Simultaneous Electrochemical Detection of Dopamine and Tryptophan Using 3D Goethite-Spongin Composites.

In this study, a facile approach for simultaneous determination of dopamine (DA) and tryptophan (TRP) using a 3D goethite-spongin-modified carbon paste electrode is reported. The prepared electrode exhibited excellent electrochemical catalytic activity towards DA and TRP oxidation. The electrochemical sensing of the modified electrode was investigated using cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectroscopy. Through differential pulse voltammetry analysis, two well-separated oxidation peaks were observed at 28 and 77 mV, corresponding to the oxidation of DA and TRP at the working electrode, with a large peak separation of up to 490 mV. DA and TRP were determined both individually and simultaneously in their dualistic mixture. As a result, the anodic peak currents and the concentrations of DA and TRP were found to exhibit linearity within the ranges of 4-246 µM for DA and 2 to 150 µM for TRP. The detection limits (S/N = 3) as low as 1.9 µM and 0.37 µM were achieved for DA and TRP, respectively. The proposed sensor was successfully applied to the simultaneous determination of DA and TRP in human urine samples with satisfactory recoveries (101% to 116%).

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.

Mechanical recycling of CFRPs based on thermoplastic acrylic resin with the addition of carbon nanotubes.

Carbon fibre-reinforced polymers (CFRPs) are commonly used in aviation, automotive and renewable energy markets, which are constantly growing. Increasing the production of composite parts leads to increased waste production and a future increase in end-of-life components. To improve the recyclability of CFRPs, new materials that fit in with the idea of a circular economy should be used as a composite matrix. One such material is a commercially available thermoplastic liquid resin, Elium® (Arkema, France). In this work, the authors investigated how the mechanical recycling process affects the properties of thermoplastic-based carbon fibre composites. CFRPs with neat Elium® resin and resin modified with 0.02 wt.% single-walled carbon nanotubes or 0.02 wt.% multi-walled carbon nanotubes were manufactured using the resin infusion process. Afterwards, prepared laminates were mechanically ground, and a new set of composites was manufactured by thermopressing. The microstructure, mechanical, thermal and electrical properties were investigated for both sets of composites. The results showed that mechanical grinding and thermopressing processes lead to a significant increase in the electrical conductivity of composites. Additionally, a sharp decrease in all mechanical properties was observed.

Nanocomposites Based on Thermoplastic Acrylic Resin with the Addition of Chemically Modified Multi-Walled Carbon Nanotubes.

The main goal of this work was an improvement in the mechanical and electrical properties of acrylic resin-based nanocomposites filled with chemically modified carbon nanotubes. For this purpose, the surface functionalization of multi-walled carbon nanotubes (MWCNTs) was carried out by means of aryl groups grafting via the diazotization reaction with selected aniline derivatives, and then nanocomposites based on ELIUM® resin were fabricated. FT-IR analysis confirmed the effectiveness of the carried-out chemical surface modification of MWCNTs as new bands on FT-IR spectra appeared in the measurements. TEM observations showed that carbon nanotube fragmentation did not occur during the modifications. According to the results from Raman spectroscopy, the least defective carbon nanotube structure was obtained for aniline modification. Transmission light microscopy analysis showed that the neat MWCNTs agglomerate strongly, while the proposed modifications improved their dispersion significantly. Viscosity tests confirmed, that as the nanofiller concentration increases, the viscosity of the mixture increases. The mixture with the highest dispersion of nanoparticles exhibited the most viscous behaviour. Finally, an enhancement in impact resistance and electrical conductivity was obtained for nanocomposites containing modified MWCNTs.

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.

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.

Creation of a 3D Goethite-Spongin Composite Using an Extreme Biomimetics Approach.

The structural biopolymer spongin in the form of a 3D scaffold resembles in shape and size numerous species of industrially useful marine keratosan demosponges. Due to the large-scale aquaculture of these sponges worldwide, it represents a unique renewable source of biological material, which has already been successfully applied in biomedicine and bioinspired materials science. In the present study, spongin from the demosponge Hippospongia communis was used as a microporous template for the development of a new 3D composite containing goethite [α-FeO(OH)]. For this purpose, an extreme biomimetic technique using iron powder, crystalline iodine, and fibrous spongin was applied under laboratory conditions for the first time. The product was characterized using SEM and digital light microscopy, infrared and Raman spectroscopy, XRD, thermogravimetry (TG/DTG), and confocal micro X-ray fluorescence spectroscopy (CMXRF). A potential application of the obtained goethite-spongin composite in the electrochemical sensing of dopamine (DA) in human urine samples was investigated, with satisfactory recoveries (96% to 116%) being obtained.

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.

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.

Deep eutectic solvent-assisted fabrication of bioinspired 3D carbon-calcium phosphate scaffolds for bone tissue engineering.

