Bio-inspired Surface Modification Research Articles

Bioinspired surface modification of mussel shells and their application as a biogenic filler in polypropylene composites

This study explores the potential of mussel shells (MS) as biogenic fillers in polymer composites. The chemical composition and crystal structures of MS were characterised. To improve MS filler dispersion and adhesion within a polypropylene (PP) matrix, three surface modification methods were evaluated: polydopamine (PDA) coating, maleic anhydride-grafted polypropylene (MAPP) modification, and PDA/MAPP co-modification. The PDA coating, inspired by the adhesive properties of mussel foot proteins, successfully functionalized the MS surface, as confirmed by X-ray photoelectron spectroscopy (XPS). Thermodynamic analysis, based on contact angle measurements, revealed that MAPP and PDA/MAPP modifications reduced surface energies and potential energy differences. These changes enhanced filler dispersion and interfacial bonding by increasing hydrophobicity and reducing agglomeration in the PP matrix. Consequently, PP composites with 20% PDA/MAPP-modified MS fillers exhibited a 2.9% increase in tensile strength and a 7.5% increase in flexural strength compared to neat PP. Scanning electron microscopy (SEM) also showed reduced filler-matrix debonding and fewer voids. The proposed mechanism attributes these macroscopic property enhancements to the ability of the PDA coating to facilitate chemical and hydrogen bonding between MS fillers and MAPP.

Vibroacoustics Analysis of Plates with Bioinspired Surface Modifications

This study presents a simplified semi-analytical model to analyze the dynamic behavior of a plate with shark skin biomimetic surface modifications. The base plate is considered to be thin isotropic homogeneous and modeled using a Kirchhoff–Love plate theory, whereas the dermal denticles are modeled as a distributed array of point mass and replicated using a Dirac delta function. A semi-analytical formulation, which takes into account closed-form beam mode shapes, with the Galerkin technique to minimize errors is utilized to study the free and forced vibration response of modified plates. Harmonic analysis is carried out to understand the dynamic behavior of the modified plate both quantitatively as well as qualitatively. A parametric study varying the array spacing and the boundary conditions is carried out to understand the effect of surface modification on power radiation characteristics. It appears that adding dermal denticles reduces the peak velocity amplitude and peak radiated power at all resonance frequencies. A separate study by varying the base plate material reveals that a higher reduction in the dynamic response and the radiated power can be achieved by increasing the mass ratio. Hence, surface modification using such a shark skin layer may prove beneficial to reduce acoustic radiation and dynamic response and to optimize the design.

Decellularized extracellular matrix-based 3D nanofibrous scaffolds functionalized with polydopamine-reduced graphene oxide for neural tissue engineering

One of the exciting prospects of using decellularized extracellular matrices (ECM) lies in their biochemical profile of preserved components, many of which are regeneration-permissive. Herein, a decellularized ECM from adipose tissue (adECM) was explored to design a scaffolding strategy for the challenging repair of the neural tissue. Targeting the recreation of the nano-scaled architecture of native ECM, adECM was first processed into nanofibers by electrospinning to produce bidimensional platforms. These were further shaped into three-dimensional (3D) nanofibrous constructs by gas foaming. The conversion into a 3D microenvironment of nanofibrous walls was assisted by blending the adECM with lactide-caprolactone copolymers, wherein tuning the adECM/copolymer ratio along with the amount of caprolactone in the copolymer led to modulating the mechanical properties towards soft, yet structurally stable, 3D constructs. In view of boosting their performance to guide neural stem cell fate, adECM-based platforms were doped with a bioinspired surface modification relying on polydopamine-functionalized reduced graphene oxide (PDA-rGO). These adECM-based 3D constructs revealed a permissive microenvironment for neural stem cells (NSCs) to adhere, grow, and migrate throughout the microporosity, owing to the synergy between the unique biochemical features of the adECM and the nanofibrous architecture. NSC responded differently depending on the adECM-based architecture–nanofibrous bidimensional, or 3D design. The 3D spatial arrangement of the nanofibers – induced by the gas foaming – exhibited a remarkable effect on NSCs’ phenotype determination and neurite formation, thereby reinforcing the critical importance of engineering scaffolds with multiple length-scale architecture. Furthermore, PDA-rGO promoted the differentiation of NSC towards the neuronal lineage. Specifically in 3D, it significantly increases the levels of Tuj1 and MAP2 a/b isoforms, confirming its effectiveness in boosting neuronal differentiation and neuritogenesis.

