Mechanisms and applications of bioinspired underwater/wet adhesives

In nature, many organisms can effectively fix to contact substrates and move and prey in complex living environments, such as underwater, seawater, and tidal environments, owing to special secreted chemical components and/or special micro/nanostructures on the adhesive surface of these organisms. Inspired by the adhesive performance of organisms, extensive research related to adhesive components and adhesive surfaces has been conducted recently. To better understand the underlying adhesive mechanisms and facilitate further continuous inspiration, a brief overview of recent wet/underwater adhesive materials is provided herein. First, the adhesive processes and underlying mechanisms of commonly researched organisms, such as mussels, octopuses, clingfish, and tree frogs, are discussed, and the corresponding bioinspired artificial adhesives are presented. Then, the applications of these bioinspired adhesives, such as intelligent robots (signal monitoring and sensing devices), wearable devices (including wet climbing and electronic skin), biomedicines (including wound dressings, bone adhesion, and rapid hemostasis), are presented and summarized. Finally, we offer our perspective on the future challenges and development of bioinspired artificial adhesives.     

Natural underwater adhesives

The general topic of this review is protein‐based underwater adhesives produced by aquatic organisms. The focus is on mechanisms of interfacial adhesion to native surfaces and controlled underwater solidification of natural water‐borne adhesives. Four genera that exemplify the broad range of function, general mechanistic features, and unique adaptations are discussed in detail: blue mussels, acorn barnacles, sandcastle worms, and freshwater caddisfly larva. Aquatic surfaces in nature are charged and in equilibrium with their environment, populated by an electrical double layer of ions as well as adsorbed natural polyelectrolytes and microbial biofilms. Surface adsorption of underwater bioadhesives likely occurs by exchange of surface bound ligands by amino acid sidechains, driven primarily by relative affinities and effective concentrations of polymeric functional groups. Most aquatic organisms exploit modified amino acid sidechains, in particular phosphorylated serines and hydroxylated tyrosines (dopa), with high‐surface affinity that form coordinative surface complexes. After delivery to the surfaces as a fluid, permanent natural adhesives solidify to bear sustained loads. Mussel plaques are assembled in a manner superficially reminiscent of in vitro layer‐by‐layer strategies, with sequentially delivered layers associated through Fe(dopa)₃ coordination bonds. The adhesives of sandcastle worms, caddisfly larva, and barnacles may be delivered in a form somewhat similar to in vitro complex coacervation. Marine adhesives are secreted, or excreted, into seawater that has a significantly higher pH and ionic strength than the internal environment. Empirical evidence suggests these environment triggers could provide minimalistic, fail‐safe timing mechanisms to prevent premature solidification (insolubilization) of the glue within the secretory system, yet allow rapid solidification after secretion. Underwater bioadhesives are further strengthened by secondary covalent curing. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

分子动力学模拟多巴在自组装膜上的黏附性

为了更好地理解贻贝在表面的黏附机理,实现水下胶黏,采用分子动力学方法研究了多巴在自组装膜上的黏附性:采用伞形取样和加权柱状图分析方法计算了多巴在不同自组装膜表面的黏附自由能,使用拉伸分子动力学模拟研究了多巴在不同自组装膜表面上黏附后的脱附力.结果表明,多巴在带负电的羧基自组装膜上的黏附能比在带正电的氨基自组装膜上的大,多巴更容易黏附到带负电表面;多巴在带电表面的黏附能比未带电表面的黏附能更强,表明在带电表面黏附更稳定.进一步分析了多巴在不同表面的取向分布,发现多巴与不同表面相互作用的方式不同:与疏水表面主要通过苯环相互作用;与亲水表面主要通过羟基相互作用;与负电表面主要通过氨基相互作用;与正电表面主要通过羧基相互作用.通过模拟比较了多巴在不同自组装膜上的脱附力,发现多巴在带电表面的脱附力比在未带电表面的大,与黏附能的趋势一致.对比4种非带电表面的脱附力,发现多巴在疏水性甲基自组装膜表面的脱附力最大,黏附更稳定,随着表面疏水性的增加,脱附力增大,黏附稳定性增强.本工作可为研发新型水下胶黏剂提供理论指导.     

