Hydrogen Bond Dynamics Research Articles

Interplay between hydrogen-bonding proton dynamics and Fe valence fluctuation in Fe3(PO4)2(OH)2 barbosalite at high pressure

Interplay between hydrogen-bonding proton dynamics and Fe valence fluctuation in Fe₃(PO₄)₂(OH)₂ barbosalite at high pressure

The impact of H/D exchange on the thermal and structural properties as well as high-pressure relaxation dynamics of melatonin

In this paper, thermal properties, atomic-scale structure, and molecular dynamics (at ambient and high pressure) of native melatonin (MLT) and its partially-deuterated derivative (MLT-d2) have been investigated. Based on infrared spectroscopy, it was shown that treating MLT with D2O causes the replacement of hydrogen atoms attached to the nitrogen by deuterium. The degree of such substitution was very high (> 99%) and the deuterated sample remained stable after exposure to the air as well as during the melting and vitrification processes. Further calorimetric studies revealed the appearance of a peculiar thermal event before the melting of crystalline MLT-d2, which was assigned by the X-ray diffraction to a local negative thermal expansion of the unit cell. Finally, the high-pressure dielectric experiments indicated a few interesting findings, including the variation in the shape of the structural relaxation peak during compression, the difference in the pressure evolution of the glass transition temperature, and the temperature dependence of activation volume for both MLT species. The variations in these parameters manifest a different impact of the compression/densification on the dynamics of hydrogen and deuterium bonds in the native and partially-deuterated MLT, respectively.

DHFR Mutants Modulate Their Synchronized Dynamics with the Substrate by Shifting Hydrogen Bond Occupancies.

Antibiotic resistance is a global health problem in which mutations occurring in functional proteins render drugs ineffective. The working mechanisms of the arising mutants are seldom apparent; a methodology to decipher these mechanisms systematically would render devising therapies to control the arising mutational pathways possible. Here we utilize Cα-Cβ bond vector relaxations obtained from moderate length MD trajectories to determine conduits for functionality of the resistance conferring mutants of Escherichia coli dihydrofolate reductase. We find that the whole enzyme is synchronized to the motions of the substrate, irrespective of the mutation introducing gain-of-function or loss-of function. The total coordination of the motions suggests changes in the hydrogen bond dynamics with respect to the wild type as a possible route to determine and classify the mode-of-action of individual mutants. As a result, nine trimethoprim-resistant point mutations arising frequently in evolution experiments are categorized. One group of mutants that display the largest occurrence (L28R, W30G) work directly by modifying the dihydrofolate binding region. Conversely, W30R works indirectly by the formation of the E139-R30 salt bridge which releases energy resulting from tight binding by distorting the binding cavity. A third group (D27E, F153S, I94L) arising as single, resistance invoking mutants in evolution experiment trajectories allosterically and dynamically affects a hydrogen bonding motif formed at residues 59-69-71 which in turn modifies the binding site dynamics. The final group (I5F, A26T, R98P) consists of those mutants that have properties most similar to the wild type; these only appear after one of the other mutants is fixed on the protein structure and therefore display clear epistasis. Thus, we show that the binding event is governed by the entire enzyme dynamics while the binding site residues play gating roles. The adjustments made in the total enzyme in response to point mutations are what make quantifying and pinpointing their effect a hard problem. Here, we show that hydrogen bond dynamics recorded on sub-μs time scales provide the necessary fingerprints to decipher the various mechanisms at play.

Local intermolecular structure, hydrogen bonding and related dynamics in the liquid cis/trans N-methylformamide mixture: A density functional theory based Born-Oppenheimer molecular dynamics study

The local intermolecular structure and related dynamics in the liquid cis/trans N-methylformamide mixture at ambient temperature and density conditions have been systematically studied by employing Born-Oppenheimer molecular dynamics simulation techniques. Particular attention has been paid to the local structure around the cis- and trans- conformers and the formation and dynamics of hydrogen bonds with their closest neighbors. The calculated atom–atom radial distribution functions are in very good agreement with available experimental data and reveal the existence of different types of hydrogen bonding intermolecular interactions. The average number of hydrogen bonds formed by the cis- conformers is higher in comparison with the one corresponding to the trans- conformers. Moreover, the lifetimes of the hydrogen bonds formed in the liquid are longer when the cis- conformers participate in the bond formation, either as donors or acceptors. These findings clearly indicate that the local structural network around the cis- conformers in the liquid is more cohesive. The latter finding is also reflected in the slower reorientational dynamics of the cis- conformers and the low- and high-frequency region of the spectral densities of the atomic velocity time correlation functions. Finally, the calculated average dipole moments of the trans- and cis- conformers are significantly higher than their corresponding gas-phase values, signifying the importance of polarization effects in this particular polar liquid solvent.

