Chemical shaping of CPO-27-M (M = Co, Ni) through an in situ crystallization within chitosan hydrogels.

The preparation of MOF composites is considered as an effective method to address the challenges of shaping MOFs and to create porous solids with enhanced properties and broader applications. In this study, CPO-27-Co was crystallized via a simple strategy within porous chitosan beads. The resulting CS@CPO-27-Co composites were tested for CO2 sorption and they demonstrated promising performances by exceeding 3 mmol(CO2) g-1. The versatility of this strategy was further demonstrated by replacing cobalt(II) ions with nickel(II), also leading to the isostructural CPO-27 framework.

Eugenol Hydrodeoxygenation Over Mixed Mo-W Carbides.

The modification of molybdenum carbide catalysts by another transition metal has raised an increasing research interest due to the significant improvement of catalyst activity in hydrodeoxygenation of lignin derivatives. At par with the commonly used Co and Ni that add a strong hydrogenation functionality, it was found that the addition of the more oxophilic W restricts ring hydrogenation while allowing the deoxygenation of oxygenated compounds and thus yielding higher selectivity toward the formation of non-oxygenated aromatic compounds. The coexistence of Mo2C with W2C along with metallic W altered the electronic properties of Mo2C which resulted in an increase of catalyst active site density and facilitated further total eugenol deoxygenation. Propyl-benzene selectivity of up to 83 % was reached at close to 100 % eugenol conversion. These findings will allow a better overview of the effect of different metal phases of mixed carbides on the catalyst performance and raise the prospect of optimizing catalyst design for a hydrodeoxygenation processing of lignin depolymerization products.

Enhanced Gas Adsorption in HKUST-1@Chitosan Aerogels, Cryogels, and Xerogels: An Evaluation Study.

This study investigates the use of chitosan hydrogel microspheres as a template for growing an extended network of MOF-type HKUST-1. Different drying methods (supercritical CO2, freeze-drying, and vacuum drying) were used to generate three-dimensional polysaccharide nanofibrils embedding MOF nanoclusters. The resulting HKUST-1@Chitosan beads exhibit uniform and stable loadings of HKUST-1 and were used for the adsorption of CO2, CH4, Xe, and Kr. The maximum adsorption capacity of CO2 was found to be 1.98 mmol·g-1 at 298 K and 1 bar, which is significantly higher than those of most MOF-based composite materials. Based on Henry's constants, thus-prepared HKUST-1@CS beads also exhibit fair selectivity for CO2 over CH4 and Xe over Kr, making them promising candidates for capture and separation applications.

Biodegradable Chitosan-Based Films as an Alternative to Plastic Packaging.

The impact of synthetic packaging on environmental pollution has been observed for years. One of the recent trends of green technology is the development of biomaterials made from food processing waste as an alternative to plastic packaging. Polymers obtained from some polysaccharides, such as chitosan, could be an excellent solution. This study investigated the biodegradability of chitosan-metal oxide films (ZnO, TiO2, Fe2O3) and chitosan-modified graphene films (CS-GO-Ag) in a soil environment. We have previously demonstrated that these films have excellent mechanical properties and exhibit antibacterial activity. This study aimed to examine these films' biodegradability and the possibility of their potential use in the packaging industry. The obtained results show that soil microorganisms were able to utilize chitosan films as the source of carbon and nitrogen, thus providing essential evidence about the biodegradability of CS, CS:Zn (20:1; 10:1), and CS:Fe2O3 (20:1) films. After 6 weeks of incubation, the complete degradation of the CS-Fe2O3 20:1 sample was noted, while after 8 weeks, CS-ZnO 20:1 and CS-ZnO 10:1 were degraded. This is a very positive result that points to the practical aspect of the biodegradability of such films in soil, where garbage is casually dumped and buried. Once selected, biodegradable films can be used as an alternative to plastic packaging, which contributes to the reduction in pollution in the environment.

The solvent-free mechano-chemical grinding of a bifunctional P25-graphene oxide adsorbent-photocatalyst and its configuration as porous beads.

