All-polysaccharide, self-healing, pH-sensitive, in situ-forming hydrogel of carboxymethyl chitosan and aldehyde-functionalized hydroxyethyl cellulose.

In situ forming hydrogels are promising for biomedical applications, especially in drug delivery. The precursor solution can be injected at the target site, where it undergoes a sol-gel transition to afford a hydrogel. In this sense, the most significant characteristic of these hydrogels is fast gelation behavior after injection. This study describes an all-polysaccharide, rapidly in situ-forming hydrogel composed of carboxymethyl chitosan (CMCHT) and hydroxyethyl cellulose functionalized with aldehyde groups (HEC-Ald). The HEC-Ald was synthesized through acetal functionalization, followed by acid deprotection. This innovative approach avoids cleavage of pyran rings, as is inherent in the periodate oxidation approach, which is the most common method currently employed for adding aldehyde groups to polysaccharides. The resulting hydrogel exhibited fast stress relaxation, self-healing properties, and pH sensitivity, which allowed it to control the release of an encapsulated model drug in response to the medium pH. Based on the collected data, the HEC-Ald/CMCHT hydrogels show promise as pH-sensitive drug carriers.

Advances in porphyrins and chlorins associated with polysaccharides and polysaccharides-based materials for biomedical and pharmaceutical applications.

Over the last decade, the convergence of advanced materials and innovative applications has fostered notable scientific progress within the biomedical and pharmaceutical fields. Porphyrins and their derivatives, distinguished by an extended conjugated π-electron system, have a relevant role in propelling these advancements, especially in drug delivery systems, photodynamic therapy, wound healing, and (bio)sensing. However, despite their promise, the practical clinical application of these macrocycles is hindered by their inherent challenges of low solubility and instability under physiological conditions. To address this limitation, researchers have exploited the synergistic association of porphyrins and chlorins with polysaccharides by engineering conjugated systems and composite/hybrid materials. This review compiles the principal advances in this growing research field, elucidating fundamental principles and critically examining the applications of such materials within biomedical and pharmaceutical contexts. Additionally, the review addresses the eventual challenges and outlines future perspectives for this poignant research field. It is expected that this review will serve as a comprehensive guide for students and researchers dedicated to exploring state-of-the-art materials for contemporary medicine and pharmaceutical applications.

Hybrid polymer aerogels containing porphyrins as catalysts for efficient photodegradation of pharmaceuticals in water.

Polymer aerogels of poly(acrylic acid)/poly(vinyl alcohol) (labeled as CPA) were prepared and tested as support materials for different cationic porphyrin organocatalysts (denoted as TMPyP, TMPyPZn, or TMPyPMn). The hybrid aerogels were characterized by various techniques, while their catalytic activity was investigated towards the photodegradation of amoxicillin (AMX), caffeine (CAF), and naproxen (NPX) under artificial visible light. Photodegradation experiments revealed that the CPA-TMPyPMn aerogel shows superior catalytic potential when compared to the others aerogels or the "free" TMPyPMn porphyrin. All pharmaceuticals were quickly degraded (before 60 min) and high COD removal rates (greater than95%) were achieved at pH 7.0 and room temperature. The CG-MS data confirm the complete degradation of all tested pharmaceuticals catalyzed by CPA-TMPyPMn. Recycling experiments revealed that this hybrid aerogel keeps its photocatalytic efficiency for at least 15 reuse runs. In short, this original photocatalytic system is promising to mediate the removal of pharmaceutical contaminants from the aqueous medium.

Chitosan-based hydrogel crosslinked through an aza-Michael addition catalyzed by boric acid.

Polysaccharide-based hydrogels are particularly attractive materials for biomedical applications. However, their use is restricted due to their brittleness and poor mechanical properties. Here, to overcome such limitations, we report an original, green, simple, and efficient strategy to synthesize a polysaccharide-based hydrogel of chitosan (Cht) and a vinyl-functionalized PVA (PVA-MA), a non-toxic synthetic polymer that is widely known to improve the mechanical properties and stability of materials containing polysaccharides. The hydrogel was crosslinked through an aza-Michael addition among the amino groups of Cht with the vinyl moieties of PVA-MA catalyzed by boric acid (B(OH)3), an eco-friendly inorganic compound. Characterization analyses revealed that the prepared hydrogel has a porous-like morphology, an outstanding liquid uptake capacity (>665%), and improved stability in a physiological fluid for long periods. In summary, this original and simple strategy showed to be efficient in the synthesis of hydrogels with attractive properties for the biomedical field application.