Intrinsically elastic and self-healing luminescent polyisoprene copolymers formed via covalent bonding and hydrogen bonding design

Although development of soft and stretchable materials exhibiting semiconducting functions, such as luminescent or electronic properties, has received growing interest, development of intrinsically self-healing semiconducting materials remains a challenge. In this study, covalent and hydrogen-bonding architectures were used to construct polyisoprene (PI)-based rubber containing luminescent poly[2,7-(9,9-dioctylfluorene)] (PF), and the material exhibited elastic behavior and spontaneous healing. The first demonstration of an engineered hard–soft multiphase, well-dispersed polymer thin film was conducted, wherein the soft phase backbone containing dynamic hydrogen bonds and rubber-like moieties imparted resistance against damage due to repeated stretching, while the hard phase comprising aggregates of rigid PF branches imparted luminescence. Under intense mechanical stress, both the bulk and thin-film states of the crosslinked PF0.16-co-PI0.37-co-PBACO0.47 impressively presented typical elastic performance. Owing to the dynamic nature of the hydrogen bonds within the crosslinked polyisoprene copolymer, the bulk and thin film states exhibited good self-healing and an 83% recovery efficiency following treatment for 24 h at room temperature. This strategy is potentially useful for fabrication of fully flexible electronics with good mechanical properties and many functionalities.

A comparative study of interfacial environments in lipid nanodiscs and vesicles

Membrane protein conformations and dynamics are driven by the protein-lipid interactions occurring within the local environment of the membrane. These environments remain challenging to accurately capture in structural and biophysical experiments using bilayers. Consequently, there is an increasing need for realistic cell-membrane mimetics for in vitro studies. Lipid nanodiscs provide certain advantages over vesicles for membrane protein studies. Nanodiscs are increasingly used for structural and spectroscopic characterization of membrane proteins. Despite the common use of nanodiscs, the interfacial environments of lipids confined to a ∼10-nm diameter area have remained relatively underexplored. Here, we use ultrafast two-dimensional infrared spectroscopy and temperature-dependent infrared absorption measurements of the ester carbonyls to compare the interfacial hydrogen bond structure and dynamics in lipid nanodiscs of varying lipid compositions and sizes with ∼100-nm vesicles. We examine the effects of lipid composition and nanodisc size. We found that nanodiscs and vesicles share largely similar lipid-water H-bond environments and interfacial dynamics. Differences in measured enthalpies of H-bonding suggest that H-bond dynamics in nanodiscs are modulated by the interaction between the annular lipids and the scaffold protein.

High-Sensitivity and Extreme Environment-Resistant Sensors Based on PEDOT:PSS@PVA Hydrogel Fibers for Physiological Monitoring.

The rapid development of flexible electronic devices has caused a boom in researching flexible sensors based on hydrogels, but most of the flexible sensors can only work at room temperature, and they are difficult to adapt to extremely cold or dry environments. Here, the flexible hydrogel fibers (PEDOT:PSS@PVA) with excellent resistance to extreme environments have been prepared by adding glycerin (GL) to the mixture of poly(vinyl alcohol) (PVA) and poly 3,4-dioxyethylene thiophene:polystyrene sulfonic acid (PEDOT:PSS) because GL molecules can form dynamic hydrogen bonds with an elastic matrix of PVA molecules. It is found that the prepared sensor exhibits very good flexibility and mechanical strength, and the ultimate tensile strength can reach up to 13.76 MPa when the elongation at break is 519.9%. Furthermore, the hydrogel fibers possess excellent water retention performance and low-temperature resistance. After being placed in the atmospheric environment for 1 year, the sensor still shows good flexibility. At a low temperature of -60 °C, the sensor can stably endure 1000 repeated stretches and shrinks (10% elongation). In addition to the response to a large strain, this fiber sensor can also detect extremely small strains as low as 0.01%. It is proved that complex human movements such as knuckle bending, vocalization, pulse, and others can be monitored perfectly by this fiber sensor. The above results mean that the PEDOT:PSS@PVA fiber sensor has great application prospects in physiological monitoring.

