Interaction between beech and spruce trees in temperate forests affects water use, root water uptake pattern and canopy structure.

Beneficial and negative effects of species interactions can strongly influence water fluxes in forest ecosystems. However, little is known about how trees dynamically adjust their water use when growing with interspecific neighbours. Therefore, we investigated the interaction effects between Fagus sylvatica (European beech) and Picea abies (Norway spruce) on water-use strategies and aboveground structural characteristics. We used continuous in situ isotope spectroscopy of xylem and soil water to investigate source water dynamics and root water uptake depths. Picea abies exhibited a reduced sun-exposed crown area in equally mixed compared with spruce-dominated sites, which was further correlated to a reduction in sap flow of -14.5 ± 8.2%. Contrarily, F. sylvatica trees showed +13.3 ± 33.3% higher water fluxes in equally mixed compared with beech-dominated forest sites. Although a significantly higher crown interference by neighbouring trees was observed, no correlation of water fluxes and crown structure was found. High time-resolved xylem δ2H values showed a large plasticity of tree water use (-74.1 to -28.5‰), reflecting the δ2H dynamics of soil and especially precipitation water sources. Fagus sylvatica in equally mixed sites shifted water uptake to deeper soil layers, while uptake of fresh precipitation was faster in beech-dominated sites. Our continuous in situ water stable isotope measurements traced root water uptake dynamics at unprecedented temporal resolution, indicating highly dynamic use of water sources in response to precipitation and to neighbouring species competition. Understanding this plasticity may be highly relevant in the context of increasing water scarcity and precipitation variability under climate change.

Silicon Oxycarbide Coatings Consisting of Defined Bottom-Up-Grown Nanostructures.

Silicon oxycarbide (SiOC) materials have arisen in the past few decades as a promising new class of glasses and glass-ceramics thanks to their advantageous chemical and thermal properties. Many applications, such as ion storage, sensing, filtering, or catalysis, require materials or coatings with high surface area and might benefit from the high thermal stability of SiOC. This work reports the first facile bottom-up approach to textured high surface area SiOC coatings obtained via direct pyrolysis of polysiloxane structures of well-defined shapes, such as nanofilaments or microrods. This work further investigates the thermal behavior of these structures by means of FT-IR, SEM, and EDX up to 1400 °C. The rods shrink in volume by ≈30% while their aspect ratio remains unaffected by pyrolysis until at least 1100 °C. The nano-sized filaments show signs of viscous flow already at a comparably low temperature of 900 °C which is very probably due to the nano-size effect. This might open a way to experimentally study the size-effect on the glass transition temperature of oxide glasses, an experimentally unexplored but very relevant topic. These structures have great potential, for example, as ion storage materials and supports in high temperature catalysis and CO2 conversion.

Droplet Memory on Liquid-Infused Surfaces.

The knowledge of droplet friction on liquid-infused surfaces (LIS) is of paramount importance for applications involving liquid manipulation. While the possible dissipation mechanisms are well-understood, the effect of surface texture has thus far been mainly investigated on LIS with highly regular solid topographies. In this work, we aim to address this experimental gap by studying the friction experienced by water droplets on LIS based on both random and regular polysilsesquioxane nanostructures. We show that the available models apply to the tested surfaces, but we observe a previously unreported droplet memory effect: as consecutive droplets travel along the same path, their velocity increases up to a plateau value before returning to the original state after a sufficiently long time. We study the features of this phenomenon by evaluating the motion of droplets when they cross the path of a previous sequence of droplets, discovering that moving droplets create a low-friction trace in their wake, whose size matches their base diameter. Finally, we attribute this to the temporary smoothing out of an initially conformal lubricant layer by means of a Landau-Levich-Derjaguin liquid film deposition behind the moving droplet. The proposed mechanism might apply to any LIS with a conformal lubricant layer.

Droplet Size-Assisted Polysiloxane Architecting.

