Search

The northwestern Tropical Atlantic Ocean is a turbulent region, filled with mesoscale eddies and regional currents. In this intense dynamical context, several water masses with thermohaline characteristics of different origins are advected, mixed, and stirred at the surface and at depth. The EUREC4A-OA/ATOMIC experiment that took place in January and February 2020 was dedicated to assessing the processes at play in this region, especially the interaction between the ocean and the atmosphere. For that reason, four oceanographic vessels and different autonomous platforms measured properties near the air–sea interface and acquired thousands of upper-ocean (up to 400–2000 m depth) profiles. However, each device had its own observing capability, varying from deep measurements acquired during vessel stations to shipboard underway near-surface observations and measurements from autonomous and uncrewed systems (such as Saildrones). These observations were undertaken with a specific sampling strategy guided by near-real-time satellite maps and adapted every half day, based on the process that was investigated. These processes were characterized by different spatiotemporal scales, from mesoscale eddies, with diameters exceeding 100 km, to submesoscale filaments of 1 km width. This article describes the datasets gathered from the different devices and how the data were calibrated and validated. In order to ensure an overall consistency, the platforms' datasets are cross-validated using a hierarchy of instruments defined by their own specificity and calibration procedures. This has enabled the quantification of the uncertainty in the measured parameters when different datasets are used together, e.g., https://doi.org/10.17882/92071 (L'Hégaret et al., 2020a).

State-of-the-art Earth system models typically employ grid spacings of O(100 km), which is too coarse to explicitly resolve main drivers of the flow of energy and matter across the Earth system. In this paper, we present the new ICON-Sapphire model configuration, which targets a representation of the components of the Earth system and their interactions with a grid spacing of 10 km and finer. Through the use of selected simulation examples, we demonstrate that ICON-Sapphire can (i) be run coupled globally on seasonal timescales with a grid spacing of 5 km, on monthly timescales with a grid spacing of 2.5 km, and on daily timescales with a grid spacing of 1.25 km; (ii) resolve large eddies in the atmosphere using hectometer grid spacings on limited-area domains in atmosphere-only simulations; (iii) resolve submesoscale ocean eddies by using a global uniform grid of 1.25 km or a telescoping grid with the finest grid spacing at 530 m, the latter coupled to a uniform atmosphere; and (iv) simulate biogeochemistry in an ocean-only simulation integrated for 4 years at 10 km. Comparison of basic features of the climate system to observations reveals no obvious pitfalls, even though some observed aspects remain difficult to capture. The throughput of the coupled 5 km global simulation is 126 simulated days per day employing 21 % of the latest machine of the German Climate Computing Center. Extrapolating from these results, multi-decadal global simulations including interactive carbon are now possible, and short global simulations resolving large eddies in the atmosphere and submesoscale eddies in the ocean are within reach.

The influence of mesoscale eddies on the flow field and the water masses, especially the oxygen distribution of the eastern tropical South Pacific, is investigated from a mooring, float, and satellite data set. Two anticyclonic (ACE1/2), one mode-water (MWE), and one cyclonic eddy (CE) are identified and followed in detail with satellite data on their westward transition with velocities of 3.2 to 6.0 cm s−1 from their generation region, the shelf of the Peruvian and Chilean upwelling regime, across the Stratus Ocean Reference Station (ORS; ∼ 20° S, 85° W) to their decaying region far west in the oligotrophic open ocean. The ORS is located in the transition zone between the oxygen minimum zone and the well oxygenated South Pacific subtropical gyre. Velocity, hydrographic, and oxygen measurements at the mooring show the impact of eddies on the weak flow region of the eastern tropical South Pacific. Strong anomalies are related to the passage of eddies and are not associated with a seasonal signal in the open ocean. The mass transport of the four observed eddies across 85° W is between 1.1 and 1.8 Sv. The eddy type-dependent available heat, salt, and oxygen anomalies are 8.1×1018 J (ACE2), 1.0×1018 J (MWE), and −8.9×1018 J (CE) for heat; 25.2×1010 kg (ACE2), −3.1×1010 kg (MWE), and −41.5×1010 kg (CE) for salt; and −3.6×1016 µmol (ACE2), −3.5×1016 µmol (MWE), and −6.5×1016 µmol (CE) for oxygen showing a strong imbalance between anticyclones and cyclones for salt transports probably due to seasonal variability in water mass properties in the formation region of the eddies. Heat, salt, and oxygen fluxes out of the coastal region across the ORS region in the oligotrophic open South Pacific are estimated based on these eddy anomalies and on eddy statistics (gained out of 23 years of satellite data). Furthermore, four profiling floats were trapped in the ACE2 during its westward propagation between the formation region and the open ocean, which allows for conclusions on lateral mixing of water mass properties with time between the core of the eddy and the surrounding water. The strongest lateral mixing was found between the seasonal thermocline and the eddy core during the first half of the eddy lifetime.

The temporal evolution of the physical and biogeochemical structure of an oxygen-depleted anticyclonic modewater eddy is investigated over a 2-month period using high-resolution glider and ship data. A weakly stratified eddy core (squared buoyancy frequency N2 ∼ 0.1 × 10−4 s−2) at shallow depth is identified with a horizontal extent of about 70 km and bounded by maxima in N2. The upper N2 maximum (3–5 × 10−4 s−2) coincides with the mixed layer base and the lower N2 maximum (0.4 × 10−4 s−2) is found at about 200 m depth in the eddy centre. The eddy core shows a constant slope in temperature/salinity (T∕S) characteristic over the 2 months, but an erosion of the core progressively narrows down the T∕S range. The eddy minimal oxygen concentrations decreased by about 5 µmol kg−1 in 2 months, confirming earlier estimates of oxygen consumption rates in these eddies. Separating the mesoscale and perturbation flow components reveals oscillating velocity finestructure ( ∼ 0.1 m s−1) underneath the eddy and at its flanks. The velocity finestructure is organized in layers that align with layers in properties (salinity, temperature) but mostly cross through surfaces of constant density. The largest magnitude in velocity finestructure is seen between the surface and 140 m just outside the maximum mesoscale flow but also in a layer underneath the eddy centre, between 250 and 450 m. For both regions a cyclonic rotation of the velocity finestructure with depth suggests the vertical propagation of near-inertial wave (NIW) energy. Modification of the planetary vorticity by anticyclonic (eddy core) and cyclonic (eddy periphery) relative vorticity is most likely impacting the NIW energy propagation. Below the low oxygen core salt-finger type double diffusive layers are found that align with the velocity finestructure. Apparent oxygen utilization (AOU) versus dissolved inorganic nitrate (NO3−) ratios are about twice as high (16) in the eddy core compared to surrounding waters (8.1). A large NO3− deficit of 4 to 6 µmol kg−1 is determined, rendering denitrification an unlikely explanation. Here it is hypothesized that the differences in local recycling of nitrogen and oxygen, as a result of the eddy dynamics, cause the shift in the AOU : NO3− ratio. High NO3− and low oxygen waters are eroded by mixing from the eddy core and entrain into the mixed layer. The nitrogen is reintroduced into the core by gravitational settling of particulate matter out of the euphotic zone. The low oxygen water equilibrates in the mixed layer by air–sea gas exchange and does not participate in the gravitational sinking. Finally we propose a mesoscale–submesoscale interaction concept where wind energy, mediated via NIWs, drives nutrient supply to the euphotic zone and drives extraordinary blooms in anticyclonic mode-water eddies.

