Marine Sponge-Derived Secondary Metabolites Modulate SARS-CoV-2 Entry Mechanisms.

The emergence of SARS-CoV 2 caused the COVID-19 pandemic, resulting in numerous global infections and deaths. In particular, people with metabolic diseases display an increased risk of severe COVID 19 and a fatal outcome. Treatment options for severe cases are limited, and the appearance of new virus variants complicates the development of novel therapies. To better manage viral infections like COVID 19, new therapeutic approaches are needed. Marine sponges offer a natural and renewable source of unique bioactive agents. These sponges produce secondary metabolites with various effects, including anti-viral, anti-inflammatory, and anti-tumorigenic properties. In the current study, we investigated the effect of five different marine sponge-derived secondary metabolites (four bromotyrosines and one sesquiterpenoid hydroquinone). Two of these, Avarol and Acetyl-dibromoverongiaquinol reduced the expression of ACE2, the main receptor for SARS-CoV 2, and the alternative receptor NRP1. Moreover, these substances derived from sponges demonstrated the ability to diminish the virus titer in SARS-CoV 2-infected cells, especially concerning the Omicron lineage. However, the reduction was not substantial enough to expect a significant impact on infected humans. Consequently, the investigated sponge-derived secondary metabolites are not likely to be effective to treat COVID 19 as a stand-alone therapy.

Structural characterization of the extracellular stalk material of the diatom Didymosphenia geminata.

The study represents new bioanalytical characterization of mainly organic components of the poorly investigated extracellular polymeric substances (EPS) of the enigmatic diatom Didymosphenia geminata, an invasive, worldwide expanding species endangering diverse ecosystems. This microalga attaches its siliceous cells to rocky substrates using fibrous stalks, which are made of an EPS-based matrix stabilized by crystalline calcite. The EPS were analyzed using selected methods, including microscopic, spectroscopic, and spectrometric techniques. We identified diverse types of biomolecules. The presence of lipids, condensed aromatics, and heteroaromatic compounds in the EPS has been confirmed using high-resolution mass spectrometry (HR-MS). Additionally, both sulfur-containing functionalities and carboxylic acids were determined too using infrared (IR) spectroscopy and nuclear magnetic resonance (NMR) spectroscopy. For the first time, lignin compounds have been detected as one of the components of the EPS of the D. geminata diatom, using HR-MS and fluorescence microscopy (FM) in combination with specific staining techniques. By increasing the understanding of the chemistry and structural features of the stalks, we aim to develop potential applications and methods for removing these stalks from affected regions in the future, or, alternatively, to use them as a large-scale source of sustainable biocomposite material.

Application of polysaccharide biopolymers as natural adsorbent in sample preparation.

Preparing samples for analyses is perhaps the most important part to analyses. The varied functional groups present on the surface of biopolymers bestow them appropriate adsorption properties. Properties like biocompatibility, biodegradability, presence of different surface functional group, high porosity, considerable absorption capacity for water, the potential for modification, etc. turn biopolymers to promising candidates for varied applications. In addition, one of the most important parts of determination of an analyte in a matrix is sample preparation step and the efficiency of this step in solid phase extraction methods is largely dependent on the type of adsorbent used. Due to the unique properties of biopolymers they are considered an appropriate choice for using as sorbent in sample preparation methods that use from a solid adsorbent. Many review articles have been published on the application of diverse adsorbents in sample preparation methods, however despite the numerous advantages of biopolymers mentioned; review articles in this field are very few. Thus, in this paper we review the reports in different areas of sample preparation that use polysaccharides-based biopolymers as sorbents for extraction and determination of diverse organic and inorganic analytes.

Fibrocyte: A missing piece in the pathogenesis of fibrous epulis.

