Helmholtz-Zentrum Hereon

Hypothesis: Injectable hydrogels are important in situ forming implants for tissue regeneration at damaged sites. Understanding the behavior of these systems in a complex in vivo environment remains a challenge. Ultrathin films as 2D model systems are expected to provide fundamental insights into formation and (bio)degradation at material-liquid interfaces, and are also applicable as bioresponsive coatings. Experiments: Hydrogel ultrathin films are prepared by covalently cross-linking four-arm PEG macromers with maleimide end-groups (PEG4MAL) at alkaline pH using two different types of dithiol-bearing cross-linkers - thio-depsipeptide (TDP) or 3,6-Dioxa-1,8-octanedithiol (DODT). This thiol-Michael addition "click" reaction is carried out at the air-water interface using the Langmuir technique. Morphological observation in real time is carried out by Brewster angle microscopy (BAM) and in coatings using atomic force microscopy (AFM). Stability against enzymatic and oxidative degradation is evaluated in the same setup. Findings: Non-cross-linked PEG or PEG incubated with cross-linkers at slightly acidic pH desorbs from the interface over time. Cross-linking of PEG at alkaline pH renders 2D hydrogel networks (thickness <1 nm) that are stable against desorption. They are easily transferrable onto solid mica surfaces, forming homogenous coatings as revealed by AFM. The type of dithiol cross-linker used to form the branching centers influences the degradability of these 2D hydrogel networks in the presence of lipase, peroxides, or bases. For example, enzymatic degradation of the 2D hydrogel networks can be switched "on" or "off" depending on the cleavable sites in the cross-linkers.

To reduce incidences of in-stent restenosis and thrombosis, the use of a thinner-strut stent has been clinically proven to be effective. Therefore, the contemporary trend is towards the use of ultrathin-strut (≤70 μm) designs for durable stents. However, stents made from biodegradable platforms have failed to achieve intergenerational breakthroughs due to their excessively thick struts. Here, microalloying was used to create an ultrathin-strut (65 μm) Zn scaffold with modified biodegradation behavior and improved biofunction, by adding Li. The scaffold backbone consists of an ultrafine-grained Zn matrix (average grain diameter 2.28 μm) with uniformly distributed nanoscale Li-containing phases. Grain refinement and precipitation strengthening enable it to achieve twice the radial strength with only 40% of the strut thickness of the pure Zn scaffold. Adding Li altered the thermodynamic formation pathways of products during scaffold biodegradation, creating an alkaline microenvironment. Li2 CO3 may actively stabilize this microenvironment due to its higher solubility and better buffering capability than Zn products. The co-release of ionic zinc and lithium enhances the beneficial differential effects on activities of endothelial cells and smooth muscle cells, resulting in good endothelialization and limited intimal hyperplasia in porcine coronary arteries. Findings here may break the predicament of the next-generation biodegradable scaffolds. This article is protected by copyright. All rights reserved.

A larva of Cleroidea in Burmese amber is described, which is the first record of an immature beetle of the basal cucujiform superfamily for the Mesozoic. Well-preserved unique specimen is described and illustrated using traditional methods as well as synchrotron-radiation-based micro-computed tomography (SRµCT) to reconstruct the specimen and discern integumental details of cephalic structures, especially the mouthparts. Cretorhadalus constantini gen. et sp. nov. is unambiguously assigned to the melyrid lineage of Cleroidea and tentatively classified within the basal family Rhadalidae. Within this family, this fossil larva has the ancestral cleroid pattern of the stemmata (2+3) and well-developed hooked urogomphi. Based on a comparison with extant rhadalids, as well as most members of the melyrid lineage, the larvae and adults of this new species were probably carnivorous, living on the trunks and branches of trees or in galleries where they foraged for soft xylophagous insects.

