Trends in polysaccharide-based hydrogels and their role in enhancing the bioavailability and bioactivity of phytocompounds.

Over the years, polysaccharides such as chitosan, alginate, hyaluronic acid, k-carrageenan, xanthan gum, carboxymethyl cellulose, pectin, and starch, alone or in combination with proteins and/or synthetic polymers, have been used to engineer an extensive portfolio of hydrogels with remarkable features. The application of polysaccharide-based hydrogels has the potential to alleviate challenges related to bioavailability, solubility, stability, and targeted delivery of phytocompounds, contributing to the development of innovative and efficient drug delivery systems and functional food formulations. This review highlights the current knowledge acquired on the preparation, features and applications of polysaccharide/phytocompounds hydrogel-based hybrid systems in wound management, drug delivery, functional foods, and food industry. The structural, functional, and biological requirements of polysaccharides and phytocompounds on the overall performance of such hybrid systems, and their impact on the application domains are also discussed.

Self-Assembled Chitosan/Dialdehyde Carboxymethyl Cellulose Hydrogels: Preparation and Application in the Removal of Complex Fungicide Formulations from Aqueous Media.

Environmental contamination with pesticides occurs at a global scale as a result of prolonged usage and, therefore, their removal by low-cost and environmentally friendly systems is actively demanded. In this context, our study was directed to investigate the feasibility of using some self-assembled hydrogels, comprising chitosan (CS) and carboxymethylcellulose (CMC) or dialdehyde (DA)-CMC, for the removal of four complex fungicide formulations, namely Melody Compact (MC), Dithane (Dt), Curzate Manox (CM), and Cabrio®Top (CT). Porous CS/CMC and CS/DA-CMC hydrogels were prepared as discs by combining the semi-dissolution acidification sol-gel transition method with a freeze-drying approach. The obtained CS/CMC and CS/DA-CMC hydrogels were characterized by gel fraction yield, FTIR, SEM, swelling kinetics, and uniaxial compression tests. The batch-sorption studies indicated that the fungicides' removal efficiency (RE%) by the CS/CMC hydrogels was increased significantly with increasing sorbent doses reaching 94%, 93%, 66% and 48% for MC, Dt, CM and CT, respectively, at 0.2 g sorbent dose. The RE values were higher for the hydrogels prepared using DA-CMC than for those prepared using non-oxidized CMC when initial fungicide concentrations of 300 mg/L or 400 mg/L were used. Our results indicated that CS/DA-CMC hydrogels could be promising biosorbents for mitigating pesticide contamination of aqueous environments.

Feather-weight cryostructured thiourea-chitosan aerogels for highly efficient removal of heavy metal ions and bacterial pathogens.

Designing of economically feasible and recyclable polysaccharide-based materials with thiourea functional groups for removal of specific metal ions such as Ag(I), Au(I), Pb(II) or Hg(II) remains a major challenge for environmental applications. Here, we introduce ultra-lightweight thiourea-chitosan (CSTU) aerogels engineered by combining successive freeze-thawing cycles with covalent formaldehyde-mediated cross-linking and lyophilization. All aerogels exhibited outstanding low densities (0.0021-0.0103 g/cm3) and remarkable high specific surface areas (416.64-447.26 m2/g), outperforming the common polysaccharide-based aerogels. Benefitting from their superior structural features (honeycomb interconnected pores and high porosity), CSTU aerogels demonstrate fast sorption rates and excellent performance in sorption of heavy metal ions from highly-concentrated single or binary-component mixtures (1.11 mmol Ag (I)/g and 0.48 mmol Pb(II)/g). A remarkable recycling stability was observed after five sorption-desorption-regeneration cycles when the removal efficiency was up to 80 %. These results support the high potential of CSTU aerogels in the treatment of metal-containing wastewater. Moreover, the Ag(I)-loaded CSTU aerogels exhibited excellent antimicrobial properties against Escherichia coli and Staphylococcus aureus bacterial strains, the killing rate being around 100 %. This data points towards the potential application of developed aerogels in circular economy, by employing the spent Ag(I)-loaded aerogels in the biological decontamination of waters.