Hydrogen generation and hydrogenation reactions efficiently mediated by a thin film of reduced graphene oxide-grafted with carboxymethyl chitosan and Ag nanoparticles.

In this work, we have investigated the use of a heterogeneous catalyst based on reduced graphene oxide-grafted with carboxymethyl chitosan (rGO-CMCHT) and silver nanoparticles (AgNPs) for hydrogen generation through straightforward borohydride decomposition reaction. Thus, an rGO-CMCHT thin film containing AgNPs was successfully prepared by using a dip-coating technique. Characterization analysis indicated that rGO-CMCHT enhances the catalytic activity of AgNPs due to its intrinsic electric capacity (i.e., low electron-mobility resistivity). The experimental results showed that the prepared thin film has a remarkable catalytic activity that boosts hydrogen generation (maximum rate 180 × 102 mL min-1 g-1), achieving TOF values (480 min-1) that exceed the previously reported data. High TOF values were also obtained in aqueous and non-aqueous media using low amounts of catalyst, confirming its versatility. Reuse experiments demonstrated that thin film could be recycled and reused for at least ten consecutive reactions without losing catalytic efficiency. Spectroscopic analyses showed that AgNPs were not leached in the reaction medium after the reuse cycles, indicating that rGO-CMCHT stabilizes the nanoparticles efficiently. Finally, the prepared thin film also showed excellent catalytic performance catalytic towards the reduction of nitroaromatic compounds in aqueous and non-aqueous media, confirming its versatility for hydrogen production and hydrogenation reactions.

Preparation, characterization and antitumor activity of a cationic starch-derivative membrane embedded with a ß-cyclodextrin/curcumin inclusion complex.

A membrane of cationic starch-derivative/poly(vinyl alcohol) was prepared and utilized as a support to immobilize a ß-cyclodextrin/curcumin inclusion complex. The resulting material (denote as ß-CD/CUR-MBN) was characterized in detail by different techniques. In vitro experiments revealed that ß-CD/CUR-MBN enables the controlling of the curcumin release process, which is guided by the relaxation of the polymer matrix. Moreover, cytotoxic assays were performed to investigate the effect of ß-CD/CUR-MBN on two cancer cell lines (melanoma and glioblastoma). The results showed that the polymeric membrane exerts higher cytotoxicity against these cells than free curcumin. Also, ß-CD/CUR-MBN exerted a prolonged cytotoxic effect (up to 96 h), even using a low concentration (50 µg mL-1), indicating that the curcumin in the polymeric membrane showed increased bioavailability under the tested condition. ß-CD/CUR-MBN was non-cytotoxic against normal cells suggesting a specific action of this material against target cancer cells. The results reported here allow ranks ß-CD/CUR-MBN as a promising biomaterial to act as a local drug delivery system to treat cancer.

Fast decolorization of azo methyl orange via heterogeneous Fenton and Fenton-like reactions using alginate-Fe2+/Fe3+ films as catalysts.

The efficiency of Fenton and Fenton-like processes can be seriously affected by the continuous loss of iron ions and by the formation of solid sludge. Here, alginate (Alg) films were synthesized to stabilize iron ions (Fe2+ and Fe3+) and to enhance their catalytic activities towards the decolorization of methyl orange via heterogeneous Fenton and Fenton-like processes. Iron ions were ionically bond to the Alg molecules resulting in a three-dimensional network with specific structural and morphological features according to the valence states of iron. Our results demonstrated that both Alg-Fe2+ and Alg-Fe3+ films show highlighted catalytic activity for the decolorization of MO and high decolorization rates. Reuse experiments demonstrated that both films could be employed in at least five consecutive decolorization processes without losing their catalytic efficiency or stability. Taken together, our findings reveal that the Alg-Fe2+ and Alg-Fe3+ films may be suitable low-cost catalysts in heterogeneous Fenton and Fenton-like processes.