Supramolecular Cross-linking Research Articles

Bioinspired nucleobase-containing polyelectrolytes as robust and tunable adhesives by balancing the adhesive and cohesive properties.

Supramolecular polymeric adhesives inspired by nature have been strongly pursued by scientists, since they possess strong but dynamic reversible adhesive behaviors concurrently. Optimizing the adhesive and cohesive properties is of vital importance for the fabrication of strong supramolecular polymeric adhesives, but common strategies often strengthen one property at the expense of another. Herein, counterion exchange of nucleobase-containing polyelectrolyte adhesives was utilized to boost the interfacial adhesion without compromising the intermolecular cohesion, achieving high adhesion strengths. By employing the cationic polyelectrolyte poly(3-acrylamidopropyltrimethylammonium chloride), the slightly enhanced intermolecular cohesion of the polyelectrolyte with hydrophobic sulfonates is capable of enhancing the adhesion strength. Intriguingly, by introducing bioinspired complementary nucleobases within adhesives, the loss of interfacial adhesion was observed for adhesives containing high supramolecular hydrogen-bonding crosslinking densities. By optimizing the cohesive and adhesive properties of nucleobase-containing polyelectrolyte adhesives using sulfonates with suitable chain lengths, 60 to 250 times improvement of adhesion strengths can be attained over that of initial supramolecular polymeric adhesives. Additionally, nucleobase-containing supramolecular polymeric adhesives tolerate different external conditions, maintaining robust adhesion strengths. This work offers us an efficient and feasible way to optimize the cohesive and adhesive properties for constructing robust and tunable supramolecular adhesives.

Acyclic cucurbit[n]uril-based nanosponges significantly enhance the photodynamic therapeutic efficacy of temoporfin in vitro and in vivo.

Acyclic cucurbit[n]uril-based nanosponges are prepared based on supramolecular vesicle-templated cross-linking. The nanosponges are capable of encapsulating the clinically approved photodynamic therapeutic (PDT) drug temoporfin. When loaded with nanosponges, the PDT bioactivity of temoporfin is enhanced 7.5-fold for HeLa cancer cells and 20.8 fold for B16-F10 cancer cells, respectively. The reason for the significant improvement in PDT efficacy is confirmed to be an enhanced cell uptake by confocal laser scanning microscopy and flow cytometry. Animal studies show that nanosponges could dramatically increase the tumor suppression effect of temoporfin. In vitro and in vivo experiments demonstrate that nanosponges are nontoxic and biocompatible.

Supramolecular Photonic Hydrogel for High-Sensitivity Alkaline Phosphatase Detection via Synergistic Driving Force.

Structurally-colored photonic hydrogels which are fabricated by introducing hydrogels into thin films or photonic crystal structures are promising candidates for biosensing. Generally, the design of photonic hydrogel biosensors is based on the sensor-analyte interactions induced charge variation within the hydrogel matrix, or chemically grafting binding sites onto the polymer chains, to achieve significant volume change and color variation of the photonic hydrogel. However, relatively low anti-interference capability or complicated synthesis hinder the facile and low-cost fabrication of high-performance photonic hydrogel biosensors. Here, a facilely prepared supramolecular photonic hydrogel biosensor is developed for high-sensitivity detection of alkaline phosphatase (ALP), which is an extensively considered clinical biomarker for a variety of diseases. Responding to ALP results in the broken supramolecular crosslinking and thus increased lattice distancing of the photonic hydrogel driven by synergistic repulsive force between nanoparticles embedded in photonic crystal structure and osmotic swelling pressure. The biosensor shows sensitivity of 7.3nm spectral shift per mUmL-1 ALP, with detection limit of 0.52 mUmL-1 . High-accuracy colorimetric detection can be realized via a smartphone, promoting point-of-care sensing and timely diagnosis of related pathological conditions.

A polyacrylamide gel containing an engineered hexameric hemoprotein as a cross-linking unit toward redox-responsive materials.