Ion-Imprinted Polymeric Materials for Selective Adsorption of Heavy Metal Ions from Aqueous Solution.

The introduction of selective recognition sites toward certain heavy metal ions (HMIs) is a great challenge, which has a major role when the separation of species with similar physicochemical features is considered. In this context, ion-imprinted polymers (IIPs) developed based on the principle of molecular imprinting methodology, have emerged as an innovative solution. Recent advances in IIPs have shown that they exhibit higher selectivity coefficients than non-imprinted ones, which could support a large range of environmental applications starting from extraction and monitoring of HMIs to their detection and quantification. This review will emphasize the application of IIPs for selective removal of transition metal ions (including HMIs, precious metal ions, radionuclides, and rare earth metal ions) from aqueous solution by critically analyzing the most relevant literature studies from the last decade. In the first part of this review, the chemical components of IIPs, the main ion-imprinting technologies as well as the characterization methods used to evaluate the binding properties are briefly presented. In the second part, synthesis parameters, adsorption performance, and a descriptive analysis of solid phase extraction of heavy metal ions by various IIPs are provided.

Chitosan Sponges with Instantaneous Shape Recovery and Multistrain Antibacterial Activity for Controlled Release of Plant-Derived Polyphenols.

Biomass-derived materials with multiple features are seldom reported so far. Herein, new chitosan (CS) sponges with complementary functions for point-of-use healthcare applications were prepared by glutaraldehyde (GA) cross-linking and tested for antibacterial activity, antioxidant properties, and controlled delivery of plant-derived polyphenols. Their structural, morphological, and mechanical properties were thoroughly assessed by Fourier-transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and uniaxial compression measurements, respectively. The main features of sponges were modulated by varying the CS concentration, cross-linking ratio, and gelation conditions (either cryogelation or room-temperature gelation). They exhibited complete water-triggered shape recovery after compression, remarkable antibacterial properties against Gram-positive (Staphylococcus aureus (S. aureus), Listeria monocytogenes (L. monocytogenes)) and Gram-negative (Escherichia coli (E. coli), Salmonella typhimurium (S. typhimurium)) strains, as well as good radical scavenging activity. The release profile of a plant-derived polyphenol, namely curcumin (CCM), was investigated at 37 °C in simulated gastrointestinal media. It was found that CCM release was dependent on the composition and the preparation strategy of sponges. By linearly fitting the CCM kinetic release data from the CS sponges with the Korsmeyer-Peppas kinetic models, a pseudo-Fickian diffusion release mechanism was predicted.

Polysaccharide-Based Composite Hydrogels as Sustainable Materials for Removal of Pollutants from Wastewater.

Nowadays, pollution has become the main bottleneck towards sustainable technological development due to its detrimental implications in human and ecosystem health. Removal of pollutants from the surrounding environment is a hot research area worldwide; diverse technologies and materials are being continuously developed. To this end, bio-based composite hydrogels as sorbents have received extensive attention in recent years because of advantages such as high adsorptive capacity, controllable mechanical properties, cost effectiveness, and potential for upscaling in continuous flow installations. In this review, we aim to provide an up-to-date analysis of the literature on recent accomplishments in the design of polysaccharide-based composite hydrogels for removal of heavy metal ions, dyes, and oxyanions from wastewater. The correlation between the constituent polysaccharides (chitosan, cellulose, alginate, starch, pectin, pullulan, xanthan, salecan, etc.), engineered composition (presence of other organic and/or inorganic components), and sorption conditions on the removal performance of addressed pollutants will be carefully scrutinized. Particular attention will be paid to the sustainability aspects in the selected studies, particularly to composite selectivity and reusability, as well as to their use in fixed-bed columns and real wastewater applications.