Bio-inspired surface modification of MoS2 nanosheets with gallium phthalocyanine for brain-like synaptic memristors

Inspired by mussel chemistry, MoS2 nanosheets coated with polydopamine were covalently functionalized with gallium phthalocyanine. Biological synaptic functions and associative learning processes were successfully simulated by using memristors.

Experimental investigation of flow characteristics over a surface-modified structured torpedo model

The present work aims to improve the aerodynamic performance of navigating objects using bio-inspired surface modification. Inspired by the denticles present over sharkskin, this work investigates the study of a surface-modified structured torpedo model. Different modified surface structures (riblets) are used to study their effect on the drag and flow characteristics. The modified structure placed in the shear layer modifies the flow above as well as behind the torpedo. A detailed flow field is studied using PIV (Particle Image Velocimetry) and CTA (Constant Temperature Anemometry) over the torpedo model. The experiments are performed in a subsonic wind tunnel for the Reynolds numbers (Re) range of 1.02–5.08 × 105, thus covering the laminar-turbulent transition range. The study reveals that riblets structure enhances the momentum flux, thus enabling the surface to reduce drag by suppressing the vorticity generation and reducing the turbulent dissipation. Different turbulent and wake characteristics are measured in the work. The velocity and fluctuation analysis shows the variation in wake width and wake velocity for different cases. The result showed that riblet effectively reduces drag coefficient by 11.7% using an optimal structure. The maximum reduction in formation length of 4.76% is observed at Re 3.05 × 105. The decrease in the formation length reduces the adverse pressure gradient zone and decreases the power requirement. The wake half-width at the 2D downstream location in the streamwise direction shows a reduction of 9% for the drag-reducing case at Re 3.05 × 105. The vorticity reduction is observed in the wake zone of drag-reducing riblets and suggests less dissipation of the eddy. The results show the perspective to improve the current research status by using riblet surface for marine application. The study could effectively reduce drag, thus improving the operating performance by reducing the energy consumption and increasing the speed of the navigating vessel.

Bioinspired Surface Modification of Graphene-Based Hybrids as Nanozyme Sensors for Simultaneous Detection of Dopamine and Uric Acid

Bioinspired Surface Modification of Graphene-Based Hybrids as Nanozyme Sensors for Simultaneous Detection of Dopamine and Uric Acid

Bio-Inspired Surface Modification of Magnetite Nanoparticles with Dopamine Conjugates.

Organically-coated nanomaterials are intensively studied and find numerous applications in a wide range of areas from optics to biomedicine. One of the recent trends in material science is the application of bio-mimetic polydopamine coatings that can be produced on a variety of substrates in a cost-efficient way under mild conditions. Such coatings not only modify the biocompatibility of the material but also add functional amino groups to the surface that can be further modified by classic conjugation techniques. Here we show an alternative strategy for substrates modification using dopamine conjugates instead of native dopamine. Compared to the classic scheme, the proposed strategy allows separation of the “organic” and “colloidal” stages, and simplified identification and purification steps. Modification with pre-modified dopamine made it possible to achieve high loading capacities with active components up to 10.5% wt. A series of organo-inorganic hybrids were synthesized and their bioactivity was analyzed.