Hydrogels containing synthetic polymers and supramolecular cross-linking units are expected to exhibit unique functions and properties. The heme-heme pocket interaction in hemeproteins may be useful for development of a cross-linking unit because heme binding depends on the redox states of the iron center. In this work, hexameric tyrosine-coordinated hemoprotein (HTHP) is employed as a cross-linking unit in a polyacrylamide gel to create redox-responsive hydrogels. First, redox-dependent stability of the heme-heme pocket interaction in HTHP was evaluated, and it was found that the heme affinity dramatically decreases in the Fe(ii) state. Second, the polymerization of acrylamide and engineered HTHP possessing acryloyl group-tethering heme moieties provided a polyacrylamide gel containing HTHP as a cross-linking unit. A reduction-triggered gel-sol transition in the presence of apomyoglobin was observed. Furthermore, the mechanical properties of the gels containing the engineered HTHP and methylene bisacrylamide were evaluated by a tensile test, and the Young's modulus value was determined to be 14 kPa, which is higher than that of the control gel containing only methylene bisacrylamide (8.5 kPa). Compression tests of the gels revealed redox-responsive mechanical behavior, resulting in a decrease in the compressive modulus upon the addition of a reductant. This behavior is qualitatively consistent with the redox-responsive heme binding of HTHP in a solution state. This finding is expected to contribute to the development of redox-responsive materials for biomedical and biological applications.

Self-healable Poly(dimethyl siloxane) Elastomers Based on Host-guest Complexation between Methylated β-Cyclodextrin and Adamantane

Recently, it has been revealed that cyclodextrin derivatives undergo host-guest complexation in hydrophobic carbon-based elastomers as well as aqueous environments, exhibiting self-healing properties. In the present report, cyclodextrin derivatives exhibited self-healing properties based on host-guest complexation in poly(dimethyl siloxane)-based materials. The cut surfaces were rejoined after being kept at room temperature for 24 hours. Despite remaining problems with healing efficiency, the cyclodextrin-based supramolecular cross-links contribute to the self-healing properties.

Biomimetic, Mechanically Strong Supramolecular Nanosystem Enabling Solvent Resistance, Reliable Fire Protection and Ultralong Fire Warning.

A graphene oxide (GO)-based smart fire alarm sensor (FAS) has gained rapidly increasing research interest in fire safety fields recently. However, it still remains a huge challenge to obtain desirable GO-based FAS materials with integrated performances of mechanical flexibility/robustness, harsh environment-tolerance, high-temperature resistance, and reliable fire warning and protection. In this work, based on bionic design, the supermolecule melamine diborate (M·2B) was combined with GO nanosheets to form supramolecular cross-linking nanosystems, and the corresponding GO-M·2B (GO/MB) hybrid papers with a nacre-like micro/nano structure were successfully fabricated via a gel-dry method. The optimized GO/MB paper exhibits enhanced mechanical properties, e.g., tensile strength and toughness up to ∼122 MPa and ∼1.72 MJ/m3, respectively, which is ∼3.5 and ∼6.6 times higher than those of the GO paper. Besides, it also shows excellent structural stability even under acid/alkaline solution immersion and water bath ultrasonication conditions. Furthermore, due to the presence of promoting reduction effect and atom doping reactions in GO network, the resulting GO/MB network displays exceptional high-temperature resistance, sensitive fire alarm response (∼0.72 s), and ultralong alarming time (>1200 s), showing promising fire safety and protection application prospects as desirable FAS and fire shielding material with excellent comprehensive performances. Therefore, this work provides inspiration for the design and fabrication of high-performance GO-based smart materials that combine fire shielding and alarm functions.

Stimulus-Responsive, Gelatin-Containing Supramolecular Nanofibers as Switchable 3D Microenvironments for Cells.

Polymer- and/or protein-based nanofibers that promote stable cell adhesion have drawn increasing attention as well-defined models of the extracellular matrix. In this study, we fabricated two classes of stimulus-responsive fibers containing gelatin and supramolecular crosslinks to emulate the dynamic cellular microenvironment in vivo. Gelatin enabled cells to adhere without additional surface functionalization, while supramolecular crosslinks allowed for the reversible switching of the Young’s modulus through changes in the concentration of guest molecules in culture media. The first class of nanofibers was prepared by coupling the host–guest inclusion complex to gelatin before electrospinning (pre-conjugation), while the second class of nanofibers was fabricated by coupling gelatin to polyacrylamide functionalized with host or guest moieties, followed by conjugation in the electrospinning solution (post-conjugation). In situ AFM nano-indentation demonstrated the reversible switching of the Young’s modulus between 2–3 kPa and 0.2–0.3 kPa under physiological conditions by adding/removing soluble guest molecules. As the concentration of additives does not affect cell viability, the supramolecular fibers established in this study are a promising candidate for various biomedical applications, such as standardized three-dimensional culture matrices for somatic cells and the regulation of stem cell differentiation.

