Marcin Wysokowski

Modification of Chitin with Kraft Lignin and Development of New Biosorbents for Removal of Cadmium(II) and Nickel(II) Ions

Novel, functional materials based on chitin of marine origin and lignin were prepared. The synthesized materials were subjected to physicochemical, dispersive-morphological and electrokinetic analysis. The results confirm the effectiveness of the proposed method of synthesis of functional chitin/lignin materials. Mechanism of chitin modification by lignin is based on formation of hydrogen bonds between chitin and lignin. Additionally, the chitin/lignin materials were studied from the perspective of waste water treatment. The synthetic method presented in this work shows an attractive and facile route for producing low-cost chitin/lignin biosorbents with high efficiency of nickel and cadmium adsorption (88.0% and 98.4%, respectively). The discovery of this facile method of synthesis of functional chitin/lignin materials will also have a significant impact on the problematic issue of the utilization of chitinous waste from the seafood industry, as well as lignin by-products from the pulp and paper industry.

Isolation and identification of chitin in three-dimensional skeleton of Aplysina fistularis marine sponge

The recent discovery of chitin within skeletons of numerous marine and freshwater sponges (Porifera) stimulates further experiments to identify this structural aminopolysaccharide in new species of these aquatical animals. Aplysina fistularis (Verongida: Demospongiae: Porifera) is well known to produce biologically active bromotyrosines. Here, we present a detailed study of the structural and physico-chemical properties of the three-dimensional skeletal scaffolds of this sponge. Calcofluor white staining, Raman and IR spectroscopy, ESI-MS as well as chitinase digestion test were applied in order to unequivocally prove the first discovery of α-chitin in skeleton of A. fistularis.

An extreme biomimetic approach: hydrothermal synthesis of β-chitin/ZnO nanostructured composites

β-Chitinous scaffolds isolated from the skeleton of marine cephalopod Sepia officinalis were used as a template for the in vitro formation of ZnO under conditions (70 °C) which are extreme for biological materials. Novel β-chitin/ZnO film-like composites were prepared for the first time by hydrothermal synthesis, and were thoroughly characterized using numerous analytical methods including Raman spectroscopy, HR-TEM and XRD. We demonstrate the growth of hexagonal ZnO nanocrystals on the β-chitin substrate. Our chitin/ZnO composites presented in this work show antibacterial properties against Gram positive bacteria and can be employed for development of inorganic-organic wound dressing materials.

Preparation of chitin-silica composites by in vitro silicification of two-dimensional Ianthella basta demosponge chitinous scaffolds under modified Stöber conditions.

Chitin is a biopolymer found in cell walls of various fungi and skeletal structures of numerous invertebrates. The occurrence of chitin within calcium- and silica-containing biominerals has inspired development of chitin-based hybrids and composites in vitro with specific physico-chemical and material properties. We show here for the first time that the two-dimensional α-chitin scaffolds isolated from the skeletons of marine demosponge Ianthella basta can be effectively silicified by the two-step method with the use of Stöber silica micro- and nanodispersions under Extreme Biomimetic conditions. The chitin-silica composites obtained at 120 °C were characterized by the presence of spherical SiO2 particles homogeneously distributed over the chitin fibers, which probably follows from the compatibility of Si-OH groups to the hydroxyl groups of chitin. The biocomposites obtained were characterized by various analytical techniques such as energy dispersive spectrometry, scanning electron microscopy, thermogravimetric/differential thermal analyses as well as X-ray photoelectron spectroscopy, Fourier transform infrared and Raman spectroscopy to determine possible interactions between silica and chitin molecule. The results presented proved that the character and course of the in vitro chitin silicification in Stöber dispersions depended considerably on the degree of hydrolysis of the SiO2 precursor.

Extreme biomimetic approach for developing novel chitin-GeO2 nanocomposites with photoluminescent properties

This work presents an extreme biomimetics route for the creation of nanostructured biocomposites utilizing a chitinous template of poriferan origin. The specific thermal stability of the nanostructured chitinous template allowed for the formation under hydrothermal conditions of a novel germanium oxide-chitin composite with a defined nanoscale structure. Using a variety of analytical techniques (FTIR, Raman, energy dispersive X-ray (EDX), near-edge X-ray absorption fine structure (NEXAFS), and photoluminescence (PL) spectroscopy, EDS-mapping, selected area for the electron diffraction pattern (SAEDP), and transmission electron microscopy (TEM)), we showed that this bioorganic scaffold induces the growth of GeO2 nanocrystals with a narrow (150–300 nm) size distribution and predominantly hexagonal phase, demonstrating the chitin template’s control over the crystal morphology. The formed GeO2–chitin composite showed several specific physical properties, such as a striking enhancement in photoluminescence exceeding values previously reported in GeO2-based biomaterials. These data demonstrate the potential of extreme biomimetics for developing new-generation nanostructured materials.

