Despite the attention given to the development of novel responsive implants for regenerative medicine applications, the lack of integration with the surrounding tissues and the mismatch with the dynamic mechanobiological nature of native soft tissues remain in the current products. Hierarchical porous membranes based on a poly (urea-urethane) (PUU) nanohybrid have been fabricated by thermally induced phase separation (TIPS) of the polymer solution at different temperatures. Thermoresponsive stiffness softening of the membranes through phase transition from the semicrystalline phase to rubber phase and reverse self-assembly of the quasi-random nanophase structure is characterized at body temperature near the melting point of the crystalline domains of soft segments. The effects of the porous structure and stiffness softening on proliferation and differentiation of human bone-marrow mesenchymal stem cells (hBM-MSCs) are investigated. The results of immunohistochemistry, histological, ELISA, and qPCR demonstrate that hBM-MSCs maintain their lineage commitment during stiffness relaxation; chondrogenic differentiation is favored on the soft and porous scaffold, while osteogenic differentiation is more prominent on the initial stiff one. Stiffness relaxation stimulates more osteogenic activity than chondrogenesis, the latter being more influenced by the synergetic coupling effect of softness and porosity.

21 Despite the attention given to the development of novel responsive implants for 22 regenerative medicine applications, the lack of integration with the surrounding tissues 23 and the mismatch with the dynamic mechanobiological nature of native soft tissues 24 remain in the current products. Hierarchical porous membranes based on a poly (urea25 urethane) (PUU) nanohybrid have been fabricated by thermally-induced phase 26 separation (TIPS) of the polymer solution at different temperatures. Thermoresponsive 27 stiffness softening of the membranes through phase transition from the semicrystalline 28 phase to rubber phase and reverse self-assembling of the quasi-random nanophase 29 structure was characterized at body temperature near the melting point of the crystalline 30 domains of soft segments. The effects of the porous structure and stiffness softening on 31 proliferation and differentiation of human bone-marrow mesenchymal stem cells (hBM32

Global contamination of the marine environment by plastic has led to the discovery of microplastics in a range of marine species, including those for human consumption. In this study, the presence of microplastics and other anthropogenic debris in seawater and mussels (Mytilus edulis) from coastal waters of the U.K., as well as supermarket sources, was investigated. These were detected in all samples from all sites with spatial differences observed. Seawater samples taken from 6 locations (in triplicates) displayed 3.5 ± 2.0 debris items/L on average (range: 1.5-6.7 items/L). In wild mussels sampled from 8 locations around the U.K. coastal environment, the number of total debris items varied from 0.7 to 2.9 items/g of tissue and from 1.1 to 6.4 items/individual. For the supermarket bought mussels, the abundance of microplastics was significantly higher in pre-cooked mussels (1.4 items/g) compared with mussels supplied live (0.9 items/g). Micro-FT-IR spectroscopy was conducted on 136 randomly selected samples, with 94 items characterized. The spectra found that 50% of these debris items characterized were microplastic, with an additional 37% made up of rayon and cotton fibers. The microplastic levels detected in the supermarket bought mussels present a route for human exposure and suggests that their quantification be included as food safety management measures as well as for environmental monitoring health measures.

Cell and tissue stiffness is an important biomechanical signalling parameter for dynamic biological processes; responsive polymeric materials conferring responsive functionality are therefore appealing for in vivo implants. We have developed thermoresponsive poly(urea-urethane) nanohybrid scaffolds with 'stiffness memory' through a versatile 3D printing-guided thermally induced phase separation (3D-TIPS) technique. 3D-TIPS, a combination of 3D printing with phase separation, allows uniform phase-separation and phase transition of the polymer solution at a large interface of network within the printed sacrificial preform, leading to the creation of full-scale scaffolds with bespoke anatomical complex geometry. A wide range of hyperelastic mechanical properties of the soft elastomer scaffolds with interconnected pores at multi-scale, controlled porosity and crystallinity have been manufactured, not previously achievable via direct printing techniques or phase-separation alone. Semi-crystalline polymeric reverse self-assembly to a ground-stated quasi-random nanophase structure, throughout a hierarchical structure of internal pores, contributes to gradual stiffness relaxation during in vitro cell culture with minimal changes to shape. This 'stiffness memory' provides initial mechanical support to surrounding tissues before gradually softening to a better mechanical match, raising hopes for personalized and biologically responsive soft tissue implants which promote human fibroblast cells growth as model and potential scaffold tissue integration. STATEMENT OF SIGNIFICANCE: Biological processes are dynamic in nature, however current medical implants are often stronger and stiffer than the surrounding tissue, with little adaptability in response to biological and physical stimuli. This work has contributed to the development of a range of thermoresponsive nanohybrid elastomer scaffolds, with tuneable stiffness and hierarchically interconnected porous structure, manufactured by a versatile indirect 3D printing technique. For the first time, stiffness memory of the scaffold was observed to be driven by phase transition and a reverse self-assembly from a semicrystalline phase to a quasi-random nanostructured rubber phase. Early insight into cell response during the stiffness relaxation of the scaffolds in vitro holds promise for personalized biologically responsive soft implants.