Localized open-ocean low-oxygen “dead zones” in the eastern tropical North Atlantic are recently discovered ocean features that can develop in dynamically isolated water masses within cyclonic eddies (CE) and anticyclonic mode-water eddies (ACME). Analysis of a comprehensive oxygen dataset obtained from gliders, moorings, research vessels and Argo floats reveals that “dead-zone” eddies are found in surprisingly high numbers and in a large area from about 4 to 22° N, from the shelf at the eastern boundary to 38° W. In total, 173 profiles with oxygen concentrations below the minimum background concentration of 40 µmol kg−1 could be associated with 27 independent eddies (10 CEs; 17 ACMEs) over a period of 10 years. Lowest oxygen concentrations in CEs are less than 10 µmol kg−1 while in ACMEs even suboxic (−1) levels are observed. The oxygen minimum in the eddies is located at shallow depth from 50 to 150 m with a mean depth of 80 m. Compared to the surrounding waters, the mean oxygen anomaly in the core depth range (50 and 150 m) for CEs (ACMEs) is −38 (−79) µmol kg−1. North of 12° N, the oxygen-depleted eddies carry anomalously low-salinity water of South Atlantic origin from the eastern boundary upwelling region into the open ocean. Here water mass properties and satellite eddy tracking both point to an eddy generation near the eastern boundary. In contrast, the oxygen-depleted eddies south of 12° N carry weak hydrographic anomalies in their cores and seem to be generated in the open ocean away from the boundary. In both regions a decrease in oxygen from east to west is identified supporting the en-route creation of the low-oxygen core through a combination of high productivity in the eddy surface waters and an isolation of the eddy cores with respect to lateral oxygen supply. Indeed, eddies of both types feature a cold sea surface temperature anomaly and enhanced chlorophyll concentrations in their center. The low-oxygen core depth in the eddies aligns with the depth of the shallow oxygen minimum zone of the eastern tropical North Atlantic. Averaged over the whole area an oxygen reduction of 7 µmol kg−1 in the depth range of 50 to 150 m (peak reduction is 16 µmol kg−1 at 100 m depth) can be associated with the dispersion of the eddies. Thus the locally increased oxygen consumption within the eddy cores enhances the total oxygen consumption in the open eastern tropical North Atlantic Ocean and seems to be an contributor to the formation of the shallow oxygen minimum zone.

The occurrence of mesoscale eddies that develop suboxic environments at shallow depth (about 40–100 m) has recently been reported for the eastern tropical North Atlantic (ETNA). Their hydrographic structure suggests that the water mass inside the eddy is well isolated from ambient waters supporting the development of severe near-surface oxygen deficits. So far, hydrographic and biogeochemical characterization of these eddies was limited to a few autonomous surveys, with the use of moorings, underwater gliders and profiling floats. In this study we present results from the first dedicated biogeochemical survey of one of these eddies conducted in March 2014 near the Cape Verde Ocean Observatory (CVOO). During the survey the eddy core showed oxygen concentrations as low as 5 µmol kg−1 with a pH of around 7.6 at approximately 100 m depth. Correspondingly, the aragonite saturation level dropped to 1 at the same depth, thereby creating unfavorable conditions for calcifying organisms. To our knowledge, such enhanced acidity within near-surface waters has never been reported before for the open Atlantic Ocean. Vertical distributions of particulate organic matter and dissolved organic matter (POM and DOM), generally showed elevated concentrations in the surface mixed layer (0–70 m), with DOM also accumulating beneath the oxygen minimum. With the use of reference data from the upwelling region where these eddies are formed, the oxygen utilization rate was calculated by determining oxygen consumption through the remineralization of organic matter. Inside the core, we found these rates were almost 1 order of magnitude higher (apparent oxygen utilization rate (aOUR); 0.26 µmol kg−1 day−1) than typical values for the open North Atlantic. Computed downward fluxes for particulate organic carbon (POC), were around 0.19 to 0.23 g C m−2 day−1 at 100 m depth, clearly exceeding fluxes typical for an oligotrophic open-ocean setting. The observations support the view that the oxygen-depleted eddies can be viewed as isolated, westwards propagating upwelling systems of their own, thereby represent re-occurring alien biogeochemical environments in the ETNA.

Coherent mesoscale features (referred to here as eddies) in the tropical northeastern Atlantic Ocean (between 12–22° N and 15–26° W) are examined and characterized. The eddies' surface signatures are investigated using 19 years of satellite-derived sea level anomaly (SLA) data. Two automated detection methods are applied, the geometrical method based on closed streamlines around eddy cores, and the Okubo–Weiß method based on the relation between vorticity and strain. Both methods give similar results. Mean eddy surface signatures of SLA, sea surface temperature (SST) and sea surface salinity (SSS) anomalies are obtained from composites of all snapshots around identified eddy cores. Anticyclones/cyclones are identified by an elevation/depression of SLA and enhanced/reduced SST and SSS in their cores. However, about 20 % of all anticyclonically rotating eddies show reduced SST and reduced SSS instead. These kind of eddies are classified as anticyclonic mode-water eddies (ACMEs). About 146 ± 4 eddies per year with a minimum lifetime of 7 days are identified (52 % cyclones, 39 % anticyclones, 9 % ACMEs) with rather similar mean radii of about 56 ± 12 km. Based on concurrent in situ temperature and salinity profiles (from Argo float, shipboard, and mooring data) taken inside of eddies, distinct mean vertical structures of the three eddy types are determined. Most eddies are generated preferentially in boreal summer and along the West African coast at three distinct coastal headland regions and carry South Atlantic Central Water supplied by the northward flow within the Mauretanian coastal current system. Westward eddy propagation (on average about 3.00 ± 2.15 km d−1) is confined to distinct zonal corridors with a small meridional deflection dependent on the eddy type (anticyclones – equatorward, cyclones – poleward, ACMEs – no deflection). Heat and salt fluxes out of the coastal region and across the Cape Verde Frontal Zone, which separates the shadow zone from the ventilated subtropical gyre, are calculated.

The eastern tropical North Atlantic (ETNA) features a mesopelagic oxygen minimum zone (OMZ) at approximately 300–600 m depth. Here, oxygen concentrations rarely fall below 40 µmol O2 kg−1, but are expected to decline under future projections of global warming. The recent discovery of mesoscale eddies that harbour a shallow suboxic (2 kg−1) OMZ just below the mixed layer could serve to identify zooplankton groups that may be negatively or positively affected by ongoing ocean deoxygenation. In spring 2014, a detailed survey of a suboxic anticyclonic modewater eddy (ACME) was carried out near the Cape Verde Ocean Observatory (CVOO), combining acoustic and optical profiling methods with stratified multinet hauls and hydrography. The multinet data revealed that the eddy was characterized by an approximately 1.5-fold increase in total area-integrated zooplankton abundance. At nighttime, when a large proportion of acoustic scatterers is ascending into the upper 150 m, a drastic reduction in mean volume backscattering (Sv) at 75 kHz (shipboard acoustic Doppler current profiler, ADCP) within the shallow OMZ of the eddy was evident compared to the nighttime distribution outside the eddy. Acoustic scatterers avoided the depth range between approximately 85 to 120 m, where oxygen concentrations were lower than approximately 20 µmol O2 kg−1, indicating habitat compression to the oxygenated surface layer. This observation is confirmed by time series observations of a moored ADCP (upward looking, 300 kHz) during an ACME transit at the CVOO mooring in 2010. Nevertheless, part of the diurnal vertical migration (DVM) from the surface layer to the mesopelagic continued through the shallow OMZ. Based upon vertically stratified multinet hauls, Underwater Vision Profiler (UVP5) and ADCP data, four strategies followed by zooplankton in response to in response to the eddy OMZ have been identified: (i) shallow OMZ avoidance and compression at the surface (e.g. most calanoid copepods, euphausiids); (ii) migration to the shallow OMZ core during daytime, but paying O2 debt at the surface at nighttime (e.g. siphonophores, Oncaea spp., eucalanoid copepods); (iii) residing in the shallow OMZ day and night (e.g. ostracods, polychaetes); and (iv) DVM through the shallow OMZ from deeper oxygenated depths to the surface and back. For strategy (i), (ii) and (iv), compression of the habitable volume in the surface may increase prey–predator encounter rates, rendering zooplankton and micronekton more vulnerable to predation and potentially making the eddy surface a foraging hotspot for higher trophic levels. With respect to long-term effects of ocean deoxygenation, we expect avoidance of the mesopelagic OMZ to set in if oxygen levels decline below approximately 20 µmol O2 kg−1. This may result in a positive feedback on the OMZ oxygen consumption rates, since zooplankton and micronekton respiration within the OMZ as well as active flux of dissolved and particulate organic matter into the OMZ will decline.

