Mechanical deformation of elastomer medical devices can enable microbial surface colonization.

Elastomers such as silicone are common in medical devices (catheters, prosthetic implants, endoscopes), but they remain prone to microbial colonization and biofilm infections. For the first time, our work shows that rates of microbial surface attachment to polydimethylsiloxane (PDMS) silicone can be significantly affected by mechanical deformation. For a section of bent commercial catheter tubing, bacteria (P. aeruginosa) show a strong preference for the 'convex' side compared to the 'concave' side, by a factor of 4.2. Further testing of cast PDMS materials in bending only showed a significant difference for samples that were manually wiped (damaged) beforehand (1.75 × 104 and 6.02 × 103 cells/mm2 on the convex and concave sides, respectively). We demonstrate that surface microcracks in elastomers are opened under tensile stress (convex bending) to become 'activated' as sites for microbial colonization. This work demonstrates that the high elastic limit of elastomers enables these microcracks to reversibly open and close, as 'dynamic defects'. Commercial catheters have relatively high surface roughness inherent to manufacturing, but we show that even manual wiping of newly-cast PDMS is sufficient to generate surface microcracks. We consider the implication for medical devices that feature sustained, surgical, or cyclic deformation, in which localized tensile conditions may expose these surface defects to opportunistic microbes. As a result, our work showcases serious potential problems in the widespread usage and development of elastomers in medical devices.

Glycoside hydrolase processing of the Pel polysaccharide alters biofilm biomechanics and Pseudomonas aeruginosa virulence.

Pel exopolysaccharide biosynthetic loci are phylogenetically widespread biofilm matrix determinants in bacteria. In Pseudomonas aeruginosa, Pel is crucial for cell-to-cell interactions and reducing susceptibility to antibiotic and mucolytic treatments. While genes encoding glycoside hydrolases have long been linked to biofilm exopolysaccharide biosynthesis, their physiological role in biofilm development is unclear. Here we demonstrate that the glycoside hydrolase activity of P. aeruginosa PelA decreases adherent biofilm biomass and is responsible for generating the low molecular weight secreted form of the Pel exopolysaccharide. We show that the generation of secreted Pel contributes to the biomechanical properties of the biofilm and decreases the virulence of P. aeruginosa in Caenorhabditis elegans and Drosophila melanogaster. Our results reveal that glycoside hydrolases found in exopolysaccharide biosynthetic systems can help shape the soft matter attributes of a biofilm and propose that secreted matrix components be referred to as matrix associated to better reflect their influence.

Multilayered optofluidics for sustainable buildings.

Indoor climate control is among the most energy-intensive activities conducted by humans. A building facade that can achieve versatile climate control directly, through independent and multifunctional optical reconfigurations, could significantly reduce this energy footprint, and its development represents a pertinent unmet challenge toward global sustainability. Drawing from optically adaptive multilayer skins within biological organisms, we report a multilayered millifluidic interface for achieving a comprehensive suite of independent optical responses in buildings. We digitally control the flow of aqueous solutions within confined milliscale channels, demonstrating independent command over total transmitted light intensity (95% modulation between 250 and 2,500 nm), near-infrared-selective absorption (70% modulation between 740 and 2,500 nm), and dispersion (scattering). This combinatorial optical tunability enables configurable optimization of the amount, wavelength, and position of transmitted solar radiation within buildings over time, resulting in annual modeled energy reductions of more than 43% over existing technologies. Our scalable "optofluidic" platform, leveraging a versatile range of aqueous chemistries, may represent a general solution for the climate control of buildings.

Room-temperature atomic layer deposition of SiO2 on microcracked ZrO2 layers.