In situ preparation of alendronate-loaded ZIF-8 nanoparticles on electrospun nanofibers for accelerating early osteogenesis in osteoporosis

Applying guided bone regeneration membrane (GBRm) to treat bone defects in osteoporotic patients remains a challenge, as they cannot restore the fundamental balance between osteoblasts and osteoclasts, resulting in the ineffectiveness of osteoporotic bone injury treatment. Herein, a multifunctional polycaprolactone/gelatin (PG)-blended membrane embedded with alendronate-loaded zeolitic imidazolate framework-8 (Aln/Zif-8) nanoparticles was fabricated by electrospun technique and a simple solution-phase synthesis. Surface characterizations confirmed the successful synthesis of PG/Aln-Zif-8 nanofibers endowed with excellent mechanical strength. The release kinetics analysis showed the synergistic effects of the coordination bonds among Aln, zinc ions (Zn2+), and organic ligands played a critical role in regulating the initial burst release and delayed release of Aln and Zn2+, respectively. The in vitro results of MC3T3-E1 and RAW264.3 cells demonstrated that the PG/Aln-Zif-8 membranes possessed superior anti-osteoporosis and osteoinductive properties. Furthermore, the PG/Aln-Zif-8 samples also exhibited significant bactericidal properties against both Staphylococcus aureus and Escherichia coli. The in vivo results further confirmed that PG/Aln-Zif-8 membranes had superior osteoinduction abilities, contributing to the accelerated osseointegration in the osteoporosis model. Altogether, these new bioinspired surface modifications highlight the promising alternative for fabricating multifunctional MOFs on electrospun membranes to accelerate early osteogenesis in osteoporosis.

Polydopamine: a bioinspired adhesive and surface modification platform

AbstractPolydopamine is a biopolymer that is gaining widespread interest as a surface modifying agent due to its simplicity of preparation, versatility and biocompatibility. The material was first described during electrochemical studies of dopamine, but recognition of its structural similarity to key components of mussel adhesive proteins, which are able to adhere to a diverse range of surfaces in water, has led to its incorporation into a host of composite materials. This review will examine some of the emerging investigations into the complex mechanism of polydopamine formation, proposed structures and potential applications, with an emphasis on its use in biomedicine. © 2021 Society of Industrial Chemistry.

Biofunctionalized Nanofibrous Bilayer Scaffolds for Enhancing Cell Adhesion, Proliferation and Osteogenesis.

A simple and efficient method for fabricating functionalized multilayered nanofibrous scaffolds has been developed by combining electrospinning and thermally induced phase separation (TIPS) techniques. In this investigation, functionalized bilayer scaffolds were constructed using this method for bone tissue engineering, which consisted of a nanofibrous poly(lactic acid-co-glycolic acid) (PLGA) membrane as the base and a nanofibrous chitosan (CS) or gelatin (Gel) mesh as the surface layer, with the PLGA nanofibers having a biomimetic polydopamine (PDA) coating. It was shown that the PDA coating strongly bonded TIPS-formed CS or Gel networks onto PDA-coated electrospun PLGA membranes. The nanofibrous PLGA membrane provided adequate mechanical support for the whole structure, and the nanofibrous CS or Gel networks enhanced cell growth and maturation. The bioinspired surface modification of PLGA scaffolds through PDA coating could not only provide strong adhesion between the two scaffold layers but also improve biological properties of scaffolds. It was demonstrated that functionalized bilayer scaffolds could promote cell adhesion, spreading and proliferation of mouse preosteoblastic MC3T3-E1 cells and rat bone-marrow-derived stromal cells (rBMSCs). Furthermore, immunofluorescence staining and calcium deposition studies revealed that functionalized bilayer scaffolds could enhance osteogenic differentiation of MC3T3-E1 cells and rBMSCs in comparison with simple electrospun PLGA scaffolds. The functionalized bilayer scaffolds are promising structures for bone tissue engineering.

Polydopamine-Based Surface Modification of Chlorella Microspheres for Multiple Environmental Applications.

