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Hypothesis: In the quest for large but well-controlled supramolecular structures, the discotic benzene-1,3,5-tricarboxamide (BTA) has received quite some attention, because it can form hydrogen-bonded stacks that can be regarded as supramolecular polymers of which the single BTA molecule is the monomer. In this report, we consider a more complex BTA-based supramolecular polymer, namely one that is built up from supramolecular ‘monomers’. Experiments: We design a tris-ligand L3 consisting of a BTA core carrying three dipicolinic acid (DPA) groups. L3 itself is too small to form polymers, but in the presence of appropriate metal ions, each L3 can form three coordination bonds and so form (L3)n clusters that are large enough to stack successfully: at an appropriate metal dose, long and stable filaments with a cross-sectional diameter of 12 nm appear. We monitor the growth process by UV–vis spectroscopy and light scattering, and use small angle X-ray scattering (SAXS), TEM as well as molecular simulation to confirm the filamentous structure of the fibers and determine their dimensions. Findings: The formation and structure of the fiber are very similar for various transition metal ions, which enables introducing different functionalities, e.g., magnetic relaxivity, by proper choice of the metal ions. Hence, we obtain a doubly supramolecular polymer, connected axially by hydrogen bonds, and radially by coordination bonds. Not only does this realize a higher level of complexity, but it also allows to easily introduce and vary metal-derived functionalities.

This paper reports the self-assembly of a donor-acceptor system into nanoscopic structures and the photo processes taking place within these structures. The donor employed is pyrene linked to two β-cyclodextrin molecules (CD-PY-CD), and adamantane-linked methyl viologen attached to the three arms of mesitylene (Ms-(MV2+-AD)3) is the acceptor. CD-PY-CD and Ms-(MV2+-AD)3 when dissolved in water self-assembled into vesicles, which joined together to give long fibers. The self-assembly was studied using spectroscopic and microscopic techniques. Fluorescence of the pyrene chromophore was quenched within the self-assembled system due to efficient photoinduced electron transfer to methyl viologen. Photoinduced electron transfer within the assembly is confirmed through identification of product radical ions in flash photolysis experiments. Steady-state irradiation of the self-assembled system in an optical bench led to the formation of methyl viologen radical cation, which was stable for a few hours. Longevity of the radical cation was attributed to the fast reaction of pyrene radical cation with adjacent pyrene to give an unstable adduct, which slows down the back electron transfer process.

Abstract Developing high-performance separation membrane with good durability is a highly desired while challenging issue. Herein, we reported the successful fabrication of chemically and mechanically durable superhydrophobic membrane that was prepared by embedding UiO-66 as size-sieving sites within the supramolecular fiber structure of collagen fiber membrane (CFM), followed by the polydimethylsiloxane (PDMS) coating. The as-prepared CFM/UiO-66(12)/PDMS membrane featured capillary effect-enhanced separation flux and homogeneous porous channels guaranteed high separation efficiency. When utilized as double-layer separation membranes, this new type of composite membranes separated various surfactant stabilized water-in-oil microemulsions and nanoemulsions, with the separation efficiency high up to 99.993 % and the flux as high as 973.3 L m− 2 h− 1. Compared with commercial polytetrafluoro ethylene (PTFE) membrane, the advantage of the double-layer CFM/UiO-66(12)/PDMS membranes in separation flux was evident, which exhibited one order of magnitude higher than that of commercial PTFE membrane. The CFM/UiO-66(12)/PDMS membrane was acid-alkali tolerant, UV-aging resistant and reusable for emulsion separation. Notably, the CFM/UiO-66(12)/PDMS membrane was mechanically durable against strong mechanical abrasion, which was still capable of separating diverse water-in-oil emulsions after the abrasion with sandpaper and assembled as double-layer separation membranes. We anticipate that the combination of CFM and metal organic frameworks (MOFs) is an effective strategy for fabricating high-performance separation membrane with high mechanical and chemical durability. Graphical Abstract

The soft electronics industry is booming. To integrate with soft tissues (e.g. skin), the materials must possess skin-like properties in terms of stretchability, toughness, elasticity, softness, self-stiffness, swelling resistance, and conductivity. Herein, a biocompatible cellulose biomimetic hydrogel (CBH) showing the characteristics of the skin is fabricated. The first step is the regulation of cellulose self-assembly to form a porous non-swelling supramolecular fiber skeleton. Then, the elastic polymers generate within the pores of skeleton. This design mimics the skin’s structures by utilizing the crystallization behavior of cellulose. Importantly, the cellulose supramolecular network has significantly strengthened the resultant hydrogels with over a 45-fold increase in toughness, and it could reach 4.3 MJ/m3. Moreover, it shows enhanced properties in terms of stretchability, modulus, self-stiffness and elasticity. Investigation on the swelling resistance shows that the utilization of non-swelling porous cellulose skeleton can limit the swelling of CBH. Finally, the fabrication of conductive CBH is performed through the in-situ polymerization of aniline within CBH. It can retain the mechanical features due to the tunable swelling, and also be used as a sensitive and stable strain sensor to monitor human motions, even under an aqueous environment. The gauge factor within the range of 90% to 600% was 1.7. This study highlights the significance of utilizing original cellulose features and provides a new avenue to prepare high-performance strain sensors.

