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Mollusk shells protect the animals that form and inhabit them. They are composites of minerals and organics, with diverse mesostructures, including nacre, prismatic calcite, crossed-lamellar aragonite, and foliated calcite. Twins, that is, crystals mirror symmetric with respect to their coherent interface, occurring as formation or deformation twins, are observed in all mollusk shell mesostructures but never within calcite prisms. Here, nanotwins and microwins within single calcite prisms are observed in different shells. Using Polarization-dependent Imaging Contrast (PIC) mapping with 20–60 nm resolution, twins are observed to be 0.2–3 µm thick layers of differently oriented and colored crystals with respect to the main prism crystal. Multiple twins are interspersed with the prism crystal, parallel to one another, and similarly oriented. When comparing images of calcite prisms and twins obtained by PIC mapping and by Electron Back-Scattered Diffraction (EBSD), the images correspond precisely. All twins are e-twin types, with 127° angular distance between c-axes. E-twins are the most common deformation twins in geologic calcite, as also observed here in Carrara marble. Location of all twins near the outer surface of all shells and e-twin type both suggest that twins within calcite prisms in mollusk shells result from deformation twinning.

Mollusk shells protect the animals that form and inhabit them. They are composites of minerals and organics, with diverse mesostructures, including nacre, prismatic calcite, crossed‐lamellar aragonite, and foliated calcite. Twins, that is, crystals mirror symmetric with respect to their coherent interface, occurring as formation or deformation twins, are observed in all mollusk shell mesostructures but never within calcite prisms. Here, nanotwins and microwins within single calcite prisms are observed in different shells. Using Polarization‐dependent Imaging Contrast (PIC) mapping with 20–60 nm resolution, twins are observed to be 0.2–3 µm thick layers of differently oriented and colored crystals with respect to the main prism crystal. Multiple twins are interspersed with the prism crystal, parallel to one another, and similarly oriented. When comparing images of calcite prisms and twins obtained by PIC mapping and by Electron Back‐Scattered Diffraction (EBSD), the images correspond precisely. All twins are e‐twin types, with 127° angular distance between c‐axes. E‐twins are the most common deformation twins in geologic calcite, as also observed here in Carrara marble. Location of all twins near the outer surface of all shells and e‐twin type both suggest that twins within calcite prisms in mollusk shells result from deformation twinning. [ABSTRACT FROM AUTHOR]

Chamid bivalves are marine organisms that live in high-energy environments and are cemented to hard substrates. To avoid shell damage, the organisms form thick, densely ornamented shells. Shell material consists of aragonite, and the ornamentation may be either aragonitic or calcitic. The latter can be developed as scaly spines, rows of blades, or comarginal, radial arched lamellae. We investigated biological crystal morphology and mode of assembly of Chama arcana and Chama gryphoides shells. Structural characteristics were obtained from electron backscatter diffraction (EBSD) measurements, complemented with laser confocal and BSE imaging. We found a wide range of crystal morphologies and sizes, ranging from irregularly shaped calcite and/or aragonite prisms to tiny and thin aragonite laths. We observed four different modes of crystal assembly patterns: 1. strongly interlocked dendritic calcite units forming the ornamentation blades; 2. aragonite laths arranged to lamellae forming the outer shell layer, the layer adjacent to the calcite; 3. aragonite laths arranged into blocks comprising inner shell layers or aragonitic ornamentations; and 4. shell portions consisting of aragonite prisms, structured in size and crystal orientation, at muscle attachment sites. These four different types of crystal arrangements were observed for the shells of the investigated chamid species; however, they had slightly different strengths of structuring and slight variations in crystal organisation. Additionally, we observed unique microstructural features in Chama shells: We report ornamentation crystals resembling idiomorphic calcite and novel, twinned entities found at the changeover between the aragonitic layers. We highlight and discuss these differences and anomalies in this contribution. [ABSTRACT FROM AUTHOR]

Inspired by nature's remarkable ability to form intricate minerals, researchers have unlocked transformative strategies for creating next-generation biosensors with exceptional sensitivity, selectivity, and biocompatibility. By mimicking how organisms orchestrate mineral growth, biomimetic and bioinspired materials are significantly impacting biosensor design. Engineered bioinspired materials offer distinct advantages over their natural counterparts, boasting superior tunability, precise controllability, and the ability to integrate specific functionalities for enhanced sensing capabilities. This remarkable versatility enables the construction of various biosensing platforms, including optical sensors, electrochemical sensors, magnetic biosensors, and nucleic acid detection platforms, for diverse applications. Additionally, bioinspired materials facilitate the development of smartphone-assisted biosensing platforms, offering user-friendly and portable diagnostic tools for point-of-care applications. This review comprehensively explores the utilization of naturally occurring and engineered biominerals and materials for diverse biosensing applications. We highlight the fabrication and design strategies that tailor their functionalities to address specific biosensing needs. This in-depth exploration underscores the transformative potential of biominerals and materials in revolutionizing biosensing, paving the way for advancements in healthcare, environmental monitoring, and other critical fields. [ABSTRACT FROM AUTHOR]

Mineral plastics are a promising class of bio‐inspired materials that offer exceptional properties, like self‐heal ability, stretchability in the hydrogel state, and high hardness, toughness, transparency, and non‐flammability in the dry state along with reversible transformation into the hydrogel by addition of water. This enables easy reshape‐ability and recycling like the solubility in mild acids to subsequently form mineral plastics again by base addition. However, current mineral plastics rely on petrochemistry, are hardly biodegradable, and thus persistent in nature. This work presents the next generation of mineral plastics, which are bio‐based and biodegradable, making them a promising, new class of polymers for the development of environmentally friendly materials. Physically cross‐linked (poly)glutamic‐acid (PGlu)‐based mineral plastics are synthesized using various alcohol‐water mixtures, metal ion ratios and molecular weights. The rheological properties are easily adjusted using these parameters. The general procedure involves addition of equimolar solution of CaCl2 to PGlu in equal volumes followed by addition of iPrOH (iPrOH:H2O = 1:1) under vigorous stirring conditions. The ready biodegradability of PGlu/CaFe mineral plastic is confirmed in this study where the elements N, Ca, and Fe present in it tend to act as additional nutrients, supporting the growth of microorganisms and consequently, promoting the biodegradation process. [ABSTRACT FROM AUTHOR]