Wet and Functional Adhesives from One‐Step Aqueous Self‐Assembly of Natural Amino Acids and Polyoxometalates

Sessile organisms have undergone long‐term evolution to develop the unique ability by positioning themselves on wet solid surface through secreting adhesive proteins. The present study reveals that natural amino acid monomers can also exhibit similar adhesion capacity. This kind of biomimetic adhesives were created by the one‐step aqueous assembly of basic amino acids with assistance of anionic polyoxometalates. The polyoxometalates not only serve as multivalent scaffold to initiate the supramolecular cross‐linking of amino acid molecules, but also function as a redox component, bestowing the wet adhesives with electrochromic features.     

Wet and Functional Adhesives from One-Step Aqueous Self-Assembly of Natural Amino Acids and Polyoxometalates

Sessile organisms have undergone long-term evolution to develop the unique ability by positioning themselves on wet solid surface through secreting adhesive proteins. The present study reveals that natural amino acid monomers can also exhibit similar adhesion capacity. This kind of biomimetic adhesives were created by the one-step aqueous assembly of basic amino acids with assistance of anionic polyoxometalates. The polyoxometalates not only serve as multivalent scaffold to initiate the supramolecular cross-linking of amino acid molecules, but also function as a redox component, bestowing the wet adhesives with electrochromic features.     

Strong Protein Adhesives through Lanthanide-enhanced Structure Folding and Stack Density

Generating strong adhesion by engineered proteins has the potential for high technical applications. Current studies of adhesive proteins are primarily limited to marine organisms, e.g., mussel adhesive proteins. Here, we present a modular engineering strategy to generate a type of exotic protein adhesives with super strong adhesion behaviors. In the protein complexes, the lanmodulin (LanM) underwent α-helical conformational transition induced by lanthanides, thereby enhancing the stacking density and molecular interactions of adhesive protein. The resulting adhesives exhibited outstanding lap-shear strength of ≈31.7 MPa, surpassing many supramolecular and polymer adhesives. The extreme temperature (−196 to 200 °C) resistance capacity and underwater adhesion performance can significantly broaden their practical application scenarios. Ex vivo and in vivo experiments further demonstrated the persistent adhesion performance for surgical sealing and healing applications.     

Biocompatible,transparent, and water-resistant adhesive films with high mechanical stability derived from post-facile chemical cross-linking

Transparent surgical adhesives with excellent underwater adhesion and mechanical strength are strongly desirable for various biomedical applications such as wound closure and tissue healing. This is addressed in the present work by the development of biocompatible, transparent, and water-resistant adhesive films prepared from catechol-modified ε-poly(ʟ-lysine) and dopamine hydrochloride modified sodium hyaluronate layers successively applied using the layer-by-layer (LbL) assembly method. The LbL-assembled films are easily released from substrates via a mechanical exfoliation method with a blade to obtain free-standing multilayer films. The exceptional wet adhesion properties of the catechol groups yield films with excellent underwater adhesion strength. The underwater stability and mechanical strength of the free-standing multilayer films are improved via post-facile chemical cross-linking using biocompatible N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride. The post-treated free-standing multilayer films achieve a tensile strength of 0.36 ± 0.20 MPa and an elongation at break of 180.05% in water. The free-standing multilayer films exhibit a high optical transmittance greater than 55% in the visible region.     

Intrinsic Surface‐Drying Properties of Bioadhesive Proteins

Sessile marine mussels must “dry” underwater surfaces before adhering to them. Synthetic adhesives have yet to overcome this fundamental challenge. Previous studies of bioinspired adhesion have largely been performed under applied compressive forces, but such studies are poor predictors of the ability of an adhesive to spontaneously penetrate surface hydration layers. In a force‐free approach to measuring molecular‐level interaction through surface‐water diffusivity, different mussel foot proteins were found to have different abilities to evict hydration layers from surfaces—a necessary step for adsorption and adhesion. It was anticipated that DOPA would mediate dehydration owing to its efficacy in bioinspired wet adhesion. Instead, hydrophobic side chains were found to be a critical component for protein–surface intimacy. This direct measurement of interfacial water dynamics during force‐free adsorptive interactions at solid surfaces offers guidance for the engineering of wet adhesives and coatings.     