Aminopolycarboxylic Acids-Functionalized Chitosan-Based Composite Cryogels as Valuable Heavy Metal Ions Sorbents: Fixed-Bed Column Studies and Theoretical Analysis.

Over the years, a large number of sorption experiments using the aminopolycarboxylic acid (APCA)-functionalized adsorbents were carried out in batch conditions, but prospective research should also be directed towards column studies to check their industrial/commercial feasibility. In this context, sorption studies of five-component heavy metal ion (HMI) solutions containing Zn2+, Pb2+, Cd2+, Ni2+, and Co2+ in equimolar concentrations were assessed in fixed-bed columns using some APCA-functionalized chitosan-clinoptilolite (CS-CPL) cryogel sorbents in comparison to unmodified composite materials. The overall sorption tendency of the APCA-functionalized composite sorbents followed the sequence Co2+ < Zn2+ < Cd2+ ≤ Pb2+ < Ni2+, meaning that Co2+ ions had the lowest affinity for the sorbent's functional groups, whereas the Ni2+ ions were strongly and preferentially adsorbed. To get more insights into the application of the composite microbeads into continuous flow set-up, the kinetic data were described by Thomas and Yoon−Nelson models. A maximum theoretical HMI sorption capacity of 145.55 mg/g and a 50% breakthrough time of 121.5 min were estimated for the column containing CSEDTA-CPL cryogel sorbents; both values were much higher than those obtained for the column filled with pristine CS-CPL sorbents. In addition, desorption of HMIs from the composite microbeads in dynamic conditions was successfully achieved using 0.1 M HCl aqueous solution. Moreover, a theoretical analysis of APCA structures attached to composite adsorbents and their spatial structures within the complex combinations with transition metals was systematically performed. Starting from the most stable conformer of EDTA, coordinative combinations with HMIs can be obtained with an energy consumption of only 1 kcal/mole, which is enough to shift the spatial structure into a favorable conformation for HMI chelation.

Chitosan-Based Polyelectrolyte Complex Cryogels with Elasticity, Toughness and Delivery of Curcumin Engineered by Polyions Pair and Cryostructuration Steps.

Chitosan (CS)-based drug delivery systems (DDSs) are often stabilized by chemical cross-linking. A much more friendly approach to deliver drugs in a controlled manner is represented by polyelectrolyte complexes (PECs) physically stabilized by spontaneous interactions between CS and natural or synthetic biocompatible polyanions. PECs with tunable structures, morphologies, and mechanical properties were fabricated in this paper by an innovative and sustainable strategy. Carboxymethyl cellulose (CMC) or poly(2-acrylamido-2-methylpropanesulfonate sodium salt) were used as aqueous solutions, while CS microparticles were evenly dispersed in the polyanion solution, at pH 6.5, where CS was not soluble. Cryostructuration of the dispersion in two steps (5 min at -196 °C, and 24 h at -18 °C), and freeze-drying at -55 °C, 48 h, conducted to pre-PEC cryogels. Next step was rearrangement of complementary polyions and the complex formation inside the pore walls of cryogels by exposure of the pre-PECs at a source of H+. PEC cryogels with impressive elasticity and toughness were engineered in this study by multiple-cryostructuration steps using CMC as polyanion with a molar mass of 250 kDa and an optimum concentration of polyanion and polycation. The performances of PEC cryogels in sustained delivery of anti-inflammatory drugs such as curcumin were demonstrated.

Preparation and Characterization of Semi-IPN Cryogels Based on Polyacrylamide and Poly(N,N-dimethylaminoethyl methacrylate); Functionalization of Carrier with Monochlorotriazinyl-ß-cyclodextrin and Release Kinetics of Curcumin.

