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Hydrogels are interesting materials as delivery systems of various therapeutic agents, mainly due to the water-swollen network and the localized and sustained drug release. Herein, single-component starch-based hydrogels with enhanced degradation rates were produced by applying a facile synthesis and proposed for a novel delivery system of therapeutic molecules. Starch was oxidized with sodium periodate in water and mild conditions to generate aldehyde derivatives that, after a freeze-thaw procedure, were allowed to compact and stable hydrogels. Oxidized starch was also cross-linked with asparagine through a Schiff base reaction to link the active molecule directly to the polysaccharide structure. The materials were structurally and morphologically characterized, and the ability to adsorb and release over time an active molecule was proven by qNMR spectroscopy. The cytotoxicity was evaluated on CAL-27 cell line (oral squamous cell carcinoma). Results indicated that synthesized hydrogels lead to a "frozen proliferative" state on cells due to the swelling capability in the cell medium. This behavior was confirmed by flow cytometry data indicating the hydrogels induced less "early apoptosis" and more "late apoptosis" in the cells, compared to the untreated control. Since the proposed materials are able to control the cell proliferation, they could open a new scenario within the field of precise therapeutic applications.

The homogeneous non-catalytic hydrogenation of several types of iso- and syndiotactic cis -1,4 poly(1,3-diene)s with diimide, formed by thermal decomposition of p -toluene-sulfonyl-hydrazide, was examined. Perfectly alternating ethylene/1-alkene copolymers having different tacticity (i.e., isotactic and syndiotactic), which in some cases are difficult to synthesize by simple stereospecific co-polymerization of the corresponding monomers, were obtained. All the copolymers synthesized were fully characterized from a structural, morphological, and rheological point of view through different analytical techniques (FT-IR, NMR, GPC, DSC, RX).

The selective detection of metal ions in water, using sustainable detection systems, is of crescent importance for monitoring water environments and drinking water safety. One of the key elements of future chemical sciences is the use of sustainable approaches in the design of new materials. In this study, we design and synthesize a low-cost, water-soluble potassium salt of 3,4,9,10-perylene tetracarboxylic acid (PTAS), which shows a selective optical response on the addition of Cu 2+ and Pb 2+ ions in aqueous solutions. By using a water-soluble chromophore, the interactions with the metal ions are definitely more intimate and efficient, with respect to standard methods employing cosolvents. The detection limits of PTAS for both Cu 2+ and Pb 2+ are found to be 2 µM by using a simple absorbance mode, and even lower (1 μM) with NMR experiments, indicating that this analyte-probe system is sensitive enough for the detection of copper ions in drinking water and lead ions in waste water. The complexation of PTAS with both ions is supported with NMR studies, which reveal the formation of new species between PTAS and analytes. By combining a low-cost water-soluble chromophore with efficient analyte-probe interactions due to the use of aqueous solutions, the results here obtained provide a basis for designing sustainable sensing systems.

Starch recovered from an agrifood waste, pea pods, was enzymatically modified and used to prepare cryogels applied as drug carriers. The enzymatic modification of starch was performed using the laccase/(2,2,6,6-tetramethylpiperidin-1-yl)oxyl TEMPO system, at a variable molar ratio. The characterization of the ensuing starches by solution NMR spectroscopy showed partial conversion of the primary hydroxyl groups versus aldehyde and carboxyl groups and successive creation of hemiacetal and ester bonds. Enzymatically modified starch after simple freezing and lyophilization process provided stable and compact cryogels with a morphology characterized by irregular pores, as determined by atomic force (AFM) and scanning electron microscopy (SEM). The application of cryogels as carriers of active molecules was successfully evaluated by following two different approaches of loading with drugs: a) as loaded sponge, by adsorption of drug from the liquid phase; and b) as dry-loaded cryogel, from a dehydration step added to loaded cryogel from route (a). The efficiency of the two routes was studied and compared by determining the drug release profile by proton NMR studies over time. Preliminary results demonstrated that cryogels from modified starch are good candidates to act as drug delivery systems due to their stability and prolonged residence times of loaded molecules, opening promising applications in biomedical and food packaging scenarios.

The supplementation of goat diets with natural products to obtain milk with nutraceutical components is a common practice. In these last years, the influence of supplementation of specifically designed diets has been studied with different analytical tools in order to explore possible beneficial effects in human consumption of animal milk and milk-derived products. In this study, the lipid fraction of milk from Alpine goats undergoing different dietary regimens was studied by 1 H-NMR spectroscopy. Alpine goats were fed with linseed or hempseed supplements, and after 14 weeks of treatment, milk was collected and analyzed. Results showed that feeding diets supplemented with seeds positively affected the fatty acid composition with a pronounced increase in unsaturated fatty acids for both diets compared to a control diet. Specifically, linolenic acid content was more than doubled for linseed diet compared with the hempseed and control groups, while linoleic acid greatly increased only upon hempseed supplementation. However, a number of conjugated linoleic acid (CLA) isomers and higher levels of fatty acids with trans configuration were found in supplemented diets, particularly in the linseed diet.

The homogeneous non-catalytic hydrogenation of cis -1,4 poly(isoprene), isotactic cis -1,4 poly(1,3-pentadiene) and syndiotactic cis -1,4 poly(1,3-pentadiene) with diimide, formed by thermal decomposition of para -toluenesulfonylhydrazide, is examined. Perfectly alternating ethylene/propylene copolymers having different tacticity (i.e., isotactic and syndiotactic), which are difficult to synthesize by stereospecific copolymerization of the corresponding monomers, are obtained. Both isotactic and syndiotactic alternating ethylene/propylene copolymers are amorphous, with very low glass transition temperatures.