The eastern tropical North Atlantic (ETNA) is characterized by a highly productive coastal upwelling system and a moderate oxygen minimum zone with lowest open-ocean oxygen (O2) concentrations of approximately 40 μmol kg−1. The recent discovery of re-occurring mesoscale eddies with close to anoxic O2 concentrations (< 1 μmol kg−1) located just below the mixed layer has challenged our understanding of O2 distribution and biogeochemical processes in this area. Here, we present the first microbial community study from a deoxygenated anticyclonic modewater eddy in the open waters of the ETNA. In the eddy, we observed significantly lower bacterial diversity compared to surrounding waters, along with a significant community shift. We detected enhanced primary productivity in the surface layer of the eddy indicated by elevated chlorophyll concentrations and carbon uptake rates of up to three times as high as in surrounding waters. Carbon uptake rates below the euphotic zone correlated to the presence of a specific high-light ecotype of Prochlorococcus, which is usually underrepresented in the ETNA. Our data indicate that high primary production in the eddy fuels export production and supports enhanced respiration in a specific microbial community at shallow depths, below the mixed-layer base. The transcription of the key functional marker gene for dentrification, nirS, further indicated a potential for nitrogen loss processes in O2-depleted core waters of the eddy. Dentrification is usually absent from the open ETNA waters. In light of future projected ocean deoxygenation, our results show that even distinct events of anoxia have the potential to alter microbial community structure with critical impacts on primary productivity and biogeochemical processes of oceanic water bodies.

Emergency management becomes more challenging in international crisis episodes because of cultural, semantic and linguistic differences between all stakeholders, especially first responders. Misunderstandings between first responders makes decision making slower and more difficult. However, spread and development of networks and IT-based emergency management systems (EMSs) have improved emergency responses, which have become more coordinated. Despite improvements made in recent years, EMSs have not still solved problems related to cultural, semantic and linguistic differences which are the real cause of slower decision making. In addition, from a technical perspective, the consolidation of current EMSs and the different formats used to exchange information offers another problem to be solved in any solution proposed for information interoperability between heterogeneous EMSs in different contexts. To overcome these problems, we present a software solution based on semantic and mediation technologies. EMERGency ELements (EMERGEL) (Fundacion CTIC and AntwortING Ingenieurbüro PartG, 2013), a common and modular ontology shared by all the stakeholders, has been defined. It offers the best solution to gather all stakeholders' knowledge in a unique and flexible data model, taking into account different countries' cultural and linguistic issues. To deal with the diversity of data protocols and formats, we have designed a service-oriented architecture for data interoperability (named DISASTER: Data Interoperability Solution At STakeholders Emergency Reaction) providing a flexible extensible solution to solve the mediation issues. Web services have been adopted as specific technology to implement this paradigm that has the most significant academic and industrial visibility and attraction. Contributions of this work have been validated through the design and development of a cross-border realistic prototype scenario, actively involving both emergency managers and emergency-first responders: the Netherlands–Germany border fire.

Here we present first observations, from instrumentation installed on moorings and a float, of unexpectedly low (−1) oxygen environments in the open waters of the tropical North Atlantic, a region where oxygen concentration does normally not fall much below 40 μmol kg−1. The low-oxygen zones are created at shallow depth, just below the mixed layer, in the euphotic zone of cyclonic eddies and anticyclonic-modewater eddies. Both types of eddies are prone to high surface productivity. Net respiration rates for the eddies are found to be 3 to 5 times higher when compared with surrounding waters. Oxygen is lowest in the centre of the eddies, in a depth range where the swirl velocity, defining the transition between eddy and surroundings, has its maximum. It is assumed that the strong velocity at the outer rim of the eddies hampers the transport of properties across the eddies boundary and as such isolates their cores. This is supported by a remarkably stable hydrographic structure of the eddies core over periods of several months. The eddies propagate westward, at about 4 to 5 km day−1, from their generation region off the West African coast into the open ocean. High productivity and accompanying respiration, paired with sluggish exchange across the eddy boundary, create the "dead zone" inside the eddies, so far only reported for coastal areas or lakes. We observe a direct impact of the open ocean dead zones on the marine ecosystem as such that the diurnal vertical migration of zooplankton is suppressed inside the eddies.

This study was conducted to evaluate the material properties of polymer-infiltrated zinc oxide networks (PICN) and the effect of using a phosphate monomer-containing primer applied before polymer infiltration. A total of 148 ZnO-network (zinc oxide) specimens were produced: n = 74 were treated with a primer before polymer infiltration and light curing, while the remaining specimens were untreated. Each group was divided into two subgroups ( n = 37) based on the infiltrating polymer: UDMA (aliphatic urethane-dimethacrylates)-TEGDMA (triethylene glycol-dimethacrylate) or BisGMA (bisphenol A-glycidyl-methacrylate)-TEGDMA. Additionally, n = 7 specimens of each polymer type were prepared for comparison. Then, biaxial flexural strength was measured before and after 150 days of water storage at 37 °C, including 37,500 thermal cycles (5 °C to 55 °C). The Vickers hardness, surface roughness, and water absorption at 37 °C were also tested. The initial biaxial flexural strength was reduced in the ZnO network specimens compared to in the pure polymers. Primer application improved the flexural strength, though the strength of BisGMA-TEGDMA significantly decreased after water storage. The ZnO network increased hardness, and the polymer-infiltrated networks showed higher roughness post-grinding and absorbed less water than the pure polymer groups. The ZnO networks did not improve the flexural strength over that of the pure polymers. However, the primer's positive impact and the network's long-term stability suggest potential if the network structure can be modified to contain thicker, more stable branches.

Alginate (Alg) is a versatile biopolymer for scaffold engineering and a bioink component widely used for direct cell printing. However, due to a lack of intrinsic cell-binding sites, Alg must be functionalized for cellular adhesion when used as a scaffold. Moreover, direct cell-laden ink 3D printing requires tedious disinfection procedures and cell viability is compromised by shear stress. Here, we demonstrate proof-of-concept, bioactive additive-free, microstructured Alg (M-Alg) scaffolds for neuron culture. The M-Alg scaffold was formed by introducing tetrapod-shaped ZnO (t-ZnO) microparticles into the ink as structural templates for interconnected channels and textured surfaces in the 3D-printed Alg scaffold, which were subsequently removed. Neurons exhibited significantly improved adhesion and growth on these M-Alg scaffolds compared with pristine Alg (P-Alg) scaffolds, with extensive neurite outgrowth and spontaneous neural activity, indicating the maturation of neuronal networks. These transparent, porous, additive-free Alg-based scaffolds with neuron affinity are promising for neuroregenerative and organoid-related research., Competing Interests: Declaration of interests The authors declare no competing interests., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

The growing interest in tin-halide semiconductors for photovoltaic applications demands in-depth knowledge of the fundamental properties of their constituents, starting from the smallest monomers entering the initial stages of formation. In this first-principles work based on time-dependent density-functional theory, we investigate the structural, electronic, and optical properties of tin-halide molecules SnX n 2-n , with n = 1 , 2 , 3 , 4 ${n = 1,2,3,4}$ and X=Cl, Br, I, simulating these compounds in vacuo as well as in an implicit solvent. We find that structural properties are very sensitive to the halogen species while the charge distribution is also affected by stoichiometry. The ionicity of the Sn-X bond is confirmed by the Bader charge analysis albeit charge displacement plots point to more complex metal-halide coordination. Particular focus is posed on the neutral molecules SnX 2 , for which electronic and optical properties are discussed in detail. Band gaps and absorption onset decrease with increasing size of the halogen species, and despite general common features, each molecule displays peculiar optical signatures. Our results are elaborated in the context of experimental and theoretical literature, including the more widely studied lead-halide analogs, aiming to contribute with microscopic insight to a better understanding of tin-halide perovskites., (© 2024 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)