Living systems achieve sophisticated functions using supramolecular protein assemblies, in which the protein building blocks possess a specific secondary structure and are noncovalently arranged in a preprogrammed manner. Herein, we demonstrate the one-step synthesis of one-dimensional macromolecular assemblies by simply mixing a glycine-based isocyanide with a nickel catalyst, in which helical constituent polymers are linked end-to-end through multiple hydrogen bonds. The applicable scope of this approach is not confined to a particular monomer bearing a specially designed pendant, but covers a wide range of glycine-based isocyanides with or without aromatic and other functional groups. Surprisingly, copolymerization with an analogous chiral isocyanide (1 mol %) afforded an almost perfect one-handed helical supramolecular fiber owing to intramolecular/intermolecular dual chiral amplifications. The simplicity and broad applicability of this approach, which can also afford exquisite chiral amplification, enable the creation of a wide variety of functional supramolecular assemblies and provide access to new supramolecular materials.

International audience; In this work, we describe how a simple single low molecular weight gelator (LMWG) molecule – N-heptyl-D-galactonamide, which is easy to produce at the gram scale – is spun into gel filaments by a wet spinning process based on solvent exchange. A solution of the gelator in DMSO is injected into water and the solvent diffusion triggers the supramolecular self-assembly of the N-heptyl-D-galactonamide molecules into nanometric fibers. These fibers entrap around 97% of water, thus forming a highly hydrated hydrogel filament, deposited in a well organized coil and locally aligned. This self-assembly mechanism also leads to a very narrow distribution of the supramolecular fiber width, around 150 nm. In addition, the self-assembled fibers are oriented radially inside the wet-spun filaments and at a high flow rate, fibers are organized in spirals. As a result, this process gives rise to a high control of the gelator self-assembly compared with the usual thermal sol–gel transition. This method also opens the way to the controlled extrusion at room temperature of these very simple, soft, biocompatible but delicate hydrogels. The gelator concentration and the flow rates leading to the formation of the gel filaments have been screened. The filament diameter, its internal morphology, the solvent exchange and the velocity of the jet have been investigated by video image analysis and electron microscopy. The stability of these delicate hydrogel ropes has been studied, revealing a polymorphic transformation into macroscopic crystals with time under some storage conditions. The cell viability of a neuronal cell line on the filaments has also been estimated

The cytoskeleton is a highly adaptive network of filamentous proteins capable of stiffening under stress even as it dynamically assembles and disassembles with time constants of minutes. Synthetic materials that combine reversibility and strain-stiffening properties remain elusive. Here, strain-stiffening hydrogels that have dynamic fibrous polymers as their main structural components are reported. The fibers form via self-assembly of bolaamphiphiles (BA) in water and have a well-defined cross-section of 9 to 10 molecules. Fiber length recovery after sonication, H/D exchange experiments, and rheology confirm the dynamic nature of the fibers. Cross-linking of the fibers yields strain-stiffening, self-healing hydrogels that closely mimic the mechanics of biological networks, with mechanical properties that can be modulated by chemical modification of the components. Comparison of the supramolecular networks with covalently fixated networks shows that the noncovalent nature of the fibers limits the maximum stress that fibers can bear and, hence, limits the range of stiffening.

Electrospinning is an attractive way to prepare nano- and macrofibers. It was demonstrated by our group that trisamides can be melt electrospun into supramolecular fibers. To establish structure–property relationships regarding spinnability and morphology, melt electrospinning experiments were conducted using several classes of compounds. The number of hydrogen bonds was systematically decreased from three for trisamides, to two for bisamide and sorbitols, and to zero for perylene bisimides and tertiary trisamides. As a result, trisamides are readily spun into fibers, whereas for bisamides and sorbitols mainly electrospraying into spheres is observed. Perylene bisimides form well-defined fibers due to strong π–π interactions. This supramolecular fiber is interesting for many scientific disciplines.

