Chitin, the second most important natural polymer in the world, and its N-deacetylated derivative chitosan, have been identified as versatile biopolymers for a broad range of applications in medicine, agriculture and the food industry. Two of the main reasons for this are firstly the unique chemical, physicochemical and biological properties of chitin and chitosan, and secondly the unlimited supply of raw materials for their production. These polymers exhibit widely differing physicochemical properties depending on the chitin source and the conditions of chitosan production. The presence of reactive functional groups as well as the polysaccharide nature of these biopolymers enables them to undergo diverse chemical modifications. A complete chemical and physicochemical characterization of chitin, chitosan and their derivatives is not possible without using spectroscopic techniques. This review focuses on the application of spectroscopic methods for the structural analysis of these compounds.
1 November 2008 in Colloids and Surfaces A: Physicochemical and Engineering Aspects
The physicochemical nature of chitin and chitosan, which influences the biomedical activity of these compounds, is strongly related to the source of chitin and the conditions of the chitin/chitosan production process. Apart from widely described key factors such as weight-averaged molecular weight (MW) and degree of N-acetylation (DA), other physicochemical parameters like polydispersity (MW/MN), crystallinity or the pattern of acetylation (PA) have to be taken into consideration. From the biological point of view, these parameters affect a very important factor—the solubility of chitin and chitosan in water and organic solvents. The physicochemical properties of chitosan solutions can be controlled by manipulating solution conditions (temperature, pH, ionic strength, concentration, solvent). The degree of substitution of the hydroxyl and the amino groups or the degree of quaternization of the amino groups also influence the mechanical and biological properties of chitosan samples. Finally, a considerable research effort has been directed towards developing safe and efficient chitin/chitosan-based products because many factors, like the size of nanoparticles, can determine the biomedical characteristics of medicinal products. The influence of these factors on the biomedical activity of chitin/chitosan-based products is presented in this report in more detail.
Liquid Organic Hydrogen Carrier (LOHC) systems offer a very attractive way to store and transport hydrogen, a technical feature that is highly desirable to link unsteady energy production from renewables with the vision of a sustainable, CO2-free, hydrogen-based energy system. LOHCs can be charged and discharged with considerable amounts of hydrogen in cyclic, catalytic hydrogenation and dehydrogenation processes. As their physico-chemical properties are very similar to diesel, today's infrastructure for liquid fuels can be used for their handling thus greatly facilitating the step-wise transition from today's fossil system to a CO2 emission free energy supply for both, stationary and mobile applications. However, for a broader application of these liquids it is mandatory to study in addition to their technical performance also their potential impact on the environment and human health. This paper presents the first account on the toxicological profile of some potential LOHC structures. Moreover, it documents the importance of an early integration of hazard assessment in technology development and reveals for the specific case of LOHC structures the need for additional research in order to overcome some challenges in the hazard assessment for these liquids.
We investigated the primary biodegradation of different N-imidazoles, imidazolium, pyridinium and 4-(dimethylamino)pyridinium compounds substituted with various alkyl side chains and their analogues containing functional groups principally based on OECD guideline 301 D. For the experiments we used two different types of inocula, a freeze-dried mix of bacteria and activated sludge microorganisms from a wastewater treatment plant. The aim of this study was to improve the knowledge base for the structural design of ionic liquids with respect to an increased biodegradability combined with a reduced (eco)toxicological hazard potential. We found a significant primary biodegradation for (eco)toxicologically unfavourable compounds carrying long alkyl side chains (C6 and C8). In contrast for (eco)toxicologically more recommendable imidazolium ionic liquids with short alkyl (⩽C6) and short functionalised side chains, no biological degradation could be found. The introduction of different functional groups into the side chain moiety thus offering a higher chemical reactivity did not lead to the expected improvement of the biological degradation. After an incubation period of 24 days for the 1-methyl-3-octylimidazolium cation we identified different biological transformation products carrying hydroxyl, carbonyl and carboxyl groups. Furthermore, shortened side chain moieties were identified indicating the degradation of the octyl side chain via β-oxidation. Moreover, we propose an electrochemical wastewater treatment as part of an alternative disposal strategy for non-biodegradable ionic liquids. We show for the first time that the 1-butyl-3-methylimidazolium cation was completely destroyed within four hours using an electrolysis double-cell (volume = 1.2 L) equipped with electrodes made of iridium oxide (anode), stainless steel (cathode), and a boron-doped diamond-coated bipolar electrode. The products formed electrochemically were easily accessible to biological degradation.