Electrochemical identification of reductive enantiomers in wood channels: A low-cost and scalable platform for chiral sensing.

Chirality, an inherent characteristic of natural substances (such as sugars, peptides, proteins, and nucleic acid), plays a vital role in human metabolism and exerts substantial impacts. In general, chiral drugs can display diverse pharmacological and pharmacokinetic properties. One enantiomer may exhibit therapeutic effects, while the other could cause adverse reactions. Selective recognition of enantiomers is thus a significant task in the biomolecular and pharmaceutical fields. Despite the development of several chiral identification techniques, low-cost enantioselective sensing methods remain highly desirable. Here, we designed and developed an electrochemical sensing device for reductive enantiomer identification using natural wood channels as the substrate. The wood channels were endowed with oxidase-like activity through the in-situ growth of cerium oxide nanoparticles (CeO2). Chiral recognition capability was further introduced by incorporating a layer of chiral ZIF-8 (L-ZIF) as the chiral selector. To demonstrate the enantioselective sensing performance, 3,4-dihydroxyphenylalanine (DOPA) enantiomers were employed as model analytes. Due to the oxidase-like activity and the confinement effect of the proposed channels, the captured DOPA enantiomers were effectively oxidized to their quinone structure, and the Ce(IV) in CeO2 was reduced to Ce(III). These changes led to alterations in the surface charge of the channels, thereby modulating their ionic transport properties. This sensing mechanism also proved useful for the identification of other reductive enantiomers. The limits of detection for l-DOPA and d-DOPA were determined as 2.41 nM and 1.56 nM, respectively. The resulting wood channel-based sensing device not only can be used for the recognition and detection of reductive enantiomers, but also is expected to be applied to the non-electochemically active substances. Moreover, this study offers a novel type of solid-state channel material with low cost, reproducibility, and easy accessibility for electrochemical chiral sensing.

Poly(3,4-dihydroxyphenylalanine)-modified cellulose paper for the extraction of deoxyribonucleic acid by a laboratory-built automated extraction device.

The success of polymerase chain reaction (PCR) depends on the quality of deoxyribonucleic acid (DNA) templates. This study developed a cost-effective and eco-friendly DNA extraction system utilizing poly(3,4-dihydroxyphenylalanine)-modified cellulose paper (polyDOPA@paper). PolyDOPA@paper was prepared by oxidatively self-polymerizing DOPA under weak alkaline conditions and utilizing the adhesive property of polyDOPA on different materials. Compared to the uncoated cellulose paper, polyDOPA coating significantly enhances DNA adsorption owing to its abundant amino, carboxyl, and hydroxyl moieties. The DNA extraction mechanism using polyDOPA@paper was discussed. The maximum adsorption capacity of polyDOPA@paper for DNA was 20.7 µg cm-2. Moreover, an automated extraction system was designed and fabricated using 3D printing technology. The device simplifies the operation and ensures the reproducibility and consistency of the results. More importantly, it eliminates the need for specialized training of operators. The feasibility of the polyDOPA@paper-based automated extraction system was evaluated by quantitatively detecting Escherichia coli in spiked milk samples via a real-time PCR. The detection limit was 102 cfu mL-1. The results suggest that the system would have significant potential in detecting pathogens.

First-in-Human Evaluation of [18F]FDOPA Produced by Organo-Photoredox Reactions.

Photoredox is a powerful synthetic tool in organic chemistry and has been widely used in various fields, including nuclear medicine and molecular imaging. In particular, acridinium-based organophotoredox radiolabeling has significantly impacted the production and discovery of positron emission tomography (PET) agents. Despite their extensive use in preclinical research, no PET agents synthesized by acridinium photoredox labeling have been tested in humans. [18F]FDOPA is clinically used for tumor diagnosis and the evaluation of neuropsychiatric disorders, but its application is limited by complex synthesis methods, the need for expensive modules, and/or the high cost of consumable materials/cassettes. In this report, we integrated a photoredox labeling unit with an automated module and produced [18F]FDOPA for human study. This research not only represents the first human study of a PET agent generated by acridinium-based organophotoredox reactions but also demonstrates the safety of this novel labeling method, serving as a milestone/reference for the clinical translation of other PET agents generated by this technique in the future.