(1) Background: This study provides novel insights into the elemental content and biomineralization processes of two halophytic species of the genus Arthrocnemum Moq. (A. macrostachyum and A. meridionale). (2) Methods: Elemental content was analyzed using ICP-MS, while biominerals were detected through electron microscopy (SEM and TEM) and X-ray diffraction. (3) Results: The elemental content showed significant concentrations of macronutrients (sodium, potassium, magnesium, and calcium) and micronutrients, especially iron. Iron was consistently found as ferritin in A. macrostachyum chloroplasts. Notably, A. macrostachyum populations from the Center of the Iberian Peninsula exhibited exceptionally high magnesium content, with values that exceeded 40,000 mg/kg d.w. Succulent stems showed elemental content consistent with the minerals identified through X-ray diffraction analysis (halite, sylvite, natroxalate, and glushinskite). Seed analysis revealed elevated levels of macro- and micronutrients and the absence of heavy metals. Additionally, the presence of reduced sodium chloride crystals in the seed edges suggested a mechanism to mitigate potential sodium toxicity. (4) Conclusions: These findings highlight the potential of Arthrocnemum species as emerging edible halophytes with nutritional properties, particularly in Western European Mediterranean territories and North Africa. They offer promising prospects for biosaline agriculture and biotechnology applications. [ABSTRACT FROM AUTHOR]

mRNA therapeutics can be readily designed, manufactured, and brought to scale, as demonstrated by widespread global vaccination against COVID-19. However, mRNA therapies require cold chain shipment and storage from manufacturing to administration, which may limit them to affluent communities. This problem could be addressed by mimicking the known ability of mineralized fossils to durably stabilize nucleic acids under extreme conditions. We synthesized and screened 40 calcium-phosphate minerals for their ability to store and maintain the activity of lyophilized mRNA complexes. The optimal mineral formulation incorporated mRNA complexes with high efficiency (77 %), and increased mRNA transfection efficiency by 5.6-fold. Lyophilized mRNA complexes stored with the optimized mineral formulation for 6 months at 25 °C were 3.2-fold more active than those stored with state-of-the-art excipients, but without a mineral. mRNA complexes stored with minerals at room temperature did not decline in transfection efficacy from 3 days to 6 months of storage, indicating that minerals can durably maintain activity of therapeutic mRNA complexes without cold chain storage. Therapeutic mRNA, such as mRNA COVID-19 vaccines, require extensive cold chain storage that limits their general application. This work screened a library of minerals to maintain the activity of mRNA complexes with freeze-drying. The optimized mineral was able to maintain mRNA activity up to 6 months of storage at room temperature outperforming current methods of freeze-drying therapeutic mRNA complexes. [Display omitted] [ABSTRACT FROM AUTHOR]

Chamid bivalves are marine organisms that live in high-energy environments and are cemented to hard substrates. To avoid shell damage, the organisms form thick, densely ornamented shells. Shell material consists of aragonite, and the ornamentation may be either aragonitic or calcitic. The latter can be developed as scaly spines, rows of blades, or comarginal, radial arched lamellae. We investigated biological crystal morphology and mode of assembly of Chama arcana and Chama gryphoides shells. Structural characteristics were obtained from electron backscatter diffraction (EBSD) measurements, complemented with laser confocal and BSE imaging. We found a wide range of crystal morphologies and sizes, ranging from irregularly shaped calcite and/or aragonite prisms to tiny and thin aragonite laths. We observed four different modes of crystal assembly patterns: 1. strongly interlocked dendritic calcite units forming the ornamentation blades; 2. aragonite laths arranged to lamellae forming the outer shell layer, the layer adjacent to the calcite; 3. aragonite laths arranged into blocks comprising inner shell layers or aragonitic ornamentations; and 4. shell portions consisting of aragonite prisms, structured in size and crystal orientation, at muscle attachment sites. These four different types of crystal arrangements were observed for the shells of the investigated chamid species; however, they had slightly different strengths of structuring and slight variations in crystal organisation. Additionally, we observed unique microstructural features in Chama shells: We report ornamentation crystals resembling idiomorphic calcite and novel, twinned entities found at the changeover between the aragonitic layers. We highlight and discuss these differences and anomalies in this contribution.

The study of well-preserved organic matter (OM) within mineral concretions has provided key insights into depositional and environmental conditions in deep time. Concretions of varied compositions, including carbonate, phosphate, and iron-based minerals, have been found to host exceptionally preserved fossils. Organic geochemical characterization of concretion-encapsulated OM promises valuable new information of fossil preservation, paleoenvironments, and even direct taxonomic information to further illuminate the evolutionary dynamics of our planet and its biota. Full exploitation of this largely untapped geochemical archive, however, requires a sophisticated understanding of the prevalence, formation controls and OM sequestration properties of mineral concretions. Past research has led to the proposal of different models of concretion formation and OM preservation. Nevertheless, the formation mechanisms and controls on OM preservation in concretions remain poorly understood. Here we provide a detailed review of the main types of concretions and formation pathways with a focus on the role of microbes and their metabolic activities. In addition, we provide a comprehensive account of organic geochemical, and complimentary inorganic geochemical, morphological, microbial and paleontological, analytical methods, including recent advancements, relevant to the characterization of concretions and sequestered OM. The application and outcome of several early organic geochemical studies of concretion-impregnated OM are included to demonstrate how this underexploited geo-biological record can provide new insights into the Earth's evolutionary record. This paper also attempts to shed light on the current status of this research and major challenges that lie ahead in the further application of geo-paleo-microbial and organic geochemical research of concretions and their host fossils. Recent efforts to bridge the knowledge and communication gaps in this multidisciplinary research area are also discussed, with particular emphasis on research with significance for interpreting the molecular record in extraordinarily preserved fossils. [ABSTRACT FROM AUTHOR]

Inspired by nature’s remarkable ability to form intricate minerals, researchers have unlocked transformative strategies for creating next-generation biosensors with exceptional sensitivity, selectivity, and biocompatibility. By mimicking how organisms orchestrate mineral growth, biomimetic and bioinspired materials are significantly impacting biosensor design. Engineered bioinspired materials offer distinct advantages over their natural counterparts, boasting superior tunability, precise controllability, and the ability to integrate specific functionalities for enhanced sensing capabilities. This remarkable versatility enables the construction of various biosensing platforms, including optical sensors, electrochemical sensors, magnetic biosensors, and nucleic acid detection platforms, for diverse applications. Additionally, bioinspired materials facilitate the development of smartphone-assisted biosensing platforms, offering user-friendly and portable diagnostic tools for point-of-care applications. This review comprehensively explores the utilization of naturally occurring and engineered biominerals and materials for diverse biosensing applications. We highlight the fabrication and design strategies that tailor their functionalities to address specific biosensing needs. This in-depth exploration underscores the transformative potential of biominerals and materials in revolutionizing biosensing, paving the way for advancements in healthcare, environmental monitoring, and other critical fields.