Extreme events like flooding, droughts, and heatwave are among the factors causing huge socio-economic losses to Cameroonians. Investigating the potential response of rainfall and temperature extremes to global warming is therefore critically needed for tailoring and adjusting the country's policies. Recent datasets have been developed for this purpose within the Coordinated Output for Regional Evaluations (CORDEX-CORE) initiative, at ~25 km grid spacing. These regional climate models were used to dynamically downscaled four global climate models participating in the Coupled Model Intercomparison Project phase 5 (CMIP5), under the optimistic and pessimistic representative concentration pathways (RCPs) 2.6 and 8.5, respectively. These models were employed in this study for characterizing the response of Cameroon's extreme precipitation and temperature events to global warming, using seven indices defined by the Expert Team on Climate Change Detection and Indices. Under global warming, the maximum number of consecutive dry (wet) days’ is expected to increase (decrease). However, the annual total rainfall amount is expected to increase, mainly due to the intensification of very wet days and daily rainfall intensity. Furthermore, the temperature-based indices reveal an increase (decrease) in the total annual hot (cold) days, and overall, changes intensify with increased radiative forcing. The high-mitigated low-emission pathway RCP2.6 features attenuated changes, and even sometimes adapts to reverse the sign of changes. Designing reliable policies to limit the risks associated with the above changes is required, as their socio-economic consequences are likely to include food insecurity, heat-related illness, population impoverishment, price rises, and market instability.

Neither fossil nor living Jacobsoniidae are found in abundance. Derolathrus cavernicolus Peck, 2010 is recorded here preserved in Holocene copal from Tanzania with an age of 210 ± 30 BP years. This leads us to three interesting conclusions: (1) This is the first time the family was found on the African continent, extending the family's distribution range to hitherto unknown localities. Derolathrus cavernicolus in Holocene copal from Tanzania expands the known distribution of the species, previously only recorded in the USA (Hawaii and Florida), Barbados, and Japan, both spatially and temporally. (2) All fossil specimens of the family have been found preserved in amber, which might be due to the small size of the specimens that prevents their discovery in other types of deposits. However, we here add a second aspect, namely the occurrence of this cryptic and currently scarce family of beetles in resinous environments, where they live in relationship with resin-producing trees. (3) The discovery of a new specimen from a family unknown on the African continent supports the relevance of these younger resins in preserving arthropods that lived in pre-Anthropocene times. Although we cannot demonstrate their extinction in the region, since it is possible that the family still survives in the already fragmented coastal forests of East Africa, we are detecting a loss of local biodiversity during the so-called Anthropocene, probably due to human activity.

The interaction of sedimentary systems with oceanographic processes in deep-water environments is not well understood yet, despite its importance for palaeoenvironmental reconstructions, and for a full understanding of source-to-sink sediment transport. The aim of this study is to improve the understanding of how contourite moats, elongated depressions formed by bottom currents associated with contourite drifts, develop and of the link between moat-drift system H. Wilckens et al. morphology and bottom current dynamics. This study provides a systematic comparison of 185 cross-sections of moat-drift systems distributed at 39 different locations worldwide, and a detailed analysis of the morphology of six moats that cover a wide range of typical geological and hydrodynamic settings. Additionally, in situ measured current data were analysed to better link hydrodynamics to moat morphology. The median of all profiles across all moat-drift systems reveals a 50 m relief, a width of 2.3 km, a relief to width ratio of 0.022, a slope angle of 6°, a drift angle of 3° and a concave-up shaped morphology. Moats can be over 100 km long. Some moats are driven by sediment erosion while others are depositional and primarily exist due to differential sedimentation inside the moat compared to the drift alongside the moat. A new sub-classification of moat-drift systems based on their stratigraphy is proposed. This classification distinguishes moats depending on the degree of erosion versus deposition. No relation is found between latitude and moat-drift morphology or stratigraphy in the analysed examples. The combined data indicate that a steeper slope focuses the current more than a gentle slope, resulting in an increase of the relief-width ratio and drift angle. Thus, this study provides new insides into the interaction of ocean currents with sedimentary morphology, which thereby affects the evolution of a poorly understood deepwater sedimentary system.