Various fields, including medical and human interaction robots, gain advantages from the development of bioinspired soft actuators. Many recently developed grippers are pneumatics that require external pressure supply systems, thereby limiting the autonomy of these robots. This necessitates the development of scalable and efficient on-board pressure generation systems. While conventional air compression systems are hard to miniaturize, thermopneumatic systems that joule heat a transducer material to generate pressure present a promising alternative. However, the transducer materials of previously reported thermopneumatic systems demonstrate high heat capacities and limited surface area resulting in long response times and low operation frequencies. This study presents a thermopneumatic pressure generator using aerographene, a highly porous (>99.99%) network of interconnected graphene microtubes, as lightweight and low heat capacity transducer material. An aerographene pressurizer module (AGPM) can pressurize a reservoir of 4.2 cm 3 to ∼14 kPa in 50 ms. Periodic operation of the AGPM for 10 s at 0.66 Hz can further increase the pressure in the reservoir to ∼36 kPa. It is demonstrated that multiple AGPMs can be operated parallelly or in series for improved performance. For example, three parallelly operated AGPMs can generate pressure pulses of ∼21.5 kPa. Connecting AGPMs in series increase the maximum pressure achievable by the system. It is shown that three AGPMs working in series can pressurize the reservoir to ∼200 kPa in about 2.5 min. The AGPM's minimalistic design can be easily adapted to circuit boards, making the concept a promising fit for the on-board pressure supply of soft robots.

The aim of this study was to evaluate the influence of weight ratio, the shape of the precursor particles, and the application of a phosphate-monomer-containing primer on the mechanical properties of polymer infiltrated ceramic networks (PICNs) using zinc oxide. Two different types of zinc oxide particles were used as precursors to produce zinc oxide networks by sintering, each with two different densities resulting in two different weight ratios of the PICNs. For each of these different networks, two subgroups were built: one involving the application of a phosphate-monomer-containing primer prior to the infiltration of Bis-GMA/TEGDMA and one without. Elastic modulus and flexural strength were determined by using the three-point bending test. Vertical substance loss determined by the chewing simulation was evaluated with a laser scanning microscope. There was a statistically significant influence of the type of precursor particles on the flexural strength and in some cases on the elastic modulus. The application of a primer lead to a significant increase in the flexural strength and in most cases also in the elastic modulus. A higher weight ratio of zinc oxide led to a significantly higher elastic modulus. Few statistically significant differences were found for the vertical substance loss. By varying the shape of the particles and the weight fraction of zinc oxide, the mechanical properties of the investigated PICN can be controlled. The use of a phosphate-monomer-containing primer strengthens the bond between the infiltrated polymer and the zinc oxide, thus increasing the strength of the composite.

Solid-state fabricated carbon nanotube (CNT) sheets have shown promise as thermoacoustic (TA) sound generators, emitting tunable sound waves across a broad frequency spectrum (1-10 5 Hz) due to their ultralow specific heat capacity. However, their applications as underwater TA sound generators are limited by the reduced mechanical strength of CNT sheets in aqueous environments. In this study, we present a mechanically robust underwater TA device constructed from a three-dimensional (3D) tetrapodal assembly of carbon nanotubes (t-CNTs). These structures feature a high porosity (>99.9%) and a double-hollowed network of well-interconnected CNTs. We systematically explore the impact of different dimensions of t-CNTs and various annealing procedures on sound generation performance. Furnace-annealed t-CNTs, in contrast to directly resistive Joule heating annealing, provide superior, continuous, and homogeneous hydrophobicity across the surface of bulk t-CNTs. As a result, the t-CNTs-based underwater TA device demonstrates stable, smooth, and broad-spectrum sound generation within the frequency range of 1 × 10 2 to 1 × 10 4 Hz, along with a weak resonance response. Furthermore, these devices exhibit enhanced and more stable sound generation performance at nonresonance frequencies compared to regular CNT-based devices. This study contributes to advancing the development of underwater TA devices with characteristics such as being nonresonant, high-performing, flexible, elastically compressible, and reliable, enabling operation across a broad frequency range.

Conversion of light into heat is essential for a broad range of technologies such as solar thermal heating, catalysis and desalination. Three-dimensional (3D) carbon nanomaterial-based aerogels have been shown to hold great promise as photothermal transducer materials. However, until now, their light-to-heat conversion is limited by near-surface absorption, resulting in a strong heat localization only at the illuminated surface region, while most of the aerogel volume remains unused. We present a fabrication concept for highly porous (>99.9%) photothermal hybrid aeromaterials, which enable an ultrarapid and volumetric photothermal response with an enhancement by a factor of around 2.5 compared to the pristine variant. The hybrid aeromaterial is based on strongly light-scattering framework structures composed of interconnected hollow silicon dioxide (SiO 2 ) microtubes, which are functionalized with extremely low amounts (in order of a few μg cm -3 ) of reduced graphene oxide (rGO) nanosheets, acting as photothermal agents. Tailoring the density of rGO within the framework structure enables us to control both light scattering and light absorption and thus the volumetric photothermal response. We further show that by rapid and repeatable gas activation, these transducer materials expand the field of photothermal applications, like untethered light-powered and light-controlled microfluidic pumps and soft pneumatic actuators.

Hydrogel-based soft actuators can operate in sensitive environments, bridging the gap of rigid machines interacting with soft matter. However, while stimuli-responsive hydrogels can undergo extreme reversible volume changes of up to ≈90%, water transport in hydrogel actuators is in general limited by their poroelastic behavior. For poly(N-isopropylacrylamide) (PNIPAM) the actuation performance is even further compromised by the formation of a dense skin layer. Here it is shown, that incorporating a bioinspired microtube graphene network into a PNIPAM matrix with a total porosity of only 5.4% dramatically enhances actuation dynamics by up to ≈400% and actuation stress by ≈4000% without sacrificing the mechanical stability, overcoming the water transport limitations. The graphene network provides both untethered light-controlled and electrically powered actuation. It is anticipated that the concept provides a versatile platform for enhancing the functionality of soft matter by combining responsive and 2D materials, paving the way toward designing soft intelligent matter., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

As the necessary transition to a supply of renewable energy moves forward rapidly, hydrogen (H 2 ) becomes increasingly important as a green chemical energy carrier. The manifold applications associated with the use of hydrogen in the energy sector require sensor materials that can efficiently detect H 2 in small quantities and in gas mixtures. As a possible candidate, we here present a metal-organic framework (MOF, namely ZIF-8) functionalized metal-oxide gas sensor (MOS, namely ZnO). The gas sensor is based on single-crystalline tetrapodal ZnO (t-ZnO) microparticles, which are coated with a thin layer of ZIF-8 ([Zn(C 4 H 5 N 2 ) 2 ]) by a ZnO conversion reaction to obtain t-ZnO@ZIF-8 (core@shell) composites. The vapor-phase synthesis enables ZIF-8 thickness control as shown by powder X-ray diffraction, thermogravimetric analysis, and N 2 sorption measurements. Gas-sensing measurements of a single microrod of t-ZnO@ZIF-8 composite demonstrate the synergistic benefits of both MOS sensors and MOFs, resulting in an outstanding high selectivity, sensitivity ( S ≅ 546), and response times (1-2 s) to 100 ppm H 2 in the air at a low operation temperature of 100 °C. Under these conditions, no response to acetone, n -butanol, methane, ethanol, ammonia, 2-propanol, and carbon dioxide was observed. Thereby, the sensor is able to reliably detect H 2 in mixtures with air and even methane, with the latter being highly important for determining the H 2 dilution level in natural gas pipelines, which is of great importance to the energy sector.

