Diatom Silica Research Articles

Intracellular morphogenesis of diatom silica is guided by local variations in membrane curvature

Silica cell-wall formation in diatoms is a showcase for the ability of organisms to control inorganic mineralization. The process of silicification by these unicellular algae is tightly regulated within a membrane-bound organelle, the silica deposition vesicle (SDV). Two opposing scenarios were proposed to explain the tight regulation of this intracellular process: a template-mediated process that relies on preformed scaffolds, or a template-independent self-assembly process. The present work points to a third scenario, where the SDV membrane is a dynamic mold that shapes the forming silica. We use in-cell cryo-electron tomography to visualize the silicification process in situ, in its native-state, and with a nanometer-scale resolution. This reveals that the plasma membrane interacts with the SDV membrane via physical tethering at membrane contact sites, where the curvature of the tethered side of the SDV membrane mirrors the intricate silica topography. We propose that silica growth and morphogenesis result from the biophysical properties of the SDV and plasma membranes.

Incorporation of Al into diatom frustule as a proxy of seawater Al/Si ratios in the Antarctic Zone of the Southern ocean: Implications for surface silicic acid concentrations during the last glacial period

Knowledge of silicic acid concentrations at the surface Southern Ocean helps better understand the role of the biological pump in regulating atmospheric CO2 concentrations in the past. While the silicon isotope compositions of diatom provide a measure of Si utilization efficiency, proxies on surface silicic acid concentration are not yet available. Here we determined the diatom frustule Al/Si ratio and dust flux to constrain the surface silicic acid concentrations in the Atlantic sector of the Southern Ocean. Our results based on multiple methods, including inductively coupled plasma mass spectrometry (ICP-MS), scanning electron microscope (SEM) and energy-dispersive spectroscopy (EDS), and nuclear magnetic resonance spectroscopy (NMR), suggest the isomorphic substitution of Al for Si by frustule biosynthesis. This enables us to transfer the diatom Al/Si ratio into seawater Al/Si ratio using the partition coefficient of Al between diatom silica and seawater. By further constraining dust flux using the sediment 230Th-normalized 232Th flux, we found that the markedly higher frustule Al/Si ratios cannot be solely explained by increased Al dissolution from dust and call for much lower surface silicic acid concentrations in the Antarctic Zone during the Last Glacial Period. The lower silicic acid concentration coupled with lower Si utilization efficiency inferred previously from silicon isotopes in the Antarctic Zone is likely due to the combined effects of reduced upwelling and iron-fertilization-regulated uptake stoichiometry, contributing to a lower atmospheric CO2 during the Last Glacial Period.

Mechanism of branching morphogenesis inspired by diatom silica formation

The silica-based cell walls of diatoms are prime examples of genetically controlled, species-specific mineral architectures. The physical principles underlying morphogenesis of their hierarchically structured silica patterns are not understood, yet such insight could indicate novel routes toward synthesizing functional inorganic materials. Recent advances in imaging nascent diatom silica allow rationalizing possible mechanisms of their pattern formation. Here, we combine theory and experiments on the model diatom Thalassiosira pseudonana to put forward a minimal model of branched rib patterns-a fundamental feature of the silica cell wall. We quantitatively recapitulate the time course of rib pattern morphogenesis by accounting for silica biochemistry with autocatalytic formation of diffusible silica precursors followed by conversion into solid silica. We propose that silica deposition releases an inhibitor that slows down up-stream precursor conversion, thereby implementing a self-replicating reaction-diffusion system different from a classical Turing mechanism. The proposed mechanism highlights the role of geometrical cues for guided self-organization, rationalizing the instructive role for the single initial pattern seed known as the primary silicification site. The mechanism of branching morphogenesis that we characterize here is possibly generic and may apply also in other biological systems.