Yttria-stabilized zirconia (Y-SZ) has become a reliable material option to restore severely compromised teeth. Y-SZ materials are prone to low-temperature degradation (LTD), which generates a tetragonal-to-monoclinic (t-m) transformed, porous layer. We suggest that room-temperature atomic layer deposition (RT-ALD) could be used for the infiltration and deposition of nanoscale SiO2 film over this layer, creating a protective hybrid surface against further degradation by LTD. This study investigated the potential of developing a Y-SZ transformed layer under controlled conditions for the infiltration of silica using RT-ALD, aiming to develop a hybrid zirconia-silica interface, and to investigate the effect of silica deposition/infiltration via RT-ALD on the surface roughness and wettability of zirconia-based materials. Sintered specimens (14 mm × 4 mm x 2 mm) were prepared from four different Y-SZ materials (n = 40): low translucency 3 mol % Y-SZ (3Y-LT; Ceramill ZI, Amann Girrbach); high translucency 4 mol % Y-SZ (4Y-HT; Ceramill Zolid); and two high translucency 5 mol % Y-SZ (5Y-HT - Lava Esthetic, 3M; 5Y-SHT - Ceramill Zolid, FX white). Specimens were exposed to hydrothermal treatment (HTT) to develop similar depths of crystalline changes. RT-ALD was used to deposit a thin film of silica (SiO2). Surface roughness and wettability analyses were performed to investigate the effect of treatment (HTT and RT-ALD) and material on Y-SZ surface properties, and data was analyzed by two-way ANOVA and Tukey HSD (p < 0.05). RT-ALD and HTT-RT-ALD treated specimens of 3Y-LT and 5Y-HT materials were exposed to further hydrothermal aging (HA) and the surface was characterized by time-of-flight secondary ion mass spectrometry (ToF-SIMS). There was a significant interaction effect of material and treatment (HTT and RT-ALD) on roughness (p = 0.02), and surface wettability (p < 0.001). Silica deposition via RT-ALD resulted in a significant increase in surface roughness of all materials tested, while surface wettability was either improved or not changed based on the material type and HTT exposure. Nanofilms of SiO2 were successfully deposited on Y-SZ materials and infiltrated 3Y-LT zirconia.

Decapod-inspired pigment modulation for active building facades.

Typical buildings are static structures, unable to adjust to dynamic temperature and daylight fluctuations. Adaptive facades that are responsive to these unsteady solar conditions can substantially reduce operational energy inefficiencies, indoor heating, cooling, and lighting costs, as well as greenhouse-gas emissions. Inspired by marine organisms that disperse pigments within their skin, we propose an adaptive building interface that uses reversible fluid injections to tune optical transmission. Pigmented fluids with tunable morphologies are reversibly injected and withdrawn from confined layers, achieving locally-adjustable shading and interior solar exposure. Multicell arrays tiled across large areas enable differential and dynamic building responses, demonstrated using both experimental and simulated approaches. Fluidic reconfigurations can find optimal states over time to reduce heating, cooling, and lighting energy in our models by over 30% compared to current available electrochromic technologies.

Long-Term Reduction of Bacterial Adhesion on Polyurethane by an Ultra-Thin Surface Modifier.

Indwelling urinary catheters are employed widely to relieve urinary retention in patients. A common side effect of the use of these catheters is the formation of urinary tract infections (UTIs), which can lead not only to severe medical complications, but even to death. A number of approaches have been used to attempt reduction in the rate of UTI development in catheterized patients, which include the application of antibiotics and modification of the device surface by coatings. Many of these coatings have not seen use on catheters in medical settings due to either the high cost of their implementation, their long-term stability, or their safety. In previous work, it has been established that the simple, stable, and easily applicable sterilization surface coating 2-(3-trichlorosilylpropyloxy)-ethyl hydroxide (MEG-OH) can be applied to polyurethane plastic, where it greatly reduces microbial fouling from a variety of species for a 1-day time period. In the present work, we establish that this coating is able to remain stable and provide a similarly large reduction in fouling against Escherichia coli and Staphylococcus aureus for time periods in an excess of 30 days. This non-specific coating functioned against both Gram-positive and Gram-negative bacteria, providing a log 1.1 to log 1.9 reduction, depending on the species and day. This stability and continued efficacy greatly suggest that MEG-OH may be capable of providing a solution to the UTI issue which occurs with urinary catheters.

Silica deposition on zirconia via room-temperature atomic layer deposition (RT-ALD): Effect on bond strength to veneering ceramic.