The emerging interest in tin halide perovskites demands a robust understanding of the fundamental properties of these materials starting from the earliest steps of their synthesis. In a first-principles work based on time dependent density functional theory, we investigate the structural, energetic, electronic, and optical properties of 14 tin iodide solution complexes formed by the SnI 2 unit tetracoordinated with molecules of common solvents, which we classify according to their Gutmann's donor number. We find that all considered complexes are energetically stable and their formation energy expectedly increases with the donating ability of the solvent. The energies of the frontier states are affected by the choice of solvent, with their absolute values decreasing with the donor number. The occupied orbitals are predominantly localized on the tin iodide unit, while the unoccupied ones are distributed also on the solvent molecules. Owing to this partial wave function overlap, the first optical excitation is generally weak, although the spectral weight is red-shifted by the solvent molecules being coordinated to SnI 2 in comparison to the reference obtained for this molecule alone. Comparisons with results obtained on the same level of theory on Pb-based counterparts corroborate our analysis. The outcomes of this study provide quantum-mechanical insight into the fundamental properties of tin iodide solution complexes. This knowledge is valuable in the research on lead-free halide perovskites and their precursors.

Local drug delivery systems (LDDS) represent a promising therapy strategy concerning the most common and malignant primary brain tumor glioblastoma (GBM). Nevertheless, to date, only a few systems have been clinically applied, and their success is very limited. Still, numerous new LDDS approaches are currently being developed. Here, (partial resection) GBM animal models play a key role, as such models are needed to evaluate the therapy prior to any human application. However, such models are complex to establish, and only a few reports detail the process. Here, we report our results of establishing a partial resection glioma model in rats suitable for evaluating LDDS. C6-bearing Wistar rats and U87MG-spheroids- and patient-derived glioma stem-like cells-bearing athymic rats underwent tumor resection followed by the implantation of an exemplary LDDS. Inoculation, tumor growth, residual tumor tissue, and GBM recurrence were reliably imaged using high-resolution Magnetic Resonance Imaging. The release from an exemplary LDDS was verified in vitro and in vivo using Fluorescence Molecular Tomography. The presented GBM partial resection model appears to be well suited to determine the efficiency of LDDS. By sharing our expertise, we intend to provide a powerful tool for the future testing of these very promising systems, paving their way into clinical application.

Glioblastoma (GBM) is a poorly treatable disease due to the fast development of tumor recurrences and high resistance to chemo- and radiotherapy. To overcome the highly adaptive behavior of GBMs, especially multimodal therapeutic approaches also including natural adjuvants have been investigated. However, despite increased efficiency, some GBM cells are still able to survive these advanced treatment regimens. Given this, the present study evaluates representative chemoresistance mechanisms of surviving human GBM primary cells in a complex in vitro co-culture model upon sequential application of temozolomide (TMZ) combined with AT101, the R(-) enantiomer of the naturally occurring cottonseed-derived gossypol. Treatment with TMZ+AT101/AT101, although highly efficient, yielded a predominance of phosphatidylserine-positive GBM cells over time. Analysis of the intracellular effects revealed phosphorylation of AKT, mTOR, and GSK3ß, resulting in the induction of various pro-tumorigenic genes in surviving GBM cells. A Torin2-mediated mTOR inhibition combined with TMZ+AT101/AT101 partly counteracted the observed TMZ+AT101/AT101-associated effects. Interestingly, treatment with TMZ+AT101/AT101 concomitantly changed the amount and composition of extracellular vesicles released from surviving GBM cells. Taken together, our analyses revealed that even when chemotherapeutic agents with different effector mechanisms are combined, a variety of chemoresistance mechanisms of surviving GBM cells must be taken into account.

The material design of functional "aero"-networks offers a facile approach to optical, catalytical, or and electrochemical applications based on multiscale morphologies, high large reactive area, and prominent material diversity. Here in this paper, the synthesis and structural characterization of a hybrid β-Ga 2 O 3 /ZnGa 2 O 4 nanocomposite aero-network are presented. The nanocomposite networks are studied on multiscale with respect to their micro- and nanostructure by X-ray diffraction (XRD) and transmission electron microscopy (TEM) and are characterized for their photoluminescent response to UV light excitation and their electrochemical performance with Li-ion conversion reaction. The structural investigations reveal the simultaneous transformation of the precursor aero-GaN(ZnO) network into hollow architectures composed of β-Ga 2 O 3 and ZnGa 2 O 4 nanocrystals with a phase ratio of ≈1:2. The photoluminescence of hybrid aero-β-Ga 2 O 3 /ZnGa 2 O 4 nanocomposite networks demonstrates narrow band (λ em  = 504 nm) green light emission of ZnGa 2 O 4 under UV light excitation (λ ex  = 300 nm). The evaluation of the metal-oxide network performance for electrochemical application for Li-ion batteries shows high initial capacities of ≈714 mAh g -1 at 100 mA g -1 paired with exceptional rate performance even at high current densities of 4 A g -1 with 347 mAh g -1 . This study provides is an exciting showcase example of novel networked materials and demonstrates the opportunities of tailored micro-/nanostructures for diverse applications a diversity of possible applications., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

The glaucoma burden increases continuously and is estimated to affect more than 100 million people by 2040. As there is currently no cure to restore the optic nerve damage caused by glaucoma, the only controllable parameter is the intraocular pressure (IOP). In recent years, minimally invasive glaucoma surgery (MIGS) has emerged as an alternative to traditional treatments. It uses micro-sized drainage stents that are inserted through a small incision, minimizing the trauma to the tissue and reducing surgical and postoperative recovery time. However, a major challenge for MIGS devices is foreign body reaction and fibrosis, which can lead to a complete failure of the device. In this work, the antifibrotic potential of tetrapodal ZnO (t-ZnO) microparticles used as an additive is elucidated by using rat embryonic fibroblasts as a model. A simple, direct solvent-free process for the fabrication of stents with an outer diameter of 200-400 μm is presented, in which a high amount of t-ZnO particles (45-75 wt %) is mixed into polydimethylsiloxane (PDMS) and a highly viscous polymer/particle mixture is extruded. The fabricated stents possess increased elastic modulus compared to pure PDMS while remaining flexible to adapt to the curvature of an eye. In vitro experiments showed that the fibroblast cell viability was inhibited to 43 ± 3% when stents with 75 wt % t-ZnO were used. The results indicate that cell inhibiting properties can be attributed to an increased amount of protruding t-ZnO particles on the stent surface, leading to an increase in local contacts with cells and a disruption of the cell membrane. As a secondary mechanism, the released Zn ions could also contribute to the cell-inhibiting properties in the close vicinity of the stent surface. Overall, the fabrication method and the antifibrotic and mechanical properties of developed stents make them promising for application in MIGS.

