Outer membrane vesicles catabolize lignin-derived aromatic compounds in Pseudomonas putida KT2440.

Lignin is an abundant and recalcitrant component of plant cell walls. While lignin degradation in nature is typically attributed to fungi, growing evidence suggests that bacteria also catabolize this complex biopolymer. However, the spatiotemporal mechanisms for lignin catabolism remain unclear. Improved understanding of this biological process would aid in our collective knowledge of both carbon cycling and microbial strategies to valorize lignin to value-added compounds. Here, we examine lignin modifications and the exoproteome of three aromatic-catabolic bacteria: Pseudomonas putida KT2440, Rhodoccocus jostii RHA1, and Amycolatopsis sp. ATCC 39116. P. putida cultivation in lignin-rich media is characterized by an abundant exoproteome that is dynamically and selectively packaged into outer membrane vesicles (OMVs). Interestingly, many enzymes known to exhibit activity toward lignin-derived aromatic compounds are enriched in OMVs from early to late stationary phase, corresponding to the shift from bioavailable carbon to oligomeric lignin as a carbon source. In vivo and in vitro experiments demonstrate that enzymes contained in the OMVs are active and catabolize aromatic compounds. Taken together, this work supports OMV-mediated catabolism of lignin-derived aromatic compounds as an extracellular strategy for nutrient acquisition by soil bacteria and suggests that OMVs could potentially be useful tools for synthetic biology and biotechnological applications.

Spectroscopic Identification of Active Sites of Oxygen-Doped Carbon for Selective Oxygen Reduction to Hydrogen Peroxide.

The electrochemical synthesis of hydrogen peroxide (H2 O2 ) via a two-electron (2 e- ) oxygen reduction reaction (ORR) process provides a promising alternative to replace the energy-intensive anthraquinone process. Herein, we develop a facile template-protected strategy to synthesize a highly active quinone-rich porous carbon catalyst for H2 O2 electrochemical production. The optimized PCC900 material exhibits remarkable activity and selectivity, of which the onset potential reaches 0.83 V vs. reversible hydrogen electrode in 0.1 M KOH and the H2 O2 selectivity is over 95 % in a wide potential range. Comprehensive synchrotron-based near-edge X-ray absorption fine structure (NEXAFS) spectroscopy combined with electrocatalytic characterizations reveals the positive correlation between quinone content and 2 e- ORR performance. The effectiveness of chair-form quinone groups as the most efficient active sites is highlighted by the molecule-mimic strategy and theoretical analysis.

Delayed Lubricant Depletion of Slippery Liquid Infused Porous Surfaces Using Precision Nanostructures.

Slippery liquid infused porous surfaces (SLIPS) are an important class of repellent materials, comprising micro/nanotextures infused with a lubricating liquid. Unlike superhydrophobic surfaces, SLIPS do not rely on a stable air-liquid interface and thus can better manage low surface tension fluids, are less susceptible to damage under physical stress, and are able to self-heal. However, these collective properties are only efficient as long as the lubricant remains infused, which has proved challenging. We hypothesized that, in comparison to a nanohole and nanopillar morphology, the "hybrid" morphology of a hole within a nanopillar, namely a nanotube, would be able to retain and redistribute lubricant more effectively, owing to capillary forces trapping a reservoir of lubricant within the tube, while lubricant between tubes can facilitate redistribution to depleted areas. By virtue of recent fabrication advances in spacer defined intrinsic multiple patterning (SDIMP), we fabricated an array of silicon nanotubes and equivalent arrays of nanoholes and nanopillars (pitch, 560 nm; height, 2 µm). After infusing the nanostructures (prerendered hydrophobic) with lubricant Krytox 1525, we probed the lubricant stability under dynamic conditions and correlated the degree of the lubricant film discontinuity to changes in the contact angle hysteresis. As a proof of concept, the durability test, which involved consecutive deposition of droplets onto the surface amounting to 0.5 L, revealed 2-fold and 1.5-fold enhancements of lubricant retention in nanotubes in comparison to nanopillars and nanoholes, respectively, showing a clear trajectory for prolonging the lifetime of a slippery surface.