PURPOSE: To develop and to characterize a hybrid interface between yttria-stabilized zirconia (Y-TZP) transformed layer and silica-based nanofilm to enable a better bonding between Y-TZP and a veneering ceramic. MATERIAL AND METHODS: Sixty-six fully-sintered rectangular Y-TZP specimens were distributed into 6 groups, according to the surface treatment applied: C (control): no treatment; Al: 27 µm-alumina particle abrasion; Ht: hydrothermal treatment in autoclave for 15h; Si20: 20 cycles of silica deposition using room-temperature atomic layer deposition (RT-ALD); Si40: 40 cycles of RT-ALD; Ht + Si40: hydrothermal treatment followed by 40 cycles of RT-ALD. RT-ALD was performed by the sequential exposure of specimens to vapor of tetramethoxysilane orthosilicate (TMOS) and ammonium hydroxide (NH4OH). Y-TZP surface wettability and shear bond strength (SBS) between Y-TZP and the veneering ceramic were analyzed for all groups after surface treatments. One-way ANOVA and Tukey's HSD test were used for data analysis (p ≤ 0.05). RESULTS: The highest contact angle was observed for the control group (64.46 ± 6.09 θ), while the lowest values (p < 0.001) were presented after Si20 (29.85 ± 4.23 θ) and Si40 (30.37 ± 5.51 θ) treatments. Hydrothermal treatment (49.3 ± 2.69 θ) and alumina abrasion (45.84 ± 4.12 θ) resulted in intermediate contact angle values. The highest SBS values were observed for Al (16.74 ± 1.68 MPa) and Ht (15.27 ± 2.11 MPa) groups (p < 0.018). Groups Si20 (9.66 ± 1.22 MPa), Si40 (9.33 ± 2.11 MPa), Ht + Si40 (9.37 ± 1.02 MPa) and C (12.54 ± 2.64 MPa) all resulted in similar SBS results (p > 0.998). CONCLUSION: The experimental treatments proposed enhanced surface wettability, but shear bond strength between Y-TZP and veneering ceramic was not improved. Alumina particle-abrasion improved SBS values while a decrease in wettability was observed.

Programmable droplets: Leveraging digitally-responsive flow fields to actively tune liquid morphologies.

Stimulus-responsive materials enable programmable and adaptive behaviors. Typical solid-phase systems can only achieve small deformations for applications where shape transformations are beneficial or required. Liquids, in contrast, can self-assemble and achieve very high strains in a multifluid environment. Here we report liquid droplet formation by tuning flow potential within a confined fluidic cell. We digitally inject small volumes of liquid-pigment into an otherwise-transparent liquid layer, generating macroscopic droplet assembly over large areas constrained between closely-spaced plates. Droplet morphology is actively controlled by modulating outlet conditions to tune flow fields. Pattern stability is maintained through control over injection rate, interfacial viscosity difference, and interfacial surface tension. We demonstrate time-dependent droplet formation and migration to achieve spatially-tunable optical properties. Applied as a multi-cell array, we imagine this liquid mechanism will enable scalable pattern dynamics for active shading and visual display technologies.

Stepwise slime mould growth as a template for urban design.

The true slime mould, Physarum polycephalum, develops as a vascular network of protoplasm, connecting node-like sources of food in an effort to solve multi-objective transport problems. The organism first establishes a dense and continuous mesh, reinforcing optimal pathways over time through constructive feedbacks of protoplasmic streaming. Resolved vascular morphologies are the result of an evolutionarily-refined mechanism of computation, which can serve as a versatile biological model for network design at the urban scale. Existing digital Physarum models typically use positive reinforcement mechanisms to capture meshing and refinement behaviours simultaneously. While these automations generate accurate descriptions of sensory and constructive feedback, they limit stepwise design control, reducing flexibility and applicability. A model that decouples the two "phases" of Physarum behaviour would enable multistage control over network growth. Here we introduce such a system, first by producing a site-responsive mesh from a population of nutrient-attracted agents, and then by independently calculating from it a flexible, proximity-defined shortest-walk to produce a final network. We develop and map networks within existing urban environments that perform similarly to those biologically grown, establishing a versatile tool for bio-inspired urban network design.

