Nanopatterned Surfaces Research Articles

Effect of Treated Time of Hydrothermal Etching Process on Oxide Layer Formation and Its Antibacterial Properties.

Inspired by natural materials, we developed an antibacterial surface on titanium (Ti) using hydrothermal etching techniques and examined the effect of treated time on oxide layer formation, its antibacterial properties, and surface defects. Hydrothermal etching was conducted on Grade 2 commercially pure Ti immersed in 5M NaOH at 250 °C during a range of time of 0–12 h. Nanopillars generated on the surface had ~100 nm thickness, which resulted in decreased attachment and rupturing of the attached bacteria. The results also showed that 6 h and 8 h of etching time provided a desirable uniform nanopillar structure with the most effective prevention of bacterial adherence on the surface. Multiscale SEM observations revealed that the longer the etching was conducted, the more cracks propagated, which led to an increase in dissociated fragments of the oxide layer. In the 12 h of etching, a higher density of bacterial adherence was observed than that of the untreated and the shorter time treated samples, indicating that etching took longer than 10 h worsened the antibacterial properties of the nano-patterned surface of Ti. This study demonstrated that the optimal time duration is 6–8 h for the oxide layer formation to maximize antibacterial activity and minimize cracking formation on the surface. For future studies, we suggest exploring many possible conditions to generate a more uniform nanopattern without structural defects to secure the integration between a newly deposited oxide layer and the substrate.

Multicomponent Copolymer Planar Membranes with Nanoscale Domain Separation

Domain separation is crucial for proper cellular function and numerous biomedical technologies, especially artificial cells. While phase separation in hybrid membranes containing lipids and copolymers is well-known, the membranes’ overall stability, limited by the lipid part, is hindering the technological applications. Here, we introduce a fully synthetic planar membrane undergoing phase separation into domains embedded within a continuous phase. The mono- and bilayer membranes are composed of two amphiphilic diblock copolymers (PEO45-b-PEHOx20 and PMOXA10-b-PDMS25) with distinct properties and mixed at various concentrations. The molar ratio of the copolymers in the mixture and the nature of the solid support were the key parameters inducing nanoscale phase separation of the planar membranes. The size of the domains and resulting morphology of the nanopatterned surfaces were tailored by adjusting the molar ratios of the copolymers and transfer conditions. Our approach opens new avenues for the development of biomimetic planar membranes with a nanoscale texture.

Surface nanopatterning of amorphous gallium oxide thin film for enhanced solar-blind photodetection

Gallium oxide is an ultra-wide band gap semiconductor (E g > 4.4 eV), best suited intrinsically for the fabrication of solar-blind photodetectors. Apart from its crystalline phases, amorphous Ga2O3 based solar-blind photodetector offer simple and facile growth without the hassle of lattice matching and high temperatures for growth and annealing. However, they often suffer from long response times which hinders any practical use. Herein, we report a simple and cost-effective method to enhance the device performance of amorphous gallium oxide thin film photodetector by nanopatterning the surface using a broad and low energy Ar+ ion beam. The ripples formed on the surface of gallium oxide thin film lead to the formation of anisotropic conduction channels along with an increase in the surface defects. The defects introduced in the system act as recombination centers for the charge carriers bringing about a reduction in the decay time of the devices, even at zero-bias. The fall time of the rippled devices, therefore, reduces, making the devices faster by more than 15 times. This approach of surface modification of gallium oxide provides a one-step, low cost method to enhance the device performance of amorphous thin films which can help in the realization of next-generation optoelectronics.