Tissue engineering is a burgeoning field focused on repairing damaged tissues through the combination of bodily cells with highly porous scaffold biomaterials, which serve as templates for tissue regeneration, thus facilitating the growth of new tissue. Carbon materials, constituting an emerging class of superior materials, are currently experiencing remarkable scientific and technological advancements. Consequently, the development of novel 3D carbon-based composite materials has become significant for biomedicine. There is an urgent need for the development of hybrids that will combine the unique bioactivity of ceramics with the performance of carbonaceous materials. Considering these requirements, herein, we propose a straightforward method of producing a 3D carbon-based scaffold that resembles the structural features of spongin, even on the nanometric level of their hierarchical organization. The modification of spongin with calcium phosphate was achieved in a deep eutectic solvent (choline chloride : urea, 1 : 2). The holistic characterization of the scaffolds confirms their remarkable structural features (i.e., porosity, connectivity), along with the biocompatibility of α-tricalcium phosphate (α-TCP), rendering them a promising candidate for stem cell-based tissue-engineering. Culturing human bone marrow mesenchymal stem cells (hMSC) on the surface of the biomimetic scaffold further verifies its growth-facilitating properties, promoting the differentiation of these cells in the osteogenesis direction. ALP activity was significantly higher in osteogenic medium compared to proliferation, indicating the differentiation of hMSC towards osteoblasts. However, no significant difference between C and C-αTCP in the same medium type was observed.

Honeycomb Biosilica in Sponges: From Understanding Principles of Unique Hierarchical Organization to Assessing Biomimetic Potential.

Structural bioinspiration in modern material science and biomimetics represents an actual trend that was originally based on the bioarchitectural diversity of invertebrate skeletons, specifically, honeycomb constructs of natural origin, which have been in humanities focus since ancient times. We conducted a study on the principles of bioarchitecture regarding the unique biosilica-based honeycomb-like skeleton of the deep-sea glass sponge Aphrocallistes beatrix. Experimental data show, with compelling evidence, the location of actin filaments within honeycomb-formed hierarchical siliceous walls. Principles of the unique hierarchical organization of such formations are discussed. Inspired by poriferan honeycomb biosilica, we designed diverse models, including 3D printing, using PLA-, resin-, and synthetic-glass-prepared corresponding microtomography-based 3D reconstruction.

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.

The immunomodulatory effects of RNA-based biomaterials on bone regeneration.

The use of RNA as therapeutic agents is a visionary idea in contemporary medicine. Some forms of RNA can modulate the immune response of the host to enhance tissue regeneration events such as osteogenesis. Herein, RNA molecules commercially available for immunomodulatory applications (imRNA) were used to prepare biomaterials for bone regeneration. The polyanionic imRNA stabilized calcium phosphate ionic clusters to produce imRNA-ACP that had the capacity to mineralize the intrafibrillar compartments of collagen fibrils. For the first time, it was shown that incorporating imRNA-ACP into collagen scaffolds resulted in rapid new bone formation in cranial defects of mice. Both in vivo and in vitro results demonstrated that macrophage polarization was highly-sensitive to the imRNA-ACP containing collagen scaffolds. Macrophages were polarized into the anti-inflammatory M2 phenotype that produced anti-inflammation cytokines and growth factors. The favorable osteoimmunological microenvironment created by the scaffolds prevented their immunorejection and facilitated osteogenesis. The potential of RNA in creating immunomodulatory biomaterials has been underestimated in the past. The overall aim of this study was to explore the potential application of imRNA-based biomaterials in bone tissue engineering, with the competitive edge of facile synthesis and excellent biocompatibility. STATEMENT OF SIGNIFICANCE: In this work, commercially available RNA extracted from bovine spleens for immunomodulatory applications (imRNA) were used to stabilize amorphous calcium phosphate (ACP) and induce mineralization within collagen fibrils. Incorporation of imRNA-ACP into collagen scaffolds regenerated new bone in-situ. Because of its immunomodulatory effects, the imRNA-ACP that was incorporated into collagen scaffolds modulated the local immune environment of murine cranial defects by altering the macrophage phenotype through JAK2/STAT3 signaling pathway. The novelty of this work existed in the discovery of RNA's potential in creating immunomodulatory biomaterials. With the competitive edge of facile synthesis and excellent biocompatibility, the imRNA-based biomaterials are potentially useful for future bone tissue engineering applications.

Electrochemical Sensing of Gallic Acid in Beverages Using a 3D Bio-Nanocomposite Based on Carbon Nanotubes/Spongin-Atacamite.

