Understanding the light induced hydrophilicity of metal-oxide thin films.

Photocatalytic effects resulting in water splitting, reduction of carbon dioxide to fuels using solar energy, decomposition of organic compounds, and light-induced hydrophilicity observed on surfaces of various metal oxides (MOx), all rely on the same basic physical mechanisms, and have attracted considerable interest over the past decades. TiO2 and ZnO, two natively n-type doped wide bandgap semiconductors exhibit the effects mentioned above. In this study we propose a model for the photo-induced hydrophilicity in MOx films, and we test the model for TiO2/Si and ZnO/Si heterojunctions. Experimentally, we employ a wet exposure technique whereby the MOx surface is exposed to UV light while a water droplet is sitting on the surface, which allows for a continuous recording of contact angles during illumination. The proposed model and the experimental techniques allow a determination of minority carrier diffusion lengths by contact angle measurements and suggest design rules for materials exhibiting photocatalytic hydrophilicity. We expect that this methodology can be extended to improve our physical understanding of other photocatalytic surface effects.

Revisiting an ecophysiological oddity: Hydathode-mediated foliar water uptake in Crassula species from southern Africa.

Hydathodes are usually associated with water exudation in plants. However, foliar water uptake (FWU) through the hydathodes has long been suspected in the leaf-succulent genus Crassula (Crassulaceae), a highly diverse group in southern Africa, and, to our knowledge, no empirical observations exist in the literature that unequivocally link FWU to hydathodes in this genus. FWU is expected to be particularly beneficial on the arid western side of southern Africa, where up to 50% of Crassula species occur and where periodically high air humidity leads to fog and/or dew formation. To investigate if hydathode-mediated FWU is operational in different Crassula species, we used the apoplastic fluorescent tracer Lucifer Yellow in combination with different imaging techniques. Our images of dye-treated leaves confirm that hydathode-mediated FWU does indeed occur in Crassula and that it might be widespread across the genus. Hydathodes in Crassula serve as moisture-harvesting structures, besides their more common purpose of guttation, an adaptation that has likely played an important role in the evolutionary history of the genus. Our observations suggest that ability for FWU is independent of geographical distribution and not restricted to arid environments under fog influence, as FWU is also operational in Crassula species from the rather humid eastern side of southern Africa. Our observations point towards no apparent link between FWU ability and overall leaf surface wettability in Crassula. Instead, the hierarchically sculptured leaf surfaces of several Crassula species may facilitate FWU due to hydrophilic leaf surface microdomains, even in seemingly hydrophobic species. Overall, these results confirm the ecophysiological relevance of hydathode-mediated FWU in Crassula and reassert the importance of atmospheric humidity for some arid-adapted plant groups.

Biosynthesis enhancement of tropodithietic acid (TDA) antibacterial compound through biofilm formation by marine bacteria Phaeobacter inhibens on micro-structured polymer surfaces.

Although aquaculture is a major player in current and future food production, the routine use of antibiotics provides ample ground for development of antibiotic resistance. An alternative route to disease control is the use of probiotic bacteria such as the marine bacteria Phaeobacter inhibens which produces tropodithietic acid (TDA) that inhibit pathogens without affecting the fish. Improving conditions for the formation of biofilm and TDA-synthesis is a promising avenue for biocontrol in aquaculture. In this study, the biosynthesis of TDA by Phaeobacter inhibens grown on micro-structured polymeric surfaces in micro-fluidic flow-cells is investigated. The formation of biofilms on three surface topographies; hexagonal micro-pit-arrays, hexagonal micro-pillar-arrays, and planar references is investigated. The biomass on these surfaces is measured by a non-invasive confocal microscopy 3D imaging technique, and the corresponding TDA production is monitored by liquid chromatography mass spectrometry (LC-MS) in samples collected from the outlets of the microfluidic channels. Although all surfaces support growth of P. inhibens, biomass appears to be decoupled from total TDA biosynthesis as the micro-pit-arrays generate the largest biomass while the micro-pillar-arrays produce significantly higher amounts of TDA. The findings highlight the potential for optimized micro-structured surfaces to maintain biofilms of probiotic bacteria for sustainable aquacultures.

Bioinspired Microstructured Polymer Surfaces with Antireflective Properties.