Towards addressing water pollution issues, the development of multifunctional chlorella with applications ranging from sensing pollutants to heavy metal and oil removal is described. The use of chlorella cells, which are widely abundant natural structures, leads to simple and low-cost mass production of effective functional materials. Bioinspired surface modification approaches mediated by polydopamine can endow chlorella with enhanced adsorption capacity for heavy metals, as well as superhydrophobic, fluorescence and magnetic properties according to the desired application. The resulting chlorella exhibits excellent heavy metal and oil removal ability, while magnetic propulsion and guidance allow directional motion over long distances for implementation in situ removal. Moreover, it is further demonstrated that chlorella can be used as a biosensor to detect metal ions by taking advantage of the fluorescence properties of carbon dots. Such use of chlorella provides a new way for the large-scale production of functional materials to tackle water pollution.

Bio-inspired surface modification of iron oxide nanoparticles for active stabilization in hydrogels.

Biological materials employ a variety of dynamic interactions in sophisticated composite structures to function adaptively on different time and length scales. Inspired by such designs we develop a novel surface modification approach to promote dynamic interactions between nanoparticles and polymer chains in physical and double network hydrogels. Physical hydrogels are formed via reversible complexation of borate ions with poly(vinyl alcohol) (PVA) and chemical crosslinks are introduced by electron beam irradiation. Dopamine is used for surface modification of magnetic iron oxide nanoparticles (MNPs) in two different ways: the direct treatment results in anchoring via catechol groups, whereas the indirect method leaves the catechol group on the free surface of MNPs. Although the former particles show very good colloidal stability, they lower the network connectivity, which results in lower plateau modulus, faster terminal relaxation, and lower yield stress, presumably due to imposing an extra distance between PVA chains. In contrast to this passive design, the latter particles actively reinforce the network by forming clusters of physical bonds between catechol groups of the individual particles and the monodiol complexes of the borate ions and PVA chains. Moreover, the additional complexes formed upon the introduction of nanoparticles with active surfaces provide further energy dissipation potential and therefore enhance the toughness. This approach can help develop novel hydrogels with superior toughness and multiple stimuli-responsiveness.

Bio-inspired surface modification of PEEK through the dual cross-linked hydrogel layers

The biocompatible high-performance material PEEK (polyetheretherketone) is an attractive implant material, however, its hydrophobicity and high friction coefficients severely hinder its biomedical applications. Thus, it is inferred from the recent advances in surface modification technology, achieving the biomimetic natural joint lubrication systems on PEEK still remains a challenge. In view of the above, herein we proposed a novel two-step strategy to fabricate a “soft (dual cross-linked hydrogel) layer-hard (PEEK) substrate” texture that mimics the structure and function of soft cartilage on the hard basal bone in joints. At first, a layer of acrylic acid-co-acryl amide (AA-AM) hydrogel is anchored to the PEEK substrate through UV-initiated polymerization. In the second step, hydrogel coated PEEK substrate is immersed in ferric nitrate solution to create the secondary cross-linkage between Fe3+ and –COOH groups in the hydrogel. As a result, the consequential top-coat hydrogel layer not only transforms the surface wettability (hydrophobic to hydrophilic) but also provides scratch resistance to the underlying PEEK substrate. The modified specimens display low friction coefficients in water under different load conditions. In addition, the obtained surface exhibits a certain self-repairing ability due to its unique physically reversible network structure. Therefore, this work provides a promising strategy for broadening the use of PEEK in orthopedic implants.

Metallic Stent Mesh Coated with Silver Nanoparticles Suppresses Stent-Induced Tissue Hyperplasia and Biliary Sludge in the Rabbit Extrahepatic Bile Duct.