OBJECTIVES: To explore the role of fibrocytes in the recurrence and calcification of fibrous epulides. METHODS: Different subtypes of fibrous epulides and normal gingival tissue specimens were first collected for histological and immunofluorescence analyses to see if fibrocytes were present and whether they differentiated into myofibroblasts and osteoblasts upon stimulated by transforming growth factor-ß1 (TGF-ß1). Electron microscopy and elemental analysis were used to characterize the extracellular microenvironment in different subtypes of fibrous epulides. Human peripheral blood mononuclear cells (PBMCs) were subsequently isolated from in vitro models to mimic the microenvironment in fibrous epulides to identify whether TGF-ß1 as well as the calcium and phosphorus ion concentration in the extracellular matrix (ECM) of a fibrous epulis trigger fibrocyte differentiation. RESULTS: Fibrous epulides contain fibrocytes that accumulate in the local inflammatory environment and have the ability to differentiate into myofibroblasts or osteoblasts. TGF-ß1 promotes fibrocytes differentiation into myofibroblasts in a concentration-dependent manner, while TGF-ß1 stimulates the fibrocytes to differentiate into osteoblasts when combined with a high calcium and phosphorus environment. CONCLUSIONS: Our study revealed fibrocytes play an important role in the fibrogenesis and osteogenesis in fibrous epulis, and might serve as a therapeutic target for the inhibition of recurrence of fibrous epulides.

The Loss of Structural Integrity of 3D Chitin Scaffolds from Aplysina aerophoba Marine Demosponge after Treatment with LiOH.

Aminopolysaccharide chitin is one of the main structural biopolymers in sponges that is responsible for the mechanical stability of their unique 3D-structured microfibrous and porous skeletons. Chitin in representatives of exclusively marine Verongiida demosponges exists in the form of biocomposite-based scaffolds chemically bounded with biominerals, lipids, proteins, and bromotyrosines. Treatment with alkalis remains one of the classical approaches to isolate pure chitin from the sponge skeleton. For the first time, we carried out extraction of multilayered, tube-like chitin from skeletons of cultivated Aplysina aerophoba demosponge using 1% LiOH solution at 65 °C following sonication. Surprisingly, this approach leads not only to the isolation of chitinous scaffolds but also to their dissolution and the formation of amorphous-like matter. Simultaneously, isofistularin-containing extracts have been obtained. Due to the absence of any changes between the chitin standard derived from arthropods and the sponge-derived chitin treated with LiOH under the same experimental conditions, we suggest that bromotyrosines in A. aerophoba sponge represent the target for lithium ion activity with respect to the formation of LiBr. This compound, however, is a well-recognized solubilizing reagent of diverse biopolymers including cellulose and chitosan. We propose a possible dissolution mechanism of this very special kind of sponge chitin.

On the Mechanical Properties of Microfibre-Based 3D Chitinous Scaffolds from Selected Verongiida Sponges.

Skeletal constructs of diverse marine sponges remain to be a sustainable source of biocompatible porous biopolymer-based 3D scaffolds for tissue engineering and technology, especially structures isolated from cultivated demosponges, which belong to the Verongiida order, due to the renewability of their chitinous, fibre-containing architecture focused attention. These chitinous scaffolds have already shown excellent and promising results in biomimetics and tissue engineering with respect to their broad diversity of cells. However, the mechanical features of these constructs have been poorly studied before. For the first time, the elastic moduli characterising the chitinous samples have been determined. Moreover, nanoindentation of the selected bromotyrosine-containing as well as pigment-free chitinous scaffolds isolated from selected verongiids was used in the study for comparative purposes. It was shown that the removal of bromotyrosines from chitin scaffolds results in a reduced elastic modulus; however, their hardness was relatively unaffected.

Spongin as a Unique 3D Template for the Development of Functional Iron-Based Composites Using Biomimetic Approach In Vitro.