A global compilation of diatom silica oxygen isotope records from lake sediment – trends and implications for climate reconstruction

Abstract. Oxygen isotopes in biogenic silica (δ18OBSi) from lake sediments allow for quantitative reconstruction of past hydroclimate and proxy-model comparison in terrestrial environments. The signals of individual records have been attributed to different factors, such as air temperature (Tair), atmospheric circulation patterns, hydrological changes, and lake evaporation. While every lake has its own local set of drivers of δ18O variability, here we explore the extent to which regional or even global signals emerge from a series of paleoenvironmental records. This study provides a comprehensive compilation and combined statistical evaluation of the existing lake sediment δ18OBSi records, largely missing in other summary publications (i.e. PAGES network). For this purpose, we have identified and compiled 71 down-core records published to date and complemented these datasets with additional lake basin parameters (e.g. lake water residence time and catchment size) to best characterize the signal properties. Records feature widely different temporal coverage and resolution, ranging from decadal-scale records covering the past 150 years to records with multi-millennial-scale resolution spanning glacial–interglacial cycles. The best coverage in number of records (N = 37) and data points (N = 2112) is available for Northern Hemispheric (NH) extratropical regions throughout the Holocene (roughly corresponding to Marine Isotope Stage 1; MIS 1). To address the different variabilities and temporal offsets, records were brought to a common temporal resolution by binning and subsequently filtered for hydrologically open lakes with lake water residence times < 100 years. For mid- to high-latitude (> 45° N) lakes, we find common δ18OBSi patterns among the lake records during both the Holocene and Common Era (CE). These include maxima and minima corresponding to known climate episodes, such as the Holocene Thermal Maximum (HTM), Neoglacial Cooling, Medieval Climate Anomaly (MCA) and the Little Ice Age (LIA). These patterns are in line with long-term air temperature changes supported by previously published climate reconstructions from other archives, as well as Holocene summer insolation changes. In conclusion, oxygen isotope records from NH extratropical lake sediments feature a common climate signal at centennial (for CE) and millennial (for Holocene) timescales despite stemming from different lakes in different geographic locations and hence constitute a valuable proxy for past climate reconstructions.

Biomimetic Marine-Sponge-Derived Spicule-Microparticle-Mediated Biomineralization and YAP/TAZ Pathway for Bone Regeneration InVivo.

Marine-sponge-derived spicule microparticles (SPMs) possess unique structural and compositional features suitable for bone tissue engineering. However, significant challenges remain in establishing their osteogenic mechanism and practical application in animal models. This study explores the biomimetic potential of SPM in orchestrating biomineralization behavior and modulating the Yes-associated protein 1/transcriptional coactivator with PDZ-binding motif (YAP/TAZ) pathway both invitro and invivo. Characterization of SPM revealed a structure comprising amorphous silica oxide mixed with collagen and trace amounts of calcium and phosphate ions, which have the potential to facilitate biomineralization. Structural analysis indicated dynamic biomineralization from SPM to hydroxyapatite, contributing to both invitro and invivo osteoconductions. Invitro assessment demonstrated dose-dependent increases in osteogenic gene expression and bone morphogenetic protein-2 protein in response to SPM. In addition, focal adhesion mediated by silica diatoms induced cell spreading on the surface of SPM, leading to cell alignment in the direction of SPM. Mechanical signals from SPM subsequently increased the expression of YAP/TAZ, thereby inducing osteogenic mechanotransduction. The osteogenic activity of SPM-reinforced injectable hydrogel was evaluated in a mouse calvaria defect model, demonstrating rapid vascularized bone regeneration. These findings suggest that biomimetic SPM holds significant promise for regenerating bone tissue.

Sustainable SiO2 Nanostructures from Different Diatom Species As Anode Material for Future Generation Lithium-Ion Batteries