Two new triphenylarsonium alkylthiolate precursors, a thiosulfate zwitterion and a thioacetate salt, have been structurally characterised and their cytotoxicity evaluated against PC3 cells. The arsonium compounds have been used to prepare gold nanoparticles decorated with triphenylarsonium groups.

The domestication of the one-grained einkorn (Triticum monococcum) in the Near East is relatively well known. However, an independent two-grained einkorn-like domestication has been archaeobotanically detected and scarce information is available. Triticum urartu, a wild wheat, was not fully described until the 1970s because the phenology does not allow it to be distinguished easily from wild einkorn (Triticum boeoticum subsp. thaoudar), although a genetic separation exists. Both species are mostly two grained and could potentially be the relatives of the extinct two-grained form. Pollen grains of several genetically well-identified wheat species, including T. urartu and T. boeoticum subsp. thaoudar, were studied by measuring the grain diameter and examining the exine sculpturing with phase-contrast microscopy and scanning electron microscopy to gain an insight into differences enabling taxonomic identification. This work showed that, although T. urartu pollen is smaller on average, grain diameter is not sufficient because of the size overlap between the species, but T. urartu presents a different exine sculpturing (scabrate) from other Triticum spp. (aerolate). This outcome is useful for taxonomists and archaeobotanists. First, it will allow a simple re-classification of herbarium materials. Second, further research could establish whether T. urartu was cultivated.

This study thoroughly explores the use of time-of-flight secondary ion mass spectrometry (ToF-SIMS) for determining the deposition sequence of fingermarks and ink on a porous paper surface. Our experimental work has demonstrated that mapping selected endogenous components present in natural fingermarks enables the observation of friction ridges on a laser-printed surface, only when a fingerprint is deposited over this layer of ink. Further investigations have shown limited success on ink-jet printing and ballpoint pen inks. 51 blind tests carried out on natural, latent fingermarks on laser-printed surfaces; up to 14th depletion with samples aged for up to 421 days have resulted in a 100% success rate. Development with ninhydrin was found to affect the fingermark residue through mobilisation of ions, therefore sequencing determination was compromised; whilst iodine fuming and 1,2-indanedione developers did not. This implied that selected development methods affected success in fingermark-ink deposition order determination. These results were further corroborated through inter-laboratory validation studies. The adopted protocol and extensive series of tests have therefore demonstrated the effectiveness and limitations of ToF-SIMS in providing chronological sequencing information of fingermarks on questioned documents; successfully resolving this order of deposition query.

This paper records the first example of a demosponge spicule framework in a single specimen of a Devonian stromatoporoid from the Frasnian of southern Belgium. The small sample (2.5 x 2 cm) is a component in a brecciated carbonate from a carbonate mound in La Boverie Quarry 30 km east of Dinant. Because of the small size of the sample, generic identification is not confirmed, but the stromatoporoid basal skeleton is similar to the genus Stromatopora. The spicules are arranged in the calcified skeleton, but not in the gallery space, and are recrystallized as multi-crystalline calcite. The spicules fall into two size ranges: 10-20 mu m diameter and 500-2000 mu m long for the large ones and between 5-15 mu m diameter and 50-100 mu m length for the small ones. In tangential section, the spicules are circular, they have a simple structure, and no axial canal has been preserved. The large spicules are always monaxons, straight or slightly curved styles or strongyles. The spicules most closely resemble halichondrid/axinellid demosponge spicules and are important rare evidence of the existence of spicules in Palaeozoic stromatoporoids, reinforcing the interpretation that stromatoporoids were sponges. The basal skeleton may have had an aragonitic spherulitic mineralogy. Furthermore, the spicules indicate that this stromatoporoid sample is a demosponge.