氢键作用驱动原花青素构筑水基抗菌黏合剂北大核心CSCD

水下黏合剂在生物医学和工程应用领域的需求越来越大。然而,目前报道的大多数水下黏合剂的制备方法中通常需要复杂的化学偶联或修饰,以及昂贵的构筑基元。本文利用低成本的葡萄籽提取物原花青素(PA)和商业化的聚乙二醇寡聚物(PEG)为构筑基元,发展了一种简单且经济的水下黏合剂的构筑策略,实现了在氢键作用下诱导仿生黏合剂生成。此黏合剂既可以在水上又可以在水下黏附不同材质的基底,且可重复使用。此外,易于制备的PA/PEG黏合剂也具有良好的抗菌活性和生物相容性。由于PA/PEG黏合剂具有制备简单、广谱黏附性、可循环使用和抗菌性等优点,将在医疗器械和制药应用中得到广泛应用。     

Surface hydration for antifouling and bio-adhesion

Antifouling properties of materials play crucial roles in many important applications such as biomedical implants, marine antifouling coatings, biosensing, and membranes for separation. Poly(ethylene glycol) (or PEG) containing polymers and zwitterionic polymers have been shown to be excellent antifouling materials. It is believed that their outstanding antifouling activity comes from their strong surface hydration. On the other hand, it is difficult to develop underwater glues, although adhesives with strong adhesion in a dry environment are widely available. This is related to dehydration, which is important for adhesion for many cases while water is the enemy of adhesion. In this research, we applied sum frequency generation (SFG) vibrational spectroscopy to investigate buried interfaces between mussel adhesive plaques and a variety of materials including antifouling polymers and control samples, supplemented by studies on marine animal (mussel) behavior and adhesion measurements. It was found that PEG containing polymers and zwitterionic polymers have very strong surface hydration in an aqueous environment, which is the key for their excellent antifouling performance. Because of the strong surface hydration, mussels do not settle on these surfaces even after binding to the surfaces with rubber bands. For control samples, SFG results indicate that their surface hydration is much weaker, and therefore mussels can generate adhesives to displace water to cause dehydration at the interface. Because of the dehydration, mussels can foul on the surfaces of these control materials. Our experiments also showed that if mussels were forced to deposit adhesives onto the PEG containing polymers and zwitterionic polymers, interfacial dehydration did not occur. However, even with the strong interfacial hydration, strong adhesion between mussel adhesives and antifouling polymer surfaces was detected, showing that under certain circumstances, interfacial water could enhance the interfacial bio-adhesion.

Antifouling properties of materials play crucial roles in many important applications such as biomedical implants, marine antifouling coatings, biosensing, and membranes for separation.     

The latest research progress on the prevention of storage pests by natural products: Species,mechanisms, and sources of inspiration

The quality of grains is influenced by storage pests, which are not only spoilers of stored grain, but also vectors of human and animal diseases. Chemical pesticides play an essential role in the cultivation and storage of cereals, however, due to the low degradability and residual toxicity of synthetic pesticides on the environment and non-target organisms, as well as the increasing resistance of target organisms to them, consideration should be given to the development of alternative pest control agents. Compounds isolated from natural sources have emerged as preferred targets for the development of novel insecticidal agents because of their eco-friendliness, safety, and effectiveness. In this review, we primarily focus on the natural product (NPs) control of storage pests. The effective monomer components of NPs and their anti-insect mechanisms were discussed, and natural sources of inspiration and models for insect repellents are described. This review aimed to provide guidelines for the exploitation and utilization of green and efficient natural insecticides.     

The Chemistry behind Catechol‐Based Adhesion

The adhesion of some marine organisms to almost any kind of surface in wet conditions has aroused increasing interest in recent decades. Numerous fundamental studies have been performed to understand the scientific basis of this behaviour, with catechols having been found to play a key role. Several novel bio‐inspired adhesives and coatings with value‐added performances have been developed by taking advantage of the knowledge gained from these studies. To date there has been no detailed overview focusing exclusively on the complex mode of action of these materials. The aim of this Review is to present recent investigations that elucidate the origin of the strong and versatile adsorption capacities of the catechol moiety and the effects of extrinsic factors that play important roles in the overall adhesion process, such as pH value, solvent, and the presence of metal ions. The aim is to detail the chemistry behind the astonishing properties of natural and synthetic catechol‐based adhesive materials.     

