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Chitin and chitosan are abundant unique sources of biologically-fixed nitrogen mainly derived from residues of the fishery productive chain. Their high potential as nitrogen-based highly added-value platform molecules is still largely unexploited and a catalytic way for their valorization would be strongly desirable within a biorefinery concept. Here we report our results obtained with a series of heterogeneous catalysts in the depolymerization of chitosan and chitin to acetylglucosamine. Copper catalysts supported on SiO2, SiO2–Al2O3, SiO2-ZrO2, ZrO2 and the corresponding bare oxides/mixed oxides were tested, together with a sulfated zirconia system (ZrO2-SO3H) that revealed to be extremely selective towards glucosamine, both for chitosan and chitin, thus giving pretty high yields with respect to the values reported so far (44% and 21%, respectively). The use of a heterogeneous catalyst alone, without the need of any additives or the combination with a mineral acid, makes these results remarkable.

Binary nano-biocomposite 3D scaffolds of cellulose nanocrystals (CNCs)—gelatine were fabricated without using chemical crosslinking additives. Controlled oxidative treatment allowed introducing carboxyl or carbonyl functionalities on the surface of CNCs responsible for the crosslinking of gelatine polymers. The obtained composites were characterized for their physical-chemical properties. Their biocompatibility towards different cell cultures was evaluated through MTT and LDH assays, cellular adhesion and proliferation experiments. Gelatine composites reinforced with carbonyl-modified CNCs showed the most performing swelling/degradation profile and the most promising adhesion and proliferation properties towards cell lines, suggesting their potential application in the field of tissue engineering.

Chitosan is a marine-origin polysaccharide obtained from the deacetylation of chitin, the main component of crustaceans’ exoskeleton, and the second most abundant in nature. Although this biopolymer has received limited attention for several decades right after its discovery, since the new millennium chitosan has emerged owing to its physicochemical, structural and biological properties, multifunctionalities and applications in several sectors. This review aims at providing an overview of chitosan properties, chemical functionalization, and the innovative biomaterials obtained thereof. Firstly, the chemical functionalization of chitosan backbone in the amino and hydroxyl groups will be addressed. Then, the review will focus on the bottom-up strategies to process a wide array of chitosan-based biomaterials. In particular, the preparation of chitosan-based hydrogels, organic–inorganic hybrids, layer-by-layer assemblies, (bio)inks and their use in the biomedical field will be covered aiming to elucidate and inspire the community to keep on exploring the unique features and properties imparted by chitosan to develop advanced biomedical devices. Given the wide body of literature that has appeared in past years, this review is far from being exhaustive. Selected works in the last 10 years will be considered.

Gelatin is a costless polypeptide material of natural origin, able to form hydrogels that are potentially useful in biomaterial scaffold design for drug delivery, cell cultures, and tissue engineering. However, gelatin hydrogels are unstable at physiological conditions, losing their features only after a few minutes at 37 °C. Accordingly, treatments to address this issue are of great interest. In the present work, we propose for the first time the use of bi- and trifunctional tetrazoles, most of them unknown to date, for photoinduced gelatin cross-linking towards the production of physiologically stable hydrogels. Indeed, after UV-B irradiation, aryl tetrazoles generate a nitrilimine intermediate that is reactive towards different functionalities, some of them constitutively present in the amino acid side chains of gelatin. The efficacy of the treatment strictly depends on the structure of the cross-linking agent used, and substantial improved stability was observed by switching from bifunctional to trifunctional cross-linkers.

The regeneration of the nervous system is a challenging task. Currently, regenerative medicine approaches that exploit nature-inspired cues are being studied and hold great promise. The possibility to use protein-based matrices functionalized with small oligo- and monosaccharides is of interest since these can be finely tuned to better mimic the native environment. Collagen has been selected as a promising material that has the potential to be further tailored to incorporate carbohydrates in order to drive cell behavior towards neuroregeneration. Indeed, the grafting of carbohydrates to collagen 2D matrices is proved to enhance its biological significance. In the present study, collagen 2D matrices were grafted with different carbohydrate epitopes, and their potential to drive F-11 neuroblastoma cells towards neuronal differentiation was evaluated. Collagen functionalized with α-glucosides was able to differentiate neuroblastoma cells into functional neurons, while sialyl α-(2→6)-galactosides stimulated cell proliferation.