Curcumin (CCM) is a natural hydrophobic polyphenol known for its numerous applications in the food industry as a colorant or jelly stabilizer, and in the pharmaceutical industry due to its anti-inflammatory, antibacterial, antioxidant, anti-cancer, and anti-Alzheimer properties. However, the large application of CCM is limited by its poor solubility in water and low stability. To enhance the bioavailability of CCM, and to protect it against the external degradation agents, a novel strategy, which consists in the preparation of semi-interpenetrating polymer networks, (s-IPNs) based on poly(N,N-dimethylaminoethyl methacrylate) entrapped in poly(acrylamide) networks, by a cryogelation technique, was developed in this work. All s-IPN cryogels were characterized by SEM, EDX, FTIR, and swelling at equilibrium as a function of pH. Functionalization of semi-IPN cryogel with monochlorotriazinyl-ß-cyclodextrin (MCT-ß-CD) led to IPN cryogel. The release profile of CCM from the composite cryogels was investigated at 37 °C, in pH 3. It was found that the cumulative release increased with the increase of the carrier hydrophobicity, as a result of increasing the cross-linking degree, the content and the molar mass of PDMAEMA. Fitting Higuchi, Korsmeyer-Peppas, and first order kinetic models on the CCM release profiles indicated the diffusion as the main driving force of drug release from the composite cryogels.

Recent developments in layer-by-layer assembled systems application in water purification.

Electrostatically-based layer-by-layer (LbL) assembly is a versatile surface functionalization technique allowing the construction of complex three-dimensional architectures on virtually any type of material using various combinations of nano-bricks. One of the most promising applications of LbL assembled systems is in water purification. The main two strategies developed in this purpose consist in either enhancing the barrier properties of separation membranes and in the construction of core-shell organic/inorganic sorbents. In this review, the recent achievements in this topic are discussed with respect to the use of LbL-based composites in desalination and removal of heavy metal ions or organic pollutants. Finally, some works dealing with economic aspects of using LbL assemblies for water purification are presented, thus highlighting forthcoming strategies to develop economically-viable materials for such applications.

Removal and Separation of Heavy Metal Ions from Multicomponent Simulated Waters Using Silica/Polyethyleneimine Composite Microparticles.

Composite solid surfaces with high content of functional groups (FGs) are useful materials in different types of applications requiring stimuli-responsive "hard/soft" architectures, their improved properties rising from the combination of organic-inorganic parts. Among different types of weak polyelectrolytes, poly(ethyleneimine) (PEI) is of great interest in the construction of composite systems with thin layer-by-layer (LbL) organic films due to the large number of amino groups per unit mass of polymer. Herein, the spherical silica microparticles were modified with linear (L) or branched (B) PEI chains using LbL deposition of a copper complex (PEIL-Cu2+ or PEIB-Cu2+) and poly(acrylic acid) (PAA), glutaraldehyde selective cross-linking, followed by copper and PAA extraction from the multilayer. The newly formed silica/(PEIL)10 and silica/(PEIB)10 composites were used in batch and column sorption/desorption experiments of four heavy metal ions (Cu2+, Ni2+, Co2+, and Cd2+). In noncompetitive conditions ([FG]/Σ[M2+] > 9), all heavy metal ions were retained on composites, demonstrating the potential application of the prepared functional microparticles in surface water treatment. However, in competitive conditions ([FG]/Σ[M2+] < 9), only Cu2+ is sorbed in high amount (∼2.5 mmol·g-1 PEI) on composites, with simultaneous displacement of already sorbed ions, demonstrating the solid-phase extraction and chromatographic properties of the synthesized silica/(PEIL)n and silica/(PEIB)n composites.

Influence of cross-linking in loading/release applications of polyelectrolyte multilayer assemblies. A review.