Energy harvesting and storage devices occupy a more prominent place in the 21st century than at any time in the past. Intensive efforts have been devoted to next-generation energy storage devices such as rechargeable lithium-ion batteries (LIBs) to develop high energy density and long cycle life electrode materials from sustainable sources. In the present anode, graphite is severely restricted by capacity and unavoidable solid electrolyte interface (SEI) formation. Besides, it has been listed as a critical material by the European Commission. Recently, silicon-based electrodes have been pinpointed as promising anode candidates due to their high theoretical capacity (~4200 mAhg-1 for Li4.4Si), low operating voltage (0.4V/Li/Li+), abundant resources, and environmental friendliness. Interestingly, nanostructures of Silica (SiO2) can be extracted from the frustules (exoskeletons) of a type of microalgae called diatoms. In this current work, SiO2 frustules were grown from two different diatom species, constituting a sustainable source for producing nanostructured Si-based materials. Scanning electron microscopy (SEM) images confirmed the highly nanoporous structure of diatom silica, which was retained even after ball-milling. The electrochemical performance of SiO2 was investigated as an anode material for LIBs. Herein, we have tested both species A & B milled and un-milled samples (denoted as SPAUM, SPAM, SPBUM, and SPBM). The diatom SiO2 un-milled species A (SPAUM) exhibited a high specific capacity of ~ 810 mAhg-1 with remarkable capacity retention and coulombic efficiency even after 100 cycles at 0.1 Ag-1 and delivered a high specific capacity of ~ 400 mAhg-1 even at high current density 3 Ag-1. For comparison and understanding, commercially available diatomaceous earth milled, and un-milled silica (denoted as EDAM & EDAUM) has been subjected to the same cycling protocol. Results clearly showed species A & B milled and un-milled displaying better electrochemical performance than diatomaceous earth milled and un-milled silica. Such improved electrochemical properties like cycle life, and rate capability of SPAUM are mainly ascribed to their highly porous nature which significantly facilitates fast Li ion diffusion, its unique morphology, which favors a faster kinetics and its complete lithiation/de-lithiation after the initial activation cycle. In view of the superior electrochemical properties, such sustainably sourced SiO2 materials can be considered a potential anode material for future LIBs. Figure 1

Efficient Ag+ adsorption of in-vivo thiol-functionalized diatoms and its application for sensitive surface-enhanced Raman scattering

Diatom silica frustules are recognized as a valuable biomaterial with hierarchically porous silica structures and can be used for many applications. To obtain targeted functional diatom-based materials, many strategies have been explored, mainly focusing on diatomite (fossilized diatoms) but rarely on living diatom silica frustules. In this work, the frustules of living diatoms (T. weissflogii) were in-vivo functionalized with thiol (-SH) groups by using (3-mercaptopropyl) trimethoxysilane (MPTMS) as silicon source, through living biomineralization process. The -SH groups were homogeneously distributed in diatom biosilica structures, as revealed by FIB-TEM-EDS result. Two applications of thiol-functionalized frustules were demonstrated. The first was for Ag+ adsorption, showing significantly enhanced adsorption capacity (87.59 mg·g−1) compared with unmodified frustules (33.21 mg·g−1). The adsorption data and the spectroscopic and microscopic analyses revealed that the inner-sphere complexation of -SH with Ag+ was the primary mechanism. The second application showed that Ag+-loaded diatom frustules exhibited a significant surface-enhanced Raman scattering (SERS), which can be used for detecting methylene blue and rhodamine 6G. The charge transfer resonance between Ag2S and probe molecules makes the primary contribution to the distinct enhancement of Raman signals. These findings demonstrate that these in-vivo functionalized -SH groups on diatom silica frustules can still maintain their excellent chemical reactivities, suggesting that this modification strategy could be extended to modify living diatom silica frustules with other functional groups. This study is of great significance for developing functional materials from living diatoms and their applications in the fields of environmental remediation, biosensing, and drug delivery, etc.

Characterization of diatom silica exoskeletons using atomic force microscopy: Topography and mechanical properties

Hierarchically structured natural objects provide a promising base for developing advanced hybrid materials and devices for a wide range of applications. Particularly high level of interest has recently been placed on diatom algae, eukaryotic unicellular microorganisms that represent a potential solution to the fundamental problems of bionics, specifically, the effective application of exoskeleton building principles to high efficiency engineering device fabrication. Developing hull engineering structures, in particular, requires a thorough understanding of the structural and mechanical characteristics of diatom frustules. The present study investigated the morphology, topography and mechanical properties of Coscinodiscus oculus-iridis diatom frustules using atomic force microscopy and scanning electron microscopy. The Young’s modulus showed a decrease from the side to the center of the frustule, with the variance up to fivefold, demonstrating the deformation of the structure. Nanostructured siliceous exoskeletons (frustules) offer unique guidance for developing a new generation of nano- and microdevices for electronic, electromechanical, photonic, and other uses by revealing the underlying relationship in the structure-properties-function chain.

