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.

Biomarkers and Corresponding Biosensors for Childhood Cancer Diagnostics.

Although tremendous progress has been made in treating childhood cancer, it is still one of the leading causes of death in children worldwide. Because cancer symptoms overlap with those of other diseases, it is difficult to predict a tumor early enough, which causes cancers in children to be more aggressive and progress more rapidly than in adults. Therefore, early and accurate detection methods are urgently needed to effectively treat children with cancer therapy. Identification and detection of cancer biomarkers serve as non-invasive tools for early cancer screening, prevention, and treatment. Biosensors have emerged as a potential technology for rapid, sensitive, and cost-effective biomarker detection and monitoring. In this review, we provide an overview of important biomarkers for several common childhood cancers. Accordingly, we have enumerated the developed biosensors for early detection of pediatric cancer or related biomarkers. This review offers a restructured platform for ongoing research in pediatric cancer diagnostics that can contribute to the development of rapid biosensing techniques for early-stage diagnosis, monitoring, and treatment of children with cancer and reduce the mortality rate.

Growing of Artificial Lignin on Cellulose Ferulate Thin Films.

Thin films of cellulose ferulate were designed to study the formation of dehydrogenation polymers (DHPs) on anchor groups of the surface. Trimethylsilyl (TMS) cellulose ferulate with degree of substitution values of 0.35 (ferulate) and 2.53 (TMS) was synthesized by sophisticated polysaccharide chemistry applying the Mitsunobu reaction. The biopolymer derivative was spin-coated into thin films to yield ferulate moieties on a smooth cellulose surface. Dehydrogenative polymerization of coniferyl alcohol was performed in a Quartz crystal microbalance with a dissipation monitoring device in the presence of H2O2 and adsorbed horseradish peroxidase. The amount of DHP formed on the surface was found to be independent of the base layer thickness from 14 to 75 nm. Pyrolysis-GC-MS measurements of the DHP revealed ß-O-4 and ß-5 linkages. Mimicking lignification of plant cell walls on highly defined model films enables reproducible investigations of structure-property relationships.

Dry sonication process for preparation of hybrid structures based on graphene and carbon nanotubes usable for chemical sensors.

The combination of graphene (G) and multi-walled carbon nanotubes (MWCNTs) creates three-dimensional hybrid structures particularly suitable as next-generation electrical interface materials. Nevertheless, efficient mixing of the nanopowders is challenging, unless previous disaggregation and eventual surface modification of both is reached. To avoid use of solvents and multistep purification process for synthesis of stable G/MWCNTs hybrids, herein, a novel dry method based on an air sonication process was used. Taking advantage from the vigorous turbulent currents generated by powerful ultrasonication in air that induces strong thermal convection or radiation to and from the particles, it simultaneously ensures disentanglement of the large MWCNT bundles and G exfoliation and their only mild surface modifications. By changing the ratio between MWCNTs and G, a range of hybrids was obtained, different in surface morphology and chemistry. These hybrids have shown great potential as sensing material for designing mass-based sensors for toxic gases and chemiresistor for vapors detection.

Product Integration of Established Crash Sensors for Safety Applications in Lightweight Vehicles.

The functionality of products increases when more sensors are used. This trend also affects future automobiles and becomes even more relevant in connected and autonomous applications. Concerning automotive lightweight design, carbon fibre-reinforced polymers (CFRP) are suitable materials. However, their drawbacks include the relatively high manufacturing costs of CFRP components in addition to the difficulty of recycling. To compensate for the increased expenditure, the integration of automotive sensors in CFRP vehicle structures provides added value. As a new approach, established sensors are integrated into fibre-reinforced polymer (FRP) structures. The sensors are usually mounted to the vehicle. The integration of sensors into the structure saves weight and space. Many other approaches specifically develop new sensors for integration into FRP structures. With the new approach, there is no need for elaborate development of new sensors since established sensors are used. The present research also showed that the range of applications of the sensors can be extended by the integration. The present paper outlines the functional behaviour of the integrated sensor utilized for crashing sensing. First of all, the integration quality of the sensor is relevant. Different requirements apply to the usual mounting of the sensor. The self-sensing structure must fulfil those requirements. Moreover, unfamiliar characteristics of the new surrounding structure might affect the sensing behaviour. Thus, the sensing behaviour of the self-sensing composite was analyzed in detail. The overarching objective is the general integration of sensors in products with reasonable effort.