We here report the development of new thermotropic colloidal liquid‐crystalline (LC) organic/inorganic hybrids consisting of a hydroxyapatite (HAp)/poly(acrylic acid) (PAA) nanorod and a dendritic forklike mesogen. Complexation of the HAp/PAA nanorod covered with negatively charged PAA and a cationic forklike mesogen through electrostatic interactions and cation metathesis results in the surface modification of the HAp/PAA nanorod with the forklike mesogen. While the HAp/PAA nanorod forms a lyotropic colloidal LC phase in the aqueous dispersion, the HAp/PAA nanorod modified with the forklike mesogen exhibits thermotropic colloidal LC phases in the solvent‐free states. The biomineral‐based organic/inorganic colloidal liquid crystals exhibiting thermotropic LC properties have potential for the development of new stimuli‐responsive sustainable materials. [ABSTRACT FROM AUTHOR]

[Display omitted] The wettability of carbonate rocks is expected to be affected by the organic components of biominerals which are complex, nanostructured organo-mineral assemblages. Elucidating the nanoscale mechanisms driving the wettability of solid surfaces will enable a better understanding of the role of biominerals in the wetting properties of carbonate rocks to control various geological, environmental and industrial processes. Using Atomic Force Microscopy and Spectroscopy (AFM/AFS) we probed the wettability properties of carbonate rocks with different amounts of organic material. The adhesion properties of two types of limestones were determined in liquid environments at different length scales (nm to mm) using functionalized tips with different chemical groups to determine the extent of surface hydrophobic and hydrophilic organo-mineral interactions. We observed homogeneous hydrophobic areas at length scales below < 5 µm. The origin of this hydrophobicity is linked to the presence of organics, whose amount and spatial distribution depend on the rock composition. Specifically, our results reveal that the biogenic vs non-biogenic origin of the mineral grains is the main rock property controlling the wettability of the solid surface. Overall, our methodology offers a multi-scale approach to unravel the role that organic moieties and biominerals play in controlling the wettability of rock-water interfaces. [ABSTRACT FROM AUTHOR]

Structural characterization of biologically formed materials is essential for understanding biological phenomena and their enviro-nment, and for generating new bio-inspired engineering concepts. For example, nacre-the inner lining of some mollusk shells-encodes local environmental conditions throughout its formation and has exceptional strength due to its nanoscale brick-and-mortar structure. This layered structure, comprising alternating transparent aragonite (CaCO3) tablets and thinner organic polymer layers, also results in stunning interference colors. Existing methods of structural characterization of nacre rely on some form of cross-sectional analysis, such as scanning or transmission electron microscopy or polarization-dependent imaging contrast (PIC) mapping. However, these techniques are destructive and too time- and resource-intensive to analyze large sample areas. Here, we present an all-optical, rapid, and nondestructive imaging technique-hyperspectral interference tomography (HIT)-to spatially map the structural parameters of nacre and other disordered layered materials. We combined hyperspectral imaging with optical-interference modeling to infer the mean tablet thickness and its disorder in nacre across entire mollusk shells from red and rainbow abalone (Haliotis rufescens and Haliotis iris) at various stages of development. We observed that in red abalone, unexpectedly, nacre tablet thickness decreases with age of the mollusk, despite roughly similar appearance of nacre at all ages and positions in the shell. Our rapid, inexpensive, and nondestructive method can be readily applied to in-field studies.

Biominerals such as seashells, coral skeletons, bone, and tooth enamel are optically anisotropic crystalline materials with unique nanoscale and microscale organization that translates into exceptional macroscopic mechanical properties, providing inspiration for engineering new and superior biomimetic structures. Using Seriatopora aculeata coral skeleton as a model, here, we experimentally demonstrate X-ray linear dichroic ptychography and map the c-axis orientations of the aragonite (CaCO3) crystals. Linear dichroic phase imaging at the oxygen K-edge energy shows strong polarization-dependent contrast and reveals the presence of both narrow (35°) c-axis angular spread in the coral samples. These X-ray ptychography results are corroborated by four-dimensional (4D) scanning transmission electron microscopy (STEM) on the same samples. Evidence of co-oriented, but disconnected, corallite subdomains indicates jagged crystal boundaries consistent with formation by amorphous nanoparticle attachment. We expect that the combination of X-ray linear dichroic ptychography and 4D STEM could be an important multimodal tool to study nano-crystallites, interfaces, nucleation, and mineral growth of optically anisotropic materials at multiple length scales.

(1) Background: This study provides novel insights into the elemental content and biomineralization processes of two halophytic species of the genus Arthrocnemum Moq. (A. macrostachyum and A. meridionale). (2) Methods: Elemental content was analyzed using ICP-MS, while biominerals were detected through electron microscopy (SEM and TEM) and X-ray diffraction. (3) Results: The elemental content showed significant concentrations of macronutrients (sodium, potassium, magnesium, and calcium) and micronutrients, especially iron. Iron was consistently found as ferritin in A. macrostachyum chloroplasts. Notably, A. macrostachyum populations from the Center of the Iberian Peninsula exhibited exceptionally high magnesium content, with values that exceeded 40,000 mg/kg d.w. Succulent stems showed elemental content consistent with the minerals identified through X-ray diffraction analysis (halite, sylvite, natroxalate, and glushinskite). Seed analysis revealed elevated levels of macro- and micronutrients and the absence of heavy metals. Additionally, the presence of reduced sodium chloride crystals in the seed edges suggested a mechanism to mitigate potential sodium toxicity. (4) Conclusions: These findings highlight the potential of Arthrocnemum species as emerging edible halophytes with nutritional properties, particularly in Western European Mediterranean territories and North Africa. They offer promising prospects for biosaline agriculture and biotechnology applications.