Prehistoric population expansion in Central Asia promoted by the Altai Holocene Climatic Optimum

How climate change in the middle to late Holocene has influenced the early human migrations in Central Asian Steppe remains poorly understood. To address this issue, we reconstructed a multiproxy-based Holocene climate history from the sediments of Kanas Lake and neighboring Tiewaike Lake in the southern Altai Mountains. The results show an exceptionally warm climate during ~6.5–3.6 kyr is indicated by the silicon isotope composition of diatom silica (δ30Sidiatom) and the biogenic silica (BSi) content. During 4.7-4.3 kyr, a peak in δ30Sidiatom reflects enhanced lake thermal stratification and periodic nutrient limitation as indicated by concomitant decreasing BSi content. Our geochemical results indicate a significantly warm and wet climate in the Altai Mountain region during 6.5–3.6 kyr, corresponding to the Altai Holocene Climatic Optimum (AHCO), which is critical for promoting prehistoric human population expansion and intensified cultural exchanges across the Central Asian steppe during the Bronze Age.

Tuning SERS Signal via Substrate Structuring: Valves of Different Diatom Species with Ultrathin Gold Coating.

The discovered light modulation capabilities of diatom silicious valves make them an excellent toolkit for photonic devices and applications. In this work, a reproducible surface-enhanced Raman scattering (SERS) enhancement was achieved with hybrid substrates employing diatom silica valves coated with an ultrathin uniform gold film. Three structurally different hybrid substrates, based on the valves of three dissimilar diatom species, have been compared to elucidate the structural contribution to SERS enhancement. The comparative analysis of obtained results showed that substrates containing cylindrical Aulacoseira sp. valves achieved the highest enhancement, up to 14-fold. Numerical analysis based on the frequency domain finite element method was carried out to supplement the experimental results. Our results demonstrate that diatom valves of different shapes can enhance the SERS signal, offering a toolbox for SERS-based sensors, where the magnitude of the enhancement depends on valve geometry and ultrastructure.

Exocytosis of the silicified cell wall of diatoms involves extensive membrane disintegration

Diatoms are unicellular algae characterized by silica cell walls. These silica elements are known to be formed intracellularly in membrane-bound silica deposition vesicles and exocytosed after completion. How diatoms maintain membrane homeostasis during the exocytosis of these large and rigid silica elements remains unknown. Here we study the membrane dynamics during cell wall formation and exocytosis in two model diatom species, using live-cell confocal microscopy, transmission electron microscopy and cryo-electron tomography. Our results show that during its formation, the mineral phase is in tight association with the silica deposition vesicle membranes, which form a precise mold of the delicate geometrical patterns. We find that during exocytosis, the distal silica deposition vesicle membrane and the plasma membrane gradually detach from the mineral and disintegrate in the extracellular space, without any noticeable endocytic retrieval or extracellular repurposing. We demonstrate that within the cell, the proximal silica deposition vesicle membrane becomes the new barrier between the cell and its environment, and assumes the role of a new plasma membrane. These results provide direct structural observations of diatom silica exocytosis, and point to an extraordinary mechanism in which membrane homeostasis is maintained by discarding, rather than recycling, significant membrane patches.

