With their superficially shark-like appearance, the Mesozoic ichthyosaurs provide a classic illustration of major morphological adaptations in an ancestrally terrestrial tetrapod lineage following the invasion of marine habitats1, 2–3. Much of what is known about ichthyosaur soft tissues derives from specimens with body outlines4, 5–6. However, despite offering insights into aspects of biology that are otherwise difficult to envisage from skeletal evidence alone (such as the presence of a crescentic fluke), information on their soft parts has hitherto been limited to a taxonomically narrow sample of small- to dolphin-sized animals2,4, 5–6. Here we report the discovery of a metre-long front flipper of the large-bodied Jurassic ichthyosaur Temnodontosaurus, including unique details of its soft-tissue anatomy. In addition to revealing a wing-like planform, the fossil preserves a serrated trailing edge that is reinforced by novel cartilaginous integumental elements, herein denominated chondroderms. We also document chordwise-parallel skin ornamentations and a protracted fleshy distal tip that presumably acted like a flexible winglet in life. By integrating morphological and numerical data, we show that the observed features probably provided hydroacoustic benefits, and conclude that the visually guided7,8Temnodontosaurus relied on stealth while hunting in dim-lit pelagic environments. This unexpected combination of control surface modifications represents a previously unrecognized mode of concealment, and underscores the importance of soft-tissue fossils when inferring aspects of palaeoethology and predator–prey palaeoecology.

A common type of inhalation medicine uses a dry powder formulation where the active pharmaceutical ingredient (API) is attached on the surface of carrier particles, often in combination with additional components. The spatial distribution of the API on the carrier particle is critical for the release into the lungs and thus for the efficacy of the drug. In this work, we use ToF-SIMS imaging in combination with argon gas cluster sputtering to determine the 3D distributions of budesonide (the API) and magnesium stearate (Mg-stearate) on the surface of lactose carrier particles in a so-called adhesive mixture formulation. The results show that the carrier particles are largely covered by Mg-stearate, with only small spots showing exposed lactose or budesonide. Upon sputtering, Mg-stearate is rapidly removed to expose flat regions of lactose as well as discrete budesonide particles distributed over the lactose surface. Depth profiles also indicate some smearing of budesonide on the lactose surface. These results provide clear evidence that budesonide, as well as lactose, is largely covered with Mg-stearate on the drug particle surface. Subsequent SEM analyses of the sample areas provide detailed microstructural information, including identification of budesonide and lactose fine particles attached on the lactose surface. Furthermore, the thickness of the Mg-stearate overlayer was estimated by XPS to be approximately 5 nm. The detailed information obtained about the 3D distribution of Mg-stearate serves to clarify the mechanisms behind its performance-enhancing effect in adhesive mixtures and also to improve formulation optimization with regard to Mg-stearate load and application process. 

Plesiosaurs are an iconic group of Mesozoic marine reptiles with an evolutionary history spanning over 140 million years (Ma).1 Their skeletal remains have been discovered worldwide; however, accompanying fossilized soft tissues are exceptionally rare.2 Here, we report a virtually complete plesiosaur from the Lower Jurassic (∼183 Ma)3 Posidonia Shale of Germany that preserves skin traces from around the tail and front flipper. The tail integument was apparently scale-less and retains identifiable melanosomes, keratinocytes with cell nuclei, and the stratum corneum, stratum spinosum, and stratum basale of the epidermis. Molecular analysis reveals aromatic and aliphatic hydrocarbons that likely denote degraded original organics. The flipper integument otherwise integrates small, sub-triangular structures reminiscent of modern reptilian scales. These may have influenced flipper hydrodynamics and/or provided traction on the substrate during benthic feeding. Similar to other sea-going reptiles,45678910 scalation covering at least part of the body therefore probably augmented the paleoecology of plesiosaurs. 

