Surface Functionalization Of Materials Research Articles

Advancing Cell-Instructive Biomaterials Through Increased Understanding of Cell Receptor Spacing and Material Surface Functionalization

Regenerative medicine is aimed at restoring normal tissue function and can benefit from the application of tissue engineering and nano-therapeutics. In order for regenerative therapies to be effective, the spatiotemporal integration of tissue-engineered scaffolds by the native tissue, and the binding/release of therapeutic payloads by nano-materials, must be tightly controlled at the nanoscale in order to direct cell fate. However, due to a lack of insight regarding cell–material interactions at the nanoscale and subsequent downstream signaling, the clinical translation of regenerative therapies is limited due to poor material integration, rapid clearance, and complications such as graft-versus-host disease. This review paper is intended to outline our current understanding of cell–material interactions with the aim of highlighting potential areas for knowledge advancement or application in the field of regenerative medicine. This is achieved by reviewing the nanoscale organization of key cell surface receptors, the current techniques used to control the presentation of cell-interactive molecules on material surfaces, and the most advanced techniques for characterizing the interactions that occur between cell surface receptors and materials intended for use in regenerative medicine.Lay SummaryThe combination of biology, chemistry, materials science, and imaging technology affords exciting opportunities to better diagnose and treat a wide range of diseases. Recent advances in imaging technologies have enabled better understanding of the specific interactions that occur between human cells and their immediate surroundings in both health and disease. This biological understanding can be used to design smart therapies and tissue replacements that better mimic native tissue. Here, we discuss the advances in molecular biology and technologies that can be employed to functionalize materials and characterize their interaction with biological entities to facilitate the design of more sophisticated medical therapies.

Effects of Plasma Treatment on the Bioactivity of Alkali-Treated Ceria-Stabilised Zirconia/Alumina Nanocomposite (NANOZR).

Zirconia ceramics such as ceria-stabilized zirconia/alumina nanocomposites (nano-ZR) are applied as implant materials due to their excellent mechanical properties. However, surface treatment is required to obtain sufficient biocompatibility. In the present study, we explored the material surface functionalization and assessed the initial adhesion of rat bone marrow mesenchymal stem cells, their osteogenic differentiation, and production of hard tissue, on plasma-treated alkali-modified nano-ZR. Superhydrophilicity was observed on the plasma-treated surface of alkali-treated nano-ZR along with hydroxide formation and reduced surface carbon. A decreased contact angle was also observed as nano-ZR attained an appropriate wettability index. Treated samples showed higher in vitro bovine serum albumin (BSA) adsorption, initial adhesion of bone marrow and endothelial vascular cells, high alkaline phosphatase activity, and increased expression of bone differentiation-related factors. Furthermore, the in vivo performance of treated nano-ZR was evaluated by implantation in the femur of male Sprague–Dawley rats. The results showed that the amount of bone formed after the plasma treatment of alkali-modified nano-ZR was higher than that of untreated nano-ZR. Thus, induction of superhydrophilicity in nano-ZR via atmospheric pressure plasma treatment affects bone marrow and vascular cell adhesion and promotes bone formation without altering other surface properties.

Controllably Engineering Mesoporous Surface and Dimensionality of SnO2 toward High‐Performance CO2 Electroreduction

AbstractCurrently, the precise control of the architecture and surface of functional materials for high‐performance still remains a great challenge. Here, a feasible approach is presented to synchronously manipulate mesoporous surface and dimensionality of SnO2 catalysts into hierarchically mesoporous nanosheets and nanospheres within one simple reaction system. By adjustment of the hydrophobic chain length of different fluorinated surfactants, 0D SnO2 nanospheres with average size of 165 nm, and 2D SnO2 ulthrathin nanosheets with thickness of 22.5 nm with the distinct dimensionalities are separately obtained (one stone, two birds), both of which are well decorated with ordered mesopore arrays on their surfaces (pore size of 16 nm). The following calcination gave rise to the formation of hierarchically mesopores (5 and 16 nm, respectively) with high crystallization and improved surface area (96.8 m2 g−1). The resultant mesoporous SnO2 nanosheets as catalyst for CO2 electroreduction reaction (CO2 RR) exhibit excellent selectivity, with a high Faraday efficiency (FE) of HCOOH reaching up to 90.0% at −1.3 V and C1 FE of 97.4% at −1.2 V versus reversible hydrogen electrode, as well as long‐term stability, which is among the best performance compared to reported SnO2 materials, thanks to the collective contributions of the unique architecture and mesoporous structure.

