Hermann Ehrlich

Chitin and collagen as universal and alternative templates in biomineralization

Biomineralized structures and tissues are composites, containing a biologically produced organic matrix and nano- or microscale amorphous or crystalline minerals. Two main examples of organic matrices – the amino-polysaccharide chitin and the asymmetric protein collagen – are presented and discussed as the basic structural modules and organo-templates for calcium and silica biomineralization in nature. Both serve as templates, providing preferential sites for nucleation and controlling the location and orientation of mineral phases. Here, for the first time, chitin and collagen are analysed from evolutionary, structural, and functional points of view with respect to their templating properties in calcification and silicification phenomena, using both in vivo and in vitro data. It is proposed that these biopolymers be characterized as fundamental templates in biomineralization, inasmuch as they are very ancient from an evolutionary point of view, common to many species and biological systems with a global distribution. The two polymers also exhibit very similar hierarchical structural organizations, in spite of the possible alternatives they provide in chemical nature and origin. In addition, the phenomenon of multi-phase mineralization – where two minerals, amorphous and crystalline CaCO3, form from one biomolecule, chitin – is also described, analysed, and discussed for the first time.

Modern Views on Desilicification: Biosilica and Abiotic Silica Dissolution in Natural and Artificial Environments

Institute of Bioanalytical Chemistry, Dresden University of Technology, D-01069 Dresden, Germany, Crystal Engineering, Growth and Design Laboratory, Department of Chemistry, University of Crete, Voutes Campus, GR-71003 Heraklion, Crete, Greece, Laboratory of Mechanisms and Transfer in Geology, Observatory Midi-Pyrenees (OMP), UMR 5563, CNRS, 14 Avenue Edouard Belin, 31400 Toulouse, France, and FORTH-ICEHT and Laboratory of Inorganic and Analytical Chemistry, Department of Chemical Engineering, University of Patras, GR-265 04 Patras, Greece[007f]

Chitin-based scaffolds are an integral part of the skeleton of the marine demosponge Ianthella basta

The skeletons of demosponges, such as Ianthella basta, are known to be a composite material containing organic constituents. Here, we show that a filigree chitin-based scaffold is an integral component of the I. basta skeleton. These chitin-based scaffolds can be isolated from the sponge skeletons using an isolation and purification technique based on treatment with alkaline solutions. Solid-state (13)C NMR, Raman, and FT-IR spectroscopies, as well as chitinase digestion, reveal that the isolated material indeed consists of chitin. The morphology of the scaffolds has been determined by light and electron microscopy. It consists of cross-linked chitin fibers approximately 40-100 nm in diameter forming a micro-structured network. The overall shape of this network closely resembles the shape of the integer sponge skeleton. Solid-state (13)C NMR spectroscopy was used to characterize the sponge skeleton on a molecular level. The (13)C NMR signals of the chitin-based scaffolds are relatively broad, indicating a high amount of disordered chitin, possibly in the form of surface-exposed molecules. X-ray diffraction confirms that the scaffolds isolated from I. basta consist of partially disordered and loosely packed chitin with large surfaces. The spectroscopic signature of these chitin-based scaffolds is closer to that of alpha-chitin than beta-chitin.

Three-dimensional chitin-based scaffolds from Verongida sponges (Demospongiae: Porifera). Part I. Isolation and identification of chitin.

Marine invertebrate organisms including sponges (Porifera) not only provide an abundant source of biologically active secondary metabolites but also inspire investigations to develop biomimetic composites, scaffolds and templates for practical use in materials science, biomedicine and tissue engineering. Here, we presented a detailed study of the structural and physico-chemical properties of three-dimensional skeletal scaffolds of the marine sponges Aiolochroia crassa, Aplysina aerophoba, A. cauliformis, A. cavernicola, and A. fulva (Verongida: Demospongiae). We show that these fibrous scaffolds have a multilayered design and are made of chitin. (13)C solid-state NMR spectroscopy, NEXAFS, and IR spectroscopy as well as chitinase digestion and test were applied in order to unequivocally prove the existence of alpha-chitin in all investigated species.

Mineralization of the metre-long biosilica structures of glass sponges is templated on hydroxylated collagen

The minerals involved in the formation of metazoan skeletons principally comprise glassy silica, calcium phosphate or carbonate. Because of their ancient heritage, glass sponges (Hexactinellida) may shed light on fundamental questions such as molecular evolution, the unique chemistry and formation of the first skeletal silica-based structures, and the origin of multicellular animals. We have studied anchoring spicules from the metre-long stalk of the glass rope sponge (Hyalonema sieboldi; Porifera, Class Hexactinellida), which are remarkable for their size, durability, flexibility and optical properties. Using slow-alkali etching of biosilica, we isolated the organic fraction, which was revealed to be dominated by a hydroxylated fibrillar collagen that contains an unusual [Gly-3Hyp-4Hyp] motif. We speculate that this motif is predisposed for silica precipitation, and provides a novel template for biosilicification in nature.