(Super)antiwetting shielding around engineering materials and protecting them against harsh environmental conditions have been achieved via growing various geometry polysiloxane (or silicone) patterns around them by using a droplet-assisted growth method, where the polymerization takes place inside of the water droplets acting as reaction vessels. The size and distribution of these reaction vessels are the main factors in making different geometry silicone patterns; however, very little is known about the fate of these droplets throughout the polymerization. Here, we propose keeping the relative humidity (% RH) inside the reactor stable throughout the polymerization as a new coating parameter to force the size of the reaction vessel water droplets to be the same for building simply shaped silicone rods with controlled geometry and distribution. In this manner, we grew simple geometry cylindric microrods on surfaces and could tune their length, diameter, inter-rod spacing, and thus the (super)hydrophobicity. Here, we also demonstrate that with changes in the amplitude and stability of the % RH, it is possible to fabricate different (super)hydrophobic nanograsses, conical silicone microrods, and isotropic silicone nanofilaments. The proposed new way of tuning initial and in situ reaction vessel droplet size can be used as a single factor to formulate different geometry silicone patterns with tunable dimensions, leading to different roughness and hydrophobicity. To a certain extent, the droplet size-assisted silicone shaping in this work provides a new way to control the length, diameter, morphology, inter-rod spacing, and thus the (super)hydrophobicity of the silicone patterns, especially those in the shape of simple cylindrical microrods. This control over silicone architecting will help to prepare new (super)hydrophobic coatings with more controlled morphology and thus wettability; on the contrary, it will support surface scientists modeling the connection between surface geometry and (super)antiwetting of such irregular pillared surfaces that remain elusive.

Silicone Nanofilament Coatings as Flexible Catalyst Supports for a Knoevenagel Condensation Reaction in Batch and Flow Systems.

In this work, silicone nanofilament (SNF) coatings were prepared via a droplet-assisted growth and shaping (DAGS) approach, where the preparation of the coatings is allowed under ambient conditions. The application of SNF coatings as catalyst supports for amino moieties from (3-aminopropyl)triethoxysilane (APTES) was investigated. With the optimized coating conditions identified, the Brunauer-Emmett-Teller surface areas of a bare glass filter substrate and bare glass beads after the coating have increased by 5-fold and 16-fold, respectively. The SNF-coated filters were readily functionalized with amino groups via a liquid-phase deposition process, and their catalytic activities for a Knoevenagel reaction were evaluated using a batch reactor and a packed bed reactor. In both reactors, the as-prepared filters demonstrated superior catalytic performance over the functionalized filters without SNF coatings. Notably, the unique flexibility of the SNF coatings allowed the facile preparation of a packed bed reactor and a scalable catalytic system. It is expected that the packed bed system established in this study will support the development and the use of various SNF-supported organocatalysts and catalytic materials.

Sand-Based Economical Micro/Nanocomposite Materials for Diverse Applications.

Sand is one of the most fundamental construction materials that is of significant importance and widely used for making concrete, plasters, and mortars, and also for filling under floor and basements. Sand-derived functional materials, for instance superhydrophobic sand, which can be used to prepare liquid marble, separate oil-water mixtures, and transport liquids, have recently been a highly topical and promising research field. However, such materials are mainly prepared using valuable surface modification agents via complicated procedures that are difficult for mass-production, which restricted their true applications. Here, we developed a simple, low-cost, and efficient method for the development of sand-based hierarchical micro/nanostructured composite materials with diverse applications. Briefly, micro/nanostructured superhydrophobic sand was synthesized by one-step in situ growth of a network layer of silicone nanofilaments on the surface of sand microparticles, using only one cheap chemical of small molecules of silanes. The as-prepared superhydrophobic sand displays excellent performance in waterproofing, water storage, soil moisturizing, and oil-water separation. Furthermore, sand-supported micro/nanocomposite catalysts were obtained through covalent attachment of polyamines on the surface of silicone nanofilaments. Such composites, packed in a glass column, were used as a simple flow reactor for Knoevenagel condensation reactions. Quantitative amounts of pure products without further purification can be obtained in such a simple way that just allowing the reactants solution flows through the composite catalysts driven by gravity. These results pave the way toward the development of sand-based multifunctional materials with great potential for industrial use, given their versatile functions and excellent performances but easy-to-fabricate, low-cost preparation procedure.