Design and fabrication of gecko-inspired adhesives

Recently, there has been significant interest in developing dry adhesives mimicking the gecko adhesive system, which offers several advantages compared to conventional pressure-sensitive adhesives. Specifically, gecko adhesive pads have anisotropic adhesion properties; the adhesive pads (spatulae) stick strongly when sheared in one direction but are non-adherent when sheared in the opposite direction. This anisotropy property is attributed to the complex topography of the array of fine tilted and curved columnar structures (setae) that bear the spatulae. In this study, we present an easy, scalable method, relying on conventional and unconventional techniques, to incorporate tilt in the fabrication of synthetic polymer-based dry adhesives mimicking the gecko adhesive system, which provides anisotropic adhesion properties. We measured the anisotropic adhesion and friction properties of samples with various tilt angles to test the validity of a nanoscale tape-peeling model of spatular function. Consistent with the peel zone model, samples with lower tilt angles yielded larger adhesion forces. The tribological properties of the synthetic arrays were highly anisotropic, reminiscent of the frictional adhesion behavior of gecko setal arrays. When a 60° tilt sample was actuated in the gripping direction, a static adhesion strength of ~1.4 N/cm(2) and a static friction strength of ~5.4 N/cm(2) were obtained. In contrast, when the dry adhesive was actuated in the releasing direction, we measured an initial repulsive normal force and negligible friction.     

仿生干湿摩擦黏附器件的研究进展

生物在自然界的演化过程中进化出了许多独特的干湿摩擦、黏附器官来适应其生存环境.研究人员通过对自然界中典型摩擦与黏附现象的研究、认识和总结,提出了相应的仿生界面摩擦、黏附理论与模型,用于指导人工合成型智能摩擦黏附材料与器件.目前,仿生摩擦、黏附材料体系与器件的设计策略主要以表面微结构、界面物理化学相互作用以及机械形变为基...     

Diffusive Adhesives for Water-Rich Materials: Strong and Tunable Adhesion Beyond the Interface

It is notoriously difficult to adhere water-rich materials, such as hydrogels and biological tissues. Existing adhesives usually suffer from weak and nonadjustable adhesion strength, in part because the contact between the adhesive and substrate is largely restrained to the adhesive/substrate interface. In this study, we have attempted to overcome this shortcoming by developing a class of diffusive adhesives (DAs) that can extend adhesion deep into the substrate to maximize the adhesive/substrate contact. The DAs consist of hydrogel matrices and preloaded water-soluble monomers and crosslinkers that can diffuse extensively into the water-rich substrates after adhesive/substrate contact. Polymerization and crosslinking of the monomers are then triggered leading to a bridging network that interpenetrates the DA and substrate skeletons and topologically binds them together. This kind of adhesion, in the absence of adhesive/substrate covalent bonding, is of high strength and toughness, comparable to those of the best-performing natural and artificial adhesives. More importantly, we can precisely tune the adhesion strength on demand by manipulating the diffusion profile. It is envisioned that the DA family could be extended to include a large pool of hydrogel matrices and monomers, and that they could be particularly useful in biological and medical applications.     

Adhesives and compounds in manufacture of electronic mechanisms

The general properties of adhesives and compounds for electronic articles are described that were elaborated by the company: TK-1 adhesive with elevated thermal conductivity; TEK-type adhesives that demonstrate higher elasticity and adhesion ability; TK-8-type all-purpose adhesives; MS-type, single-packed, thermally stable glues for long storage; electrically conductive adhesives; TPK-1 and TPK-2 magnetic adhesives and TPK-3 nonmagnetic adhesive; and some compounds, e.g., epoxide molding compositions. The functionality of all adhesives and compounds presented were tested for weather factors, including elevated humidity, higher and lower temperatures, thermal cycles, effects of vibrations for both pilot samples, and final articles of electronic mechanisms.     