Leucine enkephalin (LeuEnk), a biologically active endogenous opioid pentapeptide, has been under intense investigation because it is small enough to allow efficient use of sophisticated computational methods and large enough to provide insights into low-lying minima of its conformational space. Here, we reproduce and interpret experimental infrared (IR) spectra of this model peptide in gas phase using a combination of replica-exchange molecular dynamics simulations, machine learning, and ab initio calculations. In particular, we evaluate the possibility of averaging representative structural contributions to obtain an accurate computed spectrum that accounts for the corresponding canonical ensemble of the real experimental situation. Representative conformers are identified by partitioning the conformational phase space into subensembles of similar conformers. The IR contribution of each representative conformer is calculated from ab initio and weighted according to the population of each cluster. Convergence of the averaged IR signal is rationalized by merging contributions in a hierarchical clustering and the comparison to IR multiple photon dissociation experiments. The improvements achieved by decomposing clusters containing similar conformations into even smaller subensembles is strong evidence that a thorough assessment of the conformational landscape and the associated hydrogen bonding is a prerequisite for deciphering important fingerprints in experimental spectroscopic data.

Being strongly influenced by internal climate variability, the atmospheric circulation response to greenhouse gas forcing in the future climate is uncertain. This study addresses atmospheric circulation through representative circulation types (CTs) and investigates the CTs’ changes with respect to frequency and effect on surface temperature and precipitation over a pan-Scandinavian domain. The analysis is based on the Swedish Meteorological and Hydrological Institute Large Ensemble performed with EC-Earth3: 50-member ensembles from one historical and six scenario simulations for the twenty-first century are used to assess internal variability and significance of changes. Although the results show no strong future changes in the CTs’ sea level pressure patterns, CT frequency changes suggest a future extension of summer conditions towards spring and autumn and point towards a clearer distinction between summer and winter. The present-climate CT effect on surface temperature is found to generally weaken which is consistent with a general decrease in temperature variability. Largest-scale and strongest temperature effect changes are projected between March and May for CT3, a cyclone towards the east of the domain associated with a domain-wide cooling effect that will likely be decreased towards the end of the twenty-first century. Similarly but of opposite sign, the CT effect on precipitation is strengthening as a result of the increased precipitation variability. Here, largest-scale and strongest effect enhancement is found for CT6, thus increasing its wetting effect over southern Scandinavia and drying effect west of the Scandes. Changes are generally largest towards the end of the twenty-first century and tend to increase with the forcing strength, thus maximizing for SSP585.

Model-based reconstruction employing the time separation technique (TST) was found to improve dynamic perfusion imaging of the liver using C-arm cone-beam computed tomography (CBCT). To apply TST using prior knowledge extracted from CT perfusion data, the liver should be accurately segmented from the CT scans. Reconstructions of primary and model-based CBCT data need to be segmented for proper visualisation and interpretation of perfusion maps. This research proposes Turbolift learning, which trains a modified version of the multi-scale Attention UNet on different liver segmentation tasks serially, following the order of the trainings CT, CBCT, CBCT TST - making the previous trainings act as pre-training stages for the subsequent ones - addressing the problem of limited number of datasets for training. For the final task of liver segmentation from CBCT TST, the proposed method achieved an overall Dice scores of 0.874±0.031 and 0.905±0.007 in 6-fold and 4-fold cross-validation experiments, respectively - securing statistically significant improvements over the model, which was trained only for that task. Experiments revealed that Turbolift not only improves the overall performance of the model but also makes it robust against artefacts originating from the embolisation materials and truncation artefacts. Additionally, in-depth analyses confirmed the order of the segmentation tasks. This paper shows the potential of segmenting the liver from CT, CBCT, and CBCT TST, learning from the available limited training data, which can possibly be used in the future for the visualisation and evaluation of the perfusion maps for the treatment evaluation of liver diseases.

Magnesium‐based alloys are emerging as a capable alternative to traditional materials for bone implant applications. The implant's degradation rate is the main indicator of their performance; however, different formulas have been reported to determine it based on three‐dimensional imaging. In this technical note, we are presenting the deviation in the degradation rate determined by different equations for two sets of data and the implications for the comparison of different studies. Depending on the equation used to determine the degradation rate from 3D X‐ray tomographic images, strong deviations may occur. These may hinder the comparison of different studies.