Engineered neural tissues serve as models for studying neurological conditions and drug screening. Besides observing the cellular physiological properties, in situ monitoring of neurochemical concentrations with cellular spatial resolution in such neural tissues can provide additional valuable insights in models of disease and drug efficacy. In this work, we demonstrate the first three-dimensional (3D) tissue cultures with embedded optical dopamine (DA) sensors. We developed an alginate/Pluronic F127 based bio-ink for human dopaminergic brain tissue printing with tetrapodal-shaped-ZnO microparticles (t-ZnO) additive as the DA sensor. DA quenches the autofluorescence of t-ZnO in physiological environments, and the reduction of the fluorescence intensity serves as an indicator of the DA concentration. The neurons that were 3D printed with the t-ZnO showed good viability, and extensive 3D neural networks were formed within one week after printing. The t-ZnO could sense DA in the 3D printed neural network with a detection limit of 0.137 μM. The results are a first step toward integrating tissue engineering with intensiometric biosensing for advanced artificial tissue/organ monitoring., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Fucoidans, sulfated polysaccharides from brown algae, possess multiple bioactivities in regard to osteogenesis, angiogenesis, and inflammation, all representing key molecular processes for successful bone regeneration. To utilize fucoidans in regenerative medicine, a delivery system is needed which temporarily immobilizes the polysaccharide at the injured site. Hydrogels have become increasingly interesting biomaterials for the support of bone regeneration. Their structural resemblance with the extracellular matrix, their flexible shape, and capacity to deliver bioactive compounds or stem cells into the affected tissue make them promising materials for the support of healing processes. Especially injectable hydrogels stand out due to their minimal invasive application. In the current study, we developed an injectable thermosensitive hydrogel for the delivery of fucoidan based on chitosan, collagen, and β-glycerophosphate (β-GP). Physicochemical parameters such as gelation time, gelation temperature, swelling capacity, pH, and internal microstructure were studied. Further, human bone-derived mesenchymal stem cells (MSC) and human outgrowth endothelial cells (OEC) were cultured on top (2D) or inside the hydrogels (3D) to assess the biocompatibility. We found that the sol-gel transition occurred after approximately 1 min at 37 °C. Fucoidan integration into the hydrogel had no or only a minor impact on the mentioned physicochemical parameters compared to hydrogels which did not contain fucoidan. Release assays showed that 60% and 80% of the fucoidan was released from the hydrogel after two and six days, respectively. The hydrogel was biocompatible with MSC and OEC with a limitation for OEC encapsulation. This study demonstrates the potential of thermosensitive chitosan-collagen hydrogels as a delivery system for fucoidan and MSC for the use in regenerative medicine.

Resistive Field Grading Materials (RFGM) are used in critical regions in the electrical insulation system of high-voltage direct-current cable systems. Here, we describe a novel type of RFGM, based on a percolated network of zinc oxide (ZnO) tetrapods in a rubber matrix. The electrical conductivity of the composite increases by a factor of 10 8 for electric fields > 1 kV mm -1 , as a result of the highly anisotropic shape of the tetrapods and their significant bandgap (3.37 eV). We demonstrate that charge transport at fields < 1 kV mm -1 is dominated by thermally activated hopping of charge carriers across spatially, as well as energetically, localized states at the ZnO-polymer interface. At higher electric fields (> 1 kV mm -1 ) band transport in the semiconductive tetrapods triggers a large increase in conductivity. These geometrically enhanced ZnO semiconductors outperform standard additives such as SiC particles and ZnO micro varistors, providing a new class of additives to achieve variable conductivity in high-voltage cable system applications., (© 2022. The Author(s).)

Localized therapy approaches have emerged as an alternative drug administration route to overcome the limitations of systemic therapies, such as the crossing of the blood-brain barrier in the case of brain tumor treatment. For this, implantable drug delivery systems (DDS) have been developed and extensively researched. However, to achieve an effective localized treatment, the release kinetics of DDS needs to be controlled in a defined manner, so that the concentration at the tumor site is within the therapeutic window. Thus, a DDS, with patient-specific release kinetics, is crucial for the improvement of therapy. Here, we present a computationally supported reservoir-based DDS (rDDS) development towards patient-specific release kinetics. The rDDS consists of a reservoir surrounded by a polydimethylsiloxane (PDMS) microchannel membrane. By tailoring the rDDS, in terms of membrane porosity, geometry, and drug concentration, the release profiles can be precisely adapted, with respect to the maximum concentration, release rate, and release time. The release is investigated using a model dye for varying parameters, leading to different distinct release profiles, with a maximum release of up to 60 days. Finally, a computational simulation, considering exemplary in vivo conditions (e.g., exchange of cerebrospinal fluid), is used to study the resulting drug release profiles, demonstrating the customizability of the system. The establishment of a computationally supported workflow, for development towards a patient-specific rDDS, in combination with the transfer to suitable drugs, could significantly improve the efficacy of localized therapy approaches.

Graphene oxide (GO) is a promising material for bone tissue engineering, but the validation of its molecular biological effects, especially in the context of clinically applied materials, is still limited. In this study, we compare the effects of graphene oxide framework structures (F-GO) and reduced graphene oxide-based framework structures (F-rGO) as scaffold material with a special focus on vascularization associated processes and mechanisms in the bone. Highly porous networks of zinc oxide tetrapods serving as sacrificial templates were used to create F-GO and F-rGO with porosities >99% consisting of hollow interconnected microtubes. Framework materials were seeded with human mesenchymal stem cells (MSC), and the cell response was evaluated by confocal laser scanning microscopy (CLSM), deoxyribonucleic acid (DNA) quantification, real-time polymerase chain reaction (RT-PCR), enzyme-linked immunosorbent assay (ELISA), and alkaline phosphatase activity (ALP) to define their impact on cellular adhesion, osteogenic differentiation, and secretion of vascular growth factors. F-GO based scaffolds improved adhesion and growth of MSC as indicated by CLSM and DNA quantification. Further, F-GO showed a better vascular endothelial growth factor (VEGF) binding capacity and improved cell growth as well as the formation of microvascular capillary-like structures in co-cultures with outgrowth endothelial cells (OEC). These results clearly favored non-reduced graphene oxide in the form of F-GO for bone regeneration applications. To study GO in the context of a clinically used implant material, we coated a commercially available xenograft (Bio-Oss® block) with GO and compared the growth of MSC in monoculture and in coculture with OEC to the native scaffold. We observed a significantly improved growth of MSC and formation of prevascular structures on coated Bio-Oss®, again associated with a higher VEGF binding capacity. We conclude that graphene oxide coating of this clinically used, but highly debiologized bone graft improves MSC cell adhesion and vascularization.

Zinc oxide has widespread use in diverse applications due to its distinct properties. Many of these applications benefit from controlling the morphology on the nanoscale, where for example gas sensing is strongly enhanced for high surface-to-volume ratios. In this work the formation of novel ZnO nanobrushes by plasma etching treatment as a new approach is presented. The morphology and structure of the ZnO nanobrushes are studied in detail by transmission and scanning electron microscopy. It is revealed that ZnO nanobrush structures are fabricated by self-patterned preferential etching of ZnO microtetrapods in a hydrogen-acetylene plasma. The etching process was found to be most effective at 1% C 2 H 2 admixture. Nanowire arrays are formed enabled by sidewall passivation due to a-C:H deposition. The nanobrush structures are further stabilized by simultaneous deposition of a SiO x layer from the opposite direction. Highly sensitive (gas response S = 148), selective, and fast (response time 15 s, recovery time 6 s) hydrogen sensors are fabricated from single nanobrushes. Single nanobrush sensors show enhanced sensing performance in increased gas response S of at least 10 times and improved response as well as recovery times when compared to nonporous single ZnO nanorod sensors due to the small diameters (≈50 nm) of the formed nanowires as well as the strongly enhanced surface-to-volume ratio of the nanobrushes by a factor of more than 10.

Tetrapodal zinc oxide (t-ZnO) is used to fabricate polymer composites for many different applications ranging from biomedicine to electronics. In recent times, macroscopic framework structures from t-ZnO have been used as a versatile sacrificial template for the synthesis of multi-scaled foam structures from different nanomaterials such as graphene, hexagonal boron nitride or gallium nitride. Many of these fabrication methods rely on wet-chemical coating processes using nanomaterial dispersions, leading to a strong interest in the actual coating mechanism and factors influencing it. Depending on the type of medium (e.g. solvent) used, different results regarding the homogeneity of the nanomaterial coating can be achieved. In order to understand how a medium influences the coating behavior, the evaporation process of water and ethanol is investigated in this work using in situ synchrotron radiation-based micro computed tomography (SRµCT). By employing propagation-based phase contrast imaging, both the t-ZnO network and the medium can be visualized. Thus, the evaporation process can be monitored non-destructively in three dimensions. This investigation showed that using a polar medium such as water leads to uniform evaporation and, by that, a homogeneous coating of the entire network., (© 2021. The Author(s).)