The identity and source of flexible, semi-transparent, vascular-like components recovered from non-avian dinosaur bone are debated, because: (1) such preservation is not predicted by degradation models; (2) taphonomic mechanisms for this type of preservation are not well defined; and (3) although support for molecular endogeneity has been demonstrated in select specimens, comparable data are lacking on a broader scale. Here, we use a suite of micromorphological and molecular techniques to examine vessel-like material recovered from the skeletal remains of six non-avian dinosaurs, representing different taxa, depositional environments and geological ages, and we compare the data obtained from our analyses against vessels liberated from extant ostrich bone. The results of this in-depth, multi-faceted study present strong support for endogeneity of the fossil-derived vessels, although we also detect evidence of invasive microorganisms.

A partial ichthyosaur skeleton from the Toarcian (Lower Jurassic) bituminous shales of the ‘Schistes Carton’ unit of southern Luxembourg is described and illustrated. In addition, associated remnant soft tissues are analyzed using a combination of imaging and molecular techniques. The fossil (MNHNL TV344) comprises scattered appendicular elements, together with a consecutive series of semi-articulated vertebrae surrounded by extensive soft-tissue remains. We conclude that TV344 represents a skeletally immature individual (possibly of the genus Stenopterygius) and that the soft parts primarily consist of fossilized skin, including the epidermis (with embedded melanophore pigment cells and melanosome organelles) and dermis. Ground sections of dorsal ribs display cortical microstructures reminiscent of lines of arrested growth (LAGs), providing an opportunity for a tentative age determination of the animal at the time of death (>3 years). It is further inferred that the exceptional preservation of TV344 was facilitated by seafloor dysoxia/anoxia with periodical intervals of oxygenation, which triggered phosphatization and the subsequent formation of a carbonate concretion. 

The interaction of active substances with molecular structures in stratum corneum (SC) is crucial for the efficacy and safety of cosmetic formulations and topical drugs. However, the molecular architecture of SC is highly complex and methods to unambiguously localize exogenous molecules within SC are lacking. Consequently, little is known about the distribution of actives within SC, and proposed penetration mechanisms through SC are typically limited to simple diffusion via a tortuous (lipid only) or transverse (across corneocytes and lipid matrix) pathway. In this work, 3D mass spectrometry imaging is used to determine the spatial distributions of four active substances at subcellular resolution in SC, including partitioning between the corneocytes and the intercellular lipid matrix. The results indicate that caffeine, 2-methyl resorcinol and oxybenzone are homogeneously distributed in the corneocytes but largely absent in the lipid matrix, despite considerable differences in lipophilicity. In contrast, the distribution- of jasmonic acid derivative is more inhomogeneous and indicates considerable localization to both the lipid phase and the corneocytes.

In time-of-flight secondary ion mass spectrometry (TOF-SIMS), ionized molecules and molecular fragments (secondary ions) are generated in collisions of high-energy ions (primary ions) with a solid sample surface. Mass spectra of the emitted secondary ions are typically used to identify molecular species and to determine their spatial distribution on the sample surface. Here, we extend this application in a TOF-SIMS study of a series of polycyclic aromatic hydrocarbons (PAHs) where we focus on the fragmentation of these molecules, with the purpose of better understanding the fragmentation patterns of heavy aromatic molecules in petroleum. For all PAHs, the collision process generated (i) a series of smaller cation fragments and (ii) cations close in size to the original PAH (molecular cations). Stark differences are measured for various PAHs regarding the abundance of smaller fragments versus molecular cations. Observation of hydrogen-deficient (H-deficient) cation fragments indicates the formation of polyynes and allenes. For PAHs producing higher fractions of small cation fragments, these ions are surprisingly hydrogen rich (H-rich). The H/C ratio of fragments does not scale with the fraction of Clar sextet carbon, nor with energies of low-lying electronic transitions. Free radical cation fragments tend to be suppressed. For sufficiently large fragments, aromatic cations appear to be formed and include some free radical aromatics. There is ample production of molecular ions with loss of a single carbon atom or a methine group, which corresponds to the reduction of a 6-membered aromatic ring to a 5-membered ring. There is some enhancement of free radical molecular cations due to the corresponding formation of neutral polyynes. Fragment anions are also produced with a strong preference for very H-deficient carbon clusters, in some cases being the same as carbon cluster anions observed in space. Comparisons of PAH TOF-SIMS spectra with those of asphaltenes are discussed in detail.