Controlled metal crumpling as an alternative to folding for the fabrication of nanopatterned meta-biomaterials

We designed and fabricated a simple setup for the controlled crumpling of nanopatterned, surface-porous flat metallic sheets for the fabrication of volume-porous biomaterials and showed that crumpling can be considered as an efficient alternative to origami-inspired folding. Before crumpling, laser cutting was used to introduce pores to the sheets. We then fabricated titanium (Ti) nanopatterns through reactive ion etching on the polished Ti sheets. Thereafter, nanopatterned porous Ti sheets were crumpled at two deformation velocities (i.e., 2 and 100 mm/min). The compression tests of the scaffolds indicated that the elastic modulus of the specimens vary in the range of 11.8–13.9 MPa. Micro-computed tomography scans and computational simulations of crumpled scaffolds were performed to study the morphological properties of the resulting meta-biomaterials. The porosity and pore size of the scaffolds remained within the range of those reported for trabecular bone. Finally, the in vitro cell preosteoblasts culture demonstrated the cytocompatibility of the nanopatterned scaffolds. Moreover, the aspect ratio of the cells residing on the nanopatterned surfaces was found to be significantly higher than those cultured on the control scaffolds, indicating that the nanopatterned surface may have a higher potential for inducing the osteogenic differentiation of the preosteoblasts.

Membrane curvature regulates the spatial distribution of bulky glycoproteins

The glycocalyx is a shell of heavily glycosylated proteins and lipids distributed on the cell surface of nearly all cell types. Recently, it has been found that bulky transmembrane glycoproteins such as MUC1 can modulate membrane shape by inducing membrane protrusions. In this work, we examine the reciprocal relationship of how membrane shape affects MUC1’s spatial distribution on the cell membrane and its biological significance. By employing nanopatterned surfaces and membrane-sculpting proteins to manipulate membrane curvature, we show that MUC1 avoids positively-curved membranes (membrane invaginations) and accumulates on negatively-curved membranes (membrane protrusions). MUC1’s curvature sensitivity is dependent on the length and the extent of glycosylation of its ectodomain, with large and highly glycosylated forms preferentially staying out of positive curvature. Interestingly, MUC1’s avoidance of positive membrane curvature enables it to escape from endocytosis and being removed from the cell membrane. These findings also suggest that the truncation of MUC1’s ectodomain, often observed in breast and ovarian cancers, may enhance its endocytosis and potentiate its intracellular accumulation and signaling.

Self‐Aligned Laser‐Induced Periodic Surface Structures for Large‐Area Controllable Nanopatterning

AbstractLaser‐induced periodic surface structures (LIPSS) have become an important avenue towards surface nanopatterning and certain device applications due to their subwavelength feature size and versatility with different materials. However, the uncontrollable non‐uniformity in achievable nanostructures presents a limit towards its practical application. Here, a robust approach is proposed to obtain controllable nanostructures with long‐range order based on a new insight into one of the electromagnetic origins of nonuniformity of LIPSS, namely a half‐periodic mismatched optical enhancement (h‐MOE) effect. The h‐MOE effect originates from the interference enhancement of surface plasmon polaritons (SPPs) located between tips of every two adjacent ripples in laser scanning process. It is found that LIPSS can be self‐aligned and highly controllable if the h‐MOE effect is elaborately modulated through designed laser scanning strategies especially sequential scanning paths. The new laser nanopatterning approach based on h‐MOE demonstrates controllable patterning ability to theoretically infinitely large‐area super‐straight gratings, orientation‐controllable gratings, and half‐periodic mismatched nanohole arrays.

Influence of Indium (III) Chloride on Human Dermal Fibroblast Cell Adhesion on Tantalum/Silicon Oxide Nano-Composites.

Cell adhesion is an essential biological function for division, migration, signaling and tissue development. While it has been demonstrated that this cell function can be modified by using nanometer-scale surface topographic structures, it remains unknown how contaminants such as indium (III) ion might influence this specific cell behavior. Herein, the influence of indium chloride on human dermal fibroblast (GM5565) adhesion characteristics was investigated, given the frequent contact of contaminants with skin. The morphology of the adherent cells and their mitochondrial reticulum was characterized on cell culture dishes and nanopatterned surfaces by using fluorescence confocal microscopy and scanning electron microscopy. Results showed a significant proportion of cells lost their ability to align preferentially along the line axes of the nanopattern upon exposure to 3.2 mM indium chloride, with cells aligned within 10° of the pattern line axes reduced by as much as ~70%. Concurrent with the cell adhesion behaviors, the mitochondria in cells exposed to indium chloride exhibit a punctate staining that contrasts with the normal network of elongated tubular geometry seen in control cells. Our results demonstrate that exposure to indium chloride has detrimental effects on the behavior of human fibroblasts and adversely impacts their mitochondrial morphology. This shows the importance of evaluating the biological impacts of indium compounds.