Chemically Modulating Ceria-Based Artificial Haloperoxidase for Enhanced Antibacterial Activity and Biofilm Inhibition.

Ceria (CeO2) nanoparticles with haloperoxidase (HPO)-like activity have gained attention as a biologically benign antifoulant. 3,4-Dihydroxy-l-phenylalanine (DOPA), a main composition in mussel foot proteins, plays a crucial role in the biofouling process. However, the impact on the HPO-like activity and antifouling performance of CeO2 nanoparticles when DOPA molecules adsorb on them remains unexplored. This interesting question warrants investigation, particularly considering that it may occur in an actual marine environment. Herein, the interaction between DOPA and CeO2 is explored. Despite the higher Ce3+ fractions and the lower band gap energies due to the electron transfer from DOPA to the CeO2 surface, DOPA still had a slightly negative effect on the HPO-like activity of CeO2 since they decreased the exposed Ce3+ sites. The DOPA-CeO2 nanocomposites with HPO-like activities could kill bacteria and trigger quorum-sensing signaling quenching, achieving a biofilm inhibition performance. Amazingly, 0.1% DOPA-CeO2 nanocomposite exhibited higher antibacterial activity and better biofilm suppression activities due to its HPO-like activity and positive zeta potential. The remarkable results demonstrated that DOPA, as a participant in the biofouling process, could enhance the antibacterial activity and antifouling performance of CeO2 nanoparticles at an appropriate concentration.

Manufacturing 6-[18F]Fluoro-L-DOPA via Flow Chemistry-Enhanced Photoredox Radiofluorination.

In this study, we introduce a practical methodology for the synthesis of PET probes by seamlessly combining flow chemistry with photoredox radiofluorination. The clinical PET tracer 6-[18F]FDOPA was smoothly prepared in a 24.3% non-decay-corrected yield with over 99.0% radiochemical purity (RCP) and enantiomeric excess (ee), notably by a simple cartridge-based purification. The flow chemistry-enhanced photolabeling method supplies an efficient and versatile solution for the synthesis of 6-[18F]FDOPA and for more PET tracer development.

Alternative strategies for the recombinant synthesis, DOPA modification and analysis of mussel foot proteins - A case study for Mefp-3 from Mytilus edulis.

Mussel foot proteins (Mfps) possess unique binding properties to various surfaces due to the presence of L-3,4-dihydroxyphenylalanine (DOPA). Mytilus edulis foot protein-3 (Mefp-3) is one of several proteins in the byssal adhesive plaque. Its localization at the plaque-substrate interface approved that Mefp-3 plays a key role in adhesion. Therefore, the protein is suitable for the development of innovative bio-based binders. However, recombinant Mfp-3s are mainly purified from inclusion bodies under denaturing conditions. Here, we describe a robust and reproducible protocol for obtaining soluble and tag-free Mefp-3 using the SUMO-fusion technology. Additionally, a microbial tyrosinase from Verrucomicrobium spinosum was used for the in vitro hydroxylation of peptide-bound tyrosines in Mefp-3 for the first time. The highly hydroxylated Mefp-3, confirmed by MALDI-TOF-MS, exhibited excellent adhesive properties comparable to a commercial glue. These results demonstrate a concerted and simplified high yield production process for recombinant soluble and tag-free Mfp3-based proteins with on demand DOPA modification.

Study on the formation mechanism of blackening in damaged lotus rhizome epidermis: Effects of polyphenols and iron.