Semi-Solid Superprotonic Supramolecular Polymer Electrolytes Based on Deep Eutectic Solvents and Polyoxometalates.

Supramolecular polymers (SPs) exhibit intriguing benefits in functional soft materials due to their dynamic bonding feature. However, most SPs can only exist in the solution state and fail to form bulk materials, which limits their applications. Here, we report the fabrication of semi-solid bulk SP materials by using polyoxometalate (POM) nanoclusters as supramolecular cross-linkers to solidify a deep eutectic solvent (DES). The abundant protons and strong hydrogen bonds afforded by POMs enable these SP materials as superprotonic conductive electrolytes with sufficient mechanical strength, showing a proton conductivity more than 1×10-4 S cm-1 and a breaking strength exceeding 1 MPa at room temperature. Moreover, the thermodynamic reversibility of the SP electrolytes allows them to form a stable electrode-electrolyte interface by a facile melt-infiltration strategy upon mild heating, which leads to improved performance in supercapacitors. This work presents an innovative DES/POM hybrid system as a promising platform to develop functional supramolecular materials for energy and electronic applications.

Exploring the principles of self-healing polymers based on halogen bond interactions

In this study, novel self-healing polymers based on halogen bonds as reversible supramolecular crosslinking moieties are presented. The reversible crosslinking is facilitated by a polymer-bound bidentate halogen bond donor entity in combination with small molecule acceptor suberic acid. The binding strength of the crosslinking can be tuned via deprotonation of the diacid crosslinker. The material characteristics are investigated with several methods such as NMR and Raman spectroscopy, thermogravimetric analysis and differential scanning calorimetry as well as rheology. The tactile profile measurements have been utilized to monitor the scratch healing ability of the polymer networks revealing excellent healing efficiencies up to 99% within 2 h at a temperature of 100°C. Thus, the self-healing ability of halogen bond polymers could be quantified for the first time.

Stabilizing Entropically Driven Self-Assembly of Self-Immolative Polyurethanes in Water: A Strategy for Tunable Encapsulation Stability and Controlled Cargo Release

Stimuli-responsive amphiphilic polymer assemblies are of great interest in the area of targeted drug delivery applications as they can sequester guest molecules in one set of conditions and release them under another. Hence, developing a strategy of molar mass controlled synthesis, in-depth understanding of the thermodynamics of the self-assembly process, stabilization, and triggered guest release in a controlled fashion would be highly anticipated in the field of drug delivery applications. As polymer molar mass has a significant impact on the self-assembly process or material property of polymers, we focused on a methodology of controlled molar mass polyurethane synthesis using recycled plastic waste and synthesized a series of self-immolative amphiphilic polyurethanes of varying molar masses and polydispersity indexes. All of the polymers were equipped with periodically grafted triethyleneglycol monomethyl ether as a pendant, a redox-responsive disulfide bond, a tertiary amine, and an aromatic moiety on the backbone. In aqueous milieu, these polymers are found to form entropically driven nanoassemblies (ΔS > 0), which were further stabilized by supramolecular cross-linking via the synergistic effect of π–π stacking (aromatic moiety), H-bonding (urethane functionality), and hydrophobic interactions, which eventually amplifies the guest encapsulation stability. A guest release profile in the presence of a redox environment shows ∼65% release in a controlled fashion. Furthermore, the tertiary amine on the polymer backbone leads to the formation of positively charged nanoassemblies at the tumor-relevant pH (pH ∼ 6.5–6.8), which could potentially enhance the cellular uptake of nanocarriers in tumor cells. Thus, a strategy for molar mass controlled polyurethane synthesis, understanding the effect of polymer molar mass on thermodynamics of self-assembly, establishing a stable micellar nanostructure endowed with environment-specific surface charge modulation, and controlled guest release, we believe, will significantly contribute to the development of robust chemotherapeutics.