Design of polymeric matrices for loading/release purposes is of great interest in various applications, such as drug delivery systems, antimicrobial surfaces, biosensors, water purification. Compared with other strategies to fabricate materials for such applications, the Layer-by-Layer (LbL) assembly remarked itself by the countless possibilities to tailor the organic architectures at nanoscale owing to the structural diversity of "nano-bricks" suitable for assembly and easiness to control the deposition features. LbL assembled systems have been extensively used as matrices to load/release low molecular compounds such as drugs and dyes, proteins and enzymes, or DNA (RNA). In many studies, cross-linking the layers was investigated as a mean to stabilize and to induce new functionalities in the obtained architectures, as well as to tune their loading/release properties. In this review we discuss recent progress in the use of LbL constructions in loading/release of bioactive species, with a main focus on the role of cross-linking on such features. Overviews of the LbL assembly strategy describing the parameters which influence the build-up process and of the main synthetic routes used to cross-link the obtained architectures are briefly presented. The use of LbL systems (either as thin films deposited on solid surfaces or as hollow capsules) to load/release low molecular compounds and proteins/enzymes, highlighting the role of cross-linking in such processes (construction of porous architectures capable to load high molecular compounds or decreasing the assemblies permeability to delay the release of encapsulated compounds) was thoroughly discussed.

Poly(N,N-dimethylamino)ethyl methacrylate/sodium alginate multilayers and their interaction with proteins/enzymes.

The aim of the present work is to construct and investigate the properties of novel polyelectrolyte multilayers consisting of poly(N,N-dimethylamino)ethyl methacrylate (PDMAEMA) and sodium alginate (SA). The influence of PDMAEMA's pH dependent ionization degree on the charge balance, thickness and roughness of the multilayer films was assessed by potentiometric titrations, dye sorption and atomic force microscopy. Moreover, the cross-linking of PDMAEMA/SA films with a dihalogenated aromatic derivative with high reactivity (α,α'-dichloro-p-xylene) by means of Menshutkin reaction and the stability of the multilayer architecture to repeated treatments with NaOH are demonstrated. Also, the interaction of the obtained films with various proteins/enzymes (pepsin, bovine serum albumin, haemoglobin and lysozyme) is investigated. It was found that biomolecules with the isoelectric point in the acidic region of pH were adsorbed in a higher amount than the biomolecules with the isoelectric point in the basic region of pH.

Sorption and release of drugs in/from cross-linked poly(ethyleneimine) multilayer films deposited onto silica microparticles.

Multilayer thin films are useful materials in fabrication of controlled drug delivery systems and in controlling drug release processes. Herein, we report the fabrication of single polycation multilayers based on branched poly(ethylene imine) (PEI) mediated by dianhydrides (DA), as cross-linker and source of carboxylic groups, deposited onto Daisogel silica microparticles, and their sorption/release properties for some anionic drugs as a function of the cross-linker concentration. Pyromellitic dianhydride (PM) and 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTCDA) were used as DA reagents. The monotonous increase of the (PEI-DA)n multilayers was demonstrated by Fourier transform infrared spectroscopy, point of zero charge (pzc), and X-ray photoelectron spectroscopy. The sorption properties of the PEI multilayer films for two drugs (diclofenac sodium, DS, and indomethacin, IDM) and a model dye (Ponceau SS, PSS) were influenced by the number of PEI layers and the weight ratio between cross-linker and silica microparticles during the cross-linking steps. It was found that the adsorbed amount of drugs increased with the number of PEI layers and with the decrease of DA concentration. The Langmuir, Sips, and Dubinin-Radushkevich model isotherms were applied to fit the sorption equilibrium data of IDM onto the Daisogel//(PEI-DA)n composites. The maximum equilibrium sorption capacity, qm, evaluated by the Langmuir model, at 25 °C, was 37.05 mg IDM/g of Daisogel//(PEI-BTCDA)8.5, and 39.99 mg IDM/g of Daisogel//(PEI-PM)8.5, for a weight percentage of DA/silica of 0.1% w/w. Cumulative release of DS was almost 100% within 180 min, while IDM was desorbed at a level of 35%, in 320 min, supporting a sustained release was gained with the cross-linked PEI films. The stability of the (PEI-DA)n multilayers during the successive sorption/desorption cycles of PSS was demonstrated.