Injectable Self-Healing Adhesive Chitosan Hydrogel with Antioxidative, Antibacterial, and Hemostatic Activities for Rapid Hemostasis and Skin Wound Healing.

Engineered wound dressing materials with excellent injectability, self-healing ability, tissue-adhesiveness, especially the ones possessing potential therapeutic effects have great practical significance in healthcare. Herein, an injectable quaternary ammonium chitosan (QCS)/tannic acid (TA) hydrogel based on QCS and TA was designed and fabricated by facile mixing of the two ingredients under physiological conditions. In this system, hydrogels were mainly cross-linked by dynamic ionic bonds and hydrogen bonds between QCS and TA, which endows the hydrogel with excellent injectable, self-healing, and adhesive properties. Benefitting from the inherent antioxidative, antibacterial, and hemostatic abilities of TA and QCS, this hydrogel showed superior reactive oxygen species scavenging activity, broad-spectrum antibacterial ability, as well as rapid hemostatic capability. Moreover, the QCS/TA2.5 hydrogel (containing 2.5% TA) exhibited excellent biocompatibility. The in vivo experiments also showed that QCS/TA2.5 hydrogel dressing not only rapidly stopped the bleeding of arterial and deep incompressible wounds in mouse tail amputation, femoral artery hemorrhage, and liver incision models but also significantly accelerated wound healing in a full-thickness skin wound model. For the great potentials listed above, this multifunctional QCS/TA2.5 hydrogel offers a promising network as a dressing material for both rapid hemostasis and skin wound repair.

On water reorientation dynamics in cation hydration shells

The effects of ions on liquid water’s structural, dynamical, and thermodynamical properties have key implications for a wide range of biological and technological processes. Based on simulations and analytic modeling, we have recently developed a framework that rationalizes the effects of solutes and interfaces on water reorientation dynamics. However, this picture still misses some contributions of the cations to the experimentally measured slowdown or acceleration of water dynamics. All-atom classical simulations also face some limitations in quantitatively reproducing water structural and dynamical features in ionic aqueous solutions. Here, we show that a scaled-charge approach can successfully reproduce experimental trends and that ab initio descriptions are not required. We show that a picture where the cation would lock a water molecule dipole and lead to partial OH reorientation is both incorrect for some ions, and largely exaggerated for others. We demonstrate that a combination of two effects on the hydrogen-bond (H-bond) exchange dynamics explains the ambient temperature acceleration of water reorientation next to a cesium cation, and the retardation next to lithium and magnesium cations. First, ions create a local excluded volume, which hinders the approach of possible new H-bond partners, leading to a retarding contribution. However, they also perturb the local water structure, reducing the energetic cost of elongating the initial H-bond. For magnesium and lithium cations, the excluded volume effect dominates, which leads to an overall retardation of the H-bond exchange. For the cesium cation, at room temperature, this latter contribution overcomes the excluded volume effect, leading to an acceleration; moreover, the strong temperature dependence observed in the experiments, going from a large acceleration close to freezing to a retardation close to boiling, is understood by the key enthalpic effect of the elongation contribution. Overall, our framework now provides a comprehensive understanding of cations’ and anions’ effects on water reorientation dynamics.

Bioinspired Thermoplastic Elastomer with Flexible, Self-Healing Capabilities.

The self-healing property of biological tissues gives humans inspiration to endow artificial synthetic materials with self-healing functions. Herein, we report a thermoplastic elastomer that can be self-repaired in a short time, which uses dual dynamic bonds (hydrogen bonds and disulfide bonds) coupled to realize its self-healing function through the rapid conversion of dynamic hydrogen bonds between the hard and soft segments, as well as the dynamic bonding and dissociation of disulfide bonds. Furthermore, the maximum tensile strength and strain of the elastomer can reach 17.4 MPa and 3780%, respectively, and the maximum self-healing rate is close to 100% (temperature: 90 °C, time: 5 h). The arrays' arrangement and reversibility of hydrogen bonds endow the elastomer with high toughness and self-healing properties and thus solve the problem that ordinary polymers cannot self-heal.