Thermal Paper and Time Temperature Integrators Made From a Structural Colored Polymer Crosslinked With Hydrogen Bonded Cyclohexanoic Acid Derivatives

AbstractHydrogen‐bonded cyclohexanoic derivatives are applied in a structural colored cholesteric liquid crystal (CLC) helical polymer that demonstrates an extraordinary dual thermal response. Integration of the dynamic hydrogen‐bonded cyclohexanoic acid derivatives in the CLC polymer as supramolecular crosslinks yields an immediate and irreversible loss of the green structural color upon exposure to temperatures above the cholesteric‐to‐isotropic transition temperature (TNI) caused by the helical order loss. Exposure to temperatures below the TNI yields a gradual irreversible red color shift of the reflected wavelength over broad temperature and time ranges. Most likely due to polymerization confinement in combination with the dynamics of the carboxylic acid hydrogen bonds, helical unwinding takes place over time causing the red shift of the reflected wavelength. The temperature response can be programmed by altering the chemical composition of the liquid crystal mixture. Furthermore, the green, structural color of the polymer can also be easily changed making it possible to print different colored indicators combined with different respective temperature responses on a single substrate. The printed optical sensors can be easily delaminated by dissolving the non‐covalent crosslinked polymer. Such optical polymer materials are attractive for easy processable time–temperature integrators and thermal paper.

Supramolecular Hydrogel Based on Pseudopolyrotaxane Aggregation for Bacterial Microenvironment-Responsive Antibiotic Delivery.

Due to the extensive use of antibiotics, the variety and number of drug-resistant pathogens have increased dramatically and have become a major global health problem. This imposes significant demands on the rational and effective use of antibiotics. To this end, a supramolecular hydrogel based on pseudopolyrotaxanes aggregation is proposed for antibiotic delivery. Supramolecular cross-linking strategies allow hydrogels to be obtained under mild conditions that facilitate the encapsulation of antibiotics. The presence of pH-sensitive imine bonds allows for the reversible detachment of PEG residues from the PEGylated hyaluronic acid backbone in an acidic environment, which leads to reversible changes in hydrogel crosslink density and thus controls antibiotic release behavior. Antimicrobial assessments indicated that the hydrogel exhibited good antimicrobial efficiency against both Gram-positive and negative bacteria, while responding to the bacterial microenvironment and enabling a burst release of antibiotics in severe infections. The proposed hydrogel also has excellent biocompatibility and thus possesses great potential for biomedical applications.

A Supramolecular Hydrogel Based on Copolymers of Acrylic Acid and Maleic Anhydride Derivatives with Terpyridine Motifs.

A kind of terpyridine derivative (NH2-Tpy) in which the amino was incorporated by a short alkyl chain was synthesized. Through grafting of terpyridine units into the hydrophilic copolymers of maleic anhydride and acrylic acid PAAMa via the reaction of the amino groups in NH2-Tpy and the maleic anhydride units, a series of gelator polymers—P1, P2, and P3—containing different contents of terpyridine units was synthesized. Under coordination of Ni2+ and terpyridine ligands in linear polymers, the supramolecular hydrogels H1, H2, and H3 with different cross-linking degrees were prepared. The linear polymers P1–P3 had a strong absorption peak at about 290 nm in the UV-vis spectra which was attributed to π–π* transition, and there was a new peak at about 335 nm led by the metal-to-ligands charge transfer (MLCT) when coordinated with Ni2+ ions. According to the rheological behaviors, the storage modulus (G′) was larger than the loss modulus (G′′). These hydrogels showed typical gel-like characteristics when the terpyridine content of the hydrogels exceeded 10%, and the hydrogels showed liquid-like characteristics when the terpyridine content of the hydrogels was less than 7%. The results of the micromorphological investigation of the xerogels from SEM illustrated the metal–terpyridine coordination cross-linking could have an important influence on the microstructures of the resulting hydrogels. Furthermore, these hydrogels based on supramolecular cross-links exhibited reversible solution–gel transition at different environmental temperatures. At the same time, the equilibrium swelling of the supramolecular hydrogels was 8.0–12.3 g/g, which increased with the decrease in the content of the terpyridine units in the resulting hydrogels.

Direct Ink Writing of Recyclable Supramolecular Soft Actuators.