One-Step Synthesis of Dynamically Shaped Stiff Nanorods Using Soft Silicone Materials to Control Water Repulsion and Collection.

One-dimensional silicone nanostructures, such as filaments, wires, and tubes, have attracted significant attention, owing to their remarkable application capabilities in a large range of material and surface science. However, the soft mechanical properties of silicone cause vulnerability and irregularity in the synthesized structures, which limits their applications. Herein, a simple, solvent-free, and efficient dynamic Droplet Assisted Growth and Shaping (d-DAGS) strategy is proposed for the one-step synthesis and in situ control of the shape of silicone nanostructures. The special designed bamboo-shaped silicone nanorods (SNRs) that are produced by the repetitive dynamic regulation of growth conditions, concomitant with the periodic purging and injection of precursors, exhibit highly-regular and tunable structure with a specific number of segments, indicating that they can be tailor-made according to the requirements of various properties. The enhanced mechanical stiffness and chemical durability strongly support their excellent performances in water-resistance under both static and dynamic wetting conditions. The SNRs significantly promote buoyancy and self-cleaning properties; and exhibit very high water-harvesting efficiency compared with existing designs. Notably, the well-structured ultra-long rods with an ultrahigh aspect ratio (≈176) can also be fabricated by the d-DAGS method, and they can remain standing straight upwards and regular, even though they consist of flexible silicone.

Printable and Versatile Superhydrophobic Paper via Scalable Nonsolvent Armor Strategy.

Despite great scientific and industrial interest in waterproof cellulosic paper, its real world application is hindered by complicated and costly fabrication processes, limitations in scale-up production, and use of organic solvents. Furthermore, simultaneously achieving nonwetting properties and printability on paper surfaces still remains a technical and chemical challenge. Herein, we demonstrate a nonsolvent strategy for scalable and fast fabrication of waterproofing paper through in situ surface engineering with polysilsesquioxane nanorods (PSNRs). Excellent superhydrophobicity is attained on the functionalized paper surface with a water contact angle greater than 160°. Notably, the engineered paper features outstanding printability and writability, as well as greatly enhanced strength and integrity upon prolonged exposure to water (tensile strength ≈ 9.0 MPa). Additionally, the PSNRs concurrently armor paper-based printed items and artwork with waterproofing, self-cleaning, and antimicrobial functionalities without compromising their appearance, readability, and mechanical properties. We also demonstrate that the engineered paper holds the additional advantages of easy processing, low cost, and mechanochemical robustness, which makes it particularly promising for real world applications.

Systematic ranking of filaments regarding their particulate emissions during fused filament fabrication 3D printing by means of a proposed standard test method.

The diversity of fused filament fabrication (FFF) filaments continues to grow rapidly as the popularity of FFF-3D desktop printers for the use as home fabrication devices has been greatly increased in the past decade. Potential harmful emissions and associated health risks when operating indoors have induced many emission studies. However, the lack of standardization of measurements impeded an objectifiable comparison of research findings. Therefore, we designed a chamber-based standard method, i.e., the strand printing method (SPM), which provides a standardized printing procedure and quantifies systematically the particle emission released from individual FFF-3D filaments under controlled conditions. Forty-four marketable filament products were tested. The total number of emitted particles (TP) varied by approximately four orders of magnitude (109  ≤ TP ≤ 1013 ), indicating that origin of polymers, manufacturer-specific additives, and undeclared impurities have a strong influence. Our results suggest that TP characterizes an individual filament product and particle emissions cannot be categorized by the polymer type (e.g., PLA or ABS) alone. The user's choice of a filament product is therefore decisive for the exposure to released particles during operation. Thus, choosing a filament product awarded for low emissions seems to be an easily achievable preemptive measure to prevent health hazards.