Marine sponges of the subclass Keratosa originated on our planet about 900 million years ago and represent evolutionarily ancient and hierarchically structured biological materials. One of them, proteinaceous spongin, is responsible for the formation of 3D structured fibrous skeletons and remains enigmatic with complex chemistry. The objective of this study was to investigate the interaction of spongin with iron ions in a marine environment due to biocorrosion, leading to the occurrence of lepidocrocite. For this purpose, a biomimetic approach for the development of a new lepidocrocite-containing 3D spongin scaffold under laboratory conditions at 24 °C using artificial seawater and iron is described for the first time. This method helps to obtain a new composite as "Iron-Spongin", which was characterized by infrared spectroscopy and thermogravimetry. Furthermore, sophisticated techniques such as X-ray fluorescence, microscope technique, and X-Ray diffraction were used to determine the structure. This research proposed a corresponding mechanism of lepidocrocite formation, which may be connected with the spongin amino acids functional groups. Moreover, the potential application of the biocomposite as an electrochemical dopamine sensor is proposed. The conducted research not only shows the mechanism or sensor properties of "Iron-spongin" but also opens the door to other applications of these multifunctional materials.

Electrolysis as a Universal Approach for Isolation of Diverse Chitin Scaffolds from Selected Marine Demosponges.

Three-dimensional chitinous scaffolds often used in regenerative medicine, tissue engineering, biomimetics and technology are mostly isolated from marine organisms, such as marine sponges (Porifera). In this work, we report the results of the electrochemical isolation of the ready to use chitinous matrices from three species of verongiid demosponges (Aplysina archeri, Ianthella basta and Suberea clavata) as a perfect example of possible morphological and chemical dimorphism in the case of the marine chitin sources. The electrolysis of concentrated Na2SO4 aqueous solution showed its superiority over the chemical chitin isolation method in terms of the treatment time reduction: only 5.5 h for A. archeri, 16.5 h for I. basta and 20 h for the S. clavata sample. Further investigation of the isolated scaffolds by digital microscopy and SEM showed that the electrolysis-supported isolation process obtains chitinous scaffolds with well-preserved spatial structure and it can be competitive to other alternative chitin isolation techniques that use external accelerating factors such as microwave irradiation or atmospheric plasma. Moreover, the infrared spectroscopy (ATR-FTIR) proved that with the applied electrochemical conditions, the transformation into chitosan does not take place.

Biocatalytic System Made of 3D Chitin, Silica Nanopowder and Horseradish Peroxidase for the Removal of 17α-Ethinylestradiol: Determination of Process Efficiency and Degradation Mechanism.

The occurrence of 17α-ethinylestradiol (EE2) in the environment and its removal have drawn special attention from the scientific community in recent years, due to its hazardous effects on human and wildlife around the world. Therefore, the aim of this study was to produce an efficient enzymatic system for the removal of EE2 from aqueous solutions. For the first time, commercial silica nanopowder and 3D fibrous chitinous scaffolds from Aplysina fistularis marine sponge were used as supports for horseradish peroxidase (HRP) immobilization. The effect of several process parameters onto the removal mechanism of EE2 by enzymatic conversion and adsorption of EE2 were investigated here, including system type, pH, temperature and concentrations of H2O2 and EE2. It was possible to fully remove EE2 from aqueous solutions using system SiO2(HRP)-chitin(HRP) over a wide investigated pH range (5-9) and temperature ranges (4-45 °C). Moreover, the most suitable process conditions have been determined at pH 7, temperature 25 °C and H2O2 and EE2 concentrations equaling 2 mM and 1 mg/L, respectively. As determined, it was possible to reuse the nanoSiO2(HRP)-chitin(HRP) system to obtain even 55% EE2 degradation efficiency after five consecutive catalytic cycles.

Insights into the structure and morphogenesis of the giant basal spicule of the glass sponge Monorhaphis chuni.