Owing to their use in water-cleaning technology, titanium-dioxide-based nanomaterials have dominated the photocatalysis scene, with so-called Degussa (P25) being the most promising under UV light. However, this is not the case under visible light, where it is necessary to combine titanium dioxide with other photosensitising nanomaterials. Unfortunately, most of the strategies aimed in this direction are chemically non-facile, energy-intensive, economically expensive, and not suitable for large-scale production. We herein describe a straightforward solvent-free approach for accessing visible-light-activated titanium-dioxide-based photocatalysts via the mechanochemical grinding of Degussa P25 with a second solid partner. Upon comparing several solid-material benchmarks, P25-graphene oxide is the best combination. The resulting material showed efficient performance for the adsorption and photodegradation of different dye pollutants, namely methylene blue, malachite green, Congo red, and methyl orange. The recorded performance was nearly comparable to that reached using sol-gel materials, with the ultimate advantage of being more sustainable and industrially scalable. The recyclability can be improved through a porous-bead configuration using biomass waste chitosan hydrogel, an approach that can further fulfill the requirement for more sustainable photocatalyst designs.

Glassy-like Metal Oxide Particles Embedded on Micrometer Thicker Alginate Films as Promising Wound Healing Nanomaterials.

Micrometer-thicker, biologically responsive nanocomposite films were prepared starting from alginate-metal alkoxide colloidal solution followed by sol-gel chemistry and solvent removal through evaporation-induced assembly. The disclosed approach is straightforward and highly versatile, allowing the entrapment and growth of a set of glassy-like metal oxide within the network of alginate and their shaping as crake-free transparent and flexible films. Immersing these films in aqueous medium triggers alginate solubilization, and affords water-soluble metal oxides wrapped in a biocompatible carbohydrate framework. Biological activity of the nano-composites films was also studied including their hemolytic activity, methemoglobin, prothrombin, and thrombine time. The effect of the films on fibroblasts and keratinocytes of human skin was also investigated with a special emphasis on the role played by the incorporated metal oxide. This comparative study sheds light on the crucial biological response of the ceramic phase embedded inside of the films, with titanium dioxide being the most promising for wound healing purposes.

Insight into Factors Influencing Wound Healing Using Phosphorylated Cellulose-Filled-Chitosan Nanocomposite Films.

Marine polysaccharides are believed to be promising wound-dressing nanomaterials because of their biocompatibility, antibacterial and hemostatic activity, and ability to easily shape into transparent films, hydrogels, and porous foams that can provide a moist micro-environment and adsorb exudates. Current efforts are firmly focused on the preparation of novel polysaccharide-derived nanomaterials functionalized with chemical objects to meet the mechanical and biological requirements of ideal wound healing systems. In this contribution, we investigated the characteristics of six different cellulose-filled chitosan transparent films as potential factors that could help to accelerate wound healing. Both microcrystalline and nano-sized cellulose, as well as native and phosphorylated cellulose, were used as fillers to simultaneously elucidate the roles of size and functionalization. The assessment of their influences on hemostatic properties indicated that the tested nanocomposites shorten clotting times by affecting both the extrinsic and intrinsic pathways of the blood coagulation system. We also showed that all biocomposites have antioxidant capacity. Moreover, the cytotoxicity and genotoxicity of the materials against two cell lines, human BJ fibroblasts and human KERTr keratinocytes, was investigated. The nature of the cellulose used as a filler was found to influence their cytotoxicity at a relatively low level. Potential mechanisms of cytotoxicity were also investigated; only one (phosphorylated microcellulose-filled chitosan films) of the compounds tested produced reactive oxygen species (ROS) to a small extent, and some films reduced the level of ROS, probably due to their antioxidant properties. The transmembrane mitochondrial potential was very slightly lowered. These biocompatible films showed no genotoxicity, and very importantly for wound healing, most of them significantly accelerated migration of both fibroblasts and keratinocytes.

Antimicrobial Effect of Chitosan Films on Food Spoilage Bacteria.