Lotus rhizome is an important aquatic vegetable, but the blackening of lotus rhizome epidermis (LRE) seriously affects its appearance and quality, which makes lotus rhizome products unmarketable. In this study, the effects of polyphenols and iron on the LRE color were studied to explore the possible mechanism of LRE blackening. Results indicated that the measurable total phenols contents in the mud treatment (MT) group were significantly reduced, and the total iron contents were significantly increased compared with the bruised treatment group (p < 0.05). The high-performance liquid chromatography results showed that the main polyphenols in LRE were dopa, gallocatechin, and catechin, as well as a small amount of catechol, epicatechin, proanthocyanidin B2, and proanthocyanidin C1. Moreover, the results of color difference and ultraviolet adsorption spectroscopy showed that there were obviously black or brown-gray of dopa (525 nm), gallocatechin (504.5 nm), and catechin (550 and 504.5 nm) with FeCl2. The simulated system treatment of LRE further confirmed that the chromaticity effect of dopa and iron in bruised LRE was similar to that of the MT group, whereas 1% (w/w) ascorbic acid, 2% (w/w) EDTA-2Na, or 3% (w/w) citric acid could solely prohibit the blackening. This suggested that the dopa in LRE and FeCl2 in mud may mainly combine into [2(DOPA-2H+)+Fe3+]- through non-covalent interaction, which leads to the blackening of bruised LRE under neutral conditions. These results can guide the storage of lotus rhizomes and improve the development of the lotus rhizome industry.

Self-Healable Adhesive Hydrogel with a Preserved Underwater Adhesive Ability Based on Histidine-Zinc Coordination and a Bioengineered Hybrid Mussel Protein.

Mussels are marine organisms that are capable of constructing an underwater adhesion between their bodies and rigid structures. It is well known that mussels achieve underwater adhesion through the presence of mussel adhesive proteins (MAPs) that contain high levels of 3,4-dihydroxyphenylalanine (DOPA). Although the extraordinary underwater adhesive properties of mussels are attributed to DOPA, its capacity to play a dual role in surface adhesion and internal cohesion is inherently limited. However, mussels employ a combination of chemical moieties, not just DOPA, along with anatomical components, such as plaque and byssus, in underwater adhesion. This also involves junction proteins that connect the plaque and byssus. In this study, a novel hybrid MAP was bioengineered via the fusion of the plaque protein (foot protein type 1) and the histidine-rich domain of the junction protein (foot protein type 4). To achieve direct adhesion underwater, the adhesive should maintain surface adhesion without disintegrating. Notably, the histidine-Zn-coordinated hybrid MAP hydrogel maintained a high surface adhesion ability even after cross-linking because of the preservation of its unoxidized and non-cross-linked DOPA moieties. The formulated adhesive hydrogel system based on the bioengineered hybrid MAP exhibited self-healing properties, owing to the reversible metal coordination bonds. The developed adhesive hydrogel exhibits outstanding levels of bulk adhesion in underwater environments, highlighting its potential as an effective adhesive biomaterial. Therefore, the introduction of histidine-rich domains into MAPs may be applied in various studies to formulate mussel-inspired adhesives with self-healing properties and to fully utilize the adhesive ability of DOPA.

Selectively Positioned Catechol Moiety Supports Ultrashort Self-Assembling Peptide Hydrogel Adhesion for Coral Restoration.