Biological Materials of Marine Origin

Biological materials of marine origi , Biological materials of marine origi , کتابخانه دیجیتال جندی شاپور اهواز

Three-dimensional chitin-based scaffolds from Verongida sponges (Demospongiae: Porifera). Part II: Biomimetic potential and applications

In order to evaluate the biomedical potential of three-dimensional chitinous scaffolds of poriferan origin, chondrocyte culturing experiments were performed. It was shown for the first time that freshly isolated chondrocytes attached well to the chitin scaffold and synthesized an extracellular matrix similar to that found in other cartilage tissue engineering constructs. Chitin scaffolds also supported deposition of a proteoglycan-rich extracellular matrix of chondrocytes seeded bioconstructs in an in vivo environment. We suggest that chitin sponge scaffolds, apart from the demonstrated biomedical applications, are highly optimized structures for use as filtering systems, templates for biomineralization as well as metallization in order to produce catalysts.

Principles of demineralization: modern strategies for the isolation of organic frameworks. Part I. Common definitions and history.

In contrast to biomineralization phenomena, that are among the most widely studied topics in modern material and earth science and biomedicine, much less is systematized on modern view of demineralization. Biomineralized structures and tissues are composites, containing a biologically produced organic matrix and nano- or microscale amorphous or crystalline minerals. Demineralization is the process of removing the inorganic part, or the biominerals, that takes place in nature via either physiological or pathological pathways in organisms. In vitro demineralization processes, used to obtain mechanistic information, consist in the isolation of the mineral phase of the composite biomaterials from the organic matrix. Physiological and pathological demineralization include, for example, bone resorption mediated by osteoclasts. Bioerosion, a more general term for the process of deterioration of the composite biomaterials represents chemical deterioration of the organic and mineral phase followed by biological attack of the composite by microorganisms and enzymes. Bioerosional organisms are represented by endolithic cyanobacteria, fungi, algae, plants, sponges, phoronids and polychaetes, mollusks, fish and echinoids. In the history of demineralization studies, the driving force was based on problems of human health, mostly dental caries. In this paper we summarize and integrate a number of events, discoveries, milestone papers and books on different aspect of demineralization during the last 400 years. Overall, demineralization is a rapidly growing and challenging aspect of various scientific disciplines such as astrobiology, paleoclimatology, geomedicine, archaeology, geobiology, dentistry, histology, biotechnology, and others to mention just a few.

Principles of demineralization: modern strategies for the isolation of organic frameworks. Part II. Decalcification.

This is the second paper on principles of demineralization. The initial paper is dedicated to the common definitions and the history of demineralization. In present work we review the principles and mechanisms of decalcification, i.e., removing the mineral Ca-containing compounds (phosphates and carbonates) from the organic matrix in its two main aspects: natural and artificial. Natural chemical erosion of biominerals (cavitation of biogenic calcareous substrata by bacteria, fungi, algae, foraminifera, sponges, polychaetes, and mollusks) is driven by production of mineral and organic acids, acidic polysaccharides, and enzymes (cabonic anhydrase, alkaline and phosphoprotein phosphataes, and H(+)-ATPase). Examples of artifical decalcification includes demineralization of bone, dentin and enamel, and skeletal formations of corals and crustacean. The mechanism and kinetics of Ca-containing biomineral dissolution is analyzed within the framework of (i) diffusion-reaction theory; (ii) surface-reaction controlled, morphology-based theories, and (iii) phenomenological surface coordination models. The application of surface complexation model for describing and predicting the effect of organic ligands on calcium and magnesium dissolution kinetics is also described. Use of the electron microscopy-based methods for observation and visualization of the decalcification phenomenon is discussed.

Nanostructural organization of naturally occurring composites-part II: silica-chitin-based biocomposites

Investigations of the micro-and nanostructures and chemical composition of the sponge skeletons as examples for natural structural biocomposites are of fundamental scientific relevance. Recently, we show that some demosponges (Verongula gigantea, Aplysina sp.) and glass sponges (Farrea occa, Euplectella aspergillum) possess chitin as a component of their skeletons. The main practical approach we used for chitin isolation was based on alkali treatment of corresponding external layers of spicules sponge material with the aim of obtaining alkali-resistant compounds for detailed analysis. Here, we present a detailed study of the structural and physicochemical properties of spicules of the glass sponge Rossella fibulata. The structural similarity of chitin derived from this sponge to invertebrate alpha chitin has been confirmed by us unambiguously using physicochemical and biochemical methods. This is the first report of a silica-chitin composite biomaterial found in Rossella species. Finally, the present work includes a discussion related to strategies for the practical application of silica-chitin-based composites as biomaterials.