The environmental conditions that prevail on the surface of Mars (i.e., high levels of radiation and oxidants) are not favorable for the long-term preservation of organic compounds on which all strategies for finding life on Mars have been based to date. Since life commonly produces minerals that are considered more resilient, the search for biominerals could constitute a promising alternative approach. Carbonates are major biominerals on Earth, and although they have not been detected in large amounts at the martian surface, recent observations show that they could constitute a significant part of the inorganic component in the martian soil. Previous studies have shown that calcite and aragonite produced by eukaryotes thermally decompose at temperatures 15°C lower than those of their abiotic counterparts. By using carbonate concretions formed by microorganisms, we find that natural and experimental carbonates produced by prokaryotes decompose at 28°C below their abiotic counterparts. The study of this sample set serves as a proof of concept for the differential thermal analysis approach to distinguish abiotic from bio-related carbonates. This difference in carbonate decomposition temperature can be used as a first physical evidence of life on Mars to be searched by in situ space exploration missions with the resolution and the technical constraints of the available onboard instruments. [ABSTRACT FROM AUTHOR]

We have tested different preparation and photographic methods to define a protocol for UV analysis of fossil specimens. We also have explored its main applications while analysing specimens from different stratigraphic contexts, of different biomineralogical composition, and belonging to different fossil groups (including invertebrates and vertebrates). We have photographed specimens using a camera equipped with appropriate lens and filters both in visible light and with flashlights at two wavelengths: the 365 nm UV light and the 440 nm visible violet spectrum, the latter here tested for the first time. Our results indicate that bleach treatment is not recommended for calcite-shelled brachiopods, while it is suggested for aragonite-shelled molluscs. We show that photography in the ultraviolet and visible violet spectra are useful tools enhancing the recognition of morphological characters and colour patterns and allowing to distinguish soft-bodied fossils from the matrix. Also, it allows to discern specimen areas embedded in the sediment from those exposed to sunlight, which is helpful to reconstruct the conditions experienced by fossils. However, the mineralogy of the biomineral affects UV responses, as morphological characters of calcite shells are better emphasized with the 440 nm wavelength (visible violet spectrum), whereas those of aragonite, bioapatite and phosphatized specimens with the 365 nm (ultraviolet spectrum); also, shell microstructures with their different crystal arrangement and elemental incorporation may cause different reactions, whereas the stratigraphic context affects specimen preservation influencing pigment preservation. We thus provide a protocol for photography in the ultraviolet and visible violet spectra and show that this technique has a high potential in palaeontology, having no limitations for its application in invertebrate or vertebrate specimens.

Biominerals are extraordinary materials that provide organisms with a variety of functions to support life. The synthesis of biominerals and organization at the macroscopic level is a consequence of the interactions of these materials with proteins. The association of biominerals and proteins is very ancient and has sparked a wealth of research across biological, medical and material sciences. Calcium carbonate, hydroxyapatite, and silica represent widespread natural biominerals. The atomic details of the interface between macromolecules and these biominerals is very intriguing from a chemical perspective, considering the association of chemical entities that are structurally different. With this review I provide an overview of the available structural studies of biomineralization proteins, explored from the Protein Data Bank (wwPDB) archive and scientific literature, and of how these studies are inspiring the design and engineering of proteins able to synthesize novel biominerals. The progression of this review from classical template proteins to silica polymerization seeks to benefit researchers involved in various interdisciplinary aspects of a biomineralization project, who need background information and a quick update on advances in the field. Lessons learned from structural studies are exemplary and will guide new projects for the imaging of new hybrid biomineral/protein superstructures at the atomic level.

Simple Summary: Honey bees deliver many valuable products and pollinate many crucial crops, and pesticides impair honey bee health in many ways. It is a serious problem of the contemporary agroecosystem, but the mechanisms of these phenomena have not been sufficiently explored. Therefore, we investigated the impact of the imidacloprid pesticide (IMD) on the bioelement body content in honey bees in field experiments using both sublethal considered field-relevant (5 ppb), and adverse (200 ppb) doses, which has not been studied before. Our findings revealed for the first time that IMD causes unexpectedly severe bioelement deficiencies in 69% of bioelements (32 assayed) and disturbs the balance between the levels of the remaining ones even at sublethal doses. The increase in three toxic bioelements was alarming. Consequently, we have suggested a new physiological mechanism regarding how nicotinoids may interfere with honey bee health status. This also sets out new directions for further research, pointing to the bioelement supplementation of the diet as an important element of honey bee preventive health care when the bee farms or amateur apiaries are located in an agrocenosis exposed to pesticides. Pesticides impair honeybee health in many ways. Imidacloprid (IMD) is a pesticide used worldwide. No information exists on how IMD impact the bees' body bioelement balance, which is essential for bee health. We hypothesized that IMD disturbs this balance and fed the bees (in field conditions) with diets containing 0 ppb (control), 5 ppb (sublethal considered field-relevant), and 200 ppb (adverse) doses of IMD. IMD severely reduced the levels of K, Na, Ca, and Mg (electrolytic) and of Fe, Mo, Mn, Co, Cu, Ni, Se, and Zn, while those of Sn, V, and Cr (enzymatic) were increased. Levels of P, S, Ti, Al, Li, and Sr were also decreased, while only the B content (physiologically essential) was increased. The increase in Tl, Pb, and As levels (toxic) was alarming. Generally, IMD, even in sublethal doses, unexpectedly led to severe bioelement malnutrition in 69% of bioelements and to a stoichiometric mismatch in the remaining ones. This points to the IMD-dependent bioelement disturbance as another, yet unaccounted for, essential metabolic element which can interfere with apian health. Consequently, there is a need for developing methods of bioelement supplementation of the honey bee diet for better preventing bee colony decline and protecting apian health status when faced with pesticides. [ABSTRACT FROM AUTHOR]