Synthetic materials commonly used in the packaging industry generate a considerable amount of waste each year. Chitosan is a promising feedstock for the production of functional biomaterials. From a biological point of view, chitosan is very attractive for food packaging. The purposes of this study were to evaluate the antibacterial activity of a set of chitosan-metal oxide films and different chitosan-modified graphene (oxide) films against two foodborne pathogens: Campylobacter jejuni ATCC 33560 and Listeria monocytogenes 19115. Moreover, we wanted to check whether the incorporation of antimicrobial constituents such as TiO2, ZnO, Fe2O3, Ag, and graphene oxide (GO) into the polymer matrices can improve the antibacterial properties of these nanocomposite films. Finally, this research helps elucidate the interactions of these materials with eukaryotic cells. All chitosan-metal oxide films and chitosan-modified graphene (oxide) films displayed improved antibacterial (C. jejuni ATCC 33560 and L. monocytogenes 19115) properties compared to native chitosan films. The CS-ZnO films had excellent antibacterial activity towards L. monocytogenes (90% growth inhibition). Moreover, graphene-based chitosan films caused high inhibition of both tested strains. Chitosan films with graphene (GO, GOP, GOP-HMDS, rGO, GO-HMDS, rGOP), titanium dioxide (CS-TiO2 20:1a, CS-TiO2 20:1b, CS-TiO2 2:1, CS-TiO2 1:1a, CS-TiO2 1:1b) and zinc oxide (CS-ZnO 20:1a, CS-ZnO 20:1b) may be considered as a safe, non-cytotoxic packaging materials in the future.

Growth of binary anatase-rutile on phosphorylated graphene through strong P-O-Ti bonding affords a stable visible-light photocatalyst.

Titanium dioxide is an ubiquitous photocatalyst in water-cleaning technologies, being presently the most promising tools to resolve the global issue of sewage treatment. In this framework, titanium dioxide-graphene nanocomposites are discussed as promising visible-light activated photocatalysts but little is hitherto known about the surface and interface chemistry bridging the metal oxide and carbon phases. In an attempt to spotlight this overlooked issue, we herein designed two different hybrid nanocomposites through covalent grafting and growth of titanium dioxide clusters on graphene oxide and on phosphorylated graphene oxide, which affords GO@TiO2 and PGO@TiO2, respectively. While anatase could be selectively harvested on the surface of GO@TiO2, biphasic anatase-rutile nucleates could be obtained on PGO@TiO2. Thermal annealing treatments improve the metal oxide crystallization and further remove oxygenated groups from the surface of graphene. The interfacial stability of these photocatalysts was also investigated under irradiation, with the graphene support being sensitive to the proximal presence of titanium dioxide. The resulting nanocomposites were also assessed for methylene blue removal through adsorption and photocatalysis. Regardless of their composition, superior photoactivity was noticed for the nanocomposites compared to commercially available degussa that display marginal visible-light photoactivity (11% removal). Within our study, PGO@TiO2-500 stands as the most active catalyst, allowing nearly quantitative removal of the pollutant from water. The superior performance of PGO@TiO2-500 can be explained by the highest stability reached through P-O-Ti bonding, its improved crystallinity, and the reduction of the graphene surface during thermal treatment. On a whole, this study provides a blueprint for comparing semiconducting metal oxide grown on tuneable surface-interfacial graphene environments and highlights the utility of surface-engineering graphene sheets to access efficient visible-light oxidation photocatalysts.

Green and Functional Aerogels by Macromolecular and Textural Engineering of Chitosan Microspheres.

Tremendous interest was recently devoted to the preparation of porous and functional materials through sustainable route, including primarily the use of renewable biopolymers instead of petroleum-sourced synthetic chemicals. Among the biopolymers available in enormous quantity, chitosan - obtained by deacetylation of chitin - stands as the sole nitrogen-containing cationic amino-sugar carbohydrate. This distinctively provides chitosan derivatives with plenty of opportunities in materials science. Particularly, its pH switchable solubility allowed the preparation of three-dimensional entangled nanofibrillated self-standing microspheres. These porous hydrogels behave as nano-reactors to confine exogenous nanoobjects within the polysaccharide network, including sol-gel metal alkoxide species, organometallic derivatives and isotropic and oriented nanoparticles. Besides, the interfacial interplay of chitosan with lamellar clay and graphene oxide allowed the penetration of the biopolymer inside of the galleries, which result in a complete delamination of the layered nanomaterials. The preserved gelation memory of chitosan in these formulations provides a way to access porous microspheres entangling exfoliated nanometric sheets. CO2 supercritical drying of functional hydrogel beads enabled efficient removal of water and other liquid solvents without wall collapsing, allowing large-scale preparation of millimetric hydrocolloidal microspheres with an open macroporous network. These functionalized lightweight biopolymer aerogels find applications in heterogeneous catalysis, sensing, adsorption, insulation and for the design of other sophisticated porous nanostructures. Beyond their tailorable molecular and textural-engineering, the possibility for macroscopic shaping of these intriguing nanostructures opens many new opportunities, especially in additive-manufacturing for soft and hybrid robotics.