Three Component Composite Scaffolds Based on PCL, Hydroxyapatite, and L-Lysine Obtained in TIPS-SL: Bioactive Material for Bone Tissue Engineering.

In this research, we describe the properties of three-component composite foam scaffolds based on poly(ε-caprolactone) (PCL) as a matrix and hydroxyapatite whiskers (HAP) and L-Lysine as fillers (PCL/HAP/Lys with wt% ratio 50/48/2). The scaffolds were prepared using a thermally induced phase separation technique supported by salt leaching (TIPS-SL). All materials were precisely characterized: porosity, density, water uptake, wettability, DSC, and TGA measurements and compression tests were carried out. The microstructure of the obtained scaffolds was analyzed via SEM. It was found that the PCL/HAP/Lys scaffold has a 45% higher Young's modulus and better wettability compared to the PCL/HAP system. At the same time, the porosity of the system was ~90%. The osteoblast hFOB 1.19 cell response was also investigated in osteogenic conditions (39 °C) and the cytokine release profile of interleukin (IL)-1ß, IL-6, and tumor necrosis factor (TNF)-α was determined. Modification of PCL scaffolds with HAP and L-Lysine significantly improved the proliferation of pre-osteoblasts cultured on such materials.

Antimicrobial mechanisms of nanopatterned surfaces-a developing story.

Whilst it is now well recognized that some natural surfaces such as seemingly fragile insect wings possess extraordinary antimicrobial properties, a quest to engineer similar nanopatterned surfaces (NPSs) is ongoing. The stake is high as biofouling impacts critical infrastructure leading to massive social and economic burden with an antimicrobial resistance (AMR) issue at the forefront. AMR is one of the most imminent health challenges the world is facing today. Here, in the effort to find more sustainable solutions, the NPSs are proposed as highly promising technology as their antimicrobial activity arises from the topographical features, which could be realized on multiple material surfaces. To fully exploit these potentials however, it is crucial to mechanistically understand the underlying killing pathways. Thus far, several mechanisms have been proposed, yet they all have one thing in common. The antimicrobial process is initiated with bacteria contacting nanopatterns, which then imposes mechanical stress onto bacterial cell wall. Hence, the activity is called "mechano-bactericidal". From this point on, however, the suggested mechanisms start to diverge partly due to our limited understanding of force interactions at the interface. The aim of this mini review is to analyze the state-of-the-art in proposed killing mechanisms by categorizing them based on the characteristics of their driving force. We also highlight the current gaps and possible future directions in investigating the mechanisms, particularly by shifting towards quantification of forces at play and more elaborated biochemical assays, which can aid validating the current hypotheses.

Optimizing Horticulture Luminescent Solar Concentrators via Enhanced Diffuse Emission Enabled by Micro-Cone Arrays.

Optimizing the photon spectrum for photosynthesis concurrently with improving crop yields presents an efficient and sustainable pathway to alleviate global food shortages. Luminescent solar concentrators (LSCs), consisting of transparent host matrices doped with fluorophores, show excellent promise to achieve the desired spectral tailoring. However, conventional LSCs are predominantly engineered for photon concentration, which results in a limited outcoupling efficiency of converted photons. Here, we introduce a scheme to implement LSCs into horticulture (HLSC) by enhancing light extraction. The symmetry of the device is disrupted by incorporating microcone arrays on the bottom surface to mitigate total internal reflection. Both Monte Carlo ray tracing simulations and experimental results have verified that the greatest enhancements in converted light extraction, relative to planar LSCs, are achieved using microcone arrays (base width 50 µm, aspect ratio 1.2) with extruded and protruded profiles (85.15 and 66.55% improvement, respectively). Angularly resolved transmission measurements show that the HLSC device exhibits a broad angular radiation distribution. This characteristic indicates that the HLSC device emits diffuse light, which is conducive to optimal plant growth.

Glucose Oxidase Loading in Ordered Porous Aluminosilicates: Exploring the Potential of Surface Modification for Electrochemical Glucose Sensing.