Uncovering the Dynamics of Confined Water Using Neutron Scattering: Perspectives

The main characteristic of liquid water is the formation of dynamic hydrogen bond networks that occur over a broad range of time scales from tens of femtoseconds to picoseconds and are responsible for water’s unique properties. However, in many important processes water does not exist in its bulk form, but in confined nanometer scale environments. The investigation of this confined water dynamics is challenging since the intermediate strength of the hydrogen bonds makes it possible to alter the structure and dynamics of this constrained water. Even if no single experimental technique can give a full picture of such intricate dynamics, it is well established that quasielastic neutron scattering (QENS) is a powerful tool to study the modification of hydrogen bonds in confinement in various materials. This is possible because neutrons tell us where the atoms are and what they are doing, can detect hydrogen, are penetrative and non-destructive. Furthermore, QENS is the only spectroscopic technique that provides information on the dynamics and atomic-motion amplitudes over a predetermined length scale. However scientific value of these data is hardly exploited and never to its full potential. This perspective highlights how new developments on instrumentation and data analysis will lead to appreciable progress in our understanding of the dynamics of complex systems, ranging from biological organisms to cloud formation.

Hydrophobic π-π stacking interactions and hydrogen bonds drive self-aggregation of luteolin in water

Luteolin is a flavonoid obtained from different plant species. It is known for its versatile biological activities. However, the beneficial effects of luteolin have been limited to small concentrations as a result of poor water solubility. This study aimed at investigating the hydrophobic interaction and hydration of luteolin towards the improvement of its solubility when used as a drug. We report the aggregation properties of luteolin in water by varying the number of monomers using atomistic molecular dynamics simulation. Results show that the equilibrium structure of luteolin occurs in an aggregated state with different structural arrangements. As the monomers size increase, the antiparallel flipped conformation dominates over T-shaped antiparallel, T-shaped parallel, and antiparallel conformations. The formation of intramolecular hydrogen bonding of 0.19 nm between the keto-enol groups results in hydrophobic characteristics. A larger cluster exhibits slow hydrogen bond dynamics for luteolin-luteolin than luteolin-water interaction. Water structure at large cluster size exhibited slow dynamics and low self-diffusion of luteolin. The existence of hydrophobic π-π and hydrogen bonds between luteolin molecules drives strong self-aggregation resulting in poor water solubility. Breakage of these established interactions would result in increased solubility of luteolin in water.

A ternary heterogeneous hydrogel with strength elements for resilient, self-healing, and recyclable epidermal electronics

Epidermal sensing devices, which mimic functionalities and mechanical properties of natural skin, offer great potential for real-time health monitoring via continuous checking of vital signs. However, most existing skin-mounted electronics use a flexible film with high elastic modulus, which hinders physical activity and causes interfacial delamination and skin irritation. The compliance of hydrogel-based devices can firmly conform to complex, curved surfaces without introducing excessive interfacial stresses. However, most hydrogels still suffer from the weakness of stable and reproducible sensing. In this work, we report a skin-friendly epidermal electronic made of a resilient, self-healing, and recyclable polyvinyl alcohol (PVA) hydrogel. The hydrogel is reinforced through a ternary heterogeneous network for good mechanical robustness while maintaining high stretchability and exceptional conformability. Simultaneously, the abundant dynamic hydrogen bonds give the hydrogel rapid self-healing ability. The assembled hydrogel epidermal electronic is able to stably monitor multiple physiological signals as well as sense the strain level of the skin motion and joint bending. The unique, versatile, environmental and biological friendly epidermal electronics will have broad applications in health care, human-machine interface, augmented reality, and so on.

Spontaneously Restoring Specific Bioaffinity of RGD in Linear RGD-containing Peptides by Conjugation with Zwitterionic Dendrimers