Formation of Porous Apatite Layer after Immersion in SBF of Fluorine-Hydroxyapatite Coatings by Pulsed Laser Deposition Improved in Vitro Cell Proliferation.

Fluorine (F), a trace element in bone tissues, promotes cell proliferation and colonization. In this study, fluorine-hydroxyapatite (F-HA) coating was manufactured onto titanium substrates using pulsed laser deposition (λ = 1024 nm). The results confirmed that the surface roughness of F-HA coatings was the highest when the deposition time was 60 min. To evaluate the biological activity of the coatings, the coatings were immersed in simulated body fluids at 37 °C for 7 days. It was clearly observed that a new apatite layer showed a micro/nano foam-like porous structure. After annealing treatment, the F-HA coating can promote the transformation of the calcium phosphate crystal phase into the HA phase. Moreover, the mass of F-HA coatings with annealing was increased by 2.3% after immersion. In vitro cytocompatibility of the coatings was evaluated; the cell adhesion and proliferation exposed to F-HA coatings were significantly stimulated and promoted when compared with the control group in the first and second weeks of co-culture (p < 0.05). Thus, F-HA coatings can potentially act as osteoinductive materials for surface functionalization of the bone tissue scaffold.

Polyelectrolyte Multilayer Films Modification with Ag and rGO Influences Platelets Activation and Aggregate Formation under In Vitro Blood Flow.

Surface functionalization of materials to improve their hemocompatibility is a challenging problem in the field of blood-contacting devices and implants. Polyelectrolyte multilayer films (PEMs), which can mimic functions and structure of an extracellular matrix (ECM), are a promising solution to the urgent need for functional blood-contacting coatings. The properties of PEMs can be easily tuned in order to provide a scaffold with desired physico-chemical parameters. In this study chitosan/chondroitin sulfate (Chi/CS) polyelectrolyte multilayers were deposited on medical polyurethane. Afterwards PEMs were modified by chemical cross-linking and nanoparticles introduction. Coatings with variable properties were tested for their hemocompatibility in the cone-plate tester under dynamic conditions. The obtained results enable the understanding of how substrate properties modulate PEMs interaction with blood plasma proteins and the morphotic elements.

Precise design of microwrinkles through the independent regulation of elasticity on the surface and in the bulk of soft hydrogels

It is still difficult to precisely control microscopic wrinkles on the surface of functional materials, especially biomimetic soft hydrogels with an elastic modulus lower than 100 kPa. This is due to the difficulty in realizing the systematic and independent regulation of elasticity on the top surface and in the bulk of hydrogels, which is essential for the generation of surface microwrinkles. To overcome this problem, using a two-step photocrosslinking process with VIS and UV irradiation of a photocurable gelatinous sol, we developed a method for independently regulating the elastic modulus on the surface and in the bulk to obtain wrinkles on a biomimetic soft gel. Photocurable gelatin was first irradiated and crosslinked with VIS light in the presence of the water-soluble radical generator sulfonyl camphorquinone, which is effective in forming thick bulk gels. Next, the top surface of these precrosslinked gels was irradiated with UV light in the presence of surface-coated water-insoluble camphorquinone. As a result, this two-step photocrosslinking process enabled to independently control the elastic moduli of the surface and the bulk lower than 100 kPa and to generate several-micron-scale wrinkles on the soft hydrogel surface. To precisely design microwrinkles on a biomimetic hydrogel, a two-step photocrosslinking process with VIS and UV irradiation was developed. Photocurable gelatin was first crosslinked with VIS light in the presence of the water-soluble radical generator to form thick bulk gels. Next, the top surface of the gels was irradiated with UV light in the presence of surface-coated water-insoluble radical generator. This two-step photocrosslinking process enabled to independently control the elastic moduli of the surface and the bulk lower than 100 kPa and to generate several-micron-scale wrinkles on the soft hydrogels.