Chitosan-Functionalized Graphene Nanocomposite Films: Interfacial Interplay and Biological Activity.

Graphene oxide (GO) has recently captured tremendous attention, but only few functionalized graphene derivatives were used as fillers, and insightful studies dealing with the thermal, mechanical, and biological effects of graphene surface functionalization are currently missing in the literature. Herein, reduced graphene oxide (rGO), phosphorylated graphene oxide (PGO), and trimethylsilylated graphene oxide (SiMe3GO) were prepared by the post-modification of GO. The electrostatic interactions of these fillers with chitosan afforded colloidal solutions that provide, after water evaporation, transparent and flexible chitosan-modified graphene films. All reinforced chitosan-graphene films displayed improved mechanical, thermal, and antibacterial (S. aureus, E. coli) properties compared to native chitosan films. Hemolysis, intracellular catalase activity, and hemoglobin oxidation were also observed for these materials. This study shows that graphene functionalization provides a handle for tuning the properties of graphene-reinforced nanocomposite films and customizing their functionalities.

Aldehyde-conjugated chitosan-graphene oxide glucodynamers: Ternary cooperative assembly and controlled chemical release.

Simultaneous condensation of aromatic aldehydes (ArxCHO; x = 1-4) on chitosan biopolymer (CS) affords, after water-evaporation, structurally-conjugated aryl-functionalized CS-Arx-f films. Similarly, cooperative assembly of two-dimensional nanometric graphene oxide (GO), aromatic aldehyde and chitosan provides transparent, flexible and crack-free aldehyde-functionalized, ternary-reinforced CS-Arx-GO-f nanocomposite films. Homogenous films were obtained using ortho-hydroxybenzaldehyde Ar1 while the para-hydroxybenzaldehyde Ar4 was prone to packing inside. Textural and mechanical properties were investigated and expectedly, significant improvement was found for CS-Ar1-GO-f because of the great dispersion of the aromatic and the presence of the filler. The sensitivity of unsaturated CN imine bond to hydrolysis was explored for triggering controlled release of aromatics from the as-prepared films. All of them were found to induce a time-dependent aromatic release. It has been moreover observed that the release was significantly delayed in CS-Arx-GO-f compared to CS-Arx-f, a fact attributed to the interplay of the ring with the basal and edges of graphene oxide, through π-π stacking and additional hydrogen bonding interactions. This finding shows that beyond the conventional wisdom using fillers for improving thermal and mechanical properties, the tiny carbon sheets can act as a regulator for aldehyde release, thereby providing a way for more controlled chemical delivery from confined nanocomposites.

Phosphorus pentoxide as a cost-effective, metal-free catalyst for ring opening polymerization of ε-caprolactone.

The ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) using phosphorus pentoxide (P2O5) as a metal-free catalyst and isopropanol (iPrOH) as initiator resulted in the preparation of poly(ε-caprolactone) with narrow weight distribution. NMR spectroscopy analyses of the prepared PCL indicated the presence of the initiator residue at the end of the polymer chain, implying the occurrence of the ε-CL-catalysis ROP through a monomer activation mechanism. Kinetic experiments confirmed the controlled/living nature of ε-CL ring-opening catalyzed by phosphorus pentoxide. The commercial availability of phosphorus pentoxide and its easy-handling provide additional opportunities for polymer synthesis and nanocomposite manufacturing.

Palladium Supported on Porous Chitosan-Graphene Oxide Aerogels as Highly Efficient Catalysts for Hydrogen Generation from Formate.