Identifying the source of seafood is critical for combatting seafood fraud, but current tools are predominantly developed and applied on a species‐specific basis. This study investigates how multiple marine taxa could be geolocated at global scales by exploiting stable oxygen isotope compositions in carbonate biominerals (δ18Obiomin), where we expect to see universally expressed and predictable spatial variation in δ18Obiomin values across taxa. We constructed global ocean isoscapes of predicted δ18Obiomin values specific to fish (otoliths), cephalopod (statoliths) and shellfish (shells), and a fourth combined "universal" isoscape, and evaluated their capacity to derive δ18Obiomin values among known‐origin samples. High correspondence between isoscape‐predicted δ18Obiomin values and a compiled database of measured, georeferenced values (3954 datapoints encompassing 68 species) indicated that this δ18Obiomin approach works effectively, particularly in regions with highly resolved projections of seawater δ18O composition. When compared to taxon‐specific isoscapes, the universal isoscape demonstrated similar accuracy, indicating exciting potential for universal provenance applications. We tested the universal framework via a case study, using machine‐learning models to identify sample origins amongst regions of divergent (Tropical Asia vs Temperate Australasia) and similar (Temperate Asia vs Temperate Australasia) climates and latitudes. Classification accuracy averaged 75.3% between divergent regions, and 66% between similar regions. When endothermic tuna species were excluded from the analysis, the accuracy between divergent regions increased up to 90% between divergent regions. This study presents the first empirical step towards developing universal chemical markers, which have the potential to support a more inclusive and global approach of validating provenance of seafood. [ABSTRACT FROM AUTHOR]

Microplastics (MPs) pose risks to both aquatic ecosystems and human health. This study investigated MPs in the shells and soft tissues of hard clams (Meretrix taiwanica) cultured in the inland waters of Taiwan. This study further developed two novel risk indices for assessing the potential ecological and health consequences of MPs. Moreover, the metal concentrations in the clam's soft tissues and the associated consumption health risks were investigated. Clamshells contained significant amounts of MPs with an average abundance of 16.6 ± 6.9 MPs/ind., which was higher than in the soft tissues (2.7 ± 1.7 MPs/ind.). The distribution and sizes of MPs in shells and soft tissues were similar, primarily small-sized (<2 mm, >99 %), blue (>65 %), and fibrous (>99 %). Dominant MP polymer types included rayon (83.5 %), polyethylene terephthalate (11.8 %), and polyacrylonitrile (3.6 %). The proposed MP potential ecological risk index indicates a higher potential ecological MP risk in soft tissues (302−423) than in shells (270−278) of the clams. The MP potential hazard risk index showed that the risk of exposure to MP through shellfish consumption decreased with age. The total hazard index (THI) value suggested negligible health hazards from metal exposure through shellfish consumption. Moreover, there was no significant correlation between MPs and metal concentrations in soft tissues, suggesting that metals bound to MPs contribute minimally to the total accumulated metals in clam's soft tissues. This study confirms the presence of MPs in clam shells and provides a novel tool to assess the potential ecological and health risks associated with MPs in shellfish. [Display omitted] • Abundance of microplastics (MPs) in clamshells is greater than in soft tissues. • The majority of MPs in clams are small-sized fibrous rayon and PET polymers. • The potential ecological and health risk indices of shellfish MPs are proposed. • Exposure to metals from eating shellfish should not cause adverse health effects. • Shellfish consumption poses greater health risks to toddler than older consumers. [ABSTRACT FROM AUTHOR]

Biominerals are extraordinary materials that provide organisms with a variety of functions to support life. The synthesis of biominerals and organization at the macroscopic level is a consequence of the interactions of these materials with proteins. The association of biominerals and proteins is very ancient and has sparked a wealth of research across biological, medical and material sciences. Calcium carbonate, hydroxyapatite, and silica represent widespread natural biominerals. The atomic details of the interface between macromolecules and these biominerals is very intriguing from a chemical perspective, considering the association of chemical entities that are structurally different. With this review I provide an overview of the available structural studies of biomineralization proteins, explored from the Protein Data Bank (wwPDB) archive and scientific literature, and of how these studies are inspiring the design and engineering of proteins able to synthesize novel biominerals. The progression of this review from classical template proteins to silica polymerization seeks to benefit researchers involved in various interdisciplinary aspects of a biomineralization project, who need background information and a quick update on advances in the field. Lessons learned from structural studies are exemplary and will guide new projects for the imaging of new hybrid biomineral/protein superstructures at the atomic level. [ABSTRACT FROM AUTHOR]

The diagnosis and treatment of triple‐negative breast cancer (TNBC) is still a grand challenge, because there is rare target to be manipulated. Here, an integrated functional nanoprobe is developed for precise diagnosis and treatment of TNBC, based on biominerals of Fe3+ and rutin hydrate (RH), a type of natural flavonoid. Owing to the adjacent phenol hydroxyl groups of RH, Fe3+ can biomineralize with RH to form nanoprobe colloidally stabilized by coating of poly(vinyl pyrrolidone) (PVP). In the nanoprobe, the flavonol central scaffold as well as the glucoside and rhamnose groups can interact specifically with glucose transporters. Once taken by tumor cells, protonation of phenol hydroxyl groups in the weakly acidic lysosomes would lead to release of Fe3+, inducing tumor cell death through a ferroptosis/apoptosis hybrid pathway. Meanwhile, the remaining Fe(III)–RH complex can serve as a photothermal therapy (PTT) agent upon near infrared laser irradiation. Additionally, the Fe(III)–RH/PVP nanoprobe is expected to be eliminated through renal clearance if the nanoprobe formed in the presence of PVP have an appropriately small hydrated diameter. The present work provides a novel design integrated with magnetic resonance imaging capacity, therapeutic functions of Fe3+, and the PTT effect of nanoprobe for TNBC with anticipated biosafety. [ABSTRACT FROM AUTHOR]

It is assumed that genetic diseases affecting the metabolism of cysteine and the kidney function lead to two different kinds of pathologies, namely cystinuria and cystinosis whereby generate l-cystine crystals. Recently, the presence of l-cysteine crystal has been underlined in the case of cystinosis. Interestingly, it can be strikingly seen that cystine ([–S–CH2–CH–(NH2)–COOH]2) consists of two cysteine (C3H7NO2S) molecules connected by a disulfide (S–S) bond. Therefore, the study of cystine and cysteine is important for providing a better understanding of cystinuria and cystinosis. In this paper, we elucidate the discrepancy between l-cystine and l-cysteine by investigating the theoretical and experimental infrared spectra (IR), X-ray diffraction (XRD) as well as Raman spectra aiming to obtain a better characterization of abnormal deposits related to these two genetic pathologies. [ABSTRACT FROM AUTHOR]