Spherical Micro/Nano Hierarchical Structures for Energy and Water Harvesting Devices.

Three-dimensional (3D) hierarchical structures have been explored for various applications owing to the synergistic effects of micro- and nanostructures. However, the development of spherical micro/nano hierarchical structures (S-HSs), which can be used as energy/water harvesting systems and sensing devices, remains challenging owing to the trade-off between structural complexity and fabrication difficulty. This paper presents a new strategy for facile, scalable S-HS fabrication using a thermal expansion of microspheres and nanopatterned structures. When a specific temperature is applied to a composite film of microspheres and elastomers with nanopatterned surfaces, microspheres are expanded and 3D spherical microstructures are generated. Various nanopatterns and densities of spherical microstructures can thereby be quantitatively controlled. The fabricated S-HSs have been used in renewable electrical energy harvesting and sustainable water management applications. Compared to a triboelectric nanogenerator (TENG) with bare film, the S-HS-based TENG exhibited 4.48 times higher triboelectric performance with high mechanical durability. Furthermore, an S-HS is used as a water harvesting device to capture water in a fog environment. The water collection rate is dramatically enhanced by the increased surface area and locally concentrated vapor diffusion flux due to the spherical microstructures.

Implementation of bactericidal topographies on biomimetic calcium phosphates and the potential effect of its reactivity

Since the discovery that nanostructured surfaces were able to kill bacteria, many works have been published focusing on the design of nanopatterned surfaces with antimicrobial properties. Synthetic bone grafts, based on calcium phosphate (CaP) formulations, can greatly benefit from this discovery if adequate nanotopographies can be developed. However, CaP are reactive materials and experience ionic exchanges when placed into aqueous solutions which may in turn affect cell behaviour and complicate the interpretation of the bactericidal results. The present study explores the bactericidal potential of two nanopillared CaP prepared by hydrolysis of two different sizes of α-tricalcium phosphate (α-TCP) powders under biomimetic or hydrothermal conditions. A more lethal bactericidal response toward Pseudomonas aeruginosa (~75% killing efficiency of adhered bacteria) was obtained from the hydrothermally treated CaP which consisted in a more irregular topography in terms of pillar size (radius: 20-60nm), interpillar distances (100-1500nm) and pillar distribution (pillar groups forming bouquets) than the biomimetically treated one (radius: 20-40nm and interpillar distances: 50-200nm with a homogeneous pillar distribution). The material reactivity was greatly influenced by the type of medium (nutrient-rich versus nutrient-free) and the presence or not of bacteria. A lower reactivity and superior bacterial attachment were observed in the nutrient-free medium while a lower attachment was observed for the nutrient rich medium which was explained by a superior reactivity of the material paired with the lower tendency of planktonic bacteria to adhere on surfaces in the presence of nutrients. Importantly, the ionic exchanges produced by the presence of materials were not toxic to planktonic cells. Thus, we can conclude that topography was the main contributor to mortality in the bacterial adhesion tests.

Drawing at the Nanoscale through Macroscopic Movement.

Nanopatterns are important for applications in various nanodevice fields. Existing nanopatterning techniques mainly directly manufacture the nanopatterns through various lithographic methods, which usually are laborious, time-consuming, and need expensive equipment. Here, an extremely simple drawing at the nanoscale (DAN) concept to indirectly fabricate rational nanopatterns through controlling the macroscopic movement of the substrate , is demonstrated. The structure of the nanopatterns is completely determined by and can be shrunk by millions of times from the moving track of the substrate. Multiple surface nanopatterns of different materials with accurately tailorable relative positions can be simply stacked together by moving the substrate by macroscopic distances during different DAN processes. In combination with sophisticated lithographic methods, the DAN method is anticipated to enable substantial advances in nanofabrication.