Diatom silica frustules-doped fibers for controlled release of melatonin for bone regeneration

Sustained release of a bioactive agent from a tissue engineering scaffold is one of the most common strategies to improve regenerative potential of the construct. However, depending on the chemistry of the agent, achieving high enough loading and controlled release can be challenging depending on the scaffold materials. These shortcomings can be solved by novel scaffold design fabricated by appropriate techniques and materials for the target tissue. In this study, an electrospun scaffold was designed to improve osteogenic activity of cells and diatom silica frustules were used to sustain loading and controlled release of a hydrophilic molecule, melatonin. Fibrous scaffolds were produced via wet electrospinning of the polymer blend solution poly(hydroxybutyrate-co-hydroxyvalerate (PHBV)/poly(ε-caprolactone) (PCL) which contains melatonin loaded diatom frustules. In the 3D fiber matrix diatom frustules were covered with a polymer coat which successfully lowered melatonin release more than half through 7 days achieving a controlled release. Melatonin had a concentration dependent effect on ALP activity of cells, while scaffolds bearing melatonin loaded frustules have significantly improved ALP activity of Saos-2 cells. Developed scaffold system has successfully induced osteogenic activity by controlled melatonin delivery and silica nature of diatom frustules which hold potential use for bone tissue engineering.

Comparative analysis of the diatom microtubule center components

The diatom silica frustule formation occurs inside cells under the control of cytoskeleton and microtubule center. The composition of the diatoms microtubule center has not been previously studied. In the present study, several components of the diatom microtubule center in have been identified. Based on the genome and transcriptome data, an analysis was carried out and the structural features of the predicted amino acid sequences of GCP, protein kinase Aurora A, and centrins were revealed.

A Biomimetic, Silaffin R5-Based Antigen Delivery Platform

Nature offers a wide range of evolutionary optimized materials that combine unique properties with intrinsic biocompatibility and that can be exploited as biomimetic materials. The R5 and RRIL peptides employed here are derived from silaffin proteins that play a crucial role in the biomineralization of marine diatom silica shells and are also able to form silica materials in vitro. Here, we demonstrate the application of biomimetic silica particles as a vaccine delivery and adjuvant platform by linking the precipitating peptides R5 and the RRIL motif to a variety of peptide antigens. The resulting antigen-loaded silica particles combine the advantages of biomaterial-based vaccines with the proven intracellular uptake of silica particles. These particles induce NETosis in human neutrophils as well as IL-6 and TNF-α secretion in murine bone marrow-derived dendritic cells.

Comparative of diatom frustules, diatomite, and silica particles for constructing self-healing superhydrophobic materials with capacity for thermal energy storage

Introducing the capability of self-healing to superhydrophobic materials is an effective strategy for improving their durability. This study examined self-healing superhydrophobic coatings based on diatom frustules and paraffin wax, and systematically compared coatings based on diatom frustules with those prepared by using diatomite and synthesized silica. The diatom frustules had a much higher specific surface area (214.38 m2/g) and pore volume (0.97 cm3/g) than diatomite and synthesized silica, and thus only diatom frustule can provide sufficient micro/nanoscale roughness and adsorb a large number of low-surface-energy, healing agent paraffin wax to achieve self-healable superhydrophobicity. The superhydrophobic coatings thus obtained demonstrated the capability for repeated self-healing after heat treatment at 80 °C for 10 min when subjected to water jet-induced impact for 30 min as well as corrosion in 1 M NaOH and 1 M HCl for 4 h. As much as 60.66 % of paraffin wax was stored in the diatom frustules without leakage, much higher than the amounts in diatomite and synthesized silica. This helped ensure good thermal storage performance, with a melting enthalpy of 132.2 J/g and a freezing enthalpy of 127.9 J/g. Once equipped with the capacity for storing thermal energy, self-healing superhydrophobic materials can be used in a variety of applications that require thermal management, such as electronic devices, intelligent flexible textiles, and energy-efficient and self-cleaning buildings.

On the dissolution of sponge silica: Assessing variability and biogeochemical implications