The ability of gelatin-based hydrogels of incorporating and releasing under controlled conditions 5,6-dihydroxyindole-2-carboxylic acid (DHICA), a melanin-related metabolite endowed with marked antioxidant properties was investigated. The methyl ester of DHICA, MeDHICA, was also tested in view of its higher stability, and different solubility profile. Three types of gelatin-based hydrogels were prepared: pristine porcine skin type A gelatin (HGel-A), a pristine gelatin cross-linked by amide coupling of lysines and glutamic/aspartic acids (HGel-B), and a gelatin/chitosan blend (HGel-C). HGel-B and HGel-C differed in the swelling behavior, showed satisfactorily high mechanical strength at physiological temperatures and well-defined morphology. The extent of incorporation into all the gelatins tested using a 10% w/w indole to gelatin ratio was very satisfactory ranging from 60 to 90% for either indoles. The kinetics of indole release under conditions of physiological relevance was evaluated up to 72 h. The highest values were obtained with HGel-B and HGel-C for MeDHICA (90% after 6 h), and an appreciable release was observed for DHICA reaching 30% and 40% at 6 h for HGel-B and HGel-C, respectively. At 72 h, DHICA and MeDHICA were released at around 30% from HGel-A at pH 7.4, with an increase up to 40% at pH 5.5 in the case of DHICA. DHICA incorporated into HGel-B proved fairly stable over 6 h whereas the free compound at the same concentration was almost completely oxidized. The antioxidant power of the indole loaded gelatins was monitored by chemical assays and proved unaltered even after prolonged storage in air, suggesting that the materials could be prepared in advance with respect to their use without alteration of their efficacy.

Carminic acid, a natural hydrophilic dye extensively used in the food and cosmetic industries, is converted in hydrophobic dyes by acetylation or pivaloylation. These derivatives are successfully used as biocolourants for rubber objects. In this paper, spectroscopic properties of the carminic acid derivatives in dimethyl sulfoxide and in polybutylacrylate are studied by means of photoluminescence and time-resolved photoluminescence decays, revealing a hypsochromic effect due to the presence of bulky substituents as the acetyl or pivaloyl groups. Molecular mechanics and density functional theory calculations confirm the disruption of planarity between the sugar ring and the anthraquinoid system determined by the esterification.

The synthesis of new dendrons of the generations 0, 1 and 2 with a double bond at the focal point and a carbonyl group at the termini has been carried out. The carbonyl group has been exploited for the multivalent conjugation to a sample saccharide by reductive amination and alkoxyamine conjugation.

Gelatin is a biopolymer with interesting properties that can be useful for biomaterial design for different applications such as drug delivery systems, or 3D scaffolds for tissue engineering. However, gelatin suffers from poor mechanical stability at physiological temperature, hence methods for improving its properties are highly desirable. In the present work, a new chemical cross-linking strategy based on triazolinedione ene-type chemistry towards stable hydrogel is proposed. Two different homobifunctional 1,2,4-triazoline-3,5(4H)-diones, namely 4,4′-hexane-1,6-diylbis(3H-1,2,4-triazoline-3,5(4H)-dione) 1 and 4,4′-[methylenebis(4,1-phenylene)]bis(3H-1,2,4-triazoline-3,5(4H)-dione) 2 were used as cross-linkers in different ratio to tyrosine residues in gelatin. The reaction was proved effective in all experimented conditions and hydrogels featured with different thermal stability were obtained. In general, the higher the cross-linker/tyrosine ratio, the more thermostable the hydrogel. The swelling properties are strictly dependent upon the chemical nature of the cross-linker.

A small set of nojirimycin- and pyrrolidine-based iminosugar derivatives has been synthesized and evaluated as potential inhibitors of porcine and insect trehalases. Compounds 12, 13 and 20 proved to be active against both insect and porcine trehalases with selectivity towards the insect glycosidase, while compounds 10, 14 and 16 behaved as inhibitors only of insect trehalase. Despite the fact that the activity was found in the micromolar range, these findings may help in elucidating the structural features of this class of enzymes of different origin, which are still scarcely characterised.

Disease, trauma, and aging account for a significant number of clinical disorders. Regenerative medicine is emerging as a very promising therapeutic option. The design and development of new cell-customised biomaterials able to mimic extracellular matrix (ECM) functionalities represents one of the major strategies to control the cell fate and stimulate tissue regeneration. Recently, hydrogels have received a considerable interest for their use in the modulation and control of cell fate during the regeneration processes. Several synthetic bioresponsive hydrogels are being developed in order to facilitate cell-matrix and cell-cell interactions. In this review, new strategies and future perspectives of such synthetic cell microenvironments will be highlighted.

Covering: 2000 to 2010 [ABSTRACT FROM AUTHOR]