Konservat-Lagerstätten, such as the Toarcian (Early Jurassic) Posidonia Shale of southwestern Germany, are renowned for their spectacular fossils. Ichthyosaur skeletons recovered from this formation are frequently associated with soft tissues; however, the preserved material ranges from three-dimensional, predominantly phosphatized structures to dark films of mainly organic matter. We examined soft-tissue residues obtained from two ichthyosaur specimens using an integrated ultrastructural and geochemical approach. Our analyses revealed that the superficially-looking ‘films’ in fact comprise sections of densely aggregated melanosome (pigment) organelles sandwiched between phosphatized layers containing fibrous microstructures. We interpret this distinct layering as representing condensed and incompletely degraded integument from both sides of the animal. When compared against previously documented ichthyosaur fossils, it becomes readily apparent that a range of preservational modes exists between presumed ‘phosphatic’ and ‘carbonized’ soft-tissue remains. Some specimens show high structural fidelity (e.g. distinct integumentary layering), while others, including the fossils examined in this study, retain few original anatomical details. This diversity of soft-tissue preservational modes among Posidonia Shale ichthyosaurs offers a unique opportunity to examine different biostratinomic, taphonomic and diagenetic variables that potentially could affect the process of fossilization. It is likely that soft-tissue preservation in the Posidonia Shale was regulated by a multitude of factors, including decay efficiency and speed of phosphatic mineral nucleation; these in turn were governed by a seafloor with sustained microbial mat activity fuelled by high organic matter input and seasonally fluctuating oxygen levels. © 2023 The Authors. 

Melanin pigments play a critical role in physiological processes and shaping animal behaviour. Fossil melanin is a unique resource for understanding the functional evolution of melanin but the impact of fossilisation on molecular signatures for eumelanin and, especially, phaeomelanin is not fully understood. Here we present a model for the chemical taphonomy of fossil eumelanin and phaeomelanin based on thermal maturation experiments using feathers from extant birds. Our results reveal which molecular signatures are authentic signals for thermally matured eumelanin and phaeomelanin, which signatures are artefacts derived from the maturation of non-melanin molecules, and how these chemical data are impacted by sample preparation. Our model correctly predicts the molecular composition of eumelanins in diverse vertebrate fossils from the Miocene and Cretaceous and, critically, identifies direct molecular evidence for phaeomelanin in these fossils. This taphonomic framework adds to the geochemical toolbox that underpins reconstructions of melanin evolution and of melanin-based coloration in fossil vertebrates. 

The crucial barrier properties of the stratum corneum (SC) depend critically on the design and integrity of its layered molecular structure. However, analysis methods capable of spatially resolved molecular characterization of the SC are scarce and fraught with severe limitations, e.g., regarding molecular specificity or spatial resolution. Here, we used 3D time-of-flight secondary ion mass spectrometry to characterize the spatial distribution of skin lipids in corneocyte multilayer squams obtained by tape stripping. Depth profiles of specific skin lipids display an oscillatory behavior that is consistent with successive monitoring of individual lipid and corneocyte layers of the SC structure. Whereas the most common skin lipids, i.e., ceramides, C24:0 and C26:0 fatty acids and cholesteryl sulfate, are similarly organized, a distinct 3D distribution was observed for cholesteryl oleate, suggesting a different localization of cholesteryl esters compared to the lipid matrix separating the corneocyte layers. The possibility to monitor the composition and spatial distribution of endogenous lipids as well as active drug and cosmetic substances in individual lipid and corneocyte layers has the potential to provide important contributions to the basic understanding of barrier function and penetration in the SC. © 2022 by the authors.