Ultra-high liquid–solid thermal resistance using nanostructured gold surfaces coated with graphene

The search for materials with high thermal resistance has promising applications in thermoelectric devices and boiling crisis retardation. In this paper, we study the interfacial heat transfer between water and gold, nanostructuring the gold surface and coating it with graphene. By trapping air (or vacuum in our simulations) between graphene and the nanopatterned surface, we observe a considerable increase in the interfacial resistance compared to the planar gold situation, which is shown to scale with the effective graphene–gold contact surface for both monolayer and multilayer graphene. With the massive thermal resistances we predict (up to 200 nm in terms of Kapitza length), the system proposed here represents a robust alternative to superhydrophobic Cassie materials. Moreover, since the low thermal conductance is achieved primarily due to geometry (vacuum trapping), it is straightforward to extend our results to any material with a structure equivalent to that of the nanopatterned gold wall considered here.

Biocompatibility and Mechanical Stability of Nanopatterned Titanium Films on Stainless Steel Vascular Stents

Nanoporous ceramic coatings such as titania are promoted to produce drug-free cardiovascular stents with a low risk of in-stent restenosis (ISR) because of their selectivity towards vascular cell proliferation. The brittle coatings applied on stents are prone to cracking because they are subjected to plastic deformation during implantation. This study aims to overcome this problem by using a unique process without refraining from biocompatibility. Accordingly, a titanium film with 1 µm thickness was deposited on 316 LVM stainless-steel sheets using magnetron sputtering. Then, the samples were anodized to produce nanoporous oxide. The nanoporous oxide was removed by ultrasonication, leaving an approximately 500 nm metallic titanium layer with a nanopatterned surface. XPS studies revealed the presence of a 5 nm-thick TiO2 surface layer with a trace amount of fluorinated titanium on nanopatterned surfaces. Oxygen plasma treatment of the nanopatterned surface produced an additional 5 nm-thick fluoride-free oxide layer. The samples did not exhibit any cracking or spallation during plastic deformation. Cell viability studies showed that nanopatterned surfaces stimulate endothelial cell proliferation while reducing the proliferation of smooth muscle cells. Plasma treatment further accelerated the proliferation of endothelial cells. Activation of blood platelets did not occur on oxygen plasma-treated, fluoride-free nanopatterned surfaces. The presented surface treatment method can also be applied to other stent materials such as CoCr, nitinol, and orthopedic implants.

Laser Direct Writing of Dual-Scale 3D Structures for Cell Repelling at High Cellular Density.

The fabrication of complex, reproducible, and accurate micro-and nanostructured interfaces that impede the interaction between material’s surface and different cell types represents an important objective in the development of medical devices. This can be achieved by topographical means such as dual-scale structures, mainly represented by microstructures with surface nanopatterning. Fabrication via laser irradiation of materials seems promising. However, laser-assisted fabrication of dual-scale structures, i.e., ripples relies on stochastic processes deriving from laser–matter interaction, limiting the control over the structures’ topography. In this paper, we report on laser fabrication of cell-repellent dual-scale 3D structures with fully reproducible and high spatial accuracy topographies. Structures were designed as micrometric “mushrooms” decorated with fingerprint-like nanometric features with heights and periodicities close to those of the calamistrum, i.e., 200–300 nm. They were fabricated by Laser Direct Writing via Two-Photon Polymerization of IP-Dip photoresist. Design and laser writing parameters were optimized for conferring cell-repellent properties to the structures, even for high cellular densities in the culture medium. The structures were most efficient in repelling the cells when the fingerprint-like features had periodicities and heights of ≅200 nm, fairly close to the repellent surfaces of the calamistrum. Laser power was the most important parameter for the optimization protocol.

Nanoscale Topographical Effects on the Adsorption Behavior of Bone Morphogenetic Protein-2 on Graphite.