Peptides are more versatile than small molecule drugs, but their specific bioaffinities are usually lower than their original native proteins because of the loss of preferred conformations. To overcome this key obstacle, we demonstrated a hydrogen bond-induced conformational constraint method to enhance the specific bioaffinities of peptides to achieve a high success rate by using linear RGD-containing peptides as a model of bioactive peptides. By performing molecular simulation, we found that the chemically immobilized linear CRGDS via cysteine (C) at the N-terminus on zwitterionic PAMAM G-5 can not only spontaneously restore the natural conformation of the RGD segment through the assistance of the dynamic hydrogen bond from serine (S) at the C-terminus of the peptide, but it can also narrow the distribution of all possible conformations. Consequently, the conjugates showed comparable or even better high affinity than native proteins without the use of conventional, labor-intensive, synthesis-based structure search methods to construct a binding conformation. In addition, the conjugates showed globular protein-like characteristics chemically, physically, and physiologically. They exhibited not only high efficacy and biosafety both in vitro and in vivo, but they also showed extremely high thermostability even upon boiling in a solution. This approach offers great design flexibility for reviving functional peptides without impairing their high specific affinity for their targets. Statement of significanceIn this work, we developed a swift approach to spontaneously restore the natural conformation of a linear peptide from a nature protein and thus enhance its specific bioaffinity instead of constructing a binding conformation by the labor-intensive, synthesis-based structure search method. In details, our new approach involves dynamically constraining the linear peptide on a zwitterionic PAMAM G-5 surface by a combination of chemical bonding at one terminus and dynamic hydrogen bonding at the other terminus of the linear peptide. The zwitterionic background offers abundant interaction sites for hydrogen bonding as well as resistance to nonspecific interactions. This approach fully restores the specific bioaffinity of RGD segments on a zwitterionic PAMAM G-5 through only one conjugation point at the C-terminus of the peptide. Moreover, the bioaffinity of all three types of RGD-containing peptides is successfully restored, which indicates the high rate of success of this approach in affinity restoring.

A Repeatable Dual‐Encryption Platform from Recyclable Thermosets with Self‐Healing Ability and Shape Memory Effect

AbstractRepeatable dual‐encryption platforms, coupled with a strong protective capacity for stored information, are highly desirable for current data security but still a challenge to be realized. Herein, a new type of thermoset‐based repeatable dual‐encryption platform is designed to fulfill the challenge. Through introducing dynamic boroxine bonds and hydrogen bonds within the thermoset, self‐healing, recyclability, and shape‐memory properties can be achieved. Given the shape memory behavior of this thermoset, encryption data within complex 3D structures can be realized. Thus, shape recovery is inevitable for the decryption, providing strong protection for encrypted data. Furthermore, the encrypted data can be protected by showing misleading information before true information during the decryption process, which is caused by the different analogous “LEGO” assembly sequences of thermosets that induces different hydrophobic association interactions. The decrypted information can be erased by heating, realizing the repeatable encryption/decryption. Additionally, the thermosets can be efficiently recycled. This strategy opens up a smart prospect for high level dual‐encryption platform.

Structural independence of hydrogen-bond symmetrisation dynamics at extreme pressure conditions

The experimental study of hydrogen-bonds and their symmetrization under extreme conditions is predominantly driven by diffraction methods, despite challenges of localising or probing the hydrogen subsystems directly. Until recently, H-bond symmetrization has been addressed in terms of either nuclear quantum effects, spin crossovers or direct structural transitions; often leading to contradictory interpretations when combined. Here, we present high-resolution in-situ 1H-NMR experiments in diamond anvil cells investigating a range of systems containing linear O-H ⋯ O units at pressure ranges of up to 90 GPa covering their respective H-bond symmetrization. We found pronounced minima in the pressure dependence of the NMR resonance line-widths associated with a maximum in hydrogen mobility, precursor to a localisation of hydrogen atoms. These minima, independent of the chemical environment of the O-H ⋯ O unit, can be found in a narrow range of oxygen oxygen distances between 2.44 and 2.45 Å, leading to an average critical oxygen-oxygen distance of {bar{r}}_{{{{{{{{rm{OO}}}}}}}}}^{{{{{{{{rm{crit}}}}}}}}}=2.443(1) Å.

Graphs of Hydrogen-Bond Networks to Dissect Protein Conformational Dynamics.

Dynamic hydrogen bonds and hydrogen-bond networks are ubiquitous in proteins and protein complexes. Functional roles that have been assigned to hydrogen-bond networks include structural plasticity for protein function, allosteric conformational coupling, long-distance proton transfers, and transient storage of protons. Advances in structural biology provide invaluable insights into architectures of large proteins and protein complexes of direct interest to human physiology and disease, including G Protein Coupled Receptors (GPCRs) and the SARS-Covid-19 spike protein S, and give rise to the challenge of how to identify those interactions that are more likely to govern protein dynamics. This Perspective discusses applications of graph-based algorithms to dissect dynamical hydrogen-bond networks of protein complexes, with illustrations for GPCRs and spike protein S. H-bond graphs provide an overview of sites in GPCR structures where hydrogen-bond dynamics would be required to assemble longer-distance networks between functionally important motifs. In the case of spike protein S, graphs identify regions of the protein where hydrogen bonds rearrange during the reaction cycle and where local hydrogen-bond networks likely change in a virus variant of concern.