We have tested different preparation and photographic methods to define a protocol for UV analysis of fossil specimens. We also have explored its main applications while analysing specimens from different stratigraphic contexts, of different biomineralogical composition, and belonging to different fossil groups (including invertebrates and vertebrates). We have photographed specimens using a camera equipped with appropriate lens and filters both in visible light and with flashlights at two wavelengths: the 365 nm UV light and the 440 nm visible violet spectrum, the latter here tested for the first time. Our results indicate that bleach treatment is not recommended for calcite-shelled brachiopods, while it is suggested for aragonite-shelled molluscs. We show that photography in the ultraviolet and visible violet spectra are useful tools enhancing the recognition of morphological characters and colour patterns and allowing to distinguish soft-bodied fossils from the matrix. Also, it allows to discern specimen areas embedded in the sediment from those exposed to sunlight, which is helpful to reconstruct the conditions experienced by fossils. However, the mineralogy of the biomineral affects UV responses, as morphological characters of calcite shells are better emphasized with the 440 nm wavelength (visible violet spectrum), whereas those of aragonite, bioapatite and phosphatized specimens with the 365 nm (ultraviolet spectrum); also, shell microstructures with their different crystal arrangement and elemental incorporation may cause different reactions, whereas the stratigraphic context affects specimen preservation influencing pigment preservation. We thus provide a protocol for photography in the ultraviolet and visible violet spectra and show that this technique has a high potential in palaeontology, having no limitations for its application in invertebrate or vertebrate specimens. [ABSTRACT FROM AUTHOR]

Mineral hydrogels have caught a lot of attention for their strong competency as artificial skin-like materials. Nonetheless, it remains a great difficulty in fulfilling in one hydrogel system a range of key functionalities that are needed for practical artificial skin applications, i.e., to be biocompatible, strain-sensitive, ion-conductive, elastic and robust, anti-swelling, and anti-freezing. Here we present a such type of versatile hydrogel that is not only capable to deliver all the above-mentioned key functionalities but also highly stable. This novel hydrogel is constructed by introducing a gelatinous and amorphous multi-ionic biomineral (denoted as Mg-ACCP, containing Mg2+, Ca2+, CO32−, and PO43−) into the network of biocompatible polyvinyl alcohol (PVA) and sodium alginate (SA). The presence of Mg2+ and PO43− in this hydrogel helps prohibit the crystallization of the biominerals, leading to significantly improved stability. The hydrogel thus obtained delivers excellent mechanical performance due to the chelation between the mineral ions and the organic matrix, and high sensitivity even to subtle pressure and strain applied, such as slight finger bending and gentle tapping. Furthermore, the novel hydrogel features high ionic conductivity, high resistance to swelling, and extraordinary anti-freezing property, holding great promise for applications in different practical scenarios, particularly in aqueous or cold environments. [ABSTRACT FROM AUTHOR]

Certain biominerals, such as sea sponges and echinoderm skeletons, display a fascinating combination of mechanical properties and adaptability due to the well-defined structures spanning various length scales. These materials often possess high density normalized mechanical properties because they contain well-defined pores. The density-normalized mechanical properties of synthetic minerals are often inferior because the pores are stochastically distributed, resulting in an inhomogeneous stress distribution. The mechanical properties of synthetic materials are limited by the degree of structural and compositional control currently available fabrication methods offer. In the first part of this review, examples of structural elements nature uses to impart exceptional density normalized Young's moduli to its porous biominerals are showcased. The second part highlights recent advancements in the fabrication of bio-informed mineral-based composites possessing pores with diameters that span a wide range of length scales. The influence of the processing of mineral-based composites on their structures and mechanical properties is summarized. Thereby, it is aimed at encouraging further research directed to the sustainable, energy-efficient fabrication of synthetic lightweight yet stiff mineral-based composites., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Vertical distributions of biogenic silica (bSi), particulate inorganic carbon (PIC) and key biomineral-forming phytoplankton indicate vertical zoning, or partitioning, during the late summer stratified period in the northeast Atlantic. Coccolithophores were generally more numerous in the surface mixed layer, whilst PIC concentrations were more homogenous with depth throughout the euphotic zone. Diatoms were notably more abundant and more diverse in the lower euphotic zone beneath the mixed layer in association with subsurface maxima in chlorophyll-a, bSi and oxygen concentrations. The four dominant coccolithophore species (Emiliania huxleyi, Gephyrocapsa muellerae, Syracosphera spp., and Rhabdosphaera clavigera) represented 78 ± 20% (range 31–100%) of the observed community across all sampled depths yet simultaneously contributed an average of only 13% to measured PIC pools. The diatom community, which was dominated by Pseudo-nitzschia spp. and by a species tentatively identified as Nanoneis longta, represented only ~1% of the bSi pool on average, with contributions increasing within the chlorophyll maximum. Despite a slow gradual deepening of the surface mixed layer in the period prior to observation, and adequate nutrient availability beneath the mixed layer, biomineral pools at this time consisted largely of detrital rather than cellular material.

Tissue engineering is one of the most effective ways to treat bone defects in recent years. However, current highly active bone tissue engineering (BTE) scaffolds are mainly based on the addition of active biological components (such as growth factors) to promote bone repair. High cost, easy inactivation and complex regulatory requirements greatly limit their practical applications. In addition, conventional fabrication methods make it difficult to meet the needs of personalized customization for the macroscopic and internal structure of tissue engineering scaffolds. Herein, this paper proposes to select five natural biominerals (eggshell, pearl, turtle shell, degelatinated deer antler and cuttlebone) with widely available sources, low price and potential osteo-inductive activity as functional particles. Subsequently compounding them into L-polylactic acid (PLLA) biomaterial ink to further explore 3D printing processes of the composite scaffold, and reveal their potential as biomimetic 3D scaffolds for bone tissue repair. The research results of this project provide a new idea for the construction of a 3D scaffold with growth-factor-free biomimetic structure, personalized customization ability and osteo-inductive activity. [ABSTRACT FROM AUTHOR]