Structure-Function Relationships of Nanocarbon/Polymer Composites for Chemiresistive Sensing: A Review.

Composites of organic compounds and inorganic nanomaterials provide novel sensing platforms for high-performance sensor applications. The combination of the attractive functionalities of nanomaterials with polymers as an organic matrix offers promising materials with tunable electrical, mechanical, and chemisensitive properties. This review mainly focuses on nanocarbon/polymer composites as chemiresistors. We first describe the structure and properties of carbon nanofillers as reinforcement agents used in the manufacture of polymer composites and the sensing mechanism of developed nanocomposites as chemiresistors. Then, the design and synthesizing methods of polymer composites based on carbon nanofillers are discussed. The electrical conductivity, mechanical properties, and the applications of different nanocarbon/polymer composites for the detection of different analytes are reviewed. Lastly, challenges and the future vision for applications of such nanocomposites are described.

Molecularly Imprinted Polymer-Based Sensors for Priority Pollutants.

Globally, there is growing concern about the health risks of water and air pollution. The U.S. Environmental Protection Agency (EPA) has developed a list of priority pollutants containing 129 different chemical compounds. All of these chemicals are of significant interest due to their serious health and safety issues. Permanent exposure to some concentrations of these chemicals can cause severe and irrecoverable health effects, which can be easily prevented by their early identification. Molecularly imprinted polymers (MIPs) offer great potential for selective adsorption of chemicals from water and air samples. These selective artificial bio(mimetic) receptors are promising candidates for modification of sensors, especially disposable sensors, due to their low-cost, long-term stability, ease of engineering, simplicity of production and their applicability for a wide range of targets. Herein, innovative strategies used to develop MIP-based sensors for EPA priority pollutants will be reviewed.

Rational Design of Molecularly Imprinted Polymers Using Quaternary Ammonium Cations for Glyphosate Detection.

Molecularly imprinted polymers have emerged as cost-effective and rugged artificial selective sorbents for combination with different sensors. In this study, quaternary ammonium cations, as functional monomers, were systematically evaluated to design imprinted polymers for glyphosate as an important model compound for electrically charged and highly water-soluble chemical compounds. To this aim, a small pool of monomers were used including (3-acrylamidopropyl)trimethylammonium chloride, [2-(acryloyloxy)ethyl]trimethylammonium chloride, and diallyldimethylammonium chloride. The simultaneous interactions between three positively charged monomers and glyphosate were preliminary evaluated using statistical design of the experiment method. Afterwards, different polymers were synthesized at the gold surface of the quartz crystal microbalance sensor using optimized and not optimized glyphosate-monomers ratios. All synthesized polymers were characterized using atomic force microscopy, contact angle, Fourier-transform infrared, and X-ray photoelectron spectroscopy. Evaluated functional monomers showed promise as highly efficient functional monomers, when they are used together and at the optimized ratio, as predicted by the statistical method. Obtained results from the modified sensors were used to develop a simple model describing the binding characteristics at the surface of the different synthesized polymers. This model helps to develop new synthesis strategies for rational design of the highly selective imprinted polymers and to use as a sensing platform for water soluble and polar targets.

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.

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.

New Source of 3D Chitin Scaffolds: The Red Sea Demosponge Pseudoceratina arabica (Pseudoceratinidae, Verongiida).