Enzymatic electrochemical sensors have become the leading glucose detection technology due to their rapid response, affordability, portability, selectivity, and sensitivity. However, the performance of these sensors is highly dependent on the surface properties of the electrode material used to store glucose oxidase and its ability to retain enzymatic activity under variable environmental conditions. Mesoporous thin films have recently attracted considerable attention as promising candidates for enzyme storage and activity preservation due to their well-defined nanoarchitecture and tunable surface properties. Herein, we systematically compare pathways for the immobilization of glucose oxidase (GOx) and their effectiveness in electrochemical glucose sensing, following modification protocols that lead to the electrostatic attraction (amino functionalization), covalent bonding (aldehyde functionalization), and electrostatic repulsion (oxygen plasma treatment) of the ordered porous aluminosilicate-coated electrodes. By direct comparison using a quartz crystal microbalance, we demonstrate that glucose oxidase can be loaded in a nanoarchitecture with a pore size of ∼50 nm and pore interconnections of ∼35 nm using the native aluminosilicate surface, as well as after amino or aldehyde surface modification, while oxygen plasma exposure of the native surface inhibits glucose oxidase loading. Despite a variety of routes for enzyme loading, quantitative electrochemical glucose sensing between 0 and 20 mM was only possible when the porous surface was functionalized with amino groups, which we relate to the role of surface chemistry in accessing the underlying substrate. Our results highlight the impact of rational surface modification on electrochemical biosensing performance and demonstrate the potential of tailoring porous nanoarchitecture surfaces for biosensing applications.

A route to engineered high aspect-ratio silicon nanostructures through regenerative secondary mask lithography.

Silicon nanostructuring imparts unique material properties including antireflectivity, antifogging, anti-icing, self-cleaning, and/or antimicrobial activity. To tune these properties however, a good control over features' size and shape is essential. Here, a versatile fabrication process is presented to achieve tailored silicon nanostructures (thin/thick pillars, sharp/truncated/re-entrant cones), of pitch down to ∼50 nm, and high-aspect ratio (>10). The approach relies on pre-assembled block copolymer (BCP) micelles and their direct transfer into a glass hard mask of an arbitrary thickness, now enabled by our recently reported regenerative secondary mask lithography. During this pattern transfer, not only can the mask diameter be decreased but also uniquely increased, constituting the first method to achieve such tunability without necessitating a different molecular weight BCP. Consequently, the hard mask modulation (height, diameter) advances the flexibility in attainable inter-pillar spacing, aspect ratios, and re-entrant profiles (= glass on silicon). Combined with adjusted silicon etch conditions, the morphology of nanopatterns can be highly customized. The process control and scalability enable uniform patterning of a 6-inch wafer which is verified through cross-wafer excellent antireflectivity (<5%) and water-repellency (advancing contact angle 158°; hysteresis 1°). The implementation of this approach to silicon nanostructuring is envisioned to be far-reaching, facilitating fundamental studies and targeting applications spanning solar panels, antifogging/antibacterial surfaces, sensing, amongst many others.

Antimicrobial properties of nanostructured surfaces - demonstrating the need for a standard testing methodology.

Bioinspired nanostructured materials that exhibit antimicrobial properties are being synthesized and tested at increasing rates for use in healthcare, manufacturing processes, and diagnostics. Although progress has been made in improving and understanding their bactericidal activity, arguably, the biggest problem currently in the field is the lack of a standard testing methodology that allows for optimal characterization and better comparison of emerging nanostructures. Here, we examine two forms of nanostructured silicon that vary in their ability to kill certain bacterial species due to different physical mechanisms and derive guidelines for the comparative testing. We perform a comprehensive evaluation of methodologies used extensively in the field (e.g., colony counting and live dead analysis) and the novel application of high-throughput flow cytometry. The data reveal how the techniques are complementary but not always directly equivalent or correlative. Therefore, comparison of results obtained using different methodologies on different materials can be grossly misleading. We report significant variations in bactericidal efficiencies depending on experimental environments (medium type, etc.) and methodologies employed. In addition, we demonstrate how cytometry is yet another powerful complementary tool that can aid the mechanistic understanding of antimicrobial activities of rough surfaces. Besides standardization for comparison, ultimately, evaluation methods need to consider anticipated applications. Then and only then can the true potential (or limitation) of a novel material be determined for its suitability for advancement in a particular field of use.

Unique and universal dew-repellency of nanocones.