Biomineralized composites, which are usually composed of microscopic mineral building blocks organized in 3D intercrystalline organic matrices, have evolved unique structural designs to fulfill mechanical and other biological functionalities. While it has been well recognized that the intricate architectural designs of biomineralized composites contribute to their remarkable mechanical performance, the structural features within and corresponding mechanical properties of individual mineral building blocks are often less appreciated in the context of bio-inspired structural composites. The mineral building blocks in biomineralized composites exhibit a variety of salient intracrystalline structural features, such as, organic inclusions, inorganic impurities (or trace elements), crystalline features (e.g., amorphous phases, single crystals, splitting crystals, polycrystals, and nanograins), residual stress/strain, and twinning, which significantly modify the mechanical properties of biogenic minerals. In this review, recent progress in elucidating the intracrystalline structural features of three most common biomineral systems (calcite, aragonite, and hydroxyapatite) and their corresponding mechanical significance are discussed. Future research directions and corresponding challenges are proposed and discussed, such as the advanced structural characterizations and formation mechanisms of intracrystalline structures in biominerals, amorphous biominerals, and bio-inspired synthesis. [ABSTRACT FROM AUTHOR]

Taking silica as an exemplary material system, we studied water‐assisted densification behaviors of different crystallinities (quartz, glass, and vitreous silica). To avoid the complexity in data interpretation, we adopted a simple procedure similar to those used for pressing salt pellets for IR: compressing silica powders in a mold with pure water under ambient conditions. It is discovered that crystalline silica is compacted through liquid lubrication, while amorphous silica's densification behaviors contradict the widely regarded dissolution‐reprecipitation mechanism. Another mechanism is thus proposed: stress‐driven water incorporation into the solid structures produces hydrated silica of considerable plasticity for deformation and fusion. Inspired by this water‐assisted mechanism, a more effective sintering method is developed via repetitive stressing/destressing treatments at room temperature, enabling dramatically boosted densities (e.g., over 90% with transparent appearance for silica glass) and enhanced mechanical performance. This generic strategy may apply to a wide range of materials. Furthermore, the hydration‐enabled deformation/sintering mechanism proposed in this work offers fresh insights into the biomineralization puzzles, particularly those on how life accomplishes some of the most challenging tasks faced by humans in modern ceramic technology, for example, to fuse, mend or reshape the rigid brittle ceramic objects in aqueous environments under ambient conditions. This purely inorganic biomineralization mechanism may be particularly important for life at its early stage of evolution on earth. [ABSTRACT FROM AUTHOR]

Pesticides impair honeybee health in many ways. Imidacloprid (IMD) is a pesticide used worldwide. No information exists on how IMD impact the bees’ body bioelement balance, which is essential for bee health. We hypothesized that IMD disturbs this balance and fed the bees (in field conditions) with diets containing 0 ppb (control), 5 ppb (sublethal considered field-relevant), and 200 ppb (adverse) doses of IMD. IMD severely reduced the levels of K, Na, Ca, and Mg (electrolytic) and of Fe, Mo, Mn, Co, Cu, Ni, Se, and Zn, while those of Sn, V, and Cr (enzymatic) were increased. Levels of P, S, Ti, Al, Li, and Sr were also decreased, while only the B content (physiologically essential) was increased. The increase in Tl, Pb, and As levels (toxic) was alarming. Generally, IMD, even in sublethal doses, unexpectedly led to severe bioelement malnutrition in 69% of bioelements and to a stoichiometric mismatch in the remaining ones. This points to the IMD-dependent bioelement disturbance as another, yet unaccounted for, essential metabolic element which can interfere with apian health. Consequently, there is a need for developing methods of bioelement supplementation of the honey bee diet for better preventing bee colony decline and protecting apian health status when faced with pesticides.

A modern lithifying biofilm, associated with fluvial calcareous tufa in southern Italy, is composed of a complex community of micro‐organisms including autotrophic and heterotrophic bacteria, together with likely viruses (bacteriophages) and bacterial vesicles. Produced by most of the bacterial forms, extracellular polymeric substances are widespread and are the main sites of mineral precipitation, rather than the microbial cells themselves, but viruses and vesicles also appear to be mineralized. Neoformed biominerals replace these organic substrates starting with an amorphous phase rich in Ca, Si and several other cations followed by two different types of proto‐crystal: a granular−irregular Ca‐rich type and a lamellar/fibrous Si‐Al‐Mg‐rich type. Their growth leads to the formation of Ca‐carbonate and Mg‐silicate crystals that preserve their initial different habits. The coeval precipitation of silicate and carbonate at the initial stage of bio‐mediated mineral formation is a process common within freshwater and saline to hypersaline‐water calcareous microbialites. This is most probably related to the initial formation of poorly‐crystallized Mg‐Si phases that precipitate within the extracellular polymeric substances, related to the rise of pH in the zone of active oxygenic photosynthesis, and the mineralization of viruses, associated with the successive nucleation of Ca‐carbonate in close proximity to bacterial degradation of organic matter. [ABSTRACT FROM AUTHOR]

Refractory bone fracture, which is difficult to be treated, is a common clinical disease. Taking inspiration from the natural process of bone regeneration, we provide a biomimetic strategy to develop a new injectable biomaterial for repairing bone defects, which is mainly composed of platelets, fibrins, and biominerals. Biomineral nanoparticles (EACPNs) with an amorphous phase are prepared by an enzyme-catalyzed route and display a platelet-activating property. The composite hydrogel (EPH) of EACPNs, fibrins, and platelets is injectable, and has similar chemical properties to natural materials in bone regeneration. The dried EPH samples display a highly porous structure, which would be favorable for cell attachment and growth. The results from in vitro studies indicate that EPH has high biocompatibility and superior bioactivity in promoting the osteogenic differentiation of rat bone marrow stem cells (rBMSCs). Furthermore, the results from in vivo studies clearly indicate that EPH can induce the formation of new collagen and vessels in the defect area, thus leading to faster regeneration of bone defects at 2 weeks. Our study provides a strategy for designing new biomimetic materials, which may be favorable in the treatment of refractory bone fracture.

The leaves of two ethnotaxa of Agave karwinskii Zucc., ‘Cuishe’ and ‘Madrecuishe’, were analyzed using field emission scanning electron microscopy (FE-SEM) with energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) to characterize their occurring biominerals. The sharp and high peak at 2θ 21.4° in the XRD patterns and the prominent bands’ envelopes related to aluminosilicates in the FTIR spectra showed the occurrence of chantalite in the leaves of both ethnotaxa. For the first time, chantalite is reported as a biomineral occurring naturally in Agave plants. The FE-SEM/EDX results revealed needle-shaped calcium oxalate profusely dispersed near the upper epidermis, in addition to uncovering the presence of calcium carbonate and silica in particles of irregular shape. Intriguingly, the occurrence of both minerals in Agave plants has not been reported either, suggesting complex biomineralization patterns in Agave karwinskii. It is proposed that calcium carbonate in the leaves of Agave is formed by the reaction of chantalite with CO2.