Divisions in a Fibrillar Adhesive Increase the Adhesive Strength.

To realize the potential of bioinspired fibrillar adhesive applications ranging from biomedical devices to robotic grippers, there has been a significant effort to improve their adhesive strength and understanding of the underlying adhesion and detachment mechanisms. These efforts include changes to the backing layer, which connects the roots of all of the pillars in the fibrillar adhesive. However, previous approaches such as thickness or elastic modulus changes are selectively advantageous to the adhesive strength depending on the substrate condition because of the trade-off between conformity to misaligned/rough surfaces and increased interfacial stress concentrations. In this work, we explore mechanical divisions (cuts) in the backing layer as a new approach to improve the adhesive strength without this trade-off. We combine experiments and finite element analysis (FEA) to study the effect of the divisions, which decouples the mechanical interaction between the pillars on the divided layers, and show that the adhesive strength can be improved regardless of the substrate condition. Tensile adhesion experiments show increased adhesive strength with cuts to a micropost array (150 µm diameter posts) by approximately 25% for 4 divisions. In situ imaging of pillar detachment shows a transition of the detachment process from a peel-like detachment to a random detachment sequence. FEA simulations of the detachment process suggest that the increased strength may originate from a simultaneous enhancement of the load distribution between the pillars and the compliance of the backing layer.

Mechanical performance of a hybrid zirconia developed through hydrothermal treatment and Room-Temperature Atomic Layer Deposition (RT-ALD).

OBJECTIVE: A silica-based nanofilm has been successfully deposited via Room-Temperature Atomic Layer Deposition (RT-ALD) on the surface of a glass. The purpose of this study was to evaluate the mechanical performance of a hybrid interface created between yttria-stabilized zirconia (Y-PSZ) transformed layer and silica-based nanofilm via RT-ALD. MATERIAL AND METHODS: Fully-sintered Y-PSZ (14 × 4.0 × 1.5 mm) specimens in different translucencies (MO, MT, LT; IPS e.max Zircad, Ivoclar Vivadent) were distributed in 5 groups: control (C - no treatment); hydrothermal treatment (HT- 15h, 134°C, 2 bar); alumina blasting (B - 50 µm Al2O3); RT-ALD silica deposition (S); HT followed by silica deposition (HTS). RT-ALD cycles consisted of the sequential exposure of specimens to tetramethoxysilane orthosilicate (TMOS - 60s) and ammonium hydroxide (NH4OH - 10 min) vapors in 40 cycles. Mechanical performance was analyzed by flexural strength (FS) (n = 10) and fatigue failure load (staircase method; n = 20) tests. Surface hardness (H) and Young's modulus (YM) were analyzed by nanoindentation. For surface chemical and topographical characterization, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were performed. Data from surface H, YM, FS, and fatigue limit (FL) were analyzed by two-way analysis of variance (ANOVA). RESULTS: The interaction between material and treatment had a significant effect on FS (p < 0.001). The FS values ranged from 436.23 MPa to 856.65 MPa. HT resulted in the highest FS (856.65 MPa) for LT and the lowest FS (436.23 MPa) for MO zirconia. For all materials, S and B treatments resulted in similar FS values (p > 0.410). S did not affect FL when compared to the C group (p > 0.277) for any material investigated. HTS resulted in higher FL than S for LT and MO materials (p < 0.001). Surface hardness and modulus were similar between control and S-treated specimens for all materials analyzed. XPS analysis showed homogeneous silica content after 20 and 40 RT-ALD cycles, and SEM did not show significant changes in surface morphology between C and S-treated specimens. CONCLUSION: RT-ALD resulted in effective silica deposition without any deleterious effect on zirconia-based materials mechanical properties. Alumina blasting promoted higher alteration on surface topography. HT prior to S resulted in superior FL (for MO and MT) and flexural strength (MO) for some of the materials investigated.

Transparent Organogel Films Showing Extremely Efficient and Durable Anti-Icing Performance.