Coral reef survival is threatened globally. One way to restore this delicate ecosystem is to enhance coral growth by the controlled propagation of coral fragments. To be sustainable, this technique requires the use of biocompatible underwater adhesives. Hydrogels based on rationally designed ultrashort self-assembling peptides (USP) are of great interest for various biological and environmental applications, due to their biocompatibility and tunable mechanical properties. Implementing superior adhesion properties to the USP hydrogel compounds is crucial in both water and high ionic strength solutions and is relevant in medical and marine environmental applications such as coral regeneration. Some marine animals secrete large quantities of the aminoacids dopa and lysine to enhance their adhesion to wet surfaces. Therefore, the addition of catechol moieties to the USP sequence containing lysine (IIZK) should improve the adhesive properties of USP hydrogels. However, it is challenging to place the catechol moiety (Do) within the USP sequence at an optimal position without compromising the hydrogel self-assembly process and mechanical properties. Here, we demonstrate that, among three USP hydrogels, DoIIZK is the least adhesive and that the adhesiveness of the IIZDoK hydrogel is compromised by its poor mechanical properties. The best adhesion outcome was achieved using the IIZKDo hydrogel, the only one to show equally sound adhesive and mechanical properties. A mechanistic understanding of this outcome is presented here. This property was confirmed by the successful gluing of coral fragments by means of IIZKDo hydrogel that are still thriving after more than three years since the deployment. The validated biocompatibility of this underwater hydrogel glue suggests that it could be advantageously implemented for other applications, such as surgical interventions.

Mussel-Inspired Cation-π Interactions: Wet Adhesion and Biomimetic Materials.

Cation-π interaction is one of the most important noncovalent interactions identified in biosystems, which has been proven to play an essential role in the strong adhesion of marine mussels. In addition to the well-known catecholic amino acid, l-3,4-dihydroxyphenylalanine, mussel foot proteins are rich in various aromatic moieties (e.g., tyrosine, phenylalanine, and tryptophan) and cationic residues (e.g., lysine, arginine, and histidine), which favor a series of short-range cation-π interactions with adjustable strengths, serving as a prototype for the development of high-performance underwater adhesives. This work highlights our recent advances in understanding and utilizing cation-π interactions in underwater adhesives, focusing on three aspects: (1) the investigation of the cation-π interaction mechanisms in mussel foot proteins via force-measuring techniques; (2) the modulation of cation-π interactions in mussel mimetic polymers with the variation of cations, anions, and aromatic groups; (3) the design of wet adhesives based on these revealed principles, leading to functional materials in the form of films, coacervates, and hydrogels with biomedical and engineering applications. This review provides valuable insights into the development and optimization of smart materials based on cation-π interactions.

Statistical Copolymers that Mimic Aspects of Mussel Adhesive Proteins: Access to Robust Adhesive-Domains for Non-Covalent Surface PEGylation.

Reconstructing functional sequence motifs of proteins, using statistical copolymers greatly reduces the information content, but simplifies synthesis significantly. Key amino acid residues involved in the adhesion of mussel foot proteins are identified. The side-chain functionalities of Dopa, lysine, and arginine are abstracted and incorporated into acrylate monomers to allow controlled radical polymerization. The resulting Dopa-acrylate (Y*-acr), arginine-acrylate (R-acr), and lysine-acrylate (K-acr) monomers are polymerized in different monomer ratios and compositions by reversible addition fragmentation transfer polymerization with a poly(ethylene glycol) (PEG) macrochain transfer agent. This results in two sets of PEG-block-copolymers with statistical mixtures and different monomer ratios of catechol/primary amine and catechol/guanidine side-chain functionalities, both important pairs for mimicking π-cation interactions. The coating behavior of these PEG-block-copolymers is evaluated using quartz crystal microbalance with dissipation energy monitoring (QCM-D), leading to non-covalent PEGylation of the substrates with clear compositional optima in the coating stability and antifouling properties. The coatings prevent non-reversible albumin or serum adsorption, as well as reduce cellular adhesion and fungal spore attachment.

DOPA Residues Endow Collagen with Radical Scavenging Capacity.

Here we uncover collagen, the main structural protein of all connective tissues, as a redox-active material. We identify dihydroxyphenylalanine (DOPA) residues, post-translational oxidation products of tyrosine residues, to be common in collagen derived from different connective tissues. We observe that these DOPA residues endow collagen with substantial radical scavenging capacity. When reducing radicals, DOPA residues work as redox relay: they convert to the quinone and generate hydrogen peroxide. In this dual function, DOPA outcompetes its amino acid precursors and ascorbic acid. Our results establish DOPA residues as redox-active side chains of collagens, probably protecting connective tissues against radicals formed under mechanical stress and/or inflammation.