仿贻贝粘附蛋白聚合物的研究及动态

贻贝粘附蛋白以其对不同基材表面及在水下都具备高强的粘附能力而闻名。根据仿生学原理,通过将贻贝粘附蛋白功能元即邻苯二酚基团与合成高分子相结合制备仿贻贝粘附蛋白聚合物,达到复制重现甚至超越天然贻贝粘附蛋白粘附效力的目的,是目前贻贝仿生领域研究热点之一。本文综述了近年来国内外仿贻贝粘附蛋白聚合物的研究进展。我们按照主链结构的种类进行了分类,对仿贻贝粘附蛋白聚合物材料的发展过程、材料的设计思路以及应用领域进行了系统的归纳总结。通过研究分子结构与仿生材料功能特性之间的相互关系,希望为以后设计合成新型的功能化的贻贝仿生材料提供有益的借鉴和参考。     

Dynamic Interfacial Adhesion through Cucurbit[n]uril Molecular Recognition

Supramolecular building blocks, such as cucurbit[n]uril (CB[n])‐based host–guest complexes, have been extensively studied at the nano‐ and microscale as adhesion promoters. Herein, we exploit a new class of CB[n]‐threaded highly branched polyrotaxanes (HBP‐CB[n]) as aqueous adhesives to macroscopically bond two wet surfaces, including biological tissue, through the formation of CB[8] heteroternary complexes. The dynamic nature of these complexes gives rise to adhesion with remarkable toughness, displaying recovery and reversible adhesion upon mechanical failure at the interface. Incorporation of functional guests, such as azobenzene moieties, allows for stimuli‐activated on‐demand adhesion/de‐adhesion. Macroscopic interfacial adhesion through dynamic host–guest molecular recognition represents an innovative strategy for designing the next generation of functional interfaces, biomedical devices, tissue adhesives, and wound dressings.     

A reversible water-based electrostatic adhesive

Commercial adhesives typically fall into two categories: structural or pressure sensitive. Structural glues rely on covalent bonds formed during curing and provide high tensile strength whilst pressure-sensitive adhesives use physical bonding to provide weaker adhesion, but with considerable convenience for the user. Here, a new class of adhesive is presented that is also reversible, with a bond strength intermediate between those of pressure-sensitive and structural adhesives. Complementary water-based formulations incorporating oppositely charged polyelectrolytes form electrostatic bonds that may be reversed through immersion in a low or high pH aqueous environment. This electrostatic adhesive has the advantageous property that it exhibits good adhesion to low-energy surfaces such as polypropylene. Furthermore, it is produced by the emulsion copolymerization of commodity materials, styrene and butyl acrylate, which makes it inexpensive and opens the possibility of industrial production. Bio-based materials have been also integrated into the formulations to further increase sustainability. Moreover, unlike other water-based glues, adhesion does not significantly degrade in humid environments. Because such electrostatic adhesives do not require mechanical detachment, they are appropriate for the large-scale recycling of, e.g., bottle labels or food packaging. The adhesive is also suitable for dismantling components in areas as varied as automotive parts and electronics.     

Robust Hydrogel Adhesive with Dual Hydrogen Bond Networks

Hydrogel adhesives are attractive for applications in intelligent soft materials and tissue engineering, but conventional hydrogels usually have poor adhesion. In this study, we designed a strategy to synthesize a novel adhesive with a thin hydrogel adhesive layer integrated on a tough substrate hydrogel. The adhesive layer with positive charges of ammonium groups on the polymer backbones strongly bonds to a wide range of nonporous materials’ surfaces. The substrate layer with a dual hydrogen bond system consists of (i) weak hydrogen bonds between N,N-dimethyl acrylamide (DMAA) and acrylic acid (AAc) units and (ii) strong multiple hydrogen bonds between 2-ureido-4[1H]-pyrimidinone (UPy) units. The dual hydrogen-bond network endowed the hydrogel adhesives with unique mechanical properties, e.g., toughness, highly stretchability, and insensitivity to notches. The hydrogel adhesion to four types of materials like glass, 316L stainless steel, aluminum, Al₂O₃ ceramic, and two biological tissues including pig skin and pig kidney was investigated. The hydrogel bonds strongly to dry solid surfaces and wet tissue, which is promising for biomedical applications.