Background Tissue-engineered blood vessels (TEBVs) represent an innovative approach for overcoming reconstructive problems associated with vascular diseases by providing small-caliber vascular grafts. This study aimed to evaluate a novel biomaterial of bacterially synthesized cellulose (BC) as a potential scaffold for small-diameter TEBV. Methods Small-diameter blood vessels with a supramolecular fiber network structure consisting of tubular hydrogels from biodesigned cellulose were created using Gluconacetobacter strains and Matrix reservoir technology. BC tubes (length: 100 mm, inner diameter: 4.0–5.0 mm) were applied to replace the carotid arteries of 10 sheep for a period of 3 mo to gain further insights into (a) functional (in vivo) performance, (b) ability of providing a scaffold for the neoformation of a vascular wall and (c) their proinflammatory potential, and the (d) technical feasibility of the procedure. Results Preoperative analysis revealed a bursting strength of the grafts of approximately 800 mm Hg and suture retention strength of 4–5 N. Postexplantation analysis showed a patency rate of 50% (n = 5) and physiological performance of the patent grafts at 4, 8, and 12 wk postoperatively, compared with native arteries. Histologic analysis revealed a neoformation of a vascular wall–like structure along the BC scaffold consisting of immigrated vascular smooth muscle cells and a homogeneous endothelialization of the inner graft surface without signs of prothrombogenic or inflammatory potential. Scanning electron microscopy revealed a confluent luminal endothelial cell layer and the immigration of vascular smooth muscle cells into the BC matrix. Conclusions BC grafts provide a scaffold for the neoformation of a three-layered vascular wall exhibit attractive properties for their use in future TEBV programs for cardiovascular surgery.

A mixture of acrylated epoxidized soybean oil (AESO) with N-carbobenzyloxy-L-isoleucylaminooctadecane (CIA) or (R)-12-hydroxystrearic acid (HSA) containing photoinitiators was heated to 130 °C and gradually cooled to room temperature to give a bio-based gelatinous material. The photocuring of the AESO/CIA gel afforded a supramolecular composite composed of crosslinked AESO (cAESO) and self-assembled CIA fibers, whereas HSA crystallized in case of the photocuring of the AESO/HSA gel. Tensile strength and modulus for cAESO/CIA increased with CIA content, whereas those of cAESO/HSA decreased with HSA content.

Spider silk is a fascinating material, combining high strength and elasticity that outperforms most synthetic fibers. Another intriguing feature of spider silk is its ability to "supercontract," shrinking up to 50% when exposed to water. This is likely on account of the entropy-driven recoiling of secondary structured proteins when water penetrates the spider silk. In contrast, humidity-driven contraction in synthetic fibers is difficult to achieve. Here, inspired by the spider silk model, a supercontractile fiber (SCF), which contracts up to 50% of its original length at high humidity, comparable to spider silk, is reported. The fiber exhibits up to 300% uptake of water by volume, confirmed via environmental scanning electron microscopy. Interestingly, the SCF exhibits tunable mechanical properties by varying humidity, which is reflected by the prolonged failure strain and the reversible damping capacity. This smart supramolecular fiber material provides a new opportunity of fabricating biomimetic muscle for diverse applications.

We report on a self-sorting supramolecular fiber formation of photo- and electro-active molecules (p-type oligothiophene and n-type perylene derivatives) toward the development of a photoelectronic conversion system operated by visible light irradiation.

Self-assembled organic fibers combine facile solution processing with the performance benefits of single crystals. Here, the first evidence is shown of band-like transport in an n-type solution-processed small molecule system, a limited role of shallow traps, and a single fiber electron mobility that is several orders of magnitude higher than that measured in fiber ensembles or spin-cast films.

INTRODUCTIONCollagen II is a fibrous protein that assembles from basic tropocollagen subunits to form extracellular supramolecular fiber networks within cartilage tissue. Tropocollagen subunits of ~300 nm in length self-assemble first into pentameric uniform microfibrils, which fuse into bigger collagen fibrils that can range from 10 nm to 500 nm in diameter. The collagen fibrils display a characteristic 67-nm repeat because of the staggering of individual collagen molecules with respect to each other. This protocol demonstrates how to prepare collagen protein samples for analysis by atomic force microscopy (AFM). It also describes the steps for generating AFM images of collagen samples during and after manipulation to analyze collagen self-assembly.

Self-healing materials can prolong the lifetime of structures and products by enabling the repairing of damage. However, detecting the damage and the progress of the healing process remains an important issue. In this study, self-healing, piezoresistive strain sensor fibers (ShSFs) are used for detecting strain deformation and damage in a self-healing elastomeric matrix. The ShSFs were embedded in the self-healing matrix for the development of self-healing sensor fiber composites (ShSFC) with elongation at break values of up to 100%. A quadruple hydrogen-bonded supramolecular elastomer was used as a matrix material. The ShSFCs exhibited a reproducible and monotonic response. The ShSFCs were investigated for use as sensorized electronic skin on 3D-printed soft robotic modules, such as bending actuators. Depending on the bending actuator module, the electronic skin was loaded under either compression (pneumatic-based module) or tension (tendon-based module). In both configurations, the ShSFs could be successfully used as deformation sensors, and in addition, detect the presence of damage based on the sensor signal drift. The sensor under tension showed better recovery of the signal after healing, and smaller signal relaxation. Even with the complete severing of the fiber, the piezoresistive properties returned after the healing, but in that case, thermal heat treatment was required. With their resilient response and self-healing properties, the supramolecular fiber composites can be used for the next generation of soft robotic modules.