Direct and Efficient Incorporation of DOPA into Resilin-Like Proteins Enables Cross-Linking into Tunable Hydrogels.

3,4-Dihydroxyphenylalanine (DOPA), a naturally occurring yet noncanonical amino acid, endows protein polymers with diverse chemical reactivities and novel functionalities. Although many efforts have been made to incorporate DOPA into proteins, the incorporation efficiency and production titer remain low and severely hinder the exploration of these peculiar proteins for biomaterial fabrication. Here, we report an efficient biosynthetic strategy to produce large amounts of DOPA-incorporated structural proteins for the fabrication of hydrogels with tunable mechanical properties. First, synthetic genes were constructed that encode repetitive resilin-like proteins (RLPs) with varying proportions of tyrosine residues and molecular weights (Mw). Decoding of these genes into RLPs incorporated with DOPA was achieved via mis-aminoacylation of DOPA by endogenous tyrosyl-tRNA synthetase (TyrRS) in recombinant Escherichia coli cells. By developing a stoichiometry-guided two-phase culture strategy, we achieved independent control of the bacterial growth and protein synthesis phases. This enabled hyperproduction of the DOPA-incorporated RLPs at gram-per-liter levels and with a high DOPA incorporation yield of 76-85%. The purified DOPA-containing RLPs were then successfully cross-linked into bulk hydrogels via facile DOPA-Fe3+ complexations. Interestingly, these hydrogels exhibited viscoelastic and self-healing properties that are highly dependent on the catechol content and Mw of the RLPs. Finally, exploration of the molecular cross-linking mechanisms revealed that higher DOPA contents of the proteins would result in the concomitant occurrence of metal coordination and oxidative covalent cross-linking. In summary, our results suggest a useful platform to generate DOPA-functionalized protein materials and provide deeper insights into the gelation systems based on DOPA chemistry.

Ternary Synergy of Lys, Dopa, and Phe Results in Strong Cohesion of Peptide Films.

Synergistic interactions between 3,4-dihydroxyphenylalanine (Dopa, Y*), cationic residues, and the aromatic rings have been recently highlighted as influential factors that enhance the underwater adhesion strength of mussel foot proteins and their derivatives. In this study, we report the first ever evidence of a cation-catechol-benzene ternary synergy between Y*, lysine (Lys, K), and phenylalanine (Phe, F) in adhesive peptides. We synthesized three hexapeptides containing a different combination of Y*, K, and F, i.e., (KY*)3, (KF)3, and (KY*F)2, respectively, exploring the relationship between the cohesive performance and molecular architecture of peptides. The peptide with the (KY*F)2 sequence displays the strongest underwater cohesion energy of 10.3 ± 0.3 mJ m-2 from direct nanoscale surface force measurements. Combined with molecular dynamics simulation, we demonstrated that there are more bonding interactions (including cation-π, π-π, and hydrogen bond interactions) in (KY*F)2 compared to the other two peptides. In addition, peptide (KY*F)2 still shows the strongest cohesive energies of 7.6 ± 0.7 and 3.7 ± 0.5 mJ m-2 in acidic and high-ionic strength environments, respectively, although the cohesive energy decreases compared to the value in pure water. Our results further explain the underwater cohesion mechanisms combining multiple interactions and offer insights on designing Dopa containing underwater adhesives.

Bio-inspired conductive adhesive based on calcium-free alginate hydrogels for bioelectronic interfaces.