Direct ink writing (DIW) of liquid crystal elastomers (LCEs) has rapidly paved its way into the field of soft actuators and other stimuli-responsive devices. However, currently used LCE systems for DIW require postprinting (photo)polymerization, thereby forming a covalent network, making the process time-consuming and the material nonrecyclable. In this work, a DIW approach is developed for printing a supramolecular poly(thio)urethane LCE to overcome these drawbacks of permanent cross-linking. The thermo-reversible nature of the supramolecular cross-links enables the interplay between melt-processable behavior required for extrusion and formation of the network to fix the alignment. After printing, the actuators demonstrated a reversible contraction of 12.7% or bending and curling motions when printed on a passive substrate. The thermoplastic ink enables recyclability, as shown by cutting and printing the actuators five times. However, the actuation performance diminishes. This work highlights the potential of supramolecular LCE inks for DIW soft circular actuators and other devices.

Glycosaminoglycan-Based Hydrogel Delivery System Regulates the Wound Microenvironment to Rescue Chronic Wound Healing.

Chronic wounds cannot proceed through the normal, orderly, and timely sequence of repair. The adverse cycle between excess reactive oxide species (ROS) and a persistent inflammatory response is an important mechanism of impaired wound healing. Herein, by combining the intrinsic bioactivities of natural polysaccharides and natural drugs, a glycosaminoglycan-based hydrogel delivery system is proposed to regulate the wound microenvironment. Dynamic supramolecular cross-linking enables the hydrogel to easily encapsulate the drug and fully fill the wound area. As the backbone of the hydrogel, heparin captures inflammatory chemokines at the wound site, while hyaluronic acid mimics the function of ECM. The hydrophobic drug curcumin has been ingeniously encapsulated in the hydrogel through micellization, thereby exerting good ROS scavenging ability and anti-inflammatory activity. Evaluations in diabetic mice showed that this antioxidant and anti-inflammatory hydrogel was effective in reducing the influx of immune cells at the wound site and in down-regulating the inflammatory response. Accelerated wound healing was also observed, as evidenced by faster re-epithelialization and better ECM remodeling. The proposed hydrogel can regulate the microenvironment of wounds from multiple aspects and thereby achieve regression of wound repair, which may provide a new therapeutic strategy for chronic wounds.

Room temperature Self-healable and extremely stretchable elastomer with improved mechanical Properties: Exploring a simplistic Metal-Ligand interaction

The dynamic supramolecular crosslinking reactions like imine bond formation, disulfide metathesis reactions, Diels Alder reactions, metal–ligand interactions, H-bonding, and ionic interactions are broadly used for the self-healing application of elastomers. Herein, we have developed a new self-healable and extremely stretchable elastomer based on robustness and dynamic metal–ligand coordination bonds between the API ligand and the Zn2+ metal ion moieties incorporated onto the XNBR rubber backbone. The FT-IR analysis confirmed the formation of amide linkage and metal–ligand coordination bonds into the XNBR rubber backbone. The healing performance and mechanical properties of various rubber compounds depend on the dosages of metal ions and the type of crosslinking systems. The metal–ligand crosslink compounds exhibit excellent healing performance over the sulfur crosslinking system. Differential scanning calorimetry, rubber process analyzer, crosslinking density, and morphology studies are indicated to characterize the metal–ligand interactions in the XNBR rubber matrix. The metal–ligand cross-linked XNBR rubber with 3 parts of Zn2+ metal ion demonstrates an excellent healing performance of 91.2%, with the tensile strength of 5.7 ± 0.8 MPa at room temperature for 24 h is much higher than the covalently cross-linked elastomers. The metal–ligand coordination bonds are entirely dynamic and thermoreversible during the rebuilding process and obtain an excellent self-healing property than the sulfur curing system.

Macromolecular Solute Transport in Supramolecular Hydrogels Spanning Dynamic to Quasi-Static States.

Hydrogels prepared from supramolecular cross-linking motifs are appealing for use as biomaterials and drug delivery technologies. The inclusion of macromolecules (e.g., protein therapeutics) in these materials is relevant to many of their intended uses. However, the impact of dynamic network cross-linking on macromolecule diffusion must be better understood. Here, hydrogel networks with identical topology but disparate cross-link dynamics are explored. These materials are prepared from cross-linking with host-guest complexes of the cucurbit[7]uril (CB[7]) macrocycle and two guests of different affinity. Rheology confirms differences in bulk material dynamics arising from differences in cross-link thermodynamics. Fluorescence recovery after photobleaching (FRAP) provides insight into macromolecule diffusion as a function of probe molecular weight and hydrogel network dynamics. Together, both rheology and FRAP enable the estimation of the mean network mesh size, which is then related to the solute hydrodynamic diameters to further understand macromolecule diffusion. Interestingly, the thermodynamics of host-guest cross-linking are correlated with a marked deviation from classical diffusion behavior for higher molecular weight probes, yielding solute aggregation in high-affinity networks. These studies offer insights into fundamental macromolecular transport phenomena as they relate to the association dynamics of supramolecular networks. Translation of these materials from in vitro to in vivo is also assessed by bulk release of an encapsulated macromolecule. Contradictory in vitro to in vivo results with inverse relationships in release between the two hydrogels underscores the caution demanded when translating supramolecular biomaterials into application.