Coronary Artery Stents have been the preferred form of treatment for vascular occlusive disease, due to the minimally invasive surgical procedure, post-operative recovery time and cost, when compared to open coronary bypass surgery. The cellular response upon applying an AC electric field to type 316LM Stainless Steel stent mimics was investigated in this paper. The highest RBC adhesion was observed at voltages higher than 88 mV and lower than 74 mV. Their unique alignment along the lines of fracture on the stent surface at 88 mV was a phenomenon caused by an increase in electrical conductivity in these regions. Being able to control RBC adhesion may have various clinical implications such as inhibition of thrombus formation, and provide a basis to analyse whether electric fields may be applied to cancer therapy as well.

In years 2006–2010 particulate matter analysis was undertaken for dust samples collected from Gdansk and London area in order to compare their morphology and composition. Part of those studies was devoted to analysis of particulate matter (PM) bearing metals. Characterization of the morphology and size of the particles collected onto the filters was performed using a scanning electron microscope (SEM) and transmission electron microscope (TEM). Both electron microscopes were equipped with energy dispersive X-ray spectrometers to identify the elemental composition of the particles. On analysis of the X-ray spectra acquired by both TEM and SEM, the particles were divided into 10 groups as follows: Al-rich, Ba-rich, C-rich, Ca-rich, Cl-rich, Fe-rich, Mg-rich, Na-rich, S-rich, Si-rich. Speciation of the particles based on the major element and accompanying minor elements yielded 34 particle types. However, some pairs of elements repeat, for instance: Na-Cl and Cl-Na, Al-S and S-Al, Si-Al and Al-Si, S-Ca and Ca-S. These are undoubtedly the same types of particles; variation in peak heights of the major and minor elements is normal in a mixed particle population.

Components manufactured from 7075 aluminium alloy are used particularly by the aerospace industry because of their high strength. Anodising is often used for corrosion protection. However, adhesion failure of the anodising is occasionally observed if the anodised components are subjected to heat. A failure mechanism to explain why anodised coatings on extruded 7075 aluminium sometimes blister following heating has been determined. A variation in the density and location of rows of intermetallic compounds is shown to be a major contributory factor to failure.

The effectiveness of a plasma-deposited, diamond-like carbon (DLC) coating on aluminium alloy based surgical instruments is investigated. Surgical instruments must satisfy a number of important criteria including biocompatibility, functional performance, sterility and cleanability, structural integrity, and fatigue resistance. The integrity of the DLC layer and the diffusion barrier properties are of paramount importance due to biocompatibility considerations of the underlying aluminium metal. We investigate the optimisation of the coating with incorporation of silicon and variation in negative self bias, and highlight the design and manufacture of a lightweight laparoscopic assist instrument from aluminium alloy coated with diamond-like carbon, which has been used successfully in the clinical environment to improve operations such as cholecystectomy (gall bladder removal) and exploratory techniques for the diagnosis of cancer.

Titanium dioxide based powders are regularly used in the development of latent fingerprints on dark surfaces. For analysis of prints on adhesive tapes, the titanium dioxide can be suspended in a surfactant and used in the form of a powder suspension. Commercially available products, whilst having nominally similar composition, show varying levels of effectiveness of print development, with some powders adhering to the background as well as the print. X-ray fluorescence (XRF), analytical transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and laser particle sizing of the fingerprint powders show TiO(2) particles with a surrounding coating, tens of nanometres thick, consisting of Al and Si rich material, with traces of sodium and sulphur. Such aluminosilicates are commonly used as anti-caking agents and to aid adhesion or functionality of some fingerprint powders; however, the morphology, thickness, coverage and composition of the aluminosilicates are the primary differences between the white powder formulations and could be related to variation in the efficacy of print development.