Recent therapeutic strategies to suppress restenosis after biliary stent placement are insufficient. Here, we demonstrate the usefulness of a self-expandable metal stent (SEMS), a stent mesh coated with silver nanoparticles (AgNPs), for suppression of both stent-induced tissue hyperplasia and biliary sludge formation in the rabbit bile duct. The AgNP-coated SEMSs were prepared using a simple bio-inspired surface modification process. Then, the prepared SEMSs were successfully placed in 22 of 24 rabbits. Sludge formation in the AgNP-coated SEMS groups was significantly decreased compared to the control group on gross findings. Cholangiographic and histologic examinations demonstrated significantly decreased tissue hyperplasia in the AgNP-coated SEMS groups compared with the control group (p < 0.05 for all). There were no differences between the AgNP-coated SEMS groups (p > 0.05 for all). However, in the group coated with the greatest concentration of AgNPs (Group D), submucosal fibrosis was thicker than in the other AgNP-coated groups (p < 0.05 for all). The AgNP-coated metallic stent mesh significantly suppressed stent-induced tissue hyperplasia and biliary sludge formation in the rabbit bile duct. Taken together, the AgNP coating strategy developed in this study could be widely utilized in non-vascular medical devices for anti-bacterial and anti-inflammatory responses.

Attachable micropseudocapacitors using highly swollen laser-induced-graphene electrodes

For powering wearable electronics, extensive research has been directed toward microscale flexible and stretchable energy-storage devices. Microsupercapacitors, though promising candidates, remain limited in terms of design flexibility, scalability, reusability, and compatibility with general substrates. This paper reports a high-performance sticker-type flexible microsupercapacitor using highly swollen reduced-graphene-oxide electrodes fabricated by an ultrashort-pulse laser to promote full active-site and durability of the electrodes. Our sticker-type flexible micropseudocapacitor provides a comparable volumetric energy density of 1.08 mWh cm−3 and 13 times higher volumetric power density of 83.5 mW cm−3 compared to conventional lithium thin-film batteries. Bio-inspired surface modifications are additionally applied to the reduced-graphene-oxide electrodes, which provides a six-fold increase (10.38 mF cm−2) of the areal capacitance. A 6 × 2 micropseudocapacitor array embedded in a sub-millimeter thin PDMS film adheres to safety goggles and successfully powers a μ-LED. The total capacitance of the array is maintained at ~97% of its original value after 200 repetitive attachments and detachments showing good durability. In addition, the sticker-type micropseudocapacitor array shows a stable performance under repeated deformation, and up to ~99% of capacitance retention after 200 bending cycles. This novel re-attachable flexible micropseudocapacitor will expedite the widespread use of flexible and wearable devices.

Bioinspired aerogel based on konjac glucomannan and functionalized carbon nanotube for controlled drug release

In this study, a facile marine bioinspired surface modification approach for carboxyl-functionalized multiwalled carbon nanotube (CCNT) and enhanced interfacial adhesion with the konjac glucomannan (KGM) matrix were illustrated to develop aerogels. Combined with FT-IR, XRD, Raman, TGA, XPS and SEM results, it was indicated that functionalized CCNT (PCCNT) is a reinforcer through hydrogen bond interactions in the aerogel formation process, which could be the main reason for the enhancement. The swelling and vitro release behavior of KGM/PCCNT aerogels were studied under two conditions using the drug 5-fluorouracil (5-FU). The release amount of 5-FU incorporated into KGM/PCCNT4 aerogel was about 48% at pH 1.2 and 62% at pH 6.8 after11 h, respectively. The results showed that the release rate of 5-FU from the KGM/PCCNT4 aerogel using PCCNT could be effectively controlled, suggesting potential applications for it as a drug carrier in targeted delivery in the biomedical filed.

Mussel-inspired polydopamine-directed crystal growth of core-shell n-Al@PDA@CuO metastable intermixed composites

Over past few years, there has been increased interest in the development of metastable intermixed composites (MICs). As typical high energetic materials, MICs find important applications in aerospace and pyrotechnics. Newly developed methods based on the bioinspired surface modification enables advanced MICs with improved stability, higher energy content, and tunable performances. In this paper, the dopamine has been used to coat nano-sized Al (n-Al), forming a polydopamine (PDA) interfacial binding layer by in-situ polymerization. This interfacial binding layer makes it possible to prevent n-Al from further oxidation, and more importantly, functionalized n-Al with multiple chemical groups. Multiple oxidants could be synthesized on the coated n-Al surface under the direction of PDA on the heterogeneous nucleation and growth of crystals, affording exclusively the core-shell MICs. Typically, core-shell n-Al@PDA@CuO MICs have been fabricated. In comparison to the traditional n-Al/CuO MICs, the resulted n-Al@PDA@CuO showed an improved initial reaction temperature (528.4 °C), enhanced energy release (2934.8 J g−1) and lower combustion temperature (1606 °C). The infrared thermograph results also reveal that the n-Al@PDA@CuO has higher combustion efficiency since the n-Al core and CuO shell are better contacted at a nanoscale.