Synthesis and Characterization of Metallopolymer Networks Featuring Triple Shape-Memory Ability Based on Different Reversible Metal Complexes.

This study presents the synthesis and characterization of metallopolymer networks with a triple shape-memory ability. A covalently crosslinked polymer network featuring two different additional ligands in its side chains is synthesized via free radical polymerization (FRP). The subsequent addition of different metal salts leads to the selective formation of complexes with two different association constants (Ka), proven via isothermal titration calorimetry (ITC). Those two supramolecular crosslinks feature different activation temperatures and can act as two individual switching units enabling the fixation and recovery of two temporary shapes. The presented samples were investigated in a detailed fashion via differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and FT-Raman spectroscopy. Furthermore, thermo-mechanical analyses (TMA) revealed excellent dual and triple shape-memory abilities of the presented metallopolymer networks.

High-strength and anti-biofouling nanofiber membranes for enhanced uranium recovery from seawater and wastewater

Ultrathin fibers can increase the contact area between adsorbents and seawater during the uranium extraction process; however, their construction usually aggravates the complex spinning technology and lowers their mechanical strength. Meanwhile, high strength and antifouling ability are essential for ocean adsorbents to withstand the complex natural environment and microbial systems. Herein, we design high-strength and anti-biofouling poly(amidoxime) nanofiber membranes (HA-PAO NFMs) via a supramolecular crosslinking. Bacterial cellulose supplies the NFMs with ultrathin fiber structure, and large amounts of adsorption ligands are immobilized on the framework via the crosslinking with antibacterial ions. Thus, different from other fibers, HA-PAO NFMs achieve ultrathin diameter (20–30 nm), high BET area (51 m2 g−1), and excellent mechanical strength (13.6 MPa). The uranium adsorption capacity reaches to 409 mg-U/g-Ads in the simulated seawater, 99.2% uranium can be removed from the U-contained wastewater, and the adsorption process can be observed by the naked eye due to the significant color changes. The inhibition zones indicate their excellent anti-biofouling ability, which contributes to 1.83 times more uranium extraction amount from natural seawater than the non-antifouling adsorbents. Furthermore, they display a long service life and can be large-scale prepared, and the HA-PAO NFMs have potential in the massive uranium recovery.

Supramolecular modulation of the mechanical properties of amino acid-functionalized cellulose nanocrystal films

Cellulose nanocrystal (CNC) is a promising building block for the bottom-up assembly of novel lightweight renewable materials. The ability to engineer the interfacial properties of CNC is of paramount importance to develop assembled materials for various applications; yet it remains a challenge to manipulate the supramolecular interactions within the cellulosic nanomaterials in a controlled manner. In this context, we demonstrate in this article how the assembly and mechanical properties of cellulose thin films can be controlled by manipulating the interfacial interactions of TEMPO-oxidized cellulose nanocrystals (TOCNCs) grafted with two different amino acids, arginine and tryptophan. The amino acid grafting onto the cellulose scaffold was confirmed in aqueous solutions by 1H NMR spectroscopy and in solid form by FTIR and XPS techniques. The surface functionalization of TOCNCs with simple cationic and aromatic groups provides a strategy for tuning the assembly of the nanostructures based on different supramolecular cross-linking interactions, including hydrogen bonds, π–π stacking, and cation–π interactions. In particular, we show that nanocellulose chains cross-linked by the non-covalent cation–π interactions lead to the formation of a laminated superstructure with high deformation and load standing capabilities. Our work provides a versatile strategy for tuning the surface properties of nanocellulose and represents an important step toward the development of sustainable materials with tailored mechanical properties, which will enable a wider application range of this building block all the way from tissue-engineering scaffolds to flexible devices.