BACKGROUND: A basal spicule of the hexactinellid sponge Monorhaphis chuni may reach up to 3 m in length and 10 mm in diameter, an extreme case of large spicule size. Generally, sponge spicules are of scales from micrometers to centimeters. Due to its large size many researchers have described its structure and properties and have proposed it as a model of hexactinellid spicule development. Thorough examination of new material of this basal spicule has revealed numerous inconsistencies between our observations and earlier descriptions. In this work, we present the results of detailed examinations with transmitted light and epifluorescence microscopy, SEM, solid state NMR analysis, FTIR and X-ray analysis and staining of Monorhaphis chuni basal spicules of different sizes, collected from a number of deep sea locations, to better understand its structure and function. RESULTS: Three morphologically/structurally different silica layers i.e. plain glassy layer (PG), tuberculate layer (TL) and annular layer (AL), and an axial cylinder (AC) characterize adult spicules. Young, immature spicules display only plain glassy silica layers which dominate the spicule volume. All three layers i.e. PG, TL and AL can substitute for each other along the surface of the spicule, but equally they are superimposed in older parts of the spicules, with AL being the most external and occurring only in the lower part of the spicules and TL being intermediate between AL and PG. The TL, which is composed of several thinner layers, is formed by a progressive folding of its surface but its microstructure is the same as in the PG layer (glassy silica). The AL differs significantly from the PG and TL in being granular and porous in structure. The TL was found to display positive structures (tubercles), not depressions, as earlier suggested. The apparent perforated and non-perforated bands of the AL are an optical artefact. The new layer type that we called the Ripple Mark Layer (RML) was noted, as well as narrow spikes on the AL ridges, both structures not reported earlier. The interface of the TL and AL, where tubercles fit into depressions of the lower surface of the AL, represent tenon and mortise or dovetail joints, making the spicules more stiff/strong and thus less prone to breaking in the lower part. Early stages of the spicule growth are bidirectional, later growth is unidirectional toward the spicule apex. Growth in thickness proceeds by adding new layers. The spicules are composed of well condensed silica, but the outermost AL is characterized by slightly more condensed silica with less water than the rest. Organics permeating the silica are homogeneous and proteinaceous. The external organic net (most probably collagen) enveloping the basal spicule is a structural element that bounds the sponge body together with the spicule, rather than controlling tubercle formation. Growth of various layers may proceed simultaneously in different locations along the spicule and it is sclerosyncytium that controls formation of silica layers. The growth in spicule length is controlled by extension of the top of the axial filament that is not enclosed by silica and is not involved in further silica deposition. No structures that can be related to sclerocytes (as known in Demospongiae) in Monorhaphis were discovered during this study. CONCLUSIONS: Our studies resulted in a new insight into the structure and growth of the basal Monorhaphis spicules that contradicts earlier results, and permitted us to propose a new model of this spicule's formation. Due to its unique structure, associated with its function, the basal spicule of Monorhaphis chuni cannot serve as a general model of growth for all hexactinellid spicules.

The Anti-Viral Applications of Marine Resources for COVID-19 Treatment: An Overview.

The ongoing pandemic has led to an urgent need for novel drug discovery and potential therapeutics for Sars-CoV-2 infected patients. Although Remdesivir and the anti-inflammatory agent dexamethasone are currently on the market for treatment, Remdesivir lacks full efficacy and thus, more drugs are needed. This review was conducted through literature search of PubMed, MDPI, Google Scholar and Scopus. Upon review of existing literature, it is evident that marine organisms harbor numerous active metabolites with anti-viral properties that serve as potential leads for COVID-19 therapy. Inorganic polyphosphates (polyP) naturally found in marine bacteria and sponges have been shown to prevent viral entry, induce the innate immune response, and downregulate human ACE-2. Furthermore, several marine metabolites isolated from diverse sponges and algae have been shown to inhibit main protease (Mpro), a crucial protein required for the viral life cycle. Sulfated polysaccharides have also been shown to have potent anti-viral effects due to their anionic properties and high molecular weight. Likewise, select marine sponges produce bromotyrosines which have been shown to prevent viral entry, replication and protein synthesis. The numerous compounds isolated from marine resources demonstrate significant potential against COVID-19. The present review for the first time highlights marine bioactive compounds, their sources, and their anti-viral mechanisms of action, with a focus on potential COVID-19 treatment.