The bioactive bromotyrosine-derived alkaloids and unique morphologically-defined fibrous skeleton of chitin origin have been found recently in marine demosponges of the order Verongiida. The sophisticated three-dimensional (3D) structure of skeletal chitinous scaffolds supported their use in biomedicine, tissue engineering as well as in diverse modern technologies. The goal of this study was the screening of new species of the order Verongiida to find another renewable source of naturally prefabricated 3D chitinous scaffolds. Special attention was paid to demosponge species, which could be farmed on large scale using marine aquaculture methods. In this study, the demosponge Pseudoceratina arabica collected in the coastal waters of the Egyptian Red Sea was examined as a potential source of chitin for the first time. Various bioanalytical tools including scanning electron microscopy (SEM), fluorescence microscopy, FTIR analysis, Calcofluor white staining, electrospray ionization mass spectrometry (ESI-MS), as well as a chitinase digestion assay were successfully used to confirm the discovery of α-chitin within the skeleton of P. arabica. The current finding should make an important contribution to the field of application of this verongiid sponge as a novel renewable source of biologically-active metabolites and chitin, which are important for development of the blue biotechnology especially in marine oriented biomedicine.

Express Method for Isolation of Ready-to-Use 3D Chitin Scaffolds from Aplysina archeri (Aplysineidae: Verongiida) Demosponge.

Sponges are a valuable source of natural compounds and biomaterials for many biotechnological applications. Marine sponges belonging to the order Verongiida are known to contain both chitin and biologically active bromotyrosines. Aplysina archeri (Aplysineidae: Verongiida) is well known to contain bromotyrosines with relevant bioactivity against human and animal diseases. The aim of this study was to develop an express method for the production of naturally prefabricated 3D chitin and bromotyrosine-containing extracts simultaneously. This new method is based on microwave irradiation (MWI) together with stepwise treatment using 1% sodium hydroxide, 20% acetic acid, and 30% hydrogen peroxide. This approach, which takes up to 1 h, made it possible to isolate chitin from the tube-like skeleton of A. archeri and to demonstrate the presence of this biopolymer in this sponge for the first time. Additionally, this procedure does not deacetylate chitin to chitosan and enables the recovery of ready-to-use 3D chitin scaffolds without destruction of the unique tube-like fibrous interconnected structure of the isolated biomaterial. Furthermore, these mechanically stressed fibers still have the capacity for saturation with water, methylene blue dye, crude oil, and blood, which is necessary for the application of such renewable 3D chitinous centimeter-sized scaffolds in diverse technological and biomedical fields.

Naturally Drug-Loaded Chitin: Isolation and Applications.

Naturally occurring three-dimensional (3D) biopolymer-based matrices that can be used in different biomedical applications are sustainable alternatives to various artificial 3D materials. For this purpose, chitin-based structures from marine sponges are very promising substitutes. Marine sponges from the order Verongiida (class Demospongiae) are typical examples of demosponges with well-developed chitinous skeletons. In particular, species belonging to the family Ianthellidae possess chitinous, flat, fan-like fibrous skeletons with a unique, microporous 3D architecture that makes them particularly interesting for applications. In this work, we focus our attention on the demosponge Ianthella flabelliformis (Linnaeus, 1759) for simultaneous extraction of both naturally occurring ("ready-to-use") chitin scaffolds, and biologically active bromotyrosines which are recognized as potential antibiotic, antitumor, and marine antifouling substances. We show that selected bromotyrosines are located within pigmental cells which, however, are localized within chitinous skeletal fibers of I. flabelliformis. A two-step reaction provides two products: treatment with methanol extracts the bromotyrosine compounds bastadin 25 and araplysillin-I N20 sulfamate, and a subsequent treatment with acetic acid and sodium hydroxide exposes the 3D chitinous scaffold. This scaffold is a mesh-like structure, which retains its capillary network, and its use as a potential drug delivery biomaterial was examined for the first time. The results demonstrate that sponge-derived chitin scaffolds, impregnated with decamethoxine, effectively inhibit growth of the human pathogen Staphylococcus aureus in an agar diffusion assay.

A nanocomposite consisting of reduced graphene oxide and electropolymerized ß-cyclodextrin for voltammetric sensing of levofloxacin.