Drought reduces water uptake in beech from the drying topsoil, but no compensatory uptake occurs from deeper soil layers.

The intensity and frequency of droughts events are projected to increase in future with expected adverse effects for forests. Thus, information on the dynamics of tree water uptake from different soil layers during and after drought is crucial. We applied an in situ water isotopologue monitoring system to determine the oxygen isotope composition in soil and xylem water of European beech with a 2-h resolution together with measurements of soil water content, transpiration and tree water deficit. Using a Bayesian isotope mixing model, we inferred the relative and absolute contribution of water from four different soil layers to tree water use. Beech took up more than 50% of its water from the uppermost 5 cm soil layer at the beginning of the 2018 drought, but then reduced absolute water uptake from the drying topsoil by 84%. The trees were not able to quantitatively compensate for restricted topsoil water availability by additional uptake from deeper soil layers, which is related to the fine root depth distribution. Absolute water uptake from the topsoil was restored to pre-drought levels within 3 wk after rewetting. These uptake patterns help to explain both the drought sensitivity of beech and its high recovery potential after drought release.

Fluorescent Staining of Silicone Micro- and Nanopatterns for Their Optical Imaging.

Performance of engineered surfaces can be enhanced by making them hydrophobic or superhydrophobic via coating them with low-surface-energy micro- and nanopatterns. However, the wetting phenomena of particularly irregular shape and spacing (super)hydrophobic patterns such as polysiloxane coatings are not yet fully understood from a microscopic perspective. Here, we show a new method to collect 3D confocal images from irregular polysiloxane micro- and nanorods from a single rod resolution to discuss their wetting response over long liquid/solid interaction times and quantify the length and diameter of these rods. To collect such 3D confocal images, fluorescent dye containing water droplets were left on our superhydrophobic and hydrophobic polysiloxane coated surfaces. Then their liquid/solid interfaces were imaged at different staining scenarios: (i) using different fluorescent dyes, (ii) when the droplets were in contact with surfaces, or (iii) after the droplets were taken away from the surface at the end of staining. Using such staining strategies, we could resolve the micro- and nanorods from root to top and determine their length and diameter, which were then found to be in good agreement with those obtained from their electron microscopy images. 3D confocal images in this paper, for the first time, present the long-time existence of more than one wetting state under the same droplet in contact with surfaces, as well as external and internal three-phase contact lines shifting and pinning. In the end, these findings were used to explain the time-dependent wetting kinetics of our surfaces. We believe that the proposed imaging strategy here will, in the future, be used to study many other irregular patterned (super)antiwetting surfaces to describe their wetting theory, which is today impossible due to the complicated surface geometry of these irregular patterns.

Coral-like silicone nanofilament coatings with extremely low ice adhesion.

Passive icephobic surfaces can provide a cost and energy efficient solution to many icing problems that are currently handled with expensive active strategies. Water-repellent surface treatments are promising candidates for this goal, but commonly studied systems, such as superhydrophobic surfaces and Slippery Liquid Infused Porous Surfaces (SLIPS), still face challenges in the stability and durability of their properties in icing environments. In this work, environmental icing conditions are simulated using an Icing Wind Tunnel, and ice adhesion is evaluated with a Centrifugal Adhesion Test. We show that superhydrophobic coral-like Silicone Nanofilament (SNF) coatings exhibit extremely low ice adhesion, to the point of spontaneous ice detachment, and good durability against successive icing cycles. Moreover, SNFs-based SLIPS show stably low ice adhesion for the whole duration of the icing test. Stability of surface properties in a cold environment is further investigated with water wettability at sub-zero surface temperature, highlighting the effect of surface chemistry on superhydrophobicity under icing conditions.

Silicone Nanofilament Support Layers in an Open-Channel System for the Fast Reduction of Para-Nitrophenol.