Over the years, different approaches to obtaining antireflective surfaces have been explored, such as using index-matching, interference, or micro- and nanostructures. Structural super black colors are ubiquitous in nature, and biomimicry thus constitutes an interesting way to develop antireflective surfaces. Moth-eye nanostructures, for example, are well known and have been successfully replicated using micro- and nanofabrication. However, other animal species, such as birds of paradise and peacock spiders, have evolved to display larger structures with antireflective features. In peacock spiders, the antireflective properties of their super black patches arise from relatively simple microstructures with lens-like shapes organized in tightly packed hexagonal arrays, which makes them a good candidate for cheap mass replication techniques. In this paper, we present the fabrication and characterization of antireflective microarrays inspired by the peacock spider's super black structures encountered in nature. Firstly, different microarrays 3D models are generated from a surface equation. Secondly, the arrays are fabricated in a polyacrylate resin by super-resolution 3D printing using two-photon polymerization. Thirdly, the resulting structures are inspected using a scanning electron microscope. Finally, the reflectance and transmittance of the printed structures are characterized at normal incidence with a dedicated optical setup. The bioinspired microlens arrays display excellent antireflective properties, with a measured reflectance as low as 0.042 ± 0.004% for normal incidence, a wavelength of 550 nm, and a collection angle of 14.5°. These values were obtained using a tightly-packed array of slightly pyramidal lenses with a radius of 5 µm and a height of 10 µm.

Photolithographic Patterning of FluorAcryl for Biphilic Microwell-Based Digital Bioassays and Selection of Bacteria.

FluorAcryl 3298 (FA) is a UV-curable fluoroacrylate polymer commonly employed as a chemically resistant, hydrophobic, and oleophobic coating. Here, FA was used in a cleanroom-based microstructuring process to fabricate hydrophilic-in-hydrophobic (HiH) micropatterned surfaces containing femtoliter-sized well arrays. A short protocol involving direct UV photopatterning, an etching step, and final recovery of the hydrophobic properties of the polymer produced patterned substrates with micrometer resolution. Specifically, HiH microwell arrays were obtained with a well diameter of 10 µm and various well depths ranging from 300 nm to 1 µm with high reproducibility. The 300 nm deep microdroplet array (MDA) substrates were used for digital immunoassays, which presented a limit of detection in the attomolar range. This demonstrated the chemical functionality of the hydrophilic and hydrophobic surfaces. Furthermore, the 1 µm deep wells could efficiently capture particles such as bacteria, whereas the 300 nm deep substrates or other types of flat HiH molecular monolayers could not. Capturing a mixture of bacteria expressing red- and green-fluorescent proteins, respectively, served as a model for screening and selection of specific phenotypes using FA-MDAs. Here, green-fluorescent bacteria were specifically selected by overlaying a solution of gelatin methacryloyl (GelMA) mixed with a photoinitiator and using a high-magnification objective, together with custom pinholes, in a common fluorescence microscope to cross-link the hydrogel around the bacteria of interest. In conclusion, due to the straightforward processing, versatility, and low-price, FA is an advantageous alternative to more commonly used fluorinated materials, such as CYTOP or Teflon-AF, for the fabrication of HiH microwell arrays and other biphilic microstructures.

Fabrication of Microstructured Surface Topologies for the Promotion of Marine Bacteria Biofilm.

Several marine bacteria of the Roseobacter group can inhibit other microorganisms and are especially antagonistic when growing in biofilms. This aptitude to naturally compete with other bacteria can reduce the need for antibiotics in large-scale aquaculture units, provided that their culture can be promoted and controlled. Micropatterned surfaces may facilitate and promote the biofilm formation of species from the Roseobacter group, due to the increased contact between the cells and the surface material. Our research goal is to fabricate biofilm-optimal micropatterned surfaces and investigate the relevant length scales for surface topographies that can promote the growth and biofilm formation of the Roseobacter group of bacteria. In a preliminary study, silicon surfaces comprising arrays of pillars and pits with different periodicities, diameters, and depths were produced by UV lithography and deep reactive ion etching (DRIE) on polished silicon wafers. The resulting surface microscale topologies were characterized via optical profilometry and scanning electron microscopy (SEM). Screening of the bacterial biofilm on the patterned surfaces was performed using green fluorescent staining (SYBR green I) and confocal laser scanning microscopy (CLSM). Our results indicate that there is a correlation between the surface morphology and the spatial organization of the bacterial biofilm.

Large plasmonic color metasurfaces fabricated by super resolution deep UV lithography.