Surface structuring provides a broad range of water-repellent materials known for their ability to reflect millimetre-sized raindrops. Dispelling water at the considerably reduced scale of fog or dew, however, constitutes a significant challenge, owing to the comparable size of droplets and structures. Nonetheless, a surface comprising nanocones was recently reported to exhibit strong anti-fogging behaviour, unlike pillars of the same size. To elucidate the origin of these differences, we systematically compare families of nanotexture that transition from pillars to sharp cones. Through environmental electron microscopy and modelling, we show that microdroplets condensing on sharp cones adopt a highly non-adhesive state, even at radii as low as 1.5 µm, contrasting with the behaviour on pillars where pinning results in impedance of droplet ejection. We establish the antifogging abilities to be universal over the range of our cone geometries, which speaks to the unique character of the nanocone geometry to repel dew. Truncated cones are finally shown to provide both pinning and a high degree of hydrophobicity, opposing characteristics that lead to a different, yet efficient, mechanism of dew ejection that relies on multiple coalescences.

Bioinspired Multifunctional Glass Surfaces through Regenerative Secondary Mask Lithography.

Nature-inspired nanopatterning offers exciting multifunctionality spanning antireflectance and the ability to repel water/fog, oils, and bacteria; strongly dependent upon nanofeature size and morphology. However, such patterning in glass is notoriously difficult, paradoxically, due to the same outstanding chemical and thermal stability that make glass so attractive. Here, regenerative secondary mask lithography is introduced and exploited to enable customized glass nanopillars through dynamic nanoscale tunability of the side-wall profile and aspect ratio (>7). The method is simple and versatile, comprising just two steps. First, sub-wavelength scalable soft etch masks (55-350 nm) are generated through an example of block copolymer micelles or nanoimprinted photoresist. Second, their inherent durability problem is addressed by an innovative cyclic etching, when the original mask becomes embedded within a protective secondary organic mask, which is tuned and regenerated, permitting dynamic nanofeature profiling with etching selectivity >1:32. It is envisioned that such structuring in glass will facilitate fundamental studies and be useful for numerous practical applications-from displays to architectural windows. To showcase the potential, glass features are tailored to achieve excellent broadband omnidirectional antireflectivity, self-cleaning, and unique antibacterial activity toward Staphylococcus aureus.

Spacer-Defined Intrinsic Multiple Patterning.

Periodic nanotube arrays render enhanced functional properties through their interaction with light and matter, but to reach optimal performance for technologically prominent applications, such as wettability or photonics, structural fine-tuning is essential. Nonetheless, a universal and scalable method providing independent dimension control, high aspect ratios, and the prospect of further structural complexity remains unachieved. Here, we answer this need through an atomic layer deposition (ALD)-enabled multiple patterning. Unlike previous methods, the ALD-deposited spacer is applied directly on the prepatterned target substrate material, serving as an etching mask to generate a multitude of tailored nanotubes. By concept iteration, we further realize concentric and/or binary nanoarrays in a number of industrially important materials such as silicon, glass, and polymers. To demonstrate the achieved quality and applicability of the structures, we probe how nanotube fine-tuning induces broadband antireflection and present a surface boasting extremely low reflectance of <1% across the wavelength range of 300-1050 nm.

Tuning antimicrobial properties of biomimetic nanopatterned surfaces.

Nature has amassed an impressive array of structures that afford protection from microbial colonization/infection when displayed on the exterior surfaces of organisms. Here, controlled variation of the features of mimetics derived from etched silicon allows for tuning of their antimicrobial efficacy. Materials with nanopillars up to 7 µm in length are extremely effective against a wide range of microbial species and exceed the performance of natural surfaces; in contrast, materials with shorter/blunter nanopillars (<2 µm) selectively killed specific species. Using a combination of microscopies, the mechanisms by which bacteria are killed are demonstrated, emphasizing the dependence upon pillar density and tip geometry. Additionally, real-time imaging reveals how cells are immobilized and killed rapidly. Generic or selective protection from microbial colonization could be conferred to surfaces [for, e.g., internal medicine, implants (joint, dental, and cosmetic), food preparation, and the agricultural industry] patterned with these materials as coatings.