There is currently no causal treatment available for Parkinson’s disease (PD). However, the use of glial cell line–derived neurotrophic factor (GDNF) to provide regenerative effects for neurons is promising. Such approaches require translational delivery systems that are functional in diseased tissue. To do so, we used a non-viral Sleeping Beauty (SB) transposon system to overexpress GDNF in adipose tissue–derived mesenchymal stromal cells (adMSCs). Entrapment of cells in fibrin hydrogel was used to boost potential neurorestorative effects. Functional GDNF-adMSCs were able to secrete 1066.8 ± 169.4 ng GDNF/120,000 cells in vitro. The GDNF-adMSCs were detectable for up to 1 month after transplantation in a mild 6-hydroxydopamine (6-OHDA) hemiparkinson male rat model. Entrapment of GDNF-adMSCs enabled GDNF secretion in surrounding tissue in a more concentrated manner, also tending to prolong GDNF secretion relatively. GDNF-adMSCs entrapped in hydrogel also led to positive immunomodulatory effects via an 83% reduction of regional IL-1β levels compared to the non-entrapped GDNF-adMSC group after 1 month. Furthermore, GDNF-adMSC-treated groups showed higher recovery of tyrosine hydroxylase (TH)-expressing cells, indicating a neuroprotective function, although this was not strong enough to show significant improvement in motor performance. Our findings establish a promising GDNF treatment system in a PD model. Entrapment of GDNF-adMSCs mediated positive immunomodulatory effects. Although the durability of the hydrogel needs to be extended to unlock its full potential for motor improvements, the neuroprotective effects of GDNF were evident and safe. Further motor behavioral tests and other disease models are necessary to evaluate this treatment option adequately. Graphical Abstract

Eastward zonal jets at intermediate depths of 300–800 m connect the oxygen-rich western boundary of the Atlantic basin with the oxygen minimum zones (OMZs) on the eastern boundary. They are not well represented in climate models because the low horizontal resolution of these models yields excessive viscosity. We use two physical-biogeochemical model configurations of the Tropical Atlantic to show that the increase in resolution results in more robust intermediate zonal jets and a better representation of the OMZs. The OMZ structure is distorted at low-resolution as surface, westward jets advect low-oxygen waters from the eastern boundary much further west than in the climatology. The emergence of robust eastward jets in the high-resolution run alleviate this problem and reproduce the Atlantic OMZs more accurately. The asymmetry between westward and eastward jets occurs because the former are associated with homogenous potential vorticity regions originating in the eastern boundary while the latter are associated with potential vorticity gradients. Intermediate, eastward jets constrain the westward expansion of the OMZs by supplying oxygen to their western edge. Within the OMZs, higher resolution allows a better representation of the boundary current system and eddying processes at depth which redistribute of low oxygen values from the productive eastern boundary. Basin-scale, high-resolution simulations reproduce more accurately the transfer of energy across scales that results in robust zonal jets as well as their impact on the ocean biogeochemistry. Accurate model predictions provide a pathway to disentangle natural and anthropogenic causes of ocean deoxygenation.

An increasing prevalence of bone-related injuries and aging geriatric populations continue to drive the orthopaedic implant market. A hierarchical analysis of bone remodelling after material implantation is necessary to better understand the relationship between implant and bone. Osteocytes, which are housed and communicate through the lacuno-canalicular network (LCN), are integral to bone health and remodelling processes. Therefore, it is essential to examine the framework of the LCN in response to implant materials or surface treatments. Biodegradable materials offer an alternative solution to permanent implants, which may require revision or removal surgeries. Magnesium alloys have resurfaced as promising materials due to their bone-like properties and safe degradation in vivo. To further tailor their degradation capabilities, surface treatments such as plasma electrolytic oxidation (PEO) have demonstrated to slow degradation. For the first time, the influence of a biodegradable material on the LCN is investigated by means of non-destructive 3D imaging. In this pilot study, we hypothesize noticeable variations in the LCN caused by altered chemical stimuli introduced by the PEO-coating. Utilising synchrotron-based transmission X-ray microscopy, we have characterised morphological LCN differences around uncoated and PEO-coated WE43 screws implanted into sheep bone. Bone specimens were explanted after 4, 8, and 12 weeks and regions near the implant surface were prepared for imaging. Findings from this investigation indicate that the slower degradation of PEO-coated WE43 induces healthier lacunar shapes within the LCN. However, the stimuli perceived by the uncoated material with higher degradation rates induces a greater connected LCN better prepared for bone disturbance.