Accumulation of ice and snow on solid surfaces causes destructive problems in our daily life. Therefore, the development of functional coatings/surfaces that can effectively prevent ice/snow adhesion by natural forces, such as airflow, vibration, solar radiation, or gravity, is in high demand. In this study, transparent organogel films possessing negligible ice adhesion strength were successfully designed by a simple cross-linking of poly(dimethylsiloxane) (PDMS) in the presence of commercially available oils. Both the molecular weights (MWs) of the infusing oils and their contents in the PDMS matrices have proven to be key parameters for primarily determining the cross-linking density of PDMS matrices and syneresis/nonsyneresis behaviors of our samples, which closely reflected the final surface static/dynamic dewetting and anti-icing properties. By tuning only these two parameters, three different types of transparent organogel films, that is, nonsyneresis organogel (NSG), self-lubricating organogel (SLUG-I, infused with highly mobile oils), and SLUG-II (infused with viscous oils) films, were prepared. Among them, on the SLUG-I films, the lubricating oils were found to be continuously released from the PDMS matrices through syneresis for more than 1 year. Due to this unusual syneresis behavior, the ice adhesion strength became virtually zero, and this excellent anti-icing property also remained almost unchanged even after several cycles of icing/deicing testing. On the other hand, in the case of SLUG-II films, as the lubricated oil layers were too viscous, ice had trouble sliding off the surfaces by gravity. In contrast to these SLUG films, ice adhesion strength on NSG films was markedly decreased by increasing the amount of the infusing oils. In spite of NSG films having no distinct mobile oil layer, the ice adhesion strength reached its minimum of only about 5 kPa.

Degradation Characteristics of Electrospun Gas Diffusion Layers with Custom Pore Structures for Polymer Electrolyte Membrane Fuel Cells.

Electrospinning has been demonstrated to be a versatile technique for producing hydrophobic gas diffusion layers (GDLs) with customized pore structures for the enhanced performance of polymer electrolyte membrane (PEM) fuel cells. However, the degradation characteristics of custom hydrophobic electrospun GDLs (eGDLs) have not yet been explored. Here, for the first time, we investigate the degradation characteristics of custom hydrophobic eGDLs via an ex situ accelerated degradation protocol using H2O2. The surface contact angle of degraded eGDLs (44 ± 12°) was lower than that of pristine eGDLs (137 ± 6°). The loss of hydrophobicity was attributed to the degradation (via hydrolysis) of the fluorinated monolayers (formed via a direct fluorination treatment) on the electrospun carbon fiber surfaces as evidenced by the reduction in surface fluorine content. Degradation of the surface monolayers affected fuel cell performance under multiple operating conditions. At 100% relative humidity (RH), the loss of monolayers led to higher liquid water content and lower cell voltages compared to the pristine eGDL. At 50% RH, the degraded eGDL led to lower cell voltages due to the lower electrical conductivity of the degraded materials. The lower electrical conductivity was attributed to the oxidation of carbon fibers upon loss of the monolayers. Our results indicate the importance of designing robust hydrophobic surface treatments for the advancement of customized GDLs for effective long-term fuel cell operation.

Reduction of microbial adhesion on polyurethane by a sub-nanometer covalently-attached surface modifier.

Indwelling urinary catheters are a common medical device used to relieve urinary retention. Many patients who undergo urinary catheterization develop urinary tract infections (UTIs), which can lead to severe medical complications and high cost of subsequent treatment. Recent years have seen a number of attempts at reducing the rate of UTIs in catheterized patients via catheter surface modifications. In this work, a low cost, robust anti-thrombogenic, and sterilizable anti-fouling layer based on a covalently-bound monoethylene glycol hydroxide (MEG-OH) was attached to polyurethane, a polymeric material commonly used to fabricate catheters. Modified polyurethane tubing was compared to bare tubing after exposure to a wide spectrum of pathogens including Gram-negative bacteria (Pesudomonas aeruginosa, Escherichia coli), Gram-positive bacteria (Staphylococcus aureus) and a fungus (Candida albicans). It has been demonstrated that the MEG-OH monolayer was able to significantly reduce the amount of adhesion of pathogens present on the material surface, with between 85 and 96 % reduction after 24 h of exposure. Additionally, similar reductions in surface fouling were observed following autoclave sterilization, long term storage of samples in air, and longer exposure up to 3 days.