Chemical vapor phase deposition was used to create hydrophobic nanostructured surfaces on glass slides. Subsequently, hydrophilic channels were created by sputtering a metal catalyst on the channels while masking the outside. The surface tension gradient between the hydrophilic surface in the channels and the outside hydrophobicity formed the open-channel system. The reduction of para-nitrophenol (PNP) was studied on these devices. When compared to nanostructure-free reference systems, the created nanostructures, namely, silicone nanofilaments (SNFs) and nano-bagels, had superior catalytic performance (73% and 66% conversion to 55% at 0.5 µL/s flow rate using 20 nm platinum) and wall integrity; therefore, they could be readily used multiple times. The created nanostructures were stable under the reaction conditions, as observed with scanning electron microscopy. Transition electron microscopy studies of platinum-modified SNFs revealed that the catalyst is present as nanoparticles ranging up to 13 nm in size. By changing the target in the sputter coating unit, molybdenum, gold, nickel and copper were evaluated for their catalytic efficiency. The relative order was platinum < gold = molybdenum < nickel < copper. The decomposition of sodium borohydride (NaBH4) by platinum as a concurrent reaction to the para-nitrophenol reduction terminates the reaction before completion, despite a large excess of reducing agent. Gold had the same catalytic rate as molybdenum, while nickel was two times and copper about four times faster than gold. In all cases, there was a clear improvement in catalysis of silicone nanofilaments compared to a flat reference system.

Statistics of a Sharp GP2Y Low-Cost Aerosol PM Sensor Output Signals.

In this work, we characterise the performance of a Sharp optical aerosol sensor model GP2Y1010AU0F. The sensor was exposed to different environments: to a clean room, to a controlled atmosphere with known aerosol size distribution and to the ambient atmosphere on a busy city street. During the exposure, the output waveforms of the sensor pulses were digitised, saved and a following offline analysis enabled us to study the behaviour of the sensor pulse-by-pulse. A linear response of the sensor on number concentration of the monosized dispersed PSL particles was shown together with an almost linear dependence on particle diameters in the 0.4 to 4 micrometer range. The gathered data about the sensor were used to predict its response to an ambient atmosphere, which was observed simultaneously with a calibrated optical particle counter.

Author Correction: Global karst springs hydrograph dataset for research and management of the world's fastest-flowing groundwater.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Structure Analysis of Amyloid Aggregates at Lipid Bilayers by Supercritical Angle Raman Microscopy.

The amyloid-ß peptide is correlated with Alzheimer's disease and is assumed to cause toxicity by its interaction with the neuron membrane. A custom-made microscope objective based on the supercritical angle technique was developed by our group, which allows investigation of interfacial events by performing surface-sensitive and low-invasive spectroscopy. Applied to Raman spectroscopy, this technique was used to collect information about the structure of polypeptides that interact with a supported lipid bilayer. Notably, the conformation used by amyloid-ß(1-40) and amyloid-ß(1-42) when interacting directly with or next to the supported lipid bilayer was characterized. We observed two distinct secondary structures, α-helix and ß-sheet, which were exhibited by the peptide. These two structures were detected simultaneously. The propensity of the peptide to fold into these structures seemed dependent on both their number of amino acids and their proximity with the supported lipid bilayer. The α-helix structure was observed for amyloid-ß(1-42) fragments that were closer to the lipid bilayer. Peptides that were located further away from the bilayer favored the ß-sheet structure. Amyloid-ß(1-40) was less prone to adopt the α-helix secondary structure.

Global karst springs hydrograph dataset for research and management of the world's fastest-flowing groundwater.