A good understanding of influencing parameters is required to predict corrosivity in marine and coastal environments. This study investigated the influences of real-time data of (i) air temperature, (ii) sensor surface temperature, (iii) relative humidity, (iv) precipitation, and (v) wind on steel corrosion via data analysis. The results revealed that the time when the sensor surface temperature is below the dewpoint temperature reveals the best correlation with corrosion. Wind speed above 5 m s −1 also correlated with corrosion. At the test site, most of the corrosion occurred during autumn and winter, due to more water condensation and more wind. During spring and summer, there was little corrosion, due to little condensation and dry surfaces. npj Materials Degradation (2023) 7:10 ; https://doi.

Antimicrobial resistance has been declared one of the top 10 global public health threats. Methicillin-resistant Staphylococcus aureus (MRSA) is a leading cause of recurring skin and soft tissue infections in patients with chronic skin conditions such as diabetic foot infections, making the treatment of the ulcers challenging. Wound dressings combined with metal nanoparticles have been suggested to prevent and treat MRSA-infected wounds. However, these particles are commonly synthesized by chemical approaches. In this study, we developed bio-based silver (Bio-AgNPs) and copper oxide nanoparticles (CuONPs) polymer composites using a microbially produced polyester from the Polyhydroxyalkanoates (PHAs) family. Poly(3-hydroxyoctanoate)-co-(3-hydroxyhexanoate) (PHO) was synthesized by Pseudomonas putida and functionalized in-situ with Bio-AgNPs or ex-situ with CuONPs. PHO-CuONPs films did not inhibit MRSA growth, while a reduction of 6.0 log CFU/mL was achieved with PHO-Bio-AgNPs synthesized from silver nitrate (AgNO3) solution at 3.5 mM. Exposure of human fibroblast cells (HFF-1) to the bioactive films did not induce notable cytotoxicity and genotoxicity, as seen by a viability higher than 79% and no significant changes in basal DNA damage. However, exposure to PHO-Bio-AgNPs induced oxidative DNA damage in HFF-1 cells. No hemolytic potential was observed, while platelet aggregation was promoted and desired for wound healing. Here we demonstrate the biosynthesis of polymer-nanoparticle composites and their potential as bioactive films for MRSA treatment.

Limiting global warming to well below 2°C and pursuing efforts to limit it to 1.5°C, as agreed in the 2015 Paris Agreement, requires global carbon neutrality by mid-century at the latest. The corresponding carbon budget is decreasing steadily and significantly. To phase out carbon emissions in line with the specified temperature target, countries are formulating their mitigation efforts in their long-term low greenhouse gas emission development strategies (LT-LEDS). However, there are no standardized specifications for preparing these strategies, which is why the reports published to date differ widely in terms of structure and scope. To consider the multiple facets of reaching net-zero from a systemic perspective as comprehensively as possible, the authors propose the Net-Zero-2050 System: A novel, transferrable systems approach that supports the development of national endeavors toward carbon neutrality. The Net-Zero-2050 System is defined by three interconnected components: The Carbon-Emission-Based System, the surrounding Framing System and a set of system boundaries. For both systems levels, IPCC approaches were used as a basis and were then adjusted and supplemented by Net-Zero-2050. We suggest applying the Net-Zero-2050 System—beyond the project environment—in carbon emission based contexts at different levels. Especially at the national level, this would improve the comparability of the different national strategies to achieve carbon neutrality.

We demonstrate that oleyl phosphate ligand-stabilized iron oxide nanocubes as building blocks can be assembled into 2D supercrystalline mono- and multilayers on flat YSZ substrates within a few minutes using a simple spin-coating process. As a bottom-up process, the growth takes place in a layer-by-layer mode and therefore by tuning the spin-coating parameters, the exact number of deposited monolayers can be controlled. Furthermore, ex situ scanning electron and atomic force microscopy as well as X-ray reflectivity measurements give evidence that the choice of solvent allows the control of the lattice type of the final supercrystalline monolayers. This observation can be assigned to the different Hansen solubilities of the solvents used for the nanoparticle dispersion because it determines the size and morphology of the ligand shell surrounding the nanoparticle core. Here, by using toluene and chloroform as solvents, it can be controlled whether the resulting monolayers are ordered in a square or hexagonal supercrystalline lattice.