The dissolution of the biogenic silica that constitutes the skeletons of silicifying organisms is an important mechanism for regenerating dissolved silicon in the ocean. The silica skeletons deposited to the seafloor after the organisms die keep dissolving until becoming definitively buried. The low dissolution rate of sponge skeletons compared to that of diatom skeletons favors their burial and makes sponges (Phylum Porifera) to function as important silicon sinks in the oceans. However, it remains poorly understood whether the large variety of siliceous skeletons existing in the Porifera involves similar variability in their dissolution rates, which would affect the general conceptualization of these organisms as silicon sinks. Herein we investigated kinetics of silica dissolution for major types of skeletons in the three siliceous lineages of Porifera, following standardized digestion conditions in 1% sodium carbonate with orbital agitation at 85°C. The results are compared with those of a previous study conducted under identical conditions, which considered diatom silica, sponge silica, and lithogenic silica. Unexpectedly, the silica of homoscleromorph sponges dissolved only a bit slower than that of freshly cultured diatoms and as fast as diatom earth. However, the rest of sponge skeletons were far more resistant, although with some differences: the isolated spicules of hexactinellid sponges dissolved slightly faster than when forming frameworks of fused spicules, being hexactinellid frameworks as resistant to dissolution as the silica of demosponges, irrespective of occurring in the form of isolated spicules or frameworks. The experiments also indicated that the complexation of sponge silica with aluminum and with chitin does not increase its resistance to dissolution. Because the rapidly-dissolving homoscleromorph sponges represent less than 1% of extant sponges, the sponge skeletons are still conceptualized as important silicon sinks due to their comparative resistance to dissolution. Yet, the turnover of silica into dissolved silicon will always be faster in environments dominated by hexactinellids with isolated spicules than in environments dominated by other hexactinellids and/or demosponges. We discuss whether the time required for a given silica type to completely dissolve in 1% sodium carbonate could be a predictor of its preservation ratio in marine sediments.

The molecular basis for pore pattern morphogenesis in diatom silica.

Biomineral-forming organisms produce inorganic materials with complex, genetically encoded morphologies that are unmatched by current synthetic chemistry. It is poorly understood which genes are involved in biomineral morphogenesis and how the encoded proteins guide this process. We addressed these questions using diatoms, which are paradigms for the self-assembly of hierarchically meso- and macroporous silica under mild reaction conditions. Proteomics analysis of the intracellular organelle for silica biosynthesis led to the identification of new biomineralization proteins. Three of these, coined dAnk1-3, contain a common protein-protein interaction domain (ankyrin repeats), indicating a role in coordinating assembly of the silica biomineralization machinery. Knocking out individual dank genes led to aberrations in silica biogenesis that are consistent with liquid-liquid phase separation as underlying mechanism for pore pattern morphogenesis. Our work provides an unprecedented path for the synthesis of tailored mesoporous silica materials using synthetic biology.

Immobilization of a Broad Range of Polypeptides on the Frustule of the Diatom Thalassiosira pseudonana.

Proteins immobilized on biosilica which have superior reactivity and specificity and are innocuous to natural environments could be useful biological materials in industrial processes. One recently developed technique, living diatom silica immobilization (LiDSI), has made it possible to immobilize proteins, including multimeric and redox enzymes, via a cellular excretion system onto the silica frustule of the marine diatom Thalassiosira pseudonana. However, the number of application examples so far is limited, and the type of proteins appropriate for the technique is still enigmatic. Here, we applied LiDSI to six industrially relevant polypeptides, including protamine, metallothionein, phosphotriesterase, choline oxidase, laccase, and polyamine synthase. Protamine and metallothionein were successfully immobilized on the frustule as protein fusions with green fluorescent protein (GFP) at the N terminus, indicating that LiDSI can be used for polypeptides which are rich in arginine and cysteine. In contrast, we obtained mutants for the latter four enzymes in forms without green fluorescent protein. Immobilized phosphotriesterase, choline oxidase, and laccase showed enzyme activities even after the purification of frustule in the presence of 1% (wt/vol) octylphenoxy poly(ethyleneoxy)ethanol. An immobilized branched-chain polyamine synthase changed the intracellular polyamine composition and silica nanomorphology. These results illustrate the possibility of LiDSI for industrial applications. IMPORTANCE Proteins immobilized on biosilica which have superior reactivity and specificity and are innocuous to natural environments could be useful biological materials in industrial processes. Living diatom silica immobilization (LiDSI) is a recently developed technique for in vivo protein immobilization on the diatom frustule. We aimed to explore the possibility of using LiDSI for industrial applications by successfully immobilizing six polypeptides: (i) protamine (Oncorhynchus keta), a stable antibacterial agent; (ii) metallothionein (Saccharomyces cerevisiae), a metal adsorption molecule useful for bioremediation; (iii) phosphotriesterase (Sulfolobus solfataricus), a scavenger for toxic organic phosphates; (iv) choline oxidase (Arthrobacter globiformis), an enhancer for photosynthetic activity and yield of plants; (v) laccase (Bacillus subtilis), a phenol oxidase utilized for delignification of lignocellulosic materials; and (vi) branched-chain polyamine synthase (Thermococcus kodakarensis), which produces branched-chain polyamines important for DNA and RNA stabilization at high temperatures. This study provides new insights into the field of applied biological materials.