Water Diffusion Proceeds via a Hydrogen-Bond Jump Exchange Mechanism.

The self-diffusion of water molecules plays a key part in a broad range of essential processes in biochemistry, medical imaging, material science, and engineering. However, its molecular mechanism and the role played by the water hydrogen-bond network rearrangements are not known. Here we combine molecular dynamics simulations and analytic modeling to determine the molecular mechanism of water diffusion. We establish a quantitative connection between the water diffusion coefficient and hydrogen-bond jump exchanges, and identify the features that determine the underlying energetic barrier. We thus provide a unified framework to understand the coupling between translational, rotational, and hydrogen-bond dynamics in liquid water. It explains why these different dynamics do not necessarily exhibit identical temperature dependences although they all result from the same hydrogen-bond exchange events. The consequences for the understanding of water diffusion in supercooled conditions and for water transport in complex aqueous systems, including ionic, biological, and confined solutions, are discussed.

Ultrafast photo-induced processes in complex environments: The role of accuracy in excited-state energy potentials and initial conditions

Light induces non-equilibrium time evolving molecular phenomena. The computational modeling of photo-induced processes in large systems, embedded in complex environments (i.e., solutions, proteins, materials), demands for a quantum and statistical mechanic treatment to achieve the required accuracy in the description of both the excited-state energy potentials and the choice of the initial conditions for dynamical simulations. On the other hand, the theoretical investigation on the atomistic scale of times and sizes of the ultrafast photo-induced reactivity and non-equilibrium relaxation dynamics right upon excitation requests tailored computational protocols. These methods often exploit hierarchic computation schemes, where a large part of the degrees of freedom are required to be treated explicitly to achieve the right accuracy. Additionally, part of the explicit system needs to be treated at ab initio level, where density functional theory, using hybrid functionals, represents a good compromise between accuracy and computational cost, when proton transfers, non-covalent interactions, and hydrogen bond dynamics play important roles. Thus, the modeling strategies presented in this review stress the importance of hierarchical quantum/molecular mechanics with effective non-periodic boundary conditions and efficient phase-sampling schemes to achieve chemical accuracy in ultrafast time-resolved spectroscopy and photo-induced phenomena. These approaches can allow explicit and accurate treatment of molecule/environment interactions, including also the electrostatic and dispersion forces of the bulk. At the same time, the specificities of the different case studies of photo-induced phenomena in solutions and biological environments are highlighted and discussed, with special attention to the computational and modeling challenges.

Bioinspired dual-crosslinking strategy for fabricating soy protein-based adhesives with excellent mechanical strength and antibacterial activity

Plant-derived biomass adhesives are increasingly in demand to replace traditional non-biodegradable petrochemical materials. However, the insufficient mechanical strengths and poor antibacterial activities of biomaterials severely limit their applicability. Inspired by the amphiphilic characteristics of mussel protein, a dual-crosslinking strategy is reported here for preparing soy meal (SM)-based adhesives with excellent adhesion and antibacterial properties. Specifically, castor oil containing abundant hydroxyl groups was used to prepare the cationic waterborne polyurethane (WPU) dispersion. Subsequently, the dynamic glue bridges were synthesized from the tannic acid-functionalized borax (TA@BA) complexes via multiple coordination bonds. Finally, the enhanced cross-linking network system was then constructed in the protein matrix based on the synergy of dynamic covalent bonds, electrostatic interactions, and hydrogen bonds. As a result, the wet strength of the resultant adhesive significantly increased by 154.77% compared to the SM adhesive. Additionally, the resultant adhesive exhibited remarkably enhanced thermal stability, flame retardancy, and water resistance. Based on the synergistic effect of the cationic WPU, polyphenol components, and borate groups, the SM/WPU/TA@BA adhesive exhibited desirable anti-mildew and antibacterial properties. This biomimetic dual-crosslinking design therefore provides a novel and facile strategy for the preparation of high-performance biopolymer adhesives used in the fields of biology and engineering.