Karst aquifers provide drinking water for 10% of the world's population, support agriculture, groundwater-dependent activities, and ecosystems. These aquifers are characterised by complex groundwater-flow systems, hence, they are extremely vulnerable and protecting them requires an in-depth understanding of the systems. Poor data accessibility has limited advances in karst research and realistic representation of karst processes in large-scale hydrological studies. In this study, we present World Karst Spring hydrograph (WoKaS) database, a community-wide effort to improve data accessibility. WoKaS is the first global karst springs discharge database with over 400 spring observations collected from articles, hydrological databases and researchers. The dataset's coverage compares to the global distribution of carbonate rocks with some bias towards the latitudes of more developed countries. WoKaS database will ensure easy access to a large-sample of good quality datasets suitable for a wide range of applications: comparative studies, trend analysis and model evaluation. This database will largely contribute to research advancement in karst hydrology, supports karst groundwater management, and promotes international and interdisciplinary collaborations.

Droplet assisted growth and shaping of alumina and mixed alumina-silicone 1-dimensional nanostructures.

Since the discovery of silicone nanofilaments a decade ago, room temperature droplet assisted growth and shaping using silanes has been used to synthesize various silicone-based nanostructures. In the present work, we report an extension of this synthesis technique to synthesize nanostructures of new materials. We have successfully synthesized one-dimensional assemblies of beads or necklaces based on alumina (Al) and mixed alumina-silicone (AlSi) nanostructures exhibiting a similar structure as silicone nanofilaments. The characterization of the synthesized nanostructures was performed using different tools, including scanning and transmission electron microscopy, energy dispersive x-ray spectroscopy, and infrared and NMR spectroscopy. Selected area electron diffraction revealed that the nanostructures are amorphous in nature, and the growth behavior and thermal stability of nanostructures are also discussed.

Solvent-Free Fabrication of Flexible and Robust Superhydrophobic Composite Films with Hierarchical Micro/Nanostructures and Durable Self-Cleaning Functionality.

Superhydrophobic surfaces hold tremendous potential in a wide range of applications owing to their multifaced functionalities. However, the mechanochemical susceptibility of such materials hinders their widespread usage in practical applications. Here, we present a simple, solvent-free, and environmentally friendly approach to fabricate flexible and robust superhydrophobic composite films with durable self-cleaning functionality. The obtained composite film features unexpected but surprising hierarchical micro/nanoscopic structures as well as robust superhydrophobicity with a water contact angle of ∼170° and a sliding angle below 4°. Notably, the composite film exhibits mechanical robustness under cyclic abrasion, tape peeling, flexing, intensive finger wiping, and knife cutting; maintains excellent superhydrophobicity after long-time exposure to a high-humidity environment; and sustains exposure to highly corrosive species, such as strong acid/base solutions and organic solvents. The robust superhydrophobicity is ascribed to the induced micro/nanohierarchical surface structures, resulting in the trapped dual-scale air pockets, which could largely reduce the solid/liquid interface. In addition, even after oil contamination, the composite film maintains its water repellency and self-cleaning functionality. The robust superhydrophobic composite film developed here is expected to extend the application scope of superhydrophobic materials and should find potential usage in various industries and daily life.

A SuperLEphilic/Superhydrophobic and Thermostable Separator Based on Silicone Nanofilaments for Li Metal Batteries.

Conventional polyolefin separators suffer from poor wettability to liquid electrolytes (LEs). Although some modified separators exhibit improved wettability, they are hydrophilic, causing inevitable moisture uptake. Trace water could result in poor performance and safety hazard of Li metal batteries. Here, we report a design idea of superLEphilic/superhydrophobic and thermostable separators by modifying the Celgard separator using silicone nanofilaments. The separator features low moisture uptake (∼0%), fast LE diffusion (454 ms), and high LE uptake (287.8%), LE retention rate, and Li+ conductivity. Consequently, the Li/LiFePO4 cells show high cycling stability (96.05% after 350 cycles), good rate performance (125 mA h g-1 at 5.0 C), low resistance, and stable open circuit voltage at 160°C. Moreover, the separator could improve performance of the other Li metal batteries with high-voltage cathodes and the LiFePO4/graphite pouch cells. This work provides an avenue for designing advanced separators by using bioinspired superwetting surfaces.