Adsorption of Pd(NH3)42+ in preformed chitosan-graphene oxide (CS-GO) beads and their subsequent reduction with NaBH4 afford well-dispersed, high dispersion (~21%) of uniformly sized Pd nanoparticles (~1.7 nm). The resulting Pd/CS-GO exhibits interesting catalytic activity for hydrogen generation by ammonium formate decomposition. The optimal GO proportion of 7 wt% allows reaching, at 60 °C, a turnover frequency above 2200 h-1-being outstanding among the highest values reported for this process to date. Interestingly, no formation of CO or CH4 was detected. The catalyst did not leach, although it underwent gradual deactivation, probably caused by the increase in the Pd average size that became over 3 nm after three uses. Our results are relevant in the context of efficient on-board hydrogen generation from liquid organic hydrogen carriers in transportation.

Synthesis of poly(ε-caprolactone)-grafted guar gum by surface-initiated ring-opening polymerization.

This study reports the grafting of poly(ε-caprolactone) (PCL) on guar gum (GG) by in-situ ring-opening polymerization using tetra(phenylethynyl)tin (Sn(C≡CPh)4) as catalyst. The hydroxyl groups of guar gum act as initiators for ε-caprolactone ring-opening polymerization and the resulting poly(ε-caprolactone) binds covalently to the polysaccharide. The highest stability of Sn(C≡CPh)4 allows the reaction in open-air, thereby reducing the cost of the synthesis and provides polymers with high molar mass. Fourier transform infrared (FTIR) and the long-term stability of the suspension PCL-g-GG in dichloromethane confirmed the effectiveness of grafting of PCL into GG. The size exclusion chromatography (SEC) results show that the molar masse of grafted PCL could be modulated by varying the amount of guar gum. From thermogravimetric analysis and differential scanning calorimetry results the thermal stability of PCL-g-GG is greatly improved with different content of guar gum, also the melting temperature and crystallinity increased by increasing the GG content. The scanning electron microscopy (SEM) analyses showed the good adhesion between GG and PCL with 5% of GG contents. It was also revealed by contact angle measurements that the grafting of PCL to GG leads to a decrease of hydrophobicity of PCL. The micro-indentation hardness properties of the prepared PCL-g-GG were significantly improved, as compared to neat PCL.

Supramolecular Chemistry-Driven Preparation of Nanostructured, Transformable, and Biologically Active Chitosan-Clustered Single, Binary, and Ternary Metal Oxide Bioplastics.

Aside from their economical cost and resource depletion, petroleum-based plastics generate annually a substantial amount of waste with a negative and extremely alarming impact on the environment and public health. Consequently, rising interest was devoted to search for biobased materials to find sustainable alternatives. Herein, we report a new and straightforward method to incorporate endogenous nano-objects (exemplified herein by metal oxide clusters) within polysaccharide-based films. Supramolecular chemistry based on polysaccharide self-assembly associated with the sol-gel polymerization allowed converting soluble chitosan and metal alkoxide precursors to nanostructured chitosan-clustered metal oxide films. A broad range of discrete single, binary, and ternary mixed metal oxides was successfully incorporated in the resulting bioplastics. The multifaceted use of these films was demonstrated by transforming them under gentle thermal treatment to partially oxidized chitosan-metal oxide materials or by disintegrating them in aqueous conditions to yield stable, water-dispersed chitosan-coated-metal oxide nanoparticles. The utility of these functional films was demonstrated through their use as antimicrobial agents, where significant improvement for inhibiting growth of positive and negative bacteria was observed compared to native, nonmodified chitosan films.

Interfacial complexation driven three-dimensional assembly of cationic phosphorus dendrimers and graphene oxide sheets.

High content nitrogen, sulfur and phosphorus heteroatoms assembled in tree-like dendrimers (DG n ) are confined within the galleries of two-dimensional graphene oxide (GO). The presence of the ternary diethyl-N-ethyl-ammonium groups on the dendrimer peripheries ensures the exfoliation of graphene sheets thereby affording interfacially bridged, three-dimensional heteroatom-enriched graphene-based hybrid nanostructures (DG n -GO). Dendrimer generation (from 1 to 4) that reflects the bulkiness of these conceived nano-trees impacts increasingly the degree of dispersion-exfoliation and sheet desordering. The long-term stability of these aqueous suspensions associated with their handling flexibility allows uniform accommodation of the resulting hybrid materials as flame-retardants in bioplastics.