We report on self-propelled rotating liquid marbles fabricated using droplets of alcoholic solution encapsulated in hollow microtetrapods of GaN with hydrophilic free ends of their arms and hydrophobic lateral walls. Apart from stationary rotation, elongated-spheroid-like liquid marbles were found, for the first time, to exhibit pulsed rotation on water surfaces characterized by a threshold speed of rotation, which increased with the weight of the liquid marble while the frequency of pulses proved to decrease. To throw light upon the unusual behavior of the developed self-propelled liquid marbles, we propose a model which takes into account skimming of the liquid marbles over the water surface similar to that inherent to flying water lily beetle and the so-called helicopter effect, causing a liquid marble to rise above the level of the water surface when rotating.

The fabrication of electrically conductive hydrogels is challenging as the introduction of an electrically conductive filler often changes mechanical hydrogel matrix properties. Here, we present an approach for the preparation of hydrogel composites with outstanding electrical conductivity at extremely low filler loadings (0.34 S m -1 , 0.16 vol %). Exfoliated graphene and polyacrylamide are microengineered to 3D composites such that conductive graphene pathways pervade the hydrogel matrix similar to an artificial nervous system. This makes it possible to combine both the exceptional conductivity of exfoliated graphene and the adaptable mechanical properties of polyacrylamide. The demonstrated approach is highly versatile regarding porosity, filler material, as well as hydrogel system. The important difference to other approaches is that we keep the original properties of the matrix, while ensuring conductivity through graphene-coated microchannels. This novel approach of generating conductive hydrogels is very promising, with particular applications in the fields of bioelectronics and biohybrid robotics.

Brain implants are promising instruments for a broad variety of nervous tissue diseases with a wide range of applications, e.g. for stimulation, signal recording or local drug delivery. Recently, graphene-based scaffold materials have emerged as attractive candidates as neural interfaces, 3D scaffolds, or drug delivery systems due to their excellent properties like flexibility, high surface area, conductivity, and lightweight. To date, however, there is a lack of appropriate studies of the foreign body response, especially by glial cells, towards graphene-based materials. In this work, we investigated the effects of macroscopic, highly porous (>99.9%) graphene oxide (GO) and reduced graphene oxide (rGO) (conductivity ∼1 S m -1 ) scaffolds with tailorable macro- and microstructure on human astrocyte and microglial cell viability and proliferation as well as expression of neuroinflammation and astrogliosis associated genes in an indirect contact approach. In this in vitro model, as well as ex vivo in organotypic murine brain slices, we could demonstrate that both GO and rGO based 3D scaffolds exert slight effects on the glial cell populations which are the key players of glial scar formation. These effects were in most cases completely abolished by curcumin, a known anti-inflammatory and anti-fibrotic drug that could in perspective be applied to brain implants as a protectant.

Hierarchical, conductive, porous, three-dimensional (3D) carbon networks based on carbon nanotubes are used as a scaffold material for the incorporation of sulfur in the vapor phase to produce carbon nanotube tube/sulfur (CNTT/S) composites for application in lithium ion batteries (LIBs) as a cathode material. The high conductivity of the carbon nanotube-based scaffold material, in combination with vapor infiltration of sulfur, allows for improved utilization of insulating sulfur as the active material in the cathode. When sulfur is evenly distributed throughout the network via vapor infiltration, the carbon scaffold material confines the sulfur, allowing the sulfur to become electrochemically active in the context of an LIB. The electrochemical performance of the sulfur cathode was further investigated as a function of the temperature used for the vapor infiltration of sulfur into the carbon scaffolds (155, 175, and 200 °C) in order to determine the ideal infiltration temperature to maximize sulfur loading and minimize the polysulfide shuttle effect. In addition, the nature of the incorporation of sulfur at the interfaces within the 3D carbon network at the different vapor infiltration temperatures will be investigated via Raman, scanning electron microscopy/energy dispersive X-ray, and X-ray photoelectron spectroscopy. The resulting CNTT/S composites, infiltrated at each temperature, were incorporated into a half-cell using Li metal as a counter electrode and a 0.7 M LiTFSI electrolyte in ether solvents and characterized electrochemically using cyclic voltammetry measurements. The results indicate that the CNTT matrix infiltrated with sulfur at the highest temperature (200 °C) had improved incorporation of sulfur into the carbon network, the best electrochemical performance, and the highest sulfur loading, 8.4 mg/cm 2 , compared to the CNTT matrices infiltrated at 155 and 175 °C, with sulfur loadings of 4.8 and 6.3 mg/cm 2 , respectively., Competing Interests: The authors declare no competing financial interest., (© 2020 American Chemical Society.)

Localized therapy of the highly malignant brain tumor glioblastoma multiforme (GBM) could help to drastically improve the treatment efficiency and increase the patient's median survival. Here, a macroscopic PDMS matrix composed of interconnected microchannels for tailored drug release and localized GBM therapy is introduced. Based on a simple bottom-up fabrication method using a highly versatile sacrificial template, the presented strategy solves the scaling problem associated with the previously developed microchannel-based drug delivery systems, which were limited to two dimensions due to the commonly employed top-down microfabrication methods. Additionally, tailoring of the microchannel density, the fraction of drug-releasing microchannels and the macroscopic size of the drug delivery systems enabled precise adjustment of the drug release kinetics for more than 10 days. As demonstrated in a long-term GBM in vitro model, the release kinetics of the exemplarily chosen GBM drug AT101 could be tailored by variation of the microchannel density and the initial drug concentration, leading to diffusion-controlled AT101 release. Adapting a previously developed GBM treatment plan based on a sequential stimulation with AT101, measured anti-tumorigenic effects of free versus PDMS-released AT101 were comparable in human GBM cells and demonstrated efficient biological activity of PDMS-released AT101.

In this paper, fabrication of a new material is reported, the so-called Aero-Ga 2 O 3 or Aerogallox, which represents an ultra-porous and ultra-lightweight three-dimensional architecture made from interconnected microtubes of gallium oxide with nanometer thin walls. The material is fabricated using epitaxial growth of an ultrathin layer of gallium nitride on zinc oxide microtetrapods followed by decomposition of sacrificial ZnO and oxidation of GaN which according to the results of X-ray diffraction (XRD) and X-ray photoemission spectroscopy (XPS) characterizations, is transformed gradually in β -Ga 2 O 3 with almost stoichiometric composition. The investigations show that the developed ultra-porous Aerogallox exhibits extremely low reflectivity and high transmissivity in an ultrabroadband electromagnetic spectrum ranging from X-band (8-12 GHz) to several terahertz which opens possibilities for quite new applications of gallium oxide, previously not anticipated.

Laser diodes are efficient light sources. However, state-of-the-art laser diode-based lighting systems rely on light-converting inorganic phosphor materials, which strongly limit the efficiency and lifetime, as well as achievable light output due to energy losses, saturation, thermal degradation, and low irradiance levels. Here, we demonstrate a macroscopically expanded, three-dimensional diffuser composed of interconnected hollow hexagonal boron nitride microtubes with nanoscopic wall-thickness, acting as an artificial solid fog, capable of withstanding ~10 times the irradiance level of remote phosphors. In contrast to phosphors, no light conversion is required as the diffuser relies solely on strong broadband (full visible range) lossless multiple light scattering events, enabled by a highly porous (>99.99%) non-absorbing nanoarchitecture, resulting in efficiencies of ~98%. This can unleash the potential of lasers for high-brightness lighting applications, such as automotive headlights, projection technology or lighting for large spaces.