Chitin-Lignin Material as a Novel Matrix for Enzyme Immobilization

Innovative materials were made via the combination of chitin and lignin, and the immobilization of lipase from Aspergillus niger. Analysis by techniques including FTIR, XPS and 13C CP MAS NMR confirmed the effective immobilization of the enzyme on the surface of the composite support. The electrokinetic properties of the resulting systems were also determined. Results obtained from elemental analysis and by the Bradford method enabled the determination of optimum parameters for the immobilization process. Based on the hydrolysis reaction of para-nitrophenyl palmitate, a determination was made of the catalytic activity, thermal and pH stability, and reusability. The systems with immobilized enzymes were found to have a hydrolytic activity of 5.72 mU, and increased thermal and pH stability compared with the native lipase. The products were also shown to retain approximately 80% of their initial catalytic activity, even after 20 reaction cycles. The immobilization process, using a cheap, non-toxic matrix of natural origin, leads to systems with potential applications in wastewater remediation processes and in biosensors.

Synthesis of nanostructured chitin–hematite composites under extreme biomimetic conditions

Chitin of poriferan origin is a unique and thermostable biological material. It also represents an example of a renewable materials source due to the high regeneration ability of Aplysina sponges under marine ranching conditions. Chitinous scaffolds isolated from the skeleton of the marine sponge Aplysina aerophoba were used as a template for the in vitro formation of Fe2O3 under conditions (pH ∼ 1.5, 90 °C) which are extreme for biological materials. Novel chitin–Fe2O3 three dimensional composites, which have been prepared for the first time using hydrothermal synthesis, were thoroughly characterized using numerous analytical methods including Raman spectroscopy, XPS, XRD, electron diffraction and HR-TEM. We demonstrate the growth of uniform Fe2O3 nanocrystals into the nanostructured chitin substrate and propose a possible mechanism of chitin–hematite interactions. Moreover, we show that composites made of sponge chitin–Fe2O3 hybrid materials with active carbon can be successfully used as electrode materials for electrochemical capacitors.

Novel nanostructured hematite–spongin composite developed using an extreme biomimetic approach

The marine sponge Hippospongia communis (Demospongiae: Porifera) is a representative of bath sponges, which possess characteristic mineral-free fibrous skeletons made of a structural protein – spongin. This fibrous skeleton is mechanically robust, resistant to acidic treatment, and thermally stable up to 160 °C. Due to these properties, we decided to use this biological material for the first time for the hydrothermal synthesis of hematite (α-Fe2O3) via catalyzed hydrolysis of FeCl3 to obtain a hematite–spongin composite. The material obtained was studied with Scanning Electron Microscopy (SEM), High-Resolution Transmission Electron Microscopy (HR-TEM), X-ray Photoemission Spectroscopy (XPS) and Raman spectroscopy. The α-Fe2O3–spongin-based composite was tested for its potential application as an anode material in a capacitor. The results indicate that components constructed using this novel composite material have a positive effect on the capacitance of energy storing devices.

Preparation and characterization of multifunctional chitin/lignin materials

Multifunctional chitin/lignin materials were synthesized. In order to combine mechanical milling of the biopolymers with simultaneous mixing, a centrifugal ball mill was utilized. The resulting materials, differing in terms of the proportions of precursors used, underwent detailed physicochemical and dispersive-morphological analysis. On the basis of FT-IR spectra and results of elemental analysis, the efficiency of the preparation of the materials was determined. The influence of the precursors on the thermal stability of the resulting systems was also evaluated. Zeta potential was determined as a function of pH to describe the electrokinetic stability of aqueous dispersions. This is important for evaluating the utility of the materials and indirectly confirms the effectiveness of the proposed method of synthesis of chitin/lignin products. Measurements were performed to determine basic colorimetric parameters, crucial in the production technology of multiple colored materials. It is expected that chitin/lignin materials will find a wide range of applications (biosorbents, polymer fillers, and electrochemical sensors), as they combine the unique properties of chitin with the specific structural features of lignin to provide a multifunctional material.

Identification of chitin in 200-million-year-old gastropod egg capsules

Abstract Chitin occurs in a variety of invertebrates, especially in arthropod cuticles, but is rarely reported in the fossil record. Although it has been detected in fossils as old as Middle Cambrian and Silurian, the majority of records come from much younger, Cenozoic deposits. In this paper, we report the preservation of chitin in Early Jurassic neritimorph gastropod egg capsules deposited in bivalve shells from prodelta-deltafront and nearshore paleoenvironments of the Holy Cross Mountains, Poland. We used a number of analytical methods to confirm the presence of chitin preserved in these ancient fossils. This is the first record of chitin preservation in Mesozoic deposits that, interestingly, do not follow the conventional Konservat-Lagerstätten manner of preserving soft-bodied and non-biomineralized organisms. We believe that deltaic settings characterized by episodic, high input of fluvial deposits, oligohaline conditions, and oxygen-poor microenvironment within the sediment—as well as early cementation of sediment infilling the shells—were crucial for chitin preservation. The preservation of chitin in such recalcitrant structures as egg capsules and deposits that formed outside conventional Konservat-Lagerstätten conditions renders it likely similar deposits may yield promise for discoveries of similar biological macromolecules.