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.

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.

One of the major challenges of implantology is to design nanoscale modifications of titanium implant surfaces inducing osseointegration. The aim of this study was to investigate the behavior of rat osteoblasts cultured on anodized TiO₂ nanotubes of different crystallinity (amorphous and anatase phase) up to 24 days. TiO₂ nanotubes were fabricated on VT1–0 titanium foil via a two-step anodization at 20 V using NH₄F as an electrolyte. Anatase-phase samples were prepared by heat treatment at 500 °C for 1 h. VT1–0 samples with flat surfaces were used as controls. Primary rat osteoblasts were seeded over experimental surfaces for several incubation times. Scanning electron microscopy (SEM) was used to analyze tested surfaces and cell morphology. Cell adhesion and proliferation were investigated by cell counting. Osteogenic differentiation of cells was evaluated by qPCR of runt-related transcription factor 2 (RUNX2), osteopontin (OPN), integrin binding sialoprotein (IBSP), alkaline phosphatase (ALP) and osteocalcin (OCN). Cell adhesion and proliferation, cell morphology and the expression of osteogenic markers were affected by TiO₂ nanotube layered substrates of amorphous and anatase crystallinity. In comparison with flat titanium, along with increased cell adhesion and cell growth a large portion of osteoblasts grown on the both nanostructured surfaces exhibited an osteocyte-like morphology as early as 48 h of culture. Moreover, the expression of all tested osteogenic markers in cells cultured on amorphous and anatase TiO₂ nanotubes was upregulated at least at one of the analyzed time points. To summarize, we demonstrated that amorphous and anodized TiO₂ layered substrates are highly biocompatible with rat osteoblasts and that the surface modification with about 1500 nm length nanotubes of 35 ± 4 (amorphous phase) and 41 ± 8 nm (anatase phase) in diameter is sufficient to induce their osteogenic differentiation. Such results are significant to the engineering of coating strategies for orthopedic implants aimed to establish a more efficient bone to implant contact and enhance bone repair.

Many current-generation biomedical implants are fabricated from the Ti-6Al-4V alloy because it has many attractive properties, such as low density and biocompatibility. However, the elastic modulus of this alloy is much larger than that of the surrounding bone, leading to bone resorption and, eventually, implant failure. In the present study, we synthesized and performed a detailed analysis of a novel low elastic modulus Ti-based alloy (Ti-28Nb-5Zr-2Ta-2Sn (TNZTS alloy)) using a variety of methods, including scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and tensile test. Additionally, the in vitro biocompatibility of the TNZTS alloy was evaluated using SCP-1, SaOs-2, and THP-1 cell lines and primary human osteoblasts. Compared to Ti-6Al-4V, the elastic modulus of TNZTS alloy was significantly lower, while measures of its in vitro biocompatibility are comparable. O₂ plasma treatment of the surface of the alloy significantly increased its hydrophilicity and, hence, its in vitro biocompatibility. TNZTS alloy specimens did not induce the release of cytokines by macrophages, indicating that such scaffolds would not trigger inflammatory responses. The present results suggest that the TNZTS alloy may have potential as an alternative to Ti-6Al-4V.

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.

Three-dimensional (3D) biopolymer-based scaffolds including chitinous matrices have been widely used for tissue engineering, regenerative medicine and other modern interdisciplinary fields including extreme biomimetics. In this study, we introduce a novel, electrochemically assisted method for 3D chitin scaffolds isolation from the cultivated marine demospongeAplysina aerophobawhich consists of three main steps: (1) decellularization, (2) decalcification and (3) main deproteinization along with desilicification and depigmentation. For the first time, the obtained electrochemically isolated 3D chitinous scaffolds have been further biomineralized ex vivo using hemolymph ofCornu aspersumedible snail aimed to generate calcium carbonates-based layered biomimetic scaffolds. The analysis of prior to, during and post-electrochemical isolation samples as well as samples treated with molluscan hemolymph was conducted employing analytical techniques such as SEM, XRD, ATR–FTIR and Raman spectroscopy. Finally, the use of described method for chitin isolation combined with biomineralization ex vivo resulted in the formation of crystalline (calcite) calcium carbonate-based deposits on the surface of chitinous scaffolds, which could serve as promising biomaterials for the wide range of biomedical, environmental and biomimetic applications.