunctional bioactive substrates with unique electro-responsiveness to manipulate cell growth and functions.

Supramolecular Helical Miktoarm Star Polymers

We report a hydrogen-bonded supramolecular miktoarm star polymer containing three distinct helical arms. Our design involves two helical poly(methacrylamide) arms connected by a barbituric acid (Ba) at the center, prepared through the reversible addition-fragmentation chain-transfer polymerization with a bifunctional agent. Together with a telechelic helical poly(isocyanide) end-functionalized with a Hamilton Wedge (HW) that is complementary to Ba, the two components assemble into an AB2-type star copolymer. The assembly is driven by the hydrogen bonding between HW and Ba, which is quantified by 1H NMR titration and isothermal titration calorimetry. Gel-permeation chromatography provides evidence for the formation of the desired miktoarm star architecture. This strategy of site-specific functionalization on helical polymers provides a modular approach to preparing nonlinear supramolecular ensembles with topologically diverse building blocks.

Hydrogen-bonded supramolecular polymer micelles with pH/photothermal-responsive carmofur release and combined chemo-photothermal therapy

This work targets the construction of hydrogen-bonded (H-bonded) supramolecular polymeric micelles loaded with chemotherapy drugs (carmofur) and photothermal agents (IR780) for combined chemo-photothermal therapies (CT/PTT).

Hydrogen-Bonded Supramolecular Liquid Crystal Polymers: Smart Materials with Stimuli-Responsive, Self-Healing, and Recyclable Properties.

Hydrogen-bonded liquid crystalline polymers have emerged as promising “smart” supramolecular functional materials with stimuli-responsive, self-healing, and recyclable properties. The hydrogen bonds can either be used as chemically responsive (i.e., pH-responsive) or as dynamic structural (i.e., temperature-responsive) moieties. Responsiveness can be manifested as changes in shape, color, or porosity and as selective binding. The liquid crystalline self-organization gives the materials their unique responsive nanostructures. Typically, the materials used for actuators or optical materials are constructed using linear calamitic (rod-shaped) hydrogen-bonded complexes, while nanoporous materials are constructed from either calamitic or discotic (disk-shaped) complexes. The dynamic structural character of the hydrogen bond moieties can be used to construct self-healing and recyclable supramolecular materials. In this review, recent findings are summarized, and potential future applications are discussed.

An Ultrasoft Self-Fused Supramolecular Polymer Hydrogel for Completely Preventing Postoperative Tissue Adhesion.

The intermolecular H-bonding density heavily influences the gelation and rheological behavior of hydrogen-bonded supramolecular polymer hydrogels, thus offering a delicate pathway to tailor their physicochemical properties for meeting a specific biomedical application. Herein, one methylene spacer between two amides in the side chain of N-acryloyl glycinamide (NAGA) is introduced to generate a variant monomer, N-acryloyl alaninamide (NAAA). Polymerization of NAAA in aqueous solution affords an unprecedented ultrasoft and highly swollen supramolecular polymer hydrogel due to weakened H-bonds caused by an extra methylene spacer, which is verified by variable-temperature Fourier transform infrared (FTIR) spectroscopy and simulation calculation. Intriguingly, poly(N-acryloyl alaninamide) (PNAAA) hydrogel can be tuned to form a transient network with a self-fused and excellent antifouling capability that results from the weakened dual amide H-bonding interactions and enhanced water-amide H-bonding interactions. This self-fused PNAAA hydrogel can completely inhibit postoperative abdominal adhesion and recurrent adhesion after adhesiolysis in vivo. This transient hydrogel network allows for its disintegration and excretion from the body. The molecular mechanism studies reveal the signal pathway of PNAAA hydrogel in inhibiting inflammatory response and regulating fibrinolytic system balance. This self-fused, antifouling ultrasoft supramolecular hydrogel is promising as a barrier biomaterial for completely preventing postoperative tissue adhesion.

How Water in Aliphatic Solvents Directs the Interference of Chemical Reactivity in a Supramolecular System.