In this study, mineralization during brick preparation was performed with ureolytic bacterium, Lysinibacillus fusiformis that use urine as a substrate, omitting the heat that is normally required. Artificial urine for reasons of standardization was used to grow the bacterium for bio‐bricks made of clay and cement, but their mineralization was enabled by biological activity instead of by heat. Scanning electron microscopy and energy dispersion X‐ray spectroscopy were conducted to analyse the microstructures formed by L. fusiformis that precipitated various minerals in synthetic urine. The brick specimens were tested for compressive strength that was 59% more than control ones, whereas porosity of bio‐bricks was 13% compared to 22% of control specimens. The minerals formed in the bio‐bricks confirmed as struvite, apatite and calcite by Fourier‐transform infrared spectroscopy and X‐ray diffraction spectra, were responsible for improved strength and reduced porosity. The research provided evidence in utilizing ureolytic bacteria as a mode to mineralize clay in brick production with the use of (artificial) urine as a substrate. [ABSTRACT FROM AUTHOR]

Herbal teas are a popular beverage and are used as therapeutic vehicles in many forms of traditional medicine. As tea is a popular drink and its preparation is remarkably simple (pour hot water on various dry herbs), it is very important to monitor and develop a screening methodology for detecting metals content in herbal tea. The number of articles exploring the efficacy and clinical safety of teas and herbal teas is small, even though herbal materials are the basis of the discovery of medicines and teas are some of the most popular drinks. This research was aimed to estimate the distribution of some bioelements in different types of herbal teas used in diet therapy. We used atomic absorption spectrometry in order to determine the concentration of Ca, Mg (macroelements), Mn, Fe, Zn and Cu (trance elements) in various indigenous herbal teas. In our work we collected herbal teas from county Gorj. These herbals are chamomile (Matricaria chamomilla), peppermint (Mentha piperita), marigold (Calendula officinalis), yarrow (Achillea millefolium), and Plantain (Plantago lanceolata). Preliminary results of this study reveal an uneven distribution of the concentrations of these bioelements. Bioelements distribution in analysed herbal teas presents generally, the following trend: Ca > Mg > Fe > Mn > Zn > Cu. The study aimed at the determination of the mineral composition of medicinal herbs for evaluation of the coverage of the recommended daily intake of mineral elements by tea. The concentration of these bioelements in herbal teas shows significant variations determined by the nature and type of herbal tea and bio-elements investigated. [ABSTRACT FROM AUTHOR]

Herbal teas are a popular beverage, that can be prepared very easily (by pouring hot water on various dried herbs). It is very important to monitor and develop a screening methodology for detecting the metal content of both tea plants and herbal tea. This research aimed to estimate the distribution of metals in different types of herbal teas used in diet therapy. We used atomic absorption spectrometry to determine the concentration trance elements (Fe, Mn, Zn and Cu) of macroelements (Ca and Mg), in various native herbal teas. We used herbal teas collected from Gorj County. These plants are Tilia cordata, Hypericum perforatum, Ocimum basilicum, and Rosa canina. The study aimed at the determination of the mineral composition of medicinal herbs for evaluation of the coverage of the recommended daily intake of mineral elements by tea. The concentration of these bio-minerals in medicinal herbs shows significant variations determined by the nature and type of herbal tea and bio-elements investigated. [ABSTRACT FROM AUTHOR]

Photonic crystals, characterized by their periodic structures, have been extensively studied for their ability to manipulate light. Typically, the development of 2D photonic crystals requires either sophisticated equipment or precise orientation of spherical nanoparticles. However, liquid-crystalline (LC) materials offer a promising alternative, facilitating the formation of periodic structures without the need for complex manipulation. Despite this advantage, the development of 2D photonic periodic structures using LC materials is limited to a few colloidal nanodisk liquid crystals. Herein, 2D photonic colloidal liquid crystals composed of biomineral-based nanorods and water is reported. The soft photonic materials with 2D structure by self-assembled LC colloidal nanorods are unique and a new class of photonic materials different from conventional solid 2D photonic materials. These colloids exhibit bright structural colors with high reflectance (>50%) and significant angular dependency. The structural colors are adjusted by controlling the concentration and size of the LC colloidal nanorods. Furthermore, mechanochromic hydrogel thin films with 2D photonic structure are developed. The hydrogels exhibit reversible mechanochromic properties with angular dependency, which can be used for an advanced stimuli responsible sensor., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

The elasmoid scales in teleost fish serve as exemplary models for natural fibre composites with integrated flexibility and protection. Yet, limited research has been focused on the potential structural, chemical, and mechanical heterogeneity within individual scales. This study presents systematic characterizations of the elasmoid scales from black drum fish ( Pogonias cromis ) at different zones within individual scales as a natural fibre composite, focusing on the microscopic structural heterogeneities and corresponding mechanical effects. The focus field at the centre of the scales exhibits a classical tri-layered collagen-based composite design, consisting of the mineralized outermost limiting layer, external elasmodine layer in the middle, and the unmineralized internal elasmodine layer. In comparison, the rostral field at the anterior end of the scales exhibits a two-layered design: the mineralized outermost limiting layer exhibits radii sections on the outer surface, and the inner elasmodine layer consists of collagen fibre-based sublayers with alternating mineralization levels. Chemical and nanoindentation analysis suggests a close correlation between the mineralization levels and the local nanomechanical properties. Comparative finite element modelling shows that the rostral-field scales achieve increased flexibility under both concave and convex bending. Moreover, the evolving geometries of isolated Mandle's corpuscles in the internal elasmodine layer, transitioning from irregular shapes to faceted octahedrons, suggest the mechanisms of mineral growth and space-filling to thicken the mineralized layers in scales during growth, which enhances the bonding strength between the adjacent collagen fibre layers. This work offers new insights into the structural variations in individual elasmoid scales, providing strategies for bioinspired fibre composite designs with local-adapted functional requirements., Competing Interests: We declare we have no competing interests., (© 2024 The Author(s).)