In this paper, we demonstrate plasmonic color metasurfaces as large as ∼60 cm2 fabricated by deep UV projection lithography employing an innovative combination of resolution enhancement techniques. Briefly, in addition to the established off-axis dipole illumination, double- and cross-exposure resolution enhancement of lithography, we introduce a novel element, the inclusion of transparent assist features to the mask layout. With this approach, we demonstrate the fabrication of relief arrays having critical dimensions such as 159 nm nanopillars or 210 nm nanoholes with 300 nm pitches, which is near the theoretical resolution limit expressed by the Rayleigh criterion for the 248 nm lithography tool used in this work. The type of surface structure, i.e. nanopillar or nanohole, and their diameters can be tailored simply by changing the width of the assist features included in the mask layout. By coating the obtained nanopatterns with thin layers of either Au or Al, we observe color spectra originating from the phenomenon known as localized surface plasmon resonance (LSPR). We demonstrate the generation of color palettes representing a broad spectral range of colors, and we employ finite element modelling to corroborate the measured LSPR fingerprint spectra. Most importantly, the ∼60 cm2 nanostructure arrays can be written in only a few minutes, which is a tremendous improvement compared to the more established techniques employed for fabricating similar structures.

Recent Advances in Microswimmers for Biomedical Applications.

Microswimmers are a rapidly developing research area attracting enormous attention because of their many potential applications with high societal value. A particularly promising target for cleverly engineered microswimmers is the field of biomedical applications, where many interesting examples have already been reported for e.g., cargo transport and drug delivery, artificial insemination, sensing, indirect manipulation of cells and other microscopic objects, imaging, and microsurgery. Pioneered only two decades ago, research studies on the use of microswimmers in biomedical applications are currently progressing at an incredibly fast pace. Given the recent nature of the research, there are currently no clinically approved microswimmer uses, and it is likely that several years will yet pass before any clinical uses can become a reality. Nevertheless, current research is laying the foundation for clinical translation, as more and more studies explore various strategies for developing biocompatible and biodegradable microswimmers fueled by in vivo-friendly means. The aim of this review is to provide a summary of the reported biomedical applications of microswimmers, with focus on the most recent advances. Finally, the main considerations and challenges for clinical translation and commercialization are discussed.

Membrane interactions in drug delivery: Model cell membranes and orthogonal techniques.

To generate the desired effect in the human body, the active pharmaceutical ingredient usually needs to interact with a receptor located on the cell membrane or inside the cell. Thus, understanding membrane interactions is of great importance when it comes to the development and testing of new drug molecules or new drug delivery systems. Nowadays, there is a tremendous selection of both model cell membranes and of techniques that can be used to characterize interactions between selected model cell membranes and a drug molecule, an excipient, or a drug delivery system. Having such a wide selection of model cell membranes and techniques available makes it sometimes challenging to select the optimal combination for a specific study. Furthermore, it is difficult to compare results obtained using different model cell membranes and techniques, and not all in vitro studies translate as well to an estimation of the in vivo biological activity or understanding of mode of action. This review provides an overview of the available lipid bilayer-based model cell membranes and of the most widely employed techniques for studying membrane interactions. Finally, the need for employing complimentary characterization techniques in order to acquire more reliable and in-depth information is highlighted.

Nanoimprinting and tapering of chalcogenide photonic crystal fibers for cascaded supercontinuum generation.

Improved long-wavelength transmission and supercontinuum (SC) generation is demonstrated by antireflective (AR) nanoimprinting and tapering of chalcogenide photonic crystal fibers (PCFs). Using a SC source input spanning from 1 to 4.2 µm, the total transmission of a 15 µm core diameter PCF was improved from ∼53% to ∼74% by nanoimprinting of AR structures on both input and output facets of the fiber. Through a combined effect of reduced reflection and redshifting of the spectrum to 5 µm, the relative transmission of light >3.5 µm in the same fiber was increased by 60.2%. Further extension of the spectrum to 8 µm was achieved using tapered fibers. The spectral broadening dynamics and output power were investigated using different taper parameters and pulse repetition rates.

Nanoimprinting reflow modified moth-eye structures in chalcogenide glass for enhanced broadband antireflection in the mid-infrared.

We report on the progress towards developing a new method for fabricating more efficient, broadband antireflective (AR) moth-eye structures in As2Se3 via a direct nanoimprinting technique. Thermal reflow is used during mold fabrication to reshape a conventional deep-ultraviolet lithography in order to promote a pattern transfer of "secant ogive"-like moth-eye structures. Once replicated, structures modified by reflow displayed greater AR efficiency compared to structures replicated by a conventional mold, achieving the highest spectrum-averaged transmittance improvement of 12.36% from 3.3 to 12 µm.

Mapping the transition to superwetting state for nanotextured surfaces templated from block-copolymer self-assembly.