Aldehyde-functionalized chitosan-montmorillonite films as dynamically-assembled, switchable-chemical release bioplastics.

Temporal release of synergistic and/or complementary chemicals (e.g.: drugs) is recognized as extremely challenging because of their frequently intertwined kinetic delivery and presently, straightforward concepts enabling to circumvent this bottleneck are missing in the open literature. In this framework, we report herein on aldehyde-functionalized, transparent and flexible chitosan-montmorillonite hybrid films that act as a new generation of eco-friendly, controlled-chemical release bioplastics. These dynamically-assembled nanomaterials are designed by a ternary assembly from biowaste derived chitin biopolymer, aromatic aldehydes and layered clay nanoparticles. On the basis of their geometrical and conformational properties, the oxygenated groups on the grafted aromatics interact preferentially with either the base Schiff belonging to the carbohydrate (via intramolecular CNHO-Ar known as "imine clip") or with the hydroxyl groups belonging to the clay surface (via intermolecular Si-OHO-Ar). The exfoliated clay nanoparticles within the carbohydrate polymer enables either accelerating or slowing down of the imine (CN) hydrolysis depending on the interaction of the conjugated aromatics. This provides the driving force for fine tuning host-guest interactions at the molecular level and constitutes an entry toward subtle discrimination of different chemicals (e.g. complementary fertilizers, synergistic drugs) during their sequential release.

Chitosan-graphene oxide films and CO2-dried porous aerogel microspheres: Interfacial interplay and stability.

The intimate interplay of chitosan (CS) and graphene oxide (GO) in aqueous acidic solution has been explored to design upon casting, nanostructured "brick-and-mortar" films (CS-GO-f) and by acidic-to-basic pH inversion, porous CO2-dried aerogel microspheres (CS-GO-m). Owing to the presence of oxygenated functional groups in GO, good-quality crack-free hybrid films were obtained. Mechanical properties were improved independently of the GO content and it was found that a 20wt% loading affords hybrid film characterized with a Young modulus three times superior to that reached with the same loading of layered clay. The presence of graphene oxide was found to be detrimental for the thermal stability of the polysaccharide at T <350°C, a fact attributed to the well-established decomposition of the oxygenated functional groups of the graphene sheets. Irrespective to the graphene oxide loading, chitosan-graphene oxide mixture preserves the gelation memory of the polysaccharide. Supercritical drying of the resulting soft hydrogels provides macroporous network with surface areas ranging from 226m2g-1 to 554m2g-1. XPS and RAMAN analyses evidenced the selective reduction of GO sheets inside of these microspheres, affording the hitherto unknown macroporous chitosan-entangled-reduced graphene oxide (CS-rGO-m) aerogels. Improvement in both hydrothermal stability (under water reflux) and chemical stability (under acidic conditions) have been noticed for chitosan-graphene oxide microspheres with respect to non-modified chitosan and chitosan-clay bio-hybrids, a result rooted in the substantial hydrophobic character imparted by the addition of graphenic material to the polysaccharide skeleton. In essence, this contribution demonstrates that graphene oxide loading do not disturb neither the filmogenicity of chitosan nor its gelation ability and constitutes a promising route for novel chitosan-based functional hybrid materials.

Insightful understanding of the role of clay topology on the stability of biomimetic hybrid chitosan-clay thin films and CO2-dried porous aerogel microspheres.

Three natural clay-based microstructures, namely layered montmorillonite (MMT), nanotubular halloysite (HNT) and micro-fibrillar sepiolite (SP) were used for the synthesis of hybrid chitosan-clay thin films and porous aerogel microspheres. At a first glance, a decrease in the viscosity of the three gel-forming solutions was noticed as a result of breaking the mutual polymeric chains interaction by the clay microstructure. Upon casting, chitosan-clay films displayed enhanced hydrophilicity in the order CS