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.

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.

Extreme Biomimetics: Designing of the First Nanostructured 3D Spongin-Atacamite Composite and its Application.

The design of new composite materials using extreme biomimetics is of crucial importance for bioinspired materials science. Further progress in research and application of these new materials is impossible without understanding the mechanisms of formation, as well as structural features at the molecular and nano-level. It presents a challenge to obtain a holistic understanding of the mechanisms underlying the interaction of organic and inorganic phases under conditions of harsh chemical reactions for biopolymers. Yet, an understanding of these mechanisms can lead to the development of unusual-but functional-hybrid materials. In this work, a key way of designing centimeter-scale macroporous 3D composites, using renewable marine biopolymer spongin and a model industrial solution that simulates the highly toxic copper-containing waste generated in the production of printed circuit boards worldwide, is proposed. A new spongin-atacamite composite material is developed and its structure is confirmed using neutron diffraction, X-ray diffraction, high-resolution transmission electron microscopy/selected-area electron diffraction, X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and electron paramagnetic resonance spectroscopy. The formation mechanism for this material is also proposed. This study provides experimental evidence suggesting multifunctional applicability of the designed composite in the development of 3D constructed sensors, catalysts, and antibacterial filter systems.