Preventing Pseudomonas aeruginosa Biofilms on Indwelling Catheters by Surface-Bound Enzymes.

Implanted medical devices such as central venous catheters are highly susceptible to microbial colonization and biofilm formation and are a major risk factor for nosocomial infections. The opportunistic pathogen Pseudomonas aeruginosa uses exopolysaccharides, such as Psl, for both initial surface attachment and biofilm formation. We have previously shown that chemically immobilizing the Psl-specific glycoside hydrolase, PslGh, to a material surface can inhibit P. aeruginosa biofilm formation. Herein, we show that PslGh can be uniformly immobilized on the lumen surface of medical-grade, commercial polyethylene, polyurethane, and polydimethylsiloxane (silicone) catheter tubing. We confirmed that the surface-bound PslGh was uniformly distributed along the catheter length and remained active even after storage for 30 days at 4 °C. P. aeruginosa colonization and biofilm formation under dynamic flow culture conditions in vitro showed a 3-log reduction in the number of bacteria during the first 11 days, and a 2-log reduction by day 14 for PslGh-modified PE-100 catheters, compared to untreated catheter controls. In an in vivo rat infection model, PslGh-modified PE-100 catheters showed a ∼1.5-log reduction in the colonization of the clinical P. aeruginosa ATCC 27853 strain after 24 h. These results demonstrate the robust ability of surface-bound glycoside hydrolase enzymes to inhibit biofilm formation and their potential to reduce rates of device-associated infections.

Lubrication dynamics of swollen silicones to limit long term fouling and microbial biofilms.

Bacterial contamination and biofilm formation on medical devices remain a costly and serious healthcare problem. Silicone (polydimethylsiloxane, PDMS) elastomers are common biomaterials but are susceptible to bacterial surface contamination and biofilm growth. 'Self-lubricated' PDMS elastomers (iPDMS) have the potential to greatly reduce rates of cell attachment, biofilm formation and infection. Cross-linked PDMS elastomers immersed in PDMS oil swell to an equilibrium concentration to form a swollen network, and then form a surface liquid layer through syneresis. Herein we have measured the swelling and syneresis kinetics as a function of time, viscosity (1.5 to 10 cSt), and cross-linking density to optimize the surface lubricant layer formation, and resistance to biofouling. The lubricant layer thickness was measured in situ (optical profilometry and AFM) for flat and micro-textured surfaces, as a function of time and swelling ratio, to be in a range from 0.1 to 1 µm, and continuously increases with time. We show this continuous generation is likely due to a gradual, dynamic re-structuring of the elastomer network. Long term antifouling properties of (10 cSt) iPDMS were tested for Pseudomonas aeruginosa growth in a flow culture bioreactor, and after 30 d showed a 103 to 104 reduction of bacterial cell density for iPDMS compared to conventional PDMS elastomers. This long term performance and non-specific activity makes them highly suitable for biomedical devices, such as urinary catheters.

Antimicrobial antidegradative dental adhesive preserves restoration-tooth bond.