A glassy carbon electrode (GCE) was modified with a nanocomposite prepared from polymerized ß-cyclodextrin (ß-CD) and reduced graphene oxide (rGO). The modified GCE is shown to enable the voltammetric determination of traces of levofloxacin (LEV) by various electrochemical techniques. Experimental factors affecting the results including the amount of the substrates in preparation of the nanocomposite, accumulation time, the scan rate and pH value of the electrolyte were optimized. The modified GCE, best operated at a working potential of 1.00 V (vs. Ag/AgCl), has two linear response ranges, one for low LEV concentrations (100 pmol L-1 to 100 nmol L-1), and one for higher LEV concentrations (100 nmol L-1 to 100 µmol L-1). The limit of detection and sensitivity are calculated to be 30 pmol L-1 and 467.33 nA µmol L-1 cm-2, respectively. The modified GCE demonstrates a number of advantages such as high sensitivity and selectivity, low LOD, excellent reproducibility, high surface-to-volume ratio, and good electrocatalytic activity towards LEV. The sensor was successfully applied to the determination of LEV in spiked human serum samples. Graphical abstract.

Naturally Prefabricated Marine Biomaterials: Isolation and Applications of Flat Chitinous 3D Scaffolds from Ianthella labyrinthus (Demospongiae: Verongiida).

Marine sponges remain representative of a unique source of renewable biological materials. The demosponges of the family Ianthellidae possess chitin-based skeletons with high biomimetic potential. These three-dimensional (3D) constructs can potentially be used in tissue engineering and regenerative medicine. In this study, we focus our attention, for the first time, on the marine sponge Ianthella labyrinthus Bergquist & Kelly-Borges, 1995 (Demospongiae: Verongida: Ianthellidae) as a novel potential source of naturally prestructured bandage-like 3D scaffolds which can be isolated simultaneously with biologically active bromotyrosines. Specifically, translucent and elastic flat chitinous scaffolds have been obtained after bromotyrosine extraction and chemical treatments of the sponge skeleton with alternate alkaline and acidic solutions. For the first time, cardiomyocytes differentiated from human induced pluripotent stem cells (iPSC-CMs) have been used to test the suitability of I. labyrinthus chitinous skeleton as ready-to-use scaffold for their cell culture. Results reveal a comparable attachment and growth on isolated chitin-skeleton, compared to scaffolds coated with extracellular matrix mimetic Geltrex®. Thus, the natural, unmodified I. labyrinthus cleaned sponge skeleton can be used to culture iPSC-CMs and 3D tissue engineering. In addition, I. labyrinthus chitin-based scaffolds demonstrate strong and efficient capability to absorb blood deep into the microtubes due to their excellent capillary effect. These findings are suggestive of the future development of new sponge chitin-based absorbable hemostats as alternatives to already well recognized cellulose-based fabrics.

Marine Spongin: Naturally Prefabricated 3D Scaffold-Based Biomaterial.

The biosynthesis, chemistry, structural features and functionality of spongin as a halogenated scleroprotein of keratosan demosponges are still paradigms. This review has the principal goal of providing thorough and comprehensive coverage of spongin as a naturally prefabricated 3D biomaterial with multifaceted applications. The history of spongin's discovery and use in the form of commercial sponges, including their marine farming strategies, have been analyzed and are discussed here. Physicochemical and material properties of spongin-based scaffolds are also presented. The review also focuses on prospects and trends in applications of spongin for technology, materials science and biomedicine. Special attention is paid to applications in tissue engineering, adsorption of dyes and extreme biomimetics.

First Report on Chitin in a Non-Verongiid Marine Demosponge: The Mycale euplectellioides Case.