Bottom trawling represents the most widespread anthropogenic physical disturbance to shelf sea sediments. While trawling-induced mortality in benthic fauna has been extensively investigated, its impacts on ecosystem functioning and carbon cycling at regional scales remain unclear. Using the North Sea as an example, we address these issues by synthesizing a high-resolution dataset of bottom trawling impact on sediments, feeding this dataset into a 3-dimensional physical-biogeochemical model to estimate trawling-induced changes in biomass, bioturbation and sedimentary organic carbon, and assessing model results with field samples. Results suggest a trawling-induced net reduction in macrobenthic biomass by 10-27%. Trawling-induced resus-pension and reduction of bioturbation jointly and accumulatively reduce the regional sedimentary organic carbon sequestration capacity by 21-67%, equivalent to 0.58-1.84 Mt CO2 yr-1. Our study emphasizes the need for proper management of trawling on muddy seabeds, if the natural capacity of shelf seas for carbon sequestration should be conserved and restored. Hosted file 954687_0_art_file_10676631_rpldtx.docx available at https://authorea.com/users/536828/ articles/623152-impact-of-bottom-trawling-on-long-term-carbon-sequestration-in-shelf-sea-sediments Hosted file 954687_0_supp_10676632_rpmm4m.docx available at https://authorea.com/users/536828/articles/ 623152-impact-of-bottom-trawling-on-long-term-carbon-sequestration-in-shelf-sea-sediments 1

Triple-shape polymers can memorize two independent shapes during a controlled recovery process. This work reports the 4D printing of electro-active triple-shape composites based on thermoplastic blends. Composite blends comprising polyester urethane (PEU), polylactic acid (PLA), and multiwall carbon nanotubes (MWCNTs) as conductive fillers were prepared by conventional melt processing methods. Morphological analysis of the composites revealed a phase separated morphology with aggregates of MWCNTs uniformly dispersed in the blend. Thermal analysis showed two different transition temperatures based on the melting point of the crystallizable switching domain of the PEU (Tm~50 ± 1 °C) and the glass transition temperature of amorphous PLA (Tg~61 ± 1 °C). The composites were suitable for 3D printing by fused filament fabrication (FFF). 3D models based on single or multiple materials were printed to demonstrate and quantify the triple-shape effect. The resulting parts were subjected to resistive heating by passing electric current at different voltages. The printed demonstrators were programmed by a thermo-mechanical programming procedure and the triple-shape effect was realized by increasing the voltage in a stepwise fashion. The 3D printing of such electroactive composites paves the way for more complex shapes with defined geometries and novel methods for triggering shape memory, with potential applications in space, robotics, and actuation technologies.

Understanding the sea surface wind structure during tropical cyclones (TCs) is the key for study of ocean response and parameterization of air-sea surface in numerical simulation. However, field observations are scarce. In 2019, three wave gliders were deployed in the South China Sea and the adjacent Western Pacific region, which acquired sea surface wind structure of eight TCs. Analysis of the field data suggests that the wave glider-observed surface winds are consistent with most analysis/reanalysis data (i.e., ERA5, CCMP and NCEP-GDAS) and SMAP. Both wave glider observations and analysis/reanalysis data indicate that TC wind fields induce an obvious increase in speed toward the sea surface together with a sharp change in direction, showing an asymmetric wind structure which is sensitive to TC translation speed and intensity. Larger mean values of wind speed and inflow angle are located on the right side along TC tracks. The inflow angle shows a highly dynamic dependence on the radial distance from the TC center, the TC intensity, as well as the TC-relative azimuth. Comparisons between field observations and theoretical models indicate that the most widely used, ideal TC wind profile models can largely represent the observed sea surface wind structure, but generally underestimate the wind speed due to lack of consideration of background wind. Moreover, simple ideal models (e.g., the modified Rankine vortex model) may outperform complex models when accurate information of TCs is limited. Wave glider observations have potential for better understanding of air-sea exchanges and for improvements of the corresponding parameterization schemes.