Gallic acid (GA) is one of the most important polyphenols, being widely used in the food, cosmetic, and pharmaceutical industries due to its biological effects such as antioxidant, antibacterial, anticancer, antiviral, anti-inflammatory, and cardioprotective properties. Hence, simple, fast, and sensitive determination of GA is of particular importance. Considering the fact that GA is an electroactive compound, electrochemical sensors offer great potential for GA quantitation due to their fast response time, high sensitivity, and ease of use. A simple, fast, and sensitive GA sensor was fabricated on the basis of a high-performance bio-nanocomposite using spongin as a natural 3D polymer, atacamite, and multi-walled carbon nanotubes (MWCNTs). The developed sensor showed an excellent response toward GA oxidation with remarkable electrochemical features due to the synergistic effects of 3D porous spongin and MWCNTs, which provide a large surface area and enhance the electrocatalytic activity of atacamite. At optimal conditions by differential pulse voltammetry (DPV), a good linear relationship was obtained between peak currents and GA concentrations in a wild linear range of 500 nM to 1 mM. Subsequently, the proposed sensor was used to detect GA in red wine as well as in green and black tea, confirming its great potential as a reliable alternative to conventional methods for GA determination.

Applicability of a Green Nanocomposite Consisted of Spongin Decorated Cu2WO4(OH)2 and AgNPs as a High-Performance Aptasensing Platform in Staphylococcus aureus Detection.

This study reports the synthesis of a nanocomposite consisting of spongin and its applicability in the development of an aptasensing platform with high performance. The spongin was carefully extracted from a marine sponge and decorated with copper tungsten oxide hydroxide. The resulting spongin-copper tungsten oxide hydroxide was functionalized by silver nanoparticles and utilized in electrochemical aptasensor fabrication. The nanocomposite covered on a glassy carbon electrode surface amplified the electron transfer and increased active electrochemical sites. The aptasensor was fabricated by loading of thiolated aptamer on the embedded surface via thiol-AgNPs linkage. The applicability of the aptasensor was tested in detecting the Staphylococcus aureus bacterium as one of the five most common causes of nosocomial infectious diseases. The aptasensor measured S. aureus under a linear concentration range of 10-108 colony-forming units per milliliter and a limit of quantification and detection of 12 and 1 colony-forming unit per milliliter, respectively. The highly selective diagnosis of S. aureus in the presence of some common bacterial strains was satisfactorily evaluated. The acceptable results of the human serum analysis as the real sample may be promising in the bacteria tracking in clinical samples underlying the green chemistry principle.

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.

Patentology of chitinous biomaterials. Part II: chitosan.

Cationic chitosan is recognized as the most widely studied derivative of chitin, one of the main and the most evolutionary ancient structural biopolymer in nature. The multi-functionality of chitosan, due to its specific physicochemical properties, biodegradability and biocompatibility, is a fundamental factor in the patentability of this biopolymer in diverse fields of modern science and technology. It is shown that the chitosan-related patents were categorized mainly under biomedical, material science, biotechnology, and chemical directions; while a very small portion of the patents were mentioned under food, cosmetics, environmental protection, and agricultural fields. For the first time, the review provides a detailed analysis on the background and scope of the patents reported on chitosan so far.

Nano-architecture of MOF (ZIF-67)-based Co3O4 NPs@N-doped porous carbon polyhedral nanocomposites for oxidative degradation of antibiotic sulfamethoxazole from wastewater.

Co3O4 NPs in N-doped porous carbon (Co3O4 NPs@N-PC) materials were prepared by one-pot pyrolysis of a ZIF-67 powder under N2 atmosphere and followed by oxidation under air atmosphere (200 °C) toward promotion catalytic activity and activation of peroxymonosulfate (PMS) to degradation sulfamethoxazole (SMZ). 2-methylimidazole was used as a nitrogen source and a competitive ligand for the synthesis of Co3O4 NPs@N-PC, which in addition to affecting nucleation and growth of the crystal, promotes the production of active Co-N sites. Co3O4 NPs@N-PC nano-architecture has high specific surface areas (250 m2 g-1) and is a non-toxic, effective and stable PMS activator. The effect of operating parameters including SMZ concentration, catalyst dosage, temperature and pH in the presence of Co3O4 NPs@N-PC was investigated. The Co3O4 NPs@N-PC composite showed superior performance in activating PMS over a wide range of pH (2-10) and different temperatures so that complete degradation of SMZ (50 µM, 100 mL) was achieved within 15 min. The role of Co2+/Co3+ redox system in the mechanism before and after PMS activation was determined using XPS analysis. Surface-generated radicals led to the degradation of SMZ, in which the SMZ degradation rate attained 0.21 min-1 with the mineralization of 36.8%. The feasible degradation mechanism of SMZ was studied in the presence of different scavengers and it was revealed that the degradation reaction proceeds from the radical/non-radical pathway and in this process most of the SO4- and OH radicals are dominant. The recoverability and reuse of Co3O4 NPs@N-PC were evaluated to confirm its stability and potential for SMZ degradation and it was observed that the catalyst maintains its catalytic power for at least 5 cycles.

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.