Adding roughness to hydrophilic surfaces is generally expected to enhance their wetting by water. Indeed, global free energy minimization predicts decreasing contact angles when roughness factor or surface energy increases. However, experimentally it is often found that water spreading on rough surfaces is impeded by pinning effects originating from local free energy minima; an effect, largely neglected in scientific literature. Here, we utilize Laplace pressure as a proxy for these local minima, and we map the transition to a superwetting state of hydrophilic nano-textured surfaces in terms of surface chemistry and texture geometry. We demonstrate the effect for polymer model surfaces templated from block-copolymer self-assembly comprising dense, nano-pillar arrays exhibiting strong pinning in their pristine state. By timed argon plasma exposure, we tune surface chemistry to map the transition into the superwetting state of low contact angle, which we show coincide with the surface supporting hemiwicking flow. For the near-ideal model surfaces, the transition to the superwetting state occurs below a critical material contact angle of ∼50°. We show that superwetting surfaces possess anti-fogging properties, and demonstrate long term stability of the superwetting effect by coating the nanotextured surfaces with ∼10 nm thin films of either tungsten or silica.

Electroosmotic Flow in Microchannel with Black Silicon Nanostructures.

Although electroosmotic flow (EOF) has been applied to drive fluid flow in microfluidic chips, some of the phenomena associated with it can adversely affect the performance of certain applications such as electrophoresis and ion preconcentration. To minimize the undesirable effects, EOF can be suppressed by polymer coatings or introduction of nanostructures. In this work, we presented a novel technique that employs the Dry Etching, Electroplating and Molding (DEEMO) process along with reactive ion etching (RIE), to fabricate microchannel with black silicon nanostructures (prolate hemispheroid-like structures). The effect of black silicon nanostructures on EOF was examined experimentally by current monitoring method, and numerically by finite element simulations. The experimental results showed that the EOF velocity was reduced by 13 ± 7%, which is reasonably close to the simulation results that predict a reduction of approximately 8%. EOF reduction is caused by the distortion of local electric field at the nanostructured surface. Numerical simulations show that the EOF velocity decreases with increasing nanostructure height or decreasing diameter. This reveals the potential of tuning the etching process parameters to generate nanostructures for better EOF suppression. The outcome of this investigation enhances the fundamental understanding of EOF behavior, with implications on the precise EOF control in devices utilizing nanostructured surfaces for chemical and biological analyses.

Effect of Structure Hierarchy for Superhydrophobic Polymer Surfaces Studied by Droplet Evaporation.

Super-hydrophobic natural surfaces usually have multiple levels of structure hierarchy. Here, we report on the effect of surface structure hierarchy for droplet evaporation. The two-level hierarchical structures studied comprise micro-pillars superimposed with nanograss. The surface design is fully scalable as structures used in this study are replicated in polypropylene by a fast roll-to-roll extrusion coating method, which allows effective thermoforming of the surface structures on flexible substrates. As one of the main results, we show that the hierarchical structures can withstand pinning of sessile droplets and remain super-hydrophobic for a longer time than their non-hierarchical counterparts. The effect is documented by recording the water contact angles of sessile droplets during their evaporation from the surfaces. The surface morphology is mapped by atomic force microscopy (AFM) and used together with the theory of Miwa et al. to estimate the degree of water impregnation into the surface structures. Finally, the different behavior during the droplet evaporation is discussed in the light of the obtained water impregnation levels.

Enrichment of megabase-sized DNA molecules for single-molecule optical mapping and next-generation sequencing.

Next-generation sequencing (NGS) has caused a revolution, yet left a gap: long-range genetic information from native, non-amplified DNA fragments is unavailable. It might be obtained by optical mapping of megabase-sized DNA molecules. Frequently only a specific genomic region is of interest, so here we introduce a method for selection and enrichment of megabase-sized DNA molecules intended for single-molecule optical mapping: DNA from a human cell line is digested by the NotI rare-cutting enzyme and size-selected by pulsed-field gel electrophoresis. For demonstration, more than 600 sub-megabase- to megabase-sized DNA molecules were recovered from the gel and analysed by denaturation-renaturation optical mapping. Size-selected molecules from the same gel were sequenced by NGS. The optically mapped molecules and the NGS reads showed enrichment from regions defined by NotI restriction sites. We demonstrate that the unannotated genome can be characterized in a locus-specific manner via molecules partially overlapping with the annotated genome. The method is a promising tool for investigation of structural variants in enriched human genomic regions for both research and diagnostic purposes. Our enrichment method could potentially work with other genomes or target specified regions by applying other genomic editing tools, such as the CRISPR/Cas9 system.

Generation of micro-droplet arrays by dip-coating of biphilic surfaces; the dependence of entrained droplet volume on withdrawal velocity.