OBJECTIVE: Assess the ability of an antimicrobial drug-releasing resin adhesive, containing octenidine dihydrochloride (OCT)-silica co-assembled particles (DSPs), to enhance the biostability and preserve the interfacial fracture toughness (FT) of composite restorations bonded to dentin. Enzyme-catalyzed degradation compromises the dental restoration-tooth interface, increasing cariogenic bacterial infiltration. In addition to bacterial ingress inhibition, antimicrobial-releasing adhesives may exhibit direct interfacial biodegradation inhibition as an additional benefit. METHODS: Mini short-rod restoration bonding specimens with total-etch adhesive with/without 10% wt. DSPs were made. Interfacial fracture toughness (FT) was measured as-manufactured or post-incubation in simulated human salivary esterase (SHSE) for up to 6-months. Effect of OCT on SHSE and whole saliva/bacterial enzyme activity was assessed. Release of OCT outside the restoration interface was assessed. RESULTS: No deleterious effect of DSPs on initial bonding capacity was observed. Aging specimens in SHSE reduced FT of control but not DSP-adhesive-bonded specimens. OCT inhibited SHSE degradation of adhesive monomer and may inhibit endogenous proteases. OCT inhibited bacterial esterase and collagenase. No endogenous collagen breakdown was detected in the present study. OCT increased human saliva degradative esterase activity below its minimum inhibitory concentration towards S. mutans (MIC), but inhibited degradation above MIC. OCT release outside restoration margins was below detection. SIGNIFICANCE: DSP-adhesive preserves the restoration bond through a secondary enzyme-inhibitory effect of released OCT, which is virtually confined to the restoration interface microgap. Enzyme activity modulation may produce a positive-to-negative feedback switch, by increasing OCT concentration via biodegradation-triggered release to an effective dose, then subsequently slowing degradation and degradation-triggered release.

Multiple New Paralytic Shellfish Toxin Vectors in Offshore North Sea Benthos, a Deep Secret Exposed.

In early 2018, a large easterly storm hit the East Anglian coast of the UK, colloquially known as the 'Beast from the East', which also resulted in mass strandings of benthic organisms. There were subsequent instances of dogs consuming such organisms, leading to illness and, in some cases, fatalities. Epidemiological investigations identified paralytic shellfish toxins (PSTs) as the cause, with toxins present in a range of species and concentrations exceeding 14,000 µg STX eq./kg in the sunstar Crossaster papposus. This study sought to better elucidate the geographic spread of any toxicity and identify any key organisms of concern. During the summers of 2018 and 2019, various species of benthic invertebrates were collected from demersal trawl surveys conducted across a variety of locations in the North Sea. An analysis of the benthic epifauna using two independent PST testing methods identified a 'hot spot' of toxic organisms in the Southern Bight, with a mean toxicity of 449 µg STX eq./kg. PSTs were quantified in sea chervil (Alcyonidium diaphanum), the first known detection in the phylum bryozoan, as well as eleven other new vectors (>50 µg STX eq./kg), namely the opisthobranch Scaphander lignarius, the starfish Anseropoda placenta, Asterias rubens, Luidia ciliaris, Astropecten irregularis and Stichastrella rosea, the brittlestar Ophiura ophiura, the crustaceans Atelecyclus rotundatus and Munida rugosa, the sea mouse Aphrodita aculeata, and the sea urchin Psammechinus miliaris. The two species that showed consistently high PST concentrations were C. papposus and A. diaphanum. Two toxic profiles were identified, with one dominated by dcSTX (decarbamoylsaxitoxin) associated with the majority of samples across the whole sampling region. The second profile occurred only in North-Eastern England and consisted of mostly STX (Saxitoxin) and GTX2 (gonyautoxin 2). Consequently, this study highlights widespread and variable levels of PSTs in the marine benthos, together with the first evidence for toxicity in a large number of new species. These findings highlight impacts to 'One Health', with the unexpected sources of toxins potentially creating risks to animal, human and environmental health, with further work required to assess the severity and geographical/temporal extent of these impacts.

Nickel@Siloxene catalytic nanosheets for high-performance CO2 methanation.

Two-dimensional (2D) materials are of considerable interest for catalyzing the heterogeneous conversion of CO2 to synthetic fuels. In this regard, 2D siloxene nanosheets, have escaped thorough exploration, despite being composed of earth-abundant elements. Herein we demonstrate the remarkable catalytic activity, selectivity, and stability of a nickel@siloxene nanocomposite; it is found that this promising catalytic performance is highly sensitive to the location of the nickel component, being on either the interior or the exterior of adjacent siloxene nanosheets. Control over the location of nickel is achieved by employing the terminal groups of siloxene and varying the solvent used during its nucleation and growth, which ultimately determines the distinct reaction intermediates and pathways for the catalytic CO2 methanation. Significantly, a CO2 methanation rate of 100 mmol gNi-1 h-1 is achieved with over 90% selectivity when nickel resides specifically between the sheets of siloxene.