Self-Cleaning: From Bio-Inspired Surface Modification to MEMS/Microfluidics System Integration.

This review focuses on self-cleaning surfaces, from passive bio-inspired surface modification including superhydrophobic, superomniphobic, and superhydrophilic surfaces, to active micro-electro-mechanical systems (MEMS) and digital microfluidic systems. We describe models and designs for nature-inspired self-cleaning schemes as well as novel engineering approaches, and we discuss examples of how MEMS/microfluidic systems integrate with functional surfaces to dislodge dust or undesired liquid residues. Meanwhile, we also examine “waterless” surface cleaning systems including electrodynamic screens and gecko seta-inspired tapes. The paper summarizes the state of the art in self-cleaning surfaces, introduces available cleaning mechanisms, describes established fabrication processes and provides practical application examples.

Mussel-Inspired Polydopamine Coating: A General Strategy To Enhance Osteogenic Differentiation and Osseointegration for Diverse Implants.

Surface modifications play an important role in endowing implant surface with excellent biocompatibility and bioactivity. Among the bioinspired surface modifications, the mussel-inspired polydopamine (PDA) has aroused great interest of researchers. Herein, we fabricated PDA on diverse implant surfaces, including biopolymer, biometal, and bioceramic. Then the effects of PDA coating on cell responsive behaviors in vitro and bone formation capacity in vivo were evaluated in detail. The results showed that PDA coating was fabricated on diverse samples surface successfully, which could significantly improve the hydrophilicity of different material surfaces. Furthermore, the results indicated that PDA coating exerted direct enhancing on the adhesion, proliferation and osteogenic differentiation of bone marrow derived mesenchymal stromal cells (BMSCs) through FAK and p38 signaling pathways. During the process, the focal adhesion protein expression and osteogenic-related genes expression level (e.g., ALP, BMP2, BSP, and OPN) were considerably upregulated. Most importantly, the in vivo study confirmed that PDA coating remarkably accelerated new bone formation and enhanced osseointegration performance. Our study uncovered the biological responses stimulated by PDA coating to make a better understanding of cell/tissue-PDA interactions and affirmed that PDA, a bioinspired polymer, has great potential as a candidate and functional bioactive coating medium in bone regeneration and orthopedic application.

Oxidative Epigallocatechin Gallate Coating on Polymeric Substrates for Bone Tissue Regeneration.

Plant derived flavonoids have not been well explored in tissue engineering applications due to difficulties in efficient formulations with biomaterials for controlled presentation. Here, the authors report that surface coating of epigallocatechin gallate (EGCG) on polymeric substrates including poly (L-lactic acid) (PLLA) nanofibers can be performed via oxidative polymerization of EGCG in the presence of cations, enabling regulation of biological functions of multiple cell types implicated in bone regeneration. EGCG coating on the PLLA nanofiber promotes osteogenic differentiation of adipose-derived stem cells (ADSCs) and is potent to suppress adipogenesis of ADSCs while significantly reduces osteoclastic maturation of murine macrophages. Moreover, EGCG coating serves as a protective layer for ADSCs against oxidative stress caused by hydrogen peroxide. Finally, the in vivo implantation of EGCG-coated nanofibers into a mouse calvarial defect model significantly promotes the bone regeneration (61.52±28.10%) as compared to defect (17.48±11.07%). Collectively, the results suggest that EGCG coating is a simple bioinspired surface modification of polymeric biomaterials and importantly can thus serve as a promising interface for tuning activities of multiple cell types associated with bone fracture healing.