Investigation of plasma treatment on UHMWPE surfaces: Impact on physicochemical properties, sterilization and fibroblastic adhesion

Ultra-high molecular weight polyethylene (UHMWPE) is a prevailing bearing material applied in joint arthroplasty. Despite not being a novel biomaterial, its debris as consequence of long application and surface properties usually still lead to short lifespan. Many of the drawbacks are associated with sterilization methods that degrade the surface properties of UHMWPE. This work aims at improving the sterilizing treatment and also increasing material wettability, without losing bulk properties, which are essential for an orthopedic bearing. Cold plasma in hollow cathode setting was used for the material surface functionalization. Samples were characterized through contact angle (WCA), x-ray diffraction (XRD), optical microscopy, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and profilometry. Optimal points based on immediate surface wettability, shelf time and sterilization efficacy were chosen for biocompatibility evaluation. When comparing cell viability through MTT among treated samples (OP1, OP2 and UV), a slight reduction in OP2 viability could be seen after 7 days incubation, which is also observed in Giemsa staining and SEM images. In late incubation, OP1 loses its hydrophilic character and displays higher cell adhesion than its counterparts UV and OP2. At the end, OP2 showed less cells growing over the biomaterial after 7 days exposition compared to OP1 and UV. OP1 presented a more hydrophobic surface and improved cell adhesion, differently from OP2 and UV, which maintained their wettability conditions in late incubation. Cell analysis results indicate that surface wetting influences cell morphology and consequent cell adhesion, in which more hydrophobic surfaces are shown to favor fibroblast adhesion properties.

Spraying Fabrication of Durable and Transparent Coatings for Anti-Icing Application: Dynamic Water Repellency, Icing Delay, and Ice Adhesion.

Anti-icing/icephobic coatings, typically applied in the form of surface functional materials, are considered to be an ideal selection to solve the icing issues faced by daily life and industrial production. However, the applications of anti-icing coatings are greatly limited by the two main challenges: bonding strength with substrates and stability of the high anti-icing performance. Here, we designed and fabricated a kind of high-performance superhydrophobic fluorinated silica (F-SiO2)@polydimethylsiloxane coatings and further emphasized the improvement of the bonding strength with substrates and the maintenance of high anti-icing performance. The resultant coatings exhibited excellent water repellency with a contact angle up to 155.3° and a very short contact time (∼10.2 ms) of impact droplets. At low temperatures, the coming droplets still rapidly rebounded off the coating surface, and the superhydrophobic coatings displayed a more than 50-fold increase of freezing time comparing with bare aluminum. The ice adhesion strength on the coatings was only 26.3 kPa, which was far less than that (821.9 kPa) of bare aluminum. Furthermore, the nanoporous structures constructed by anodic oxidation could tremendously enhance the bonding strength of the coatings with the substrate, which was evaluated through a standard method (ASTM D3359). The anti-icing properties still retained high stability under the conditions of 30 icing/deicing cycles, soaking, and scouring of acid solution (pH = 5.6). This work can effectively push the anti-icing coatings toward a real-world application.

Correlations between High-Temperature Oxidation Kinetics and Thermal Radiation Characteristics of Micro-Structured Nickel Surfaces Oxidized at 1173 K

Micro-structured surface functional materials were widely used in electronics, batteries, solar cells, and many other products. However, oxidation at high temperatures greatly affects the material service life and performance. This study focuses on the oxide layer characteristics after high-temperature oxidation and the thermal emissivity of metal materials with micro-structured surfaces. Micro-structured surfaces with various groove morphologies were prepared on 99.9% purity nickel samples. The high-temperature oxidation characteristics of the nickel samples with the microstructure surfaces and the total hemispherical emissivities were measured after various oxidation times in high-temperature (1173 K) air to characterize the correlations between the micro-structure surface oxidization and the emissivity at elevated temperatures. The initial surface roughness greatly affects the surface roughness after oxidation with the oxidation increasing the surface roughness on smooth or less rough surfaces but making the surface smoother for very rough surfaces. The oxidation results show that rougher initial surfaces have larger oxide grain sizes with longer oxidation times leading to smaller grain sizes. The measured total hemispherical emissivity increased with the temperature (500–1400 K) and the oxide layer thickness. The experiments further illustrates that, for the same oxide layer thickness, the measured emissivities become larger for oxides with larger grain sizes caused by the rougher original surfaces. This analysis provides an understanding of the oxidation kinetics of microstructured surfaces and how the oxidized microstructure surfaces affect the thermal radiation properties.