Water is typically considered to be insoluble in alkanes. Recently, however, monomerically dissolved water in alkanes has been shown to dramatically impact the structure of hydrogen-bonded supramolecular polymers. Here, we report that water in methylcyclohexane (MCH) also determines the outcome of combining a Michael reaction with a porphyrin-based supramolecular system. In dry conditions, the components of the reaction do not affect or destabilize the supramolecular polymer, whereas in ambient or wet conditions the polymers are rapidly destabilized. Although spectroscopic investigations show no effect of water on the molecular structure of the supramolecular polymer, light scattering and atomic force microscopy experiments show that water increases the flexibility of the supramolecular polymer and decreases the polymer length. Through a series of titrations, we show that a cooperative interaction, involving the coordination of the amine catalyst to the porphyrin and complexation of the substrates to the flexible polymers invokes the depolymerization of the aggregates. Water crucially stabilizes these cooperative interactions to cause complete depolymerization in humid conditions. Additionally, we show that the humidity-controlled interference in the polymer stability occurs with various substrates, indicating that water may play a ubiquitous role in supramolecular polymerizations in oils. By controlling the amount of water, the influence of a covalent chemical process on noncovalent aggregates can be mediated, which holds great potential to forge a connection between chemical reactivity and supramolecular material structure. Moreover, our findings highlight that understanding cooperative interactions in multicomponent noncovalent systems is crucial to design complex molecular systems.

Push-pull ligands and the oxidation of monomethylplatinum(II) complexes with oxygen or hydrogen peroxide

A rare example of the oxidation of a monomethylplatinum(II) complex with dioxygen is reported, aided by an appended phenol group. The ligands X-2-HO-C6H3CH2N(CH2-2-C5H4N)2 (L1, X = H; L2, X = 5-Cl; L3, X = 5-NO2; L4, X = 4-Me) react with [PtClMe(SMe2)2] to give the corresponding complexes [PtMe(κ3-N,N’,N’’-L)]Cl in which L acts as a tridentate pincer ligand, binding through all three nitrogen donors with the phenol group not coordinated. When L = L1 – L3, the complexes react rapidly with hydrogen peroxide and slowly with dioxygen from air to give the corresponding platinum(IV) complexes [Pt(OH)Me(κ4-N,N’,N”,O-L-H)]Cl, in which the deprotonated phenol group is coordinated trans to the hydroxo ligand. The structures of three of these complexes are determined and all are shown to self-assemble with water molecules to form hydrogen-bonded supramolecular polymers. The mechanisms of the oxidation reactions are discussed.

Hydrogen-bonded supramolecular micelle-mediated drug delivery enhances the efficacy and safety of cancer chemotherapy

Multiple hydrogen-bonded supramolecular polymers tend to form stable spherical micelles with oppositely charged anticancer drugs in biological environments, which improves cellular drug uptake and more effectively induces apoptosis in cancer cells.

Addition to “Dominance of Chain Entanglement over Transient Sticking on Chain Dynamics in Hydrogen-Bonded Supramolecular Polymer Networks in the Melt”

Addition to “Dominance of Chain Entanglement over Transient Sticking on Chain Dynamics in Hydrogen-Bonded Supramolecular Polymer Networks in the Melt”

3D Printing of Supramolecular Polymers: Impact of Nanoparticles and Phase Separation on Printability.

3D printing of linear and three-arm star supramolecular polymers with attached hydrogen bonds and their nanocomposites is reported. The concept is based on hydrogen-bonded supramolecular polymers, known to form nano-sized micellar clusters. Printability is based on reversible thermal- and shear-induced dissociation of a supramolecular polymer network, which generates stable and self-supported structures after printing, as checked via melt-rheology and X-ray scattering. The linear and three-arm star poly(isobutylene)s PIB-B2 (Mn = 8500 g mol -1 ), PIB-B3 (Mn = 16 000 g mol -1 ), and linear poly(ethylene glycol)s PEG-B2 (Mn = 900 g mol-1 , 8500 g mol -1 ) are prepared and then probed by melt-rheology to adjust the viscosity to address the proper printing window. The supramolecular PIB polymers show a rubber-like behavior and are able to form self-supported 3D printed objects at room temperature and below, reaching polymer strand diameters down to 200-300 µm. Nanocomposites of PIB-B2 with silica nanoparticles (12 nm, 5-15 wt%) are generated, in turn leading to an improvement of their shape persistence. A blend of the linear polymer PIB-B2 and the three-arm star polymer PIB-B3 (ratio ≈ 3/1 mol) reaches an even higher structural stability, able to build free-standing structures.

Fast photoinduced deformation of hydrogen-bonded supramolecular polymers containing α-cyanostilbene derivative

This is the first example of photoinduced deformation displayed by α-cyanostilbene-based supramolecular polymers.