Droplet array chips were realized using an alignment-free fabrication process in silicon. The chips were textured with a homogeneous nano-scale surface roughness but were partially covered with a self-assembled monolayer of perfluorodecyltrichlorosilane (FDTS), resulting in a super-biphilic surface. When submerged in water and withdrawn again, microliter sized droplets are formed due to pinning of water on the hydrophilic spots. The entrained droplet volumes were investigated under variation of spot size and withdrawal velocity. Two regimes of droplet formation were revealed: at low speeds, the droplet volume achieved finite values even for vanishing speeds, while at higher speeds the volume was governed by fluid inertia. A simple 2D boundary layer model describes the behavior at high speeds well. Entrained droplet volume could be altered, post-fabrication, by more than a factor of 15, which opens up for more applications of the dip-coating technique due to the significant increase in versatility of the micro-droplet array platform.

Plasmonic color metasurfaces fabricated by a high speed roll-to-roll method.

Lab-scale plasmonic color printing using nano-structured and subsequently metallized surfaces have been demonstrated to provide vivid colors. However, upscaling these structures for large area manufacturing is extremely challenging due to the requirement of nanometer precision of metal thickness. In this study, we have investigated a plasmonic color meta-surface design that can be easily upscaled. We have demonstrated the feasibility of fabrication of these plasmonic color surfaces by a high-speed roll-to-roll method, comprising roll-to-roll extrusion coating at 10 m min-1 creating a polymer foil having 100 nm deep pits of varying sub-wavelength diameter and pitch length. Subsequently this polymer foil was metallized and coated also by high-speed roll-to-roll methods. The perceived colors have high tolerance towards the thickness of the metal layer, when this thickness exceeds the depths of the pits, which enables the robust high-speed fabrication. This finding can pave the way for plasmonic meta-surfaces to be implemented in a broader range of applications such as printing, memory, surface enhanced Raman scattering (SERS), biosensors, flexible displays, photovoltaics, security, and product branding.

Spatial Control of Condensation on Chemically Homogeneous Pillar-Built Surfaces.

The random nature of dropwise condensation impedes spatial control hereof and its use for creating microdroplet arrays, yet here we demonstrate the spatial control of dropwise condensation on a chemically homogeneous pillar array surface, yielding ∼8000 droplets/mm2 under normal atmospheric pressure conditions. The studied pillar array surface is defined by photolithography and etched in silicon by deep reactive ion etching. Subsequently, the surface is covered with a self-assembled monolayer of perfluorodecyltrichlorosilane (FDTS) to render the surface hydrophobic. To obtain a perfect droplet array, with one droplet per pillar, we exploit a phenomenon where the water vapor flux is focused on the apexes of surface asperities by diffusion while matching the nucleation point density to the array dimensions. Matching is here achieved through the variation of interpillar distance and vapor flow conditions.

Effect of nanostructures orientation on electroosmotic flow in a microfluidic channel.

Electroosmotic flow (EOF) is an electric-field-induced fluid flow that has numerous micro-/nanofluidic applications, ranging from pumping to chemical and biomedical analyses. Nanoscale networks/structures are often integrated in microchannels for a broad range of applications, such as electrophoretic separation of biomolecules, high reaction efficiency catalytic microreactors, and enhancement of heat transfer and sensing. Their introduction has been known to reduce EOF. Hitherto, a proper study on the effect of nanostructures orientation on EOF in a microfluidic channel is yet to be carried out. In this investigation, we present a novel fabrication method for nanostructure designs that possess maximum orientation difference, i.e. parallel versus perpendicular indented nanolines, to examine the effect of nanostructures orientation on EOF. It consists of four phases: fabrication of silicon master, creation of mold insert via electroplating, injection molding with cyclic olefin copolymer, and thermal bonding and integration of practical inlet/outlet ports. The effect of nanostructures orientation on EOF was studied experimentally by current monitoring method. The experimental results show that nanolines which are perpendicular to the microchannel reduce the EOF velocity significantly (approximately 20%). This flow velocity reduction is due to the distortion of local electric field by the perpendicular nanolines at the nanostructured surface as demonstrated by finite element simulation. In contrast, nanolines which are parallel to the microchannel have no effect on EOF, as it can be deduced that the parallel nanolines do not distort the local electric field. The outcomes of this investigation contribute to the precise control of EOF in lab-on-chip devices, and fundamental understanding of EOF in devices which utilize nanostructured surfaces for chemical and biological analyses.

Spatial characterization of nanotextured surfaces by visual color imaging.

We present a method using an ordinary color camera to characterize nanostructures from the visual color of the structures. The method provides a macroscale overview image from which micrometer-sized regions can be analyzed independently, hereby revealing long-range spatial variations of the structures. The method is tested on injection-molded polymer line gratings, and the height and filling factor are determined with confidence intervals similar to more advanced imaging scatterometry setups.