Direct Evidence for the Polymeric Nature of Polydopamine

AbstractInspired by the adhesive proteins of mussels, polydopamine (pDA) has emerged as one of the most widely employed materials for surface functionalization. Despite numerous attempts at characterization, little consensus has emerged regarding whether pDA is a covalent polymer or a noncovalent aggregate of low molecular weight species. Here, we employed single‐molecule force spectroscopy (SMFS) to characterize pDA films. Retraction of a pDA‐coated cantilever from an oxide surface shows the characteristic features of a polymer with contour lengths of up to 200 nm. pDA polymers are generally weakly bound to the surface through much of their contour length, with occasional “sticky” points. Our findings represent the first direct evidence for the polymeric nature of pDA and provide a foundation upon which to better understand and tailor its physicochemical properties.

Direct Evidence for the Polymeric Nature of Polydopamine.

Inspired by the adhesive proteins of mussels, polydopamine (pDA) has emerged as one of the most widely employed materials for surface functionalization. Despite numerous attempts at characterization, little consensus has emerged regarding whether pDA is a covalent polymer or a noncovalent aggregate of low molecular weight species. Here, we employed single-molecule force spectroscopy (SMFS) to characterize pDA films. Retraction of a pDA-coated cantilever from an oxide surface shows the characteristic features of a polymer with contour lengths of up to 200 nm. pDA polymers are generally weakly bound to the surface through much of their contour length, with occasional "sticky" points. Our findings represent the first direct evidence for the polymeric nature of pDA and provide a foundation upon which to better understand and tailor its physicochemical properties.

Surface Separation and in Situ Structural Regulation of Photosensitive Oligomer in a Flexible Template.

Surface-selective adsorption and separation are very important for the application of surface functional materials. In this study, a photosensitive diazo-macrocycle has been synthesized by the solvent method with a very low yield, which can adsorb onto the substrate surface modified with a template molecule. By using this flexible template on the graphite surface, a simple separation strategy for the macrocyclic molecule with specific shape and size from reaction mixtures was developed. Additionally, one of the two azo units in this trapped photosensitive macrocycle could convert from trans to cis conformation under UV irradiation due to the steric effect. Our results provide a new way to construct functional nanodevices using a surface flexible template as the separation and regulation medium.

Facile spraying fabrication of highly flexible and mechanically robust superhydrophobic F-SiO2@PDMS coatings for self-cleaning and drag-reduction applications

Superhydrophobic coatings treated as surface functional materials are endowed with great application potential with respect to self-cleaning, drag-reduction, anti-icing, etc.

Development of Nano-Composites and Applications to Surface Functional Materials

Development of Nano-Composites and Applications to Surface Functional Materials

A novel protocol for enzymatic digestion based on covalent binding by protein immobilization.

The process of protein digestion is a critical step for successful protein identification in proteomic analysis. Many efforts have been dedicated to enhancing the digestion efficiency for sufficient digestion. Among these approaches, protein complete denaturation with denaturants is a common process for better digestion. However, the removal of denaturants was tedious or would cause protein loss and other problems. In this work, a feasible digestion approach, immobilized protein digestion (IPD), based on covalent binding has been developed. Proteins can be completely denatured and immobilized on the surface of functional materials by covalent binding to form a monolayer. Subsequently, varieties of denaturants or contaminants would be removed thoroughly by washing. To achieve fast immobilization and high digestion efficiency, different functional materials and denaturants were selected. Compared with traditional in-solution digestion, the method achieved a prominent increase in identified peptides numbers and sequence coverage of proteins. Data analysis also showed that covalent binding could evidently decrease enzymatic missed cleavage for various protein sequences. Furthermore, possible peptide losses due to covalent binding were also investigated. Also, it has been proved to be efficient for complex biological sample digestion. Graphical abstract Workflow of the IPD method, including protein denaturation, immobilization, digestion, and identification.

Effect of carbonization temperature on adsorption property of ZIF-8 derived nanoporous carbon for water treatment

The heat treatment effect on the adsorption capabilities of nanoporous carbon particles derived from Zeolitic Imidazolate Framework-8 (ZIF-8) was investigated at 600, 1000 and 1200°C in this study. The results showed that heat treatment at 1000°C had a significant effect on the adsorption capacity of ZIF-8 (almost 10 times) for the removal of methylene blue (MB) dye from water. Nanoporous carbons were synthesized by direct carbonization of ZIF-8. SEM and TEM images showed that the carbon resulting from ZIF-8 carbonization at various temperatures retained the original structure and morphology of ZIF-8. The carbon nanoparticles carbonized at 1000°C exhibited outstanding adsorption capacities (186.3 mg/g) compared to nanoparticles carbonized at 600°C (49.5 mg/g) and 1200°C (36.7 mg/g) as well as ZIF-8 (19.5 mg/g) due to the change in surface charge and pore size distribution. The surface functionalities of materials were also characterized by Raman Spectroscopy, N2 adsorption-desorption, FTIR and TGA. The surface charge of the carbon particles changed from positive (ZIF-8) to negative as a result of conversion to carbon confirmed by zeta potential of the samples. The ZIF-8 derived carbon nanoparticles were found to be efficient adsorbents for water treatment purposes due to the satisfactory adsorption properties such as high adsorption capacity and good wettability.