Electrode impedance is one of the greatest challenges facing neural interfacing medical devices and the use of electrical stimulation-based therapies in the fields of neurology and regenerative medicine. Maximizing contact between electronics and tissue would allow for more accurate recordings of neural activity and to stimulate with less power in implantable devices as electric signals could be more precisely transferred by a stable interfacial area. Neural environments, inherently wet and ion-rich, present a unique challenge for traditional conductive adhesives. As such, we look to marine mussels that use a 3,4-dihydroxyphenyl-L-analine (DOPA)-containing proteinaceous excretion to adhere to a variety of substrates for inspiration. By functionalizing alginate, which is an abundantly available natural polymer, with the catechol residues DOPA contains, we developed a hydrogel-based matrix to which carbon-based nanofiller was added to render it conductive. The synthesized product had adhesive energy within the range of previously reported mussel-based polymers, good electrical properties and was not cytotoxic to brain derived neural precursor cells.

Mussels Fabricate Porous Glues via Multiphase Liquid-Liquid Phase Separation of Multiprotein Condensates.

Mussels (Mytilus edulis) adhere to hard surfaces in intertidal marine habitats with a porous underwater glue called the byssus plaque. The plaque is an established role model for bioinspired underwater glues and comprises at least six proteins, most of which are highly cationic and enriched in the post-translationally modified amino acid 3,4-dihydroxyphenylalanine (DOPA). While much is known about the chemistry of plaque adhesion, less is understood about the natural plaque formation process. Here, we investigated plaque structure and formation using 3D electron microscopic imaging, revealing that micro- and nanopores form spontaneously during secretion of protein-filled secretory vesicles. To better understand this process, we developed a method to purify intact secretory vesicles for in vitro assembly studies. We discovered that each vesicle contains a sulfate-associated fluid condensate consisting of ∼9 histidine- and/or DOPA-rich proteins, which are presumably the required ingredients for building a plaque. Rupturing vesicles under specific buffering conditions relevant for natural assembly led to controlled multiphase liquid-liquid phase separation (LLPS) of different proteins, resulting in formation of a continuous phase with coexisting droplets. Rapid coarsening of the droplet phase was arrested through pH-dependent cross-linking of the continuous phase, producing native-like solid porous "microplaques" with droplet proteins remaining as fluid condensates within the pores. Results indicate that histidine deprotonation and sulfates figure prominently in condensate cross-linking. Distilled concepts suggest that combining phase separation with tunable cross-linking kinetics could be effective for microfabricating hierarchically porous materials via self-assembly.

Design, synthesis, and characterization of a novel dual cross-linked gelatin-based bioadhesive for hard and soft tissues adhesion capability.

Many surgical treatments require a suitable tissue adhesive that maintains its performance in wet conditions and can be applied simultaneously for hard and soft tissues. In the present study, a dual cross-linked tissue adhesive was synthesized by mixing the gelatin methacryloyl (Gel-MA) and gelatin-dopamine conjugate (Gel-Dopa). The setting reaction was based on a photopolymerization process in the presence of a combination of riboflavin and triethanolamine and a chemical cross-linking process attributed to the genipin as a natural cross-linker. Modified gelatin macromolecules were characterized and the best wavelength for free radical generation in the presence of riboflavin was obtained. Tissue adhesives were prepared with 30% hydrogels of Gel-MA and Gel-Dopa with different ratios in distilled water. The gelation occurred in a short time after light irradiation. The chemical, mechanical, physical, and cytotoxicity properties of the tissue adhesives were evaluated. The results showed that despite photopolymerization, chemical crosslinking with genipin played a more critical role in the setting process. Water uptake, degradation behavior, cytotoxicity, and adhesion properties of the adhesives were correlated with the ratio of the components. The SEM images showed a porous structure that could ensure the entry of cells and nutrients into the surgical area. While acceptable properties in most experiments were observed, all features were improved as the Gel-Dopa ratio increased. Also, the obtained hydrogels revealed excellent adhesive properties, particularly with bone even after wet incubation, and it was attributed to the amount of gelatin-dopamine conjugate. From the obtained results, it was concluded that a dual adhesive hydrogel based on gelatin macromolecules could be a good candidate as a tissue adhesive in wet condition.

A highly stretchable, UV resistant and underwater adhesive hydrogel based on xylan derivative for sensing.