Sponges (Porifera) are recognized as aquatic multicellular organisms which developed an effective biochemical pathway over millions of years of evolution to produce both biologically active secondary metabolites and biopolymer-based skeletal structures. Among marine demosponges, only representatives of the Verongiida order are known to synthetize biologically active substances as well as skeletons made of structural polysaccharide chitin. The unique three-dimensional (3D) architecture of such chitinous skeletons opens the widow for their recent applications as adsorbents, as well as scaffolds for tissue engineering and biomimetics. This study has the ambitious goal of monitoring other orders beyond Verongiida demosponges and finding alternative sources of naturally prestructured chitinous scaffolds; especially in those demosponge species which can be cultivated at large scales using marine farming conditions. Special attention has been paid to the demosponge Mycale euplectellioides(Heteroscleromorpha: Poecilosclerida: Mycalidae) collected in the Red Sea. For the first time, we present here a detailed study of the isolation of chitin from the skeleton of this sponge, as well as its identification using diverse bioanalytical tools. Calcofluor white staining, Fourier-transform Infrared Spcetcroscopy (FTIR), electrospray ionization mass spectrometry (ESI-MS), scanning electron microscopy (SEM), and fluorescence microscopy, as well as a chitinase digestion assay were applied in order to confirm with strong evidence the finding of a-chitin in the skeleton of M. euplectellioides. We suggest that the discovery of chitin within representatives of the Mycale genus is a promising step in their evaluation of these globally distributed sponges as new renewable sources for both biologically active metabolites and chitin, which are of prospective use for pharmacology and biomaterials oriented biomedicine, respectively.

Assembly Behavior of Organically Interlinked Gold Nanoparticle Composite Films: A Quartz Crystal Microbalance Investigation.

Thin films based on dodecylamine stabilized gold nanoparticles interlinked with different organic molecules are prepared by automatic layer-by-layer self-assembly in a microfluidic quartz crystal microbalance (QCM) cell, to obtain an in situ insight on the film formation by ligand/linker exchange reactions. The influence of interlinking functional groups and the length of the organic linker molecule on the assembly behavior is investigated. Alkyldithiols with different lengths are compared to alkyldiamines and alkylbisdithiocarbamates with a C8 alkylic molecular backbone. The stepwise layer-by-layer assembly occurs independently of the linker molecule, while the largest frequency changes always correspond to the gold nanoparticle step. During the solvent rinsing and ligand/linker exchange reaction step, the frequency is almost constant with slight increases or decreases dependent on the molar mass of the linker compared to the exchanged ligand. The assembly efficiency is higher for shorter molecules and for molecules with stronger interacting functional groups. The densities of the composite films are calculated from QCM data and independent thickness measurements. They reflect the higher fraction of organic material in the films comprising longer organic linkers. The plasmon resonance band of the gold nanoparticles in the final assemblies is measured with UV/vis spectroscopy. Band positions in films prepared from dithiols and diamines of comparable lengths are very similar, while the spectrum of the bisdithiocarbamate film exhibits a distinct blue-shift. This observation is explained by the longer molecular structure of the linker due to a larger binding group, in conjunction with a delocalization of particle charge on the organic molecule. Obtained results play an essential role in the understanding of thin film layer-by-layer self-assembly processes, and enable the formation of new gold nanoparticle networks with organic diamine and bisdithiocarbamate molecules.

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%).

Biomimetic Dehydrogenation of Non-Conventional Lignin Monomers on Cellulose Ferulate Interfaces.

Cellulose ferulate, synthesized by Mitsunobu reaction, is shaped into thin films and also used as an aqueous dispersion to perform artificial lignin polymerization on anchor groups. This biomimetic approach is carried out in a Quartz crystal microbalance with a dissipation monitoring (QCM-D) device to enable online monitoring of the dehydrogenation, applying H2O2 and adsorbed horseradish peroxidase (HRP). The systematic use of phenylpropanoids with different oxidation states, i.e., ferulic acid, coniferyl aldehyde, coniferyl alcohol, and eugenol allowed to conclude structure-property relationships. Both the deposited material, as well as the surface roughness increased with the hydrophobicity of the monomers. Beyond surface characterizations, py-GC-MS, HSQC NMR spectroscopy and Size exclusion chromatography (SEC) measurements revealed the linkage types ß-ß, ß-5, 5-5, and ß-O-4, as well as the oligomeric character of the dehydrogenation products. All samples possessed an antibacterial activity against B. subtilis and can be used in the field of antimicrobial biomaterials.