Functionalization of 3D Chitinous Skeletal Scaffolds of Sponge Origin Using Silver Nanoparticles and Their Antibacterial Properties.

Chitin, as one of nature's most abundant structural polysaccharides, possesses worldwide, high industrial potential and a functionality that is topically pertinent. Nowadays, the metallization of naturally predesigned, 3D chitinous scaffolds originating from marine sponges is drawing focused attention. These invertebrates represent a unique, renewable source of specialized chitin due to their ability to grow under marine farming conditions. In this study, the development of composite material in the form of 3D chitin-based skeletal scaffolds covered with silver nanoparticles (AgNPs) and Ag-bromide is described for the first time. Additionally, the antibacterial properties of the obtained materials and their possible applications as a water filtration system are also investigated.

The Effect of Molecular Weight on the Antibacterial Activity of N,N,N-Trimethyl Chitosan (TMC).

N,N,N-trimethyl chitosan (TMC) with 93% degree of trimethylation was synthesized. TMC and the chitosan starting material were subjected to acidic hydrolysis to produce 49 different samples with a reduced average molecular weight (Mw) ranging from 2 to 144 kDa. This was done to allow the investigation of the relationship between antibacterial activity and Mw over a wide Mw range. NMR investigation showed that hydrolysis did not affect the degree of trimethylation (DSTRI) or the structure of the polymer backbone. The activity of TMC against Staphylococcus aureus (S. aureus) increased sharply with Mw until a certain Mw value (critical Mw for high activity, CMW) was reached. After the CMW, the activity was not affected by a further increase in the Mw. A similar pattern of activity was observed for chitosan. The CMW was determined to be 20 kDa for TMC and 50 kDa for chitosan.

Poly(N,N-dimethylaminoethyl methacrylate) as a bioactive polyelectrolyte-production and properties.

Poly(N,N-dimethylaminoethyl methacrylate) is a polyelectrolyte with many important chemical and physical properties and, above all, offers a wide range of interesting biological properties. Currently, research on this polymer is ongoing in several centres around the world. The process of polymerizing the monomer is not easy, as there are difficulties in obtaining a product with repeatable properties. This work collected and described most of the currently known and used polymerization methods of N,N-dimethylaminoethyl methacrylate, taking into account the type of method, the solvent used, the initiator, as well as the process temperature and the average molecular weight of the polymer obtained. The most important properties of the discussed polymer, such as solubility, bioactivity, hydrophilicity, cytotoxicity, conductivity, and thermal and hydrodynamic parameters, are discussed on the basis of the available scientific literature. This work aims, among other things, to increase the possibility of using poly(N,N-dimethylaminoethyl methacrylate) as a material in advanced practical applications. Therefore, various methods of applied use of the polymer in question have also been described so far. Copolymers of the N,N-dimethylaminoethyl methacrylate are now too large a collection to fit in a single publication. Therefore, only the most interesting examples were cited in this work.

Antibacterial properties of poly (N,N-dimethylaminoethyl methacrylate) obtained at different initiator concentrations in solution polymerization.

The samples of poly(N,N-dimethylaminoethyl methacrylate) were synthesized by radical polymerization. The amount of monomer and solvent was constant as opposed to an amount of initiator which was changing. No clear relationship between polymerization conditions and the molecular weight of the polymer was found, probably due to the branched configuration of produced polymer. Bactericidal interactions in all samples against Gram-positive and Gram-negative bacteria have been demonstrated. However, the observed effect has various intensities, depending on the type of bacteria and the type of sample.

Thermal properties of poly(N,N-dimethylaminoethyl methacrylate).

Poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) is a promising quite new polymer with very interesting properties. The thermal degradation process of PDMAEMA was investigated. The polymer was heated at specific time intervals, then heating was stopped, and infrared analysis was performed to obtain information on the structure of the solid residue. The thermal degradation process has a two-stage character. The limit temperature for the first decomposition step was about 390°C, after which the second stage of sample decomposition began. The order of disintegration of the macromolecules was determined. Activation energy values for the thermal decomposition process have been calculated; they are 89.8 kJ/mol for the first stage and 17.7 kJ/mol for the second stage of the degradation process.

Preparation of monolithic silica-chitin composite under extreme biomimetic conditions.

Chitin is a widespread renewable biopolymer that is extensively distributed in the natural world. The high thermal stability of chitin provides an opportunity to develop novel inorganic-organic composites under hydrothermal synthesis conditions in vitro. For the first time, in this work we prepared monolithic silica-chitin composite under extreme biomimetic conditions (80°C and pH 1.5) using three dimensional chitinous matrices isolated from the marine sponge Aplysina cauliformis. The resulting material was studied using light and fluorescence microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy. A mechanism for the silica-chitin interaction after exposure to these hydrothermal conditions is proposed and discussed.

Solvothermal synthesis of hydrophobic chitin-polyhedral oligomeric silsesquioxane (POSS) nanocomposites.

Chitinous scaffolds isolated from the skeleton of marine sponge Aplysina cauliformis were used as a template for the deposition of polyhedral oligomeric silsesquioxanes (POSS). These chitin-POSS based composites with hydrophobic properties were prepared for the first time using solvothermal synthesis (pH 3, temp 80 °C), and were thoroughly characterized. The resulting material was studied using scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and thermogravimetry. A mechanism for the chitin-POSS interaction after exposure to these solvothermal conditions is proposed and discussed.

Extreme Biomimetics: formation of zirconium dioxide nanophase using chitinous scaffolds under hydrothermal conditions.

Chitinous scaffolds isolated from the skeleton of marine sponge Aplysina cauliformis were used as a template for the in vitro formation of zirconium dioxide nanophase from ammonium zirconium(iv) carbonate (AZC) under extreme conditions (150 °C). These novel zirconia-chitin based composites were prepared for the first time using hydrothermal synthesis, and were thoroughly characterized using a plethora of analytical methods. The thermostability of the chitinous 3D matrix makes it ideal for use in the hydrothermal synthesis of monoclinic nanostructured zirconium dioxide from precursors like AZC. These zirconium-chitin composites have a high potential for use in a broad range of applications ranging from synthetic catalysis to biocompatible materials for bone and dental repair. The synthetic methods presented in this work show an attractive route for producing monoclinic zirconium dioxide on a 3D biocompatible scaffold with ease.