Hydrogels with fascinating adhesion have been demonstrated great potential in various applications. However, most hydrogels lose their adhesion in wet or underwater environments due to the influence of interfacial water. Inspired by mussel, an underwater adhesive hydrogel was facilely fabricated by introducing electrostatic interactions, which consisted of poly (acrylic acid) (PAA), quaternized xylan (QAX) and tannic acid (TA). In this hydrogel, -COO- from PAA, -N+(CH3)3 from QAX and catechol group from TA resembled amino acids with negative and positive charges and 3,4-dihydroxyphenylalanine units in mussel, which endowed the hydrogels with great underwater adhesion through multiple interactions. Notably, acrylic acid (AA) played a key role in the dispersion of the system. QAX, a biomass derived from plants with excellent properties, worked with PAA to construct hydrogel networks. The resultant hydrogels exhibited excellent mechanical properties including remarkable stretchability (>4000 %) and compressibility. Moreover, the hydrogels had superior UV-blocking (~99.96 %), and showed good adhesion both in air and underwater. The hydrogels can be exploited as a wearable sensor to monitor human motions and even subtle motions, which have the potential to be explored in human health monitoring.

Metal-ligand complexation and clustering in mussel-inspired side-chain functionalized supramolecular hydrogels.

Byssus threads of mussels have high resistance against abrasion in wave-swept habitats because of their outer cuticle, which is rich in amino acid dopa complexes with Fe3+ ions. This stems from the transient nature of metal-ligand complexes that creates extra relaxation mechanisms. Inspired by this concept, in this work, supramolecular hydrogels based on poly(acrylic acid) functionalized with nitrocatechol groups are synthesized. Polymer chains are physically crosslinked via nitrocatechol-Fe3+ complexes. The hydrogels have different polymer volume fractions as well as different nitrocatechol : Fe3+ molar ratios. The strength of the supramolecular crosslinks strongly depends on the pH of the medium. The dynamics of these hydrogels are studied by stress relaxation experiments followed by calculation of the relaxation time spectrum. Generally, samples have three relaxation modes, including dissociation of distinct metal-ligand complexes, reptation of sticky polymer chains, and disengagement of network segments from supramolecular aggregates and clusters. Such clusters hinder the terminal relaxation and potentially increase the stability of supramolecular hydrogels.

Mussel-inspired polyurethane coating for bio-surface functionalization to enhance substrate adhesion and cell biocompatibility.

Considerable implant materials are prone to cause a severe inflammatory reaction due to poor histocompatibility, which leads to various complications and implant failure. Surface coating modification of these implant materials is one of the most important techniques to settle this problem. However, fabricating a coating with both adequate adhesiveness and excellent biocompatibility remains a challenge. Inspired by the adhesion mechanism of mussels, a series of mussel-inspired polyurethanes (PU-LDAs) were synthysized through a step growth polymerization based on hexamethylene diisocyanate as a hard segment, polytetra-methylene-ether-glycol as a soft segment, lysine-dopamine (LDA) and butanediol as chain extenders with different mole ratios.The coatings of PU-LDAs were applied to various substrates, such as stainless steel, glass and PP using a facile one-step coating process. The introduction of 3,4-dihydroxyphenylalanine (DOPA) groups can greatly improve the adhesion ability of the coatings to the substrates demonstrated by a 180° peel test. The peel strength of the PU-LDA100 coating containing high LDA content was 76.3, 48.5 and 67.5 N/m, which was 106.2%, 246.4% and 192.2% higher than that of the PU-LDA00 coating without LDA on the surface of stainless steel, glass and PP, respectively. Meanwhile, this PU coating has a lower immune inflammatory response which provides a universal method for surface modification of implant materials. Moreover, the DOPA groups in PU-LDAs could combine with the amino and thiol groups on cell membrane surface, leading to the improvement of cell adhesion and growth. Therefore, it has great potential application in the field of biomedical implant materials for the clinic.