The interaction between bone morphogenetic protein-2 (BMP-2) and the surface of biomaterials is essential for the restoration of bone and cartilage tissue, inducing cellular differentiation and proliferation. The properties of the surface, including topology features, regulate the conformation and bioactivity of the protein. In this research, we investigated the influence of nanopatterned surfaces on the interaction of a homodimer BMP-2 with graphite material by combining molecular dynamics (MD) and steered molecular dynamics (SMD) simulations. The graphite substrates were patterned as flat, linear grating, square, and circular profiles in combination with BMP-2 conformation in the side-on configuration. Ramachandran plots for the wrist and knuckle epitopes indicated no steric hindrances and provided binding sites to type I and type II receptors. Results showed two optimal patterns that increased protein adsorption of the lower monomer while preserving the secondary structure and leaving the upper monomer free to interact with the cells. Charged residues arginine and lysine and polar residues histidine and tyrosine were the main residues responsible for the strong interaction with the graphite surface. This research provides new molecular-level insights to further understand the mechanisms underlying protein adsorption on nanoscale patterned substrates.

Wet electrospinning-aided self-assembly of multifunctional GO-CNT@PCL core-shell nanocomposites with spider leg bioinspired hierarchical architectures

We report a fast route enabling the multiscale design of nanohybrid structures comprising a 3D fibrous network of polycaprolactone (PCL) wrapped by graphene oxide (GO) sheets onto which carbon nanotube (CNT) brushes are anchored. The method relies on electrospinning PCL solutions onto a suspension of GO and CNTs in ethanol. Self-assembly is due to electrostatic wrapping of GO sheets around PCL fibers and π-π stacking between GO and CNTs. Hierarchical architecture and nanopatterned surface allow gathering the starting properties of PCL, GO and CNTs into lightweight (99% porosity) yet robust (1575% stiffness improvement), amphiphilic monoliths that can remove methylene blue and/or methyl orange from stagnant water with ca.100% efficiency.

Effect of Local Topography on Cell Division of Staphylococcus spp.

Surface engineering is a promising strategy to limit or prevent the formation of biofilms. The use of topographic cues to influence early stages of biofilm formationn has been explored, yet many fundamental questions remain unanswered. In this work, we develop a topological model supported by direct experimental evidence, which is able to explain the effect of local topography on the fate of bacterial micro-colonies of Staphylococcus spp. We demonstrate how topological memory at the single-cell level, characteristic of this genus of Gram-positive bacteria, can be exploited to influence the architecture of micro-colonies and the average number of surface anchoring points over nano-patterned surfaces, formed by vertically aligned silicon nanowire arrays that can be reliably produced on a commercial scale, providing an excellent platform to investigate the effect of topography on the early stages of Staphylococcus spp. colonisation. The surfaces are not intrinsically antimicrobial, yet they delivered a topography-based bacteriostatic effect and a significant disruption of the local morphology of micro-colonies at the surface. The insights from this work could open new avenues towards designed technologies for biofilm engineering and prevention, based on surface topography.

Fabrication of color-toned micro/nanopattern surface by submerged photosynthesis method

Nanosurface patterning can be advantageous for novel opto-electrical devices application. In this study, we utilized the electron beam lithography (EBL) technique to fabricate ZnO nanorods(NRs)/ZnO/Si surface nanopatterning via galvanic submerged photo-synthesis of crystallites (G-SPSC) method, which combines galvanic reactions between two semiconducting surfaces and a photo-induced crystallization in water. By controlling the UV illumination time, high aspect ratio of ZnO NRs were precisely grown on 500 nm size of circular, linear, and lattice patterns. Using bromothymol blue (BTB) gel, a “photo-induced” galvanic reaction was visualized in G-SPSC. Room-temperature photoluminescence (PL) and cathodoluminescence (CL) results dictates oxygen vacancy (VO), ZnO/Si interface luminescence, as well as localized surface plasmon resonance (LSPR) phenomena on the ZnO NRs/ZnO/Si surface. Distinct luminescence behavior was illustrated by color-toned surface patterning (CTSP), opening a possibility for facile fabrication of miniaturized LED application in nanoscale surface area.