Supramolecular Fluorescent Polymers Containing α-Cyanostilbene-Based Stereoisomers: Z/E-Isomerization Induced Multiple Reversible Switching

Photoresponsive materials play an important role in smart sensors and readable optical devices. The α-cyanostilbene moiety gathers Z/E-isomerization, mesogenic, and aggregation-induced enhanced emission (AIEE) properties together and can be considered as a multifunctional building block bearing luminogen, AIEgen, mesogen, and chromphore characteristics. Here, we report isomerization induced a series of notable reversible switching based on α-cyanostilbene containing hydrogen-bonded supramolecular polymers. Z- and E-stereoisomers of dendritic α-cyanostilbene derivatives (Z-CNBP and E-CNBP) were hydrogen-bonded with poly(4-vinylpyridine) (P4VP), giving rise to P4VP(Z-CNBP)x and P4VP(E-CNBP)x. P4VP(Z-CNBP)x exhibit a hexagonal columnar (Φh) phase at 0.4 ≤ x ≤ 1.0, while the lamellar phase could be formed for P4VP(E-CNBP)x at 0.3 ≤ x ≤ 0.7. P4VP(Z-CNBP)0.8 shows photothermal E/Z-isomerization induced reversible switching, including phase structures, surface topographies, birefringence, and fluorescence proper...

Photoresponsive supramolecular polymers based on quadruple hydrogen-bonding and a photochromic azobenzene motif

A photoresponsive quadruple hydrogen-bonded supramolecular polymer was constructed using photochromic azobenzene and ureidopyrimidinone motifs.

Unexpected Solvent Influence on the Rheology of Supramolecular Polymers

A very limited change in the nature of the solvent (toluene versus pentylbenzene) can have an unexpectedly strong effect on the viscosity of a hydrogen-bonded supramolecular polymer. In pentylbenzene, slightly stronger hydrogen bonds are formed than in toluene, but the supramolecular polymer solution is ca. 25 times less viscous. Several hypotheses can be envisaged to explain this counterintuitive result. We propose that this effect is actually related to a solvation effect involving the outer corona of the supramolecular objects. When the cohesive energy density of the solvent approaches the cohesive energy density of the outer corona of the supramolecular objects, the viscosity of solution is reduced, possibly because of faster local dynamics.

Visible-light responsive hydrogen-bonded supramolecular polymers based on ortho-tetrafluorinated azobenzene

Visible-light responsive hydrogen-bonded supramolecular polymers have been fabricated, whose properties could be regulated through the visible-light-triggered photoisomerization of the ortho-tetrafluorinated azobenzene.

A Phosphorescent Platinum(II) Bipyridyl Supramolecular Polymer Based on Quadruple Hydrogen Bonds.

A platinum(II) bipyridyl complex bearing bis-ureidopyrimidinone (Pt-bisUPy) has been designed and its self-assembling behavior has been thoroughly investigated by 1 H NMR, DOSY NMR, Ubbelohde viscometry analysis, UV/Vis, and emission spectroscopies. Pt-bisUPy underwent concentration-dependent ring-chain polymerization in apolar solvents. Hydrogen-bonding interactions play an important role during the formation of the supramolecular polymers. Hydrogen-bonded supramolecular polymers were transformed to nanoparticles in water through the miniemulsion method. These nanoparticles showed strong π-π excimeric emission. Metal-metal-to-ligand charge transfer (MMLCT) from Pt-Pt interactions was not significant in the emission spectrum. The phosphorescence of the nanoparticle persisted even under aerobic conditions. The triplet state of these phosphorescent nanomaterials were long-lived and possessed moderate emission quantum yields. Furthermore, the low toxicity of these materials promises a place for them in in vitro and in vivo bioimaging.

High impact resistance epoxy resins by incorporation of quadruply hydrogen bonded supramolecular polymers

A bisphenol A based epoxy was incorporated with a quadruply hydrogen bonded supramolecular polymer as a toughening agent to prepare a composite epoxy resin with higher impact resistance. The supramolecular polymer comprising poly-(propylene glycol) bis(2-aminopropyl) ether chains and 2-ureido-4[1H]-pyrimidinone moieties (UPy) self-assembled into spherical domains with sizes of 300 nm to 600 nm in diameter by micro phase separation in bulk epoxy matrixes. A significant improvement of 300% in impact resistance of the supramolecular polymer incorporated epoxy resin was obtained when the content of supramolecular polymer was 10 wt%. Tensile tests showed that the mechanical properties of the modified epoxy resin containing the hydrogen-bonded supramolecular polymers are also improved compared with those of the neat epoxy resin.

Responsive Polymer Photonics.

Responsive Polymer Photonics.