High-resolution δ13CCARB analysis of the Permian–Triassic boundary (PTB) interval at the Laolongdong section, Beibei, near the city of Chongqing, south China, encompasses the latest Permian and earliest Triassic major facies changes in the South China Block (SCB). Microbialites form a distinctive unit in the lowermost 190cm above the top of the Changhsing Formation (latest Permian) at Laolongdong, comparable to a range of earliest Triassic sites in low latitudes in the Tethyan area. The data show that declining values of δ13CCARB, well-known globally, began at the base of the microbialite. High positive values (+3 to 4ppt) of δ13CCARB in the Late Permian are interpreted to indicate storage of 12C in the deep waters of a stratified ocean, that was released during ocean overturn in the earliest Triassic, contributing to the distinctive fall in isotope values; this interpretation has been stated by other authors and is followed here. The δ13CCARB curve shows fluctuations within the microbialite unit, which are not reflected in the microbialite structure. Comparisons between microbialite branches and adjacent micritic sediment show little difference in δ13CCARB, demonstrating that the microbialite grew in equilibrium with surrounding seawater. The Early Triassic microbialites are interpreted to be a response to upwelling of bicarbonate-rich poorly oxygenated water in low latitudes of Tethys Ocean, consistent with current ocean models for the PTB interval. However, the decline of δ13CCARB may be due to a combination of processes, including productivity collapse resulting from mass extinction, return of deep water to ocean surface, oxidation of methane released from methane hydrate destabilisation, and atmospheric deterioration. Nevertheless, build-up of bicarbonate-rich anoxic deep waters may be expected as a result of the partial isolation of Tethys, due to continental geography; release of bicarbonate-rich deep water, by ocean upwelling, in the earliest Triassic may have been an inevitable consequence of this combination of circumstances.

Titanium dioxide based powders are regularly used in the development of latent fingerprints on dark surfaces. For analysis of prints on adhesive tapes, the titanium dioxide is suspended in a surfactant and used in the form of a small particle reagent (SPR). Analysis of commercially available products shows varying levels of effectiveness of print development, with some powders adhering to the background as well as the print. Scanning electron microscopy (SEM) images of prints developed with different powders show a range of levels of aggregation of particles. Analytical transmission electron microscopy (TEM) of the fingerprint powder shows TiO2 particles with a surrounding coating, tens of nanometres thick, consisting of Al and Si rich material. X ray photoelectron spectroscopy (XPS) is used to determine the composition and chemical state of the surface of the powders; with a penetration depth of approximately 10nm, this technique demonstrates differing Ti : Al : Si ratios and oxidation states between the surfaces of different powders. Levels of titanium detected with this technique demonstrate variation in the integrity of the surface coating. The thickness, integrity and composition of the Al/Si-based coating is related to the level of aggregation of TiO2 particles and efficacy of print development.

Diamond-like carbon (DLC) films were deposited utilising plasma enhanced chemical vapour deposition (PECVD) with acetylene precursor, diluted with 0–45% argon. Electron paramagnetic resonance (EPR) measurements show the presence of one paramagnetic centre with no change in spin population over the range of film deposition conditions. However, the EPR linewidth decreases with increasing argon content of the precursor mix, suggesting an enhancement of motional narrowing due to an increase in electron delocalization, related to an increase in the sp2 cluster size. Atomic force microscopy (AFM) measurements indicate that the surface of the DLC is formed of nanoscale asperities of material. With radii of tens of nanometres for films deposited with zero argon, the size of the features increases with the argon dilution of the acetylene. Energy dispersive X-ray analysis and electrical measurements further elucidate the changes in film structure.

Earliest Triassic microbialites (ETMs) and inorganic carbonate crystal fans formed after the end-Permian mass extinction (ca. 251.4 Ma) within the basal Triassic Hindeodus parvus conodont zone. ETMs are distinguished from rarer, and more regional, subsequent Triassic microbialites. Large differences in ETMs between northern and southern areas of the South China block suggest geographic provinces, and ETMs are most abundant throughout the equatorial Tethys Ocean with further geographic variation. ETMs occur in shallow-marine shelves in a superanoxic stratified ocean and form the only widespread Phanerozoic microbialites with structures similar to those of the Cambro-Ordovician, and briefly after the latest Ordovician, Late Silurian and Late Devonian extinctions. ETMs disappeared long before the mid-Triassic biotic recovery, but it is not clear why, if they are interpreted as disaster taxa. In general, ETM occurrence suggests that microbially mediated calcification occurred where upwelled carbonate-rich anoxic waters mixed with warm aerated surface waters, forming regional dysoxia, so that extreme carbonate supersaturation and dysoxic conditions were both required for their growth. Long-term oceanic and atmospheric changes may have contributed to a trigger for ETM formation. In equatorial western Pangea, the earliest microbialites are late Early Triassic, but it is possible that ETMs could exist in western Pangea, if well-preserved earliest Triassic facies are discovered in future work.