Potential Biomedical Applications of Collagen Filaments derived from the Marine Demosponges Ircinia oros (Schmidt, 1864) and Sarcotragus foetidus (Schmidt, 1862).

Collagen filaments derived from the two marine demosponges Ircinia oros and Sarcotragus foetidus were for the first time isolated, biochemically characterised and tested for their potential use in regenerative medicine. SDS-PAGE of isolated filaments revealed a main collagen subunit band of 130 kDa in both of the samples under study. DSC analysis on 2D membranes produced with collagenous sponge filaments showed higher thermal stability than commercial mammalian-derived collagen membranes. Dynamic mechanical and thermal analysis attested that the membranes obtained from filaments of S. foetidus were more resistant and stable at the rising temperature, compared to the ones derived from filaments of I. oros. Moreover, the former has higher stability in saline and in collagenase solutions and evident antioxidant activity. Conversely, their water binding capacity results were lower than that of membranes obtained from I. oros. Adhesion and proliferation tests using L929 fibroblasts and HaCaT keratinocytes resulted in a remarkable biocompatibility of both developed membrane models, and gene expression analysis showed an evident up-regulation of ECM-related genes. Finally, membranes from I. oros significantly increased type I collagen gene expression and its release in the culture medium. The findings here reported strongly suggest the biotechnological potential of these collagenous structures of poriferan origin as scaffolds for wound healing.

Adsorption of Cationic Dyes on a Magnetic 3D Spongin Scaffold with Nano-Sized Fe3O4 Cores.

The renewable, proteinaceous, marine biopolymer spongin is yet the focus of modern research. The preparation of a magnetic three-dimensional (3D) spongin scaffold with nano-sized Fe3O4 cores is reported here for the first time. The formation of this magnetic spongin-Fe3O4 composite was characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential thermal analysis (DTA) (TGA-DTA), vibrating sample magnetometer (VSM), Fourier-transform infrared spectroscopy (FTIR), and zeta potential analyses. Field emission scanning electron microscopy (FE-SEM) confirmed the formation of well-dispersed spherical nanoparticles tightly bound to the spongin scaffold. The magnetic spongin-Fe3O4 composite showed significant removal efficiency for two cationic dyes (i.e., crystal violet (CV) and methylene blue (MB)). Adsorption experiments revealed that the prepared material is a fast, high-capacity (77 mg/g), yet selective adsorbent for MB. This behavior was attributed to the creation of strong electrostatic interactions between the spongin-Fe3O4 and MB or CV, which was reflected by adsorption mechanism evaluations. The adsorption of MB and CV was found to be a function of pH, with maximum removal performance being observed over a wide pH range (pH = 5.5-11). In this work, we combined Fe3O4 nanoparticles and spongin scaffold properties into one unique composite, named magnetic spongin scaffold, in our attempt to create a sustainable absorbent for organic wastewater treatment. The appropriative mechanism of adsorption of the cationic dyes on a magnetic 3D spongin scaffold is proposed. Removal of organic dyes and other contaminants is essential to ensure healthy water and prevent various diseases. On the other hand, in many cases, dyes are used as models to demonstrate the adsorption properties of nanostructures. Due to the good absorption properties of magnetic spongin, it can be proposed as a green and uncomplicated adsorbent for the removal of different organic contaminants and, furthermore, as a carrier in drug delivery applications.

Calcite Nanotuned Chitinous Skeletons of Giant Ianthella basta Marine Demosponge.