Biocompatible mechano-bactericidal nanopatterned surfaces with salt-responsive bacterial release

Bio-inspired nanostructures have demonstrated highly efficient mechano-bactericidal performances with no risk of bacterial resistance; however, they are prone to become contaminated with the killed bacterial debris. Herein, a biocompatible mechano-bactericidal nanopatterned surface with salt-responsive bacterial releasing behavior is developed by grafting salt-responsive polyzwitterionic (polyDVBAPS) brushes on a bio-inspired nanopattern surface. Benefiting from the salt-triggered configuration change of the grafted polymer brushes, this dual-functional surface shows high mechano-bactericidal efficiency in water (low ionic strength condition), while the dead bacterial residuals can be easily lifted by the extended polymer chains and removed from the surface in 1 M NaCl solution (high ionic strength conditions). Notably, this functionalized nanopatterned surface shows selective biocidal activity between bacterial cells sand eukaryotic cells. The biocompatibility with red blood cells (RBCs) and mammalian cells was tested in vitro. The histocompatibility and prevention of perioperative contamination activity were verified by in vivo evaluation in a rat subcutaneous implant model. This nanopatterned surface with bacterial killing and releasing activities may open new avenues for designing bio-inspired mechano-bactericidal platforms with long-term efficacy, thus presenting a facile alternative in combating perioperative-related bacterial infection. Statement of significanceBioinspired nanostructured surfaces with noticeable mechano-bactericidal activity showed great potential in moderating drug-resistance. However, the nanopatterned surfaces are prone to be contaminated by the killed bacterial debris and compromised the bactericidal performance. In this study, we provide a dual-functional antibacterial conception with both mechano-bactericidal and bacterial releasing performances not requiring external chemical bactericidal agents. Additionally, this functionalized antibacterial surface also shows selective biocidal activity between bacteria and eukaryotic cells, and the excellent biocompatibility was tested in vitro and in vivo. The new concept for the functionalized mechano-bactericidal surface here illustrated presents a facile antibiotic-free alternative in combating perioperative related bacterial infection in practical application.

Label-Free Classification of Bacterial Extracellular Vesicles by Combining Nanoplasmonic Sensors With Machine Learning

Bacterial extracellular vesicles (EVs) are nano- scale lipid-enclosed packages that are released by bacteria cells and shuttle various biomolecules between bacteria or host cells. They are implicated in playing several important roles, from infectious disease progression to maintaining proper gut health, however the tools available to characterise and classify them are limited and impractical for many applications. Surface-enhanced Raman Spectroscopy (SERS) provides a promising means of rapidly fingerprinting bacterial EVs in a label-free manner by taking advantage of plasmonic resonances that occur on nanopatterned surfaces, effectively amplifying the inelastic scattering of incident light. In this study, we demonstrate that by applying machine learning algorithms to bacterial EV SERS spectra, EVs from cultures of the same bacterial species ( <italic xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">Escherichia coli</i> ) can be classified by strain, culture conditions, and purification method. While these EVs are highly purified and homogeneous compared to complex samples, the ability to classify them from a single species demonstrates the incredible power of SERS when combined with machine learning, and the importance of considering these parameters in future applications. We anticipate that these findings will play a crucial role in developing the laboratory and clinical utility of bacterial EVs, such as the label-free, noninvasive, and rapid diagnosis of infections without the need to culture samples from blood, urine, or other fluids.

Confining the growth of mesoporous silica films into nanospaces: towards surface nanopatterning.

The combination of lithographic methods and sol gel bottom-up techniques is a promising approach for nanopatterning substrates. The integration and scalable fabrication of such substrates are of great interest for the development of nanowire-based materials opening potentialities in new technologies. We demonstrate the deposition of ordered mesoporous silica into nanopatterned silica substrates by dip coating. Using scanning electron microscopy and grazing incidence small angle X-ray scattering, the effect of the sol composition on the pore ordering was probed. Optimising the sol composition using anodic alumina membranes as confined spaces, we showed how the pH controlled the transformation from circular to columnar mesophase. Vertical mesopores were obtained with very good repeatability. The effect of the sol chemistry on the surfactant curvature was then shown to be similar in nanopatterned substrates made by e-beam lithography.