Periostracum of bivalve mollusk shells for sampling engineered metal nanoparticles: A case study of silver-based nanoparticles in Canada's experimental lake.

Given the ability of engineered metal nanoparticles to be transformed in natural waters in unpredictable manners, various sampling methods must be developed. Here, we took a novel approach to collection silver nanoparticles (AgNPs) that involved the use of the intact periostracum, the outer proteinaceous organic layer, of freshwater unionid mussels Pyganodon sp. Eight adult mussels were collected in August 2019 from a small boreal lake (L222) at the International Institute for Sustainable Development - Experimental Lakes Area (northwestern Ontario), which had been dosed with 15kg of poly(vinylpyrrolidone)-coated silver nanoparticles (PVP-AgNPs) in 2014-2015. Additionally, three adult mussels were collected from a control lake (L375). Numerous silica (SiO2) diatom frustules were adhered to periostracum of all mussels. Intact periostracum promotes the formation of layer composed of diatoms and sand grains. The Ag content in soft tissues and shells of the mussels from L375 was as low as ≤ 0.1 μg/g. In mussels from L222, Ag concentrations in the periostracum of five shells were in detectable amounts (1-4 μg/g); in three shells concentrations were as high as 86, 122, and 494 μg/g. The underlying mineral shell is depleted in Ag (<0.1 μg/g). The Ag content in soft tissue organs (whole body) ranged from 44 to 191 μg/g. AgNPs occur on the surface of both periostracum and diatoms. Single AgNPs (d=20-60nm) were partly sulfidized to Ag2S. The observed AgNPs often form aggregates with an average and a maximal size of circa 100nm and 1.5 μm, respectively. Scraping small fragments of intact periostracum of unionid shell is non-lethal to mussels, and is easy to do under field conditions. This simple sampling protocol could be used to detect metal-based nanoparticles (engineered or accidental) with the use of unionid and dreissenid bivalves.

Manganese Oxide Nanozyme-Doped Diatom for Safe and Efficient Treatment of Peri-Implantitis.

Peri-implantitis is a major cause of dental implant failure. Bacterial biofilm contamination on the implant induces surrounding bone resorption and soft tissue inflammation, leading to severe deterioration of oral health. However, conventional biofilm removal procedures, such as mechanical decontamination and antiseptic application, are not effective enough to induce reosseointegration on decontaminated implant surfaces. This is due to (1) incomplete decontamination of the biofilm from inaccessible areas and (2) physicochemical alteration of implant surfaces caused by decontamination procedures. Herein, a safe and effective therapeutic approach for peri-implantitis is developed, which involves decontamination of implant-bound biofilms using the kinetic energy of microsized oxygen bubbles generated from the catalytic reaction between hydrogen peroxide (H2O2) and manganese oxide (MnO2) nanozyme sheet-doped silica diatom microparticles (Diatom Microbubbler, DM). Rapidly moving microsized DM particles are able to penetrate narrow spaces between implant screws, exerting just the right amount of force to entirely destroy biofilms without harming the surrounding mucosa or implant surfaces, as opposed to conventional antiseptics such as chlorhexidine or 3% H2O2 when used alone. Consequently, decontamination with DM facilitates successful reosseointegration on the peri-implantitis-affected implant surface. In summary, our new DM-based therapeutic approach will become a promising alternative to resolve clinically challenging aspects of peri-implantitis.