Marine sponges were among the first multicellular organisms on our planet and have survived to this day thanks to their unique mechanisms of chemical defense and the specific design of their skeletons, which have been optimized over millions of years of evolution to effectively inhabit the aquatic environment. In this work, we carried out studies to elucidate the nature and nanostructural organization of three-dimensional skeletal microfibers of the giant marine demosponge Ianthella basta, the body of which is a micro-reticular, durable structure that determines the ideal filtration function of this organism. For the first time, using the battery of analytical tools including three-dimensional micro-X-ray Fluorescence (3D-µXRF), X-ray diffraction (XRD), infra-red (FTIR), Raman and Near Edge X-ray Fine Structure (NEXAFS) spectroscopy, we have shown that biomineral calcite is responsible for nano-tuning the skeletal fibers of this sponge species. This is the first report on the presence of a calcitic mineral phase in representatives of verongiid sponges which belong to the class Demospongiae. Our experimental data suggest a possible role for structural amino polysaccharide chitin as a template for calcification. Our study suggests further experiments to elucidate both the origin of calcium carbonate inside the skeleton of this sponge and the mechanisms of biomineralization in the surface layers of chitin microfibers saturated with bromotyrosines, which have effective antimicrobial properties and are responsible for the chemical defense of this organism. The discovery of the calcified phase in the chitinous template of I. basta skeleton is expected to broaden the knowledge in biomineralization science where the calcium carbonate is regarded as a valuable material for applications in biomedicine, environmental science, and even in civil engineering.

Progress in Modern Marine Biomaterials Research.

The growing demand for new, sophisticated, multifunctional materials has brought natural structural composites into focus, since they underwent a substantial optimization during long evolutionary selection pressure and adaptation processes. Marine biological materials are the most important sources of both inspiration for biomimetics and of raw materials for practical applications in technology and biomedicine. The use of marine natural products as multifunctional biomaterials is currently undergoing a renaissance in the modern materials science. The diversity of marine biomaterials, their forms and fields of application are highlighted in this review. We will discuss the challenges, solutions, and future directions of modern marine biomaterialogy using a thorough analysis of scientific sources over the past ten years.

Anti-Tumor Activity vs. Normal Cell Toxicity: Therapeutic Potential of the Bromotyrosines Aerothionin and Homoaerothionin In Vitro.

Novel strategies to treat cancer effectively without adverse effects on the surrounding normal tissue are urgently needed. Marine sponges provide a natural and renewable source of promising anti-tumor agents. Here, we investigated the anti-tumor activity of Aerothionin and Homoaerothionin, two bromotyrosines isolated from the marine demosponge Aplysina cavernicola, on two mouse pheochromocytoma cells, MPC and MTT. To determine the therapeutic window of these metabolites, we furthermore explored their cytotoxicity on cells of the normal tissue. Both metabolites diminished the viability of the pheochromocytoma cell lines significantly from a concentration of 25 µM under normoxic and hypoxic conditions. Treatment of MPC cells leads moreover to a reduction in the number of proliferating cells. To confirm the anti-tumor activity of these bromotyrosines, 3D-pheochromocytoma cell spheroids were treated with 10 µM of either Aerothionin or Homoaerothionin, resulting in a significant reduction or even complete inhibition of the spheroid growth. Both metabolites reduced viability of normal endothelial cells to a comparable extent at higher micromolar concentration, while the viability of fibroblasts was increased. Our in vitro results show promise for the application of Aerothionin and Homoaerothionin as anti-tumor agents against pheochromocytomas and suggest acceptable toxicity on normal tissue cells.

Electrochemical Approach for Isolation of Chitin from the Skeleton of the Black Coral Cirrhipathes sp. (Antipatharia).

The development of novel and effective methods for the isolation of chitin, which remains one of the fundamental aminopolysaccharides within skeletal structures of diverse marine invertebrates, is still relevant. In contrast to numerous studies on chitin extraction from crustaceans, mollusks and sponges, there are only a few reports concerning its isolation from corals, and especially black corals (Antipatharia). In this work, we report the stepwise isolation and identification of chitin from Cirrhipathes sp. (Antipatharia, Antipathidae) for the first time. The proposed method, aiming at the extraction of the chitinous scaffold from the skeleton of black coral species, combined a well-known chemical treatment with in situ electrolysis, using a concentrated Na2SO4 aqueous solution as the electrolyte. This novel method allows the isolation of α-chitin in the form of a microporous membrane-like material. Moreover, the extracted chitinous scaffold, with a well-preserved, unique pore distribution, has been extracted in an astoundingly short time (12 h) compared to the earlier reported attempts at chitin isolation from Antipatharia corals.