Graphene hydrophobic coatings paved the way towards a new generation of optoelectronic and fluidic devices. Nevertheless, such hydrophobic thin films rely only on graphene non-polar surface, rather than taking advantage of its surface roughness. Furthermore, graphene is typically not self-standing. Differently, carbon aerogels have high porosity, large effective surface area due to their surface roughness, and very low mass density, which make them a promising candidate as a super-hydrophobic material for novel technological applications. However, despite a few works reporting the general super-hydrophobic and lipophilic behavior of the carbon aerogels, a detailed characterization of their wetting properties is still missing, to date. Here, the wetting properties of graphene aerogels are demonstrated in detail. Without any chemical functionalization or patterning of their surface, the samples exhibit a super-lipophilic state and a stationary super-hydrophobic state with a contact angle up to 150 ± 15° and low contact angle hysteresis  ≈ 15°, owing to the fakir effect. In addition, the adhesion force of the graphene aerogels in contact with the water droplets and their surface tension are evaluated. For instance, the unique wettability and enhanced liquid absorption of the graphene aerogels can be exploited for reducing contamination from oil spills and chemical leakage accidents.

Despite tremendous efforts toward fabrication of three-dimensional macrostructures of two-dimensional (2D) materials, the existing approaches still lack sufficient control over microscopic (morphology, porosity, pore size) and macroscopic (shape, size) properties of the resulting structures. In this work, a facile fabrication method for the wet-chemical assembly of carbon 2D nanomaterials into macroscopic networks of interconnected, hollow microtubes is introduced. As demonstrated for electrochemically exfoliated graphene, graphene oxide, and reduced graphene oxide, the approach allows for the preparation of highly porous (> 99.9%) and lightweight (<2 mg cm -3 ) aeromaterials with tailored porosity and pore size as well as tailorable shape and size. The unique tubelike morphology with high aspect ratio enables ultralow-percolation-threshold graphene composites (0.03 S m -1 , 0.05 vol%) which even outperform most of the carbon nanotube-based composites, as well as highly conductive aeronetworks (8 S m -1 , 4 mg cm -3 ). On top of that, long-term compression cycling of the aeronetworks demonstrates remarkable mechanical stability over 10 000 cycles, even though no chemical cross-linking is employed. The developed strategy could pave the way for fabrication of various macrostructures of 2D nanomaterials with defined shape, size, as well as micro- and nanostructure, crucial for numerous applications such as batteries, supercapacitors, and filters.

The coating of porous scaffolds with nanoparticles is crucial in many applications, for example to generate scaffolds for catalysis or to make scaffolds bioactive. A standard and well-established method for coating surfaces with charged nanoparticles is electrophoresis, but when used on porous scaffolds, this method often leads to a blockage of the pores so that only the outermost layers of the scaffolds are coated. In this study, the electrophoretic coating process is monitored in situ and the kinetics of nanoparticle deposition are investigated. This concept can be extended to design a periodic electrophoretic deposition (PEPD) strategy, thus avoiding the typical blockage of surface pores. In the present work we demonstrate successful and homogeneous electrophoretic deposition of hydroxyapatite nanoparticles (HAn, diameter ≤200 nm) on a fibrous graphitic 3D structure (ultralightweight aerographite) using the PEPD strategy. The microfilaments of the resulting scaffold are covered with HAn both internally and on the surface. Furthermore, protein adsorption assays and cell proliferation assays were carried out and revealed that the HAn-decorated aerographite scaffolds are biocompatible. The HAn decoration of the scaffolds also significantly increases the alkaline phosphatase activity of osteoblast cells, showing that the scaffolds are able to promote their osteoblastic activity.

Novel gas sensors have been realized by decorating clusters of tubular Aerographite with CdTe using magnetron sputtering techniques. Subsequently, individual microtubes were separated and electrically contacted on a SiO 2 /Si substrate with pre-patterned electrodes. Cathodoluminescence, electron microscopy and electrical characterization prove the successful formation of a polycrystalline CdTe thin film on Aerographite enabling an excellent gas response to ammonia. Furthermore, the dynamical response to ammonia exposure has been investigated, highlighting the quick response and recovery times of the sensor, which is highly beneficial for extremely short on/off cycles. Therefore, this gas sensor reveals a large potential for cheap, highly selective, reliable and low-power gas sensors, which are especially important for hazardous gases such as ammonia.

Carbon-based fibrous scaffolds are highly attractive for all biomaterial applications that require electrical conductivity. It is additionally advantageous if such materials resembled the structural and biochemical features of the natural extracellular environment. Here, we show a novel modular design strategy to engineer biomimetic carbon fiber-based scaffolds. Highly porous ceramic zinc oxide (ZnO) microstructures serve as three-dimensional (3D) sacrificial templates and are infiltrated with carbon nanotubes (CNTs) or graphene dispersions. Once the CNTs and graphene coat the ZnO template, the ZnO is either removed by hydrolysis or converted into carbon by chemical vapor deposition. The resulting 3D carbon scaffolds are both hierarchically ordered and free-standing. The properties of the microfibrous scaffolds were tailored with a high porosity (up to 93%), a high Young's modulus (ca. 0.027-22 MPa), and an electrical conductivity of ca. 0.1-330 S/m, as well as different surface compositions. Cell viability, fibroblast proliferation rate and protein adsorption rate assays have shown that the generated scaffolds are biocompatible and have a high protein adsorption capacity (up to 77.32 ± 6.95 mg/cm 3 ) so that they are able to resemble the extracellular matrix not only structurally but also biochemically. The scaffolds also allow for the successful growth and adhesion of fibroblast cells, showing that we provide a novel, highly scalable modular design strategy to generate biocompatible carbon fiber systems that mimic the extracellular matrix with the additional feature of conductivity.

Bone, nerve, and heart tissue engineering place high demands on the conductivity of three-dimensional (3D) scaffolds. Fibrous carbon-based scaffolds are excellent material candidates to fulfill these requirements. Here, we show that highly porous (up to 94%) hybrid 3D framework structures with hierarchical architecture, consisting of microfiber composites of self-entangled carbon nanotubes (CNTs) and bioactive nanoparticles are highly suitable for growing cells. The hybrid 3D structures are fabricated by infiltrating a combination of CNTs and bioactive materials into a porous (∼94%) zinc oxide (ZnO) sacrificial template, followed by the removal of the ZnO backbone via a H 2 thermal reduction process. Simultaneously, the bioactive nanoparticles are sintered. In this way, conductive and mechanically stable 3D composites of free-standing CNT-based microfibers and bioactive nanoparticles are formed. The adopted strategy demonstrates great potential for implementing low-dimensional bioactive materials, such as hydroxyapatite (HA) and bioactive glass nanoparticles (BGN), into 3D carbon-based microfibrous networks. It is demonstrated that the incorporation of HA nanoparticles and BGN promotes the biomineralization ability and the protein adsorption capacity of the scaffolds significantly, as well as fibroblast and osteoblast adhesion. These results demonstrate that the developed carbon-based bioactive scaffolds are promising materials for bone tissue engineering and related applications.

In the present work, we report on development of three-dimensional flexible architectures consisting of an extremely porous three-dimensional Aerographite (AG) backbone decorated by InP micro/nanocrystallites grown by a single step hydride vapor phase epitaxy process. The systematic investigation of the hybrid materials by scanning electron microscopy demonstrates a rather uniform spatial distribution of InP crystallites without agglomeration on the surface of Aerographite microtubular structures. X-ray diffraction, transmission electron microscopy and Raman scattering analysis demonstrate that InP crystallites grown on bare Aerographite are of zincblende structure, while a preliminary functionalization of the Aerographite backbone with Au nanodots promotes the formation of crystalline In 2 O 3 nanowires as well as gold-indium oxide core-shell nanostructures. The electromechanical properties of the hybrid AG-InP composite material are shown to be better than those of previously reported bare AG and AG-GaN networks. Robustness, elastic behavior and excellent translation of the mechanical deformation to variations in electrical conductivity highlight the prospects of AG-InP applications in tactile/strain sensors and other device structures related to flexible electronics.