Peptide-functionalized ZCIS QDs as fluorescent nanoprobe for targeted HER2-positive breast cancer cells imaging.

In this paper, the synthesis of alloyed CuInZnxS2+x quantum dots (ZCIS QDs), their transfer into aqueous solution via a polymer coating technique, and the use of these nanocrystals to selectively target HER2-positive cells, are reported. By optimizing first the ZnS shell deposition process onto the CuInS2 core, and next the encapsulation of the dots with the amphiphilic poly(maleic anhydride-alt-1-octadecene) (PMAO) polymer, water-dispersible ZCIS QDs were successfully prepared. The nanocrystals with a photoluminescence quantum yield of 35% were purified via centrifugation and ultracentrifugation and high quality nanoparticles with narrow size distributions and surface charges were obtained. After verifying the biocompatibility of PMO-coated ZCIS QDs, we coupled these nanocrystals with the LTVSPWY peptide and demonstrated via MTT assay that both bare and the peptide-linked QDs exhibit low cytotoxicity. The HER2-mediated delivery of the peptide-linked QDs was confirmed by confocal microscopy. This study indicates that as engineered QDs can efficiently be used as fluorescent nanoprobes for selective labelling of HER2-positive SKBR3 cancer cells.

iRGD peptide as effective transporter of CuInZnxS2+x quantum dots into human cancer cells.

In this paper, iRGD peptide-mediated quantum dots (QDs) delivery was studied. In the first step, dodecanethiol-capped CuInZnxS2+x (ZCIS) QDs were prepared and subsequently transferred into water using a standard and facile ligand exchange approach involving 3-mercaptopropionic acid (MPA). ZCIS@MPA nanocrystals possess a photoluminescence quantum yield (PL QY) of 25%, a PL emission centered at ca. 640nm and low distributions in size and shape. Next, the iRGD peptide was electrostatically associated to ZCIS@MPA QDs. After cytotoxicity evaluation, the tumor-targeting and penetrating activities of the iRGD/QD assembly were investigated by confocal microscopy. The experiments performed on various cancer cell lines revealed a high penetration ability of the assembly, while the bare QDs were not internalized. Additionally, imaging experiments were conducted on three-dimensional multicellular tumor spheroids in order to mimic the tumor microenvironment in vivo. iRGD/QD assemblies were found to be evenly distributed throughout the whole HeLa spheroid contrary to normal cells where they were not present. Therefore, iRGD/QD assemblies have a great potential to be used as targeted imaging agents and/or nanocarriers specific to cancer cells.

Ce-doped YAG nanophosphor and red emitting CuInS2/ZnS core/shell quantum dots for warm white light-emitting diode with high color rendering index.

In this work, we report the solvothermal synthesis of Ce-doped YAG (YAG:Ce) nanoparticles (NPs) and their association with a free-Cd CuInS2/ZnS (CIS/ZnS) core/shell QDs for application into white light emitting diode (WLED). 1500 °C-annealed YAG:Ce NPs and CIS/ZnS core/shell QDs exhibited intense yellow and red emissions band with maxima at 545 and 667 nm, respectively. Both YAG:Ce nanophosphor and CIS/ZnS QDs showed high photoluminescence quantum yield (PL QY) of about 50% upon 460 nm excitation. YAG:Ce nanophosphor layer and bilayered YAG:Ce nanophosphor-CIS/ZnS QDs were applied on blue InGaN chip as converter wavelength to achieve WLED. While YAG:Ce nanophosphor converter layer showed low color rendering index (CRI) and cold white light, bilayered YAG:Ce nanophosphor-CIS/ZnS QDs displayed higher CRI of about 84 and warm white light with a correlated color temperature (CCT) of 2784 K. WLED characteristics were measured as a function of forward current from 20 to 1200 mA. The white light stability of bilayered nanophosphor-QDs-based WLED operated at 200 mA was also studied as a function of operating time up to 40 h. Interestingly, CRI and CCT of such device tend to remain constant after 7 h of operating time suggesting that layer-by-layer structure of YAG:Ce phosphor and red-emitting CIS/ZnS QDs could be a good solution to achieve stable warm WLED, especially when high current density is applied.