Adding Functions to Biomaterial Surfaces through Protein Incorporation.

The concept of biomaterials has evolved from one of inert mechanical supports with a long-term, biologically inactive role in the body into complex matrices that exhibit selective cell binding, promote proliferation and matrix production, and may ultimately become replaced by newly generated tissues in vivo. Functionalization of material surfaces with biomolecules is critical to their ability to evade immunorecognition, interact productively with surrounding tissues and extracellular matrix, and avoid bacterial colonization. Antibody molecules and their derived fragments are commonly immobilized on materials to mediate coating with specific cell types in fields such as stent endothelialization and drug delivery. The incorporation of growth factors into biomaterials has found application in promoting and accelerating bone formation in osteogenerative and related applications. Peptides and extracellular matrix proteins can impart biomolecule- and cell-specificities to materials while antimicrobial peptides have found roles in preventing biofilm formation on devices and implants. In this progress report, we detail developments in the use of diverse proteins and peptides to modify the surfaces of hard biomaterials in vivo and in vitro. Chemical approaches to immobilizing active biomolecules are presented, as well as platform technologies for isolation or generation of natural or synthetic molecules suitable for biomaterial functionalization.

Free-Radical-Induced Grafting from Plasma Polymer Surfaces.

With the advances in science and engineering in the second part of the 20th century, emerging plasma-based technologies continuously find increasing applications in the domain of polymer chemistry, among others. Plasma technologies are predominantly used in two different ways: for the treatment of polymer substrates by a reactive or inert gas aiming at a specific surface functionalization or for the synthesis of a plasma polymer with a unique set of properties from an organic or mixed organic-inorganic precursor. Plasma polymer films (PPFs), often deposited by plasma-enhanced chemical vapor deposition (PECVD), currently attract a great deal of attention. Such films are widely used in various fields for the coating of solid substrates, including membranes, semiconductors, metals, textiles, and polymers, because of a combination of interesting properties such as excellent adhesion, highly cross-linked structures, and the possibility of tuning properties by simply varying the precursor and/or the synthesis parameters. Among the many appealing features of plasma-synthesized and -treated polymers, a highly reactive surface, rich in free radicals arising from deposition/treatment specifics, offers a particular advantage. When handled carefully, these reactive free radicals open doors to the controllable surface functionalization of materials without affecting their bulk properties. The goal of this review is to illustrate the increasing application of plasma-based technologies for tuning the surface properties of polymers, principally through free-radical chemistry.

Electrochemical buckling microfabrication.

Can isotropic wet chemical etching be controlled with a spatial resolution at the nanometer scale, especially, for the repetitive microfabrication of hierarchical 3D μ-nanostructures on the continuously curved surface of functional materials? We present an innovative wet chemical etching method called "electrochemical buckling microfabrication": first, a constant contact force is applied to generate a hierarchical 3D μ-nanostructure on a mold electrode surface through a buckling effect; then, the etchant is electrogenerated on-site and confined close to the mold electrode surface; finally, the buckled hierarchical 3D μ-nanostructures are transferred onto the surface of a Ga x In1-x P coated GaAs wafer through WCE. The concave microlens, with a Fresnel structure, has an enhanced photoluminescence at 630 nm. Comparing with energy beam direct writing techniques and nanoimprint lithography, this method provides an electrochemical microfabrication pathway for the semiconductor industry, with low cost and high throughput.

Photoisomerization-induced morphology and transparency transition in an azobenzene based two-component organogel system

A two-component gel containing long chain alkylated gallic acid (GA) and photochromic phenazopyridine (PAP) was prepared. The gel was thoroughly characterized by UV–visible and IR spectra, SEM and POM images, XRD diffraction and dynamic oscillatory measurements. The structure and transparency of the two-component gel can be reversibly changed by alternative UV light irradiation and warming in the palm of the hand. This kind of soft material has potential application in upscale surface functional materials.