3D Chitin Scaffolds of Marine Demosponge Origin for Biomimetic Mollusk Hemolymph-Associated Biomineralization Ex-Vivo.

Structure-based tissue engineering requires large-scale 3D cell/tissue manufacture technologies, to produce biologically active scaffolds. Special attention is currently paid to naturally pre-designed scaffolds found in skeletons of marine sponges, which represent a renewable resource of biomaterials. Here, an innovative approach to the production of mineralized scaffolds of natural origin is proposed. For the first time, a method to obtain calcium carbonate deposition ex vivo, using living mollusks hemolymph and a marine-sponge-derived template, is specifically described. For this purpose, the marine sponge Aplysin aarcheri and the terrestrial snail Cornu aspersum were selected as appropriate 3D chitinous scaffold and as hemolymph donor, respectively. The formation of calcium-based phase on the surface of chitinous matrix after its immersion into hemolymph was confirmed by Alizarin Red staining. A direct role of mollusks hemocytes is proposed in the creation of fine-tuned microenvironment necessary for calcification ex vivo. The X-ray diffraction pattern of the sample showed a high CaCO3 amorphous content. Raman spectroscopy evidenced also a crystalline component, with spectra corresponding to biogenic calcite. This study resulted in the development of a new biomimetic product based on ex vivo synthetized ACC and calcite tightly bound to the surface of 3D sponge chitin structure.

Functionalization of 3D Chitinous Skeletal Scaffolds of Sponge Origin Using Silver Nanoparticles and Their Antibacterial Properties.

Chitin, as one of nature's most abundant structural polysaccharides, possesses worldwide, high industrial potential and a functionality that is topically pertinent. Nowadays, the metallization of naturally predesigned, 3D chitinous scaffolds originating from marine sponges is drawing focused attention. These invertebrates represent a unique, renewable source of specialized chitin due to their ability to grow under marine farming conditions. In this study, the development of composite material in the form of 3D chitin-based skeletal scaffolds covered with silver nanoparticles (AgNPs) and Ag-bromide is described for the first time. Additionally, the antibacterial properties of the obtained materials and their possible applications as a water filtration system are also investigated.

Naturally pre-designed biomaterials: Spider molting cuticle as a functional crude oil sorbent.

Diverse fields of modern environmental technology are nowadays focused on the discovery and development of new sources for oil spill removal. An especially interesting type of sorbents is those of natural origin-biosorbents-as ready-to-use constructs with biodegradable, nontoxic, renewable and cost-efficient properties. Moreover, the growing problem of microplastic-related contamination in the oceans further encourages the use of biosorbents. Here, for the first time, naturally pre-designed molting cuticles of the Theraphosidae spider Avicularia sp. "Peru purple", as part of constituting a large-scale spider origin waste material, were used for efficient sorption of crude oil. Compared with currently used materials, the proposed biosorbent of spider cuticular origin demonstrates excellent ability to remain on the water surface for a long time. In this study the morphology and hydrophobic features of Theraphosidae cuticle are investigated for the first time. The unique surface morphology and very low surface free energy (4.47 ± 0.08 mN/m) give the cuticle-based, tube-like, porous biosorbent excellent oleophilic-hydrophobic properties. The crude oil sorption capacities of A. sp. "Peru purple" molt structures in sea water, distilled water and fresh water were measured at 12.6 g/g, 15.8 g/g and 16.6 g/g respectively. These results indicate that this biomaterial is more efficient than such currently used fibrous sorbents as human hairs or chicken feathers. Four cycles of desorption were performed and confirmed the reusability of the proposed biosorbent. We suggest that the oil adsorption mechanism is related to the brush-like and microporous structure of the tubular spider molting cuticles and may also involve interaction between the cuticular wax layers and crude oil.