Natural Polysaccharide-Based Hydrogels Used for Dye Removal.

Removal of contaminants from discharge water is vital and demands urgent assistance with the goal to keep clean water. Adsorption is one of the most common, efficient, and low-priced methods used in water treatment. Various polysaccharide-based gels have been used as efficient dye adsorbents from wastewater. This review summarizes cutting-edge research of the last decade of different hydrogels based on natural polysaccharides (chitin, chitosan, cellulose, starch, pullulan, and dextran) concerning their dye adsorption efficiency. Beyond their natural abundance, attributes of polysaccharides such as biocompatibility, biodegradability, and low cost make them not only efficient, but also environmentally sustainable candidates for water purification. The synthesis and dye removal performance together with the effect of diverse factors on gels retaining ability, kinetic, and isotherm models encountered in adsorption studies, are introduced. Thermodynamic parameters, sorbent recycling capacity along with conclusions and future prospects are also presented.

Bile Acid Sequestrants Based on Natural and Synthetic Gels.

Bile acid sequestrants (BASs) are non-systemic therapeutic agents used for the management of hypercholesterolemia. They are generally safe and not associated with serious systemic adverse effects. Usually, BASs are cationic polymeric gels that have the ability to bind bile salts in the small intestine and eliminate them by excretion of the non-absorbable polymer-bile salt complex. This review gives a general presentation of bile acids and the characteristics and mechanisms of action of BASs. The chemical structures and methods of synthesis are shown for commercial BASs of first- (cholestyramine, colextran, and colestipol) and second-generation (colesevelam and colestilan) and potential BASs. The latter are based on either synthetic polymers such as poly((meth)acrylates/acrylamides), poly(alkylamines), poly(allylamines) and vinyl benzyl amino polymers or biopolymers, such as cellulose, dextran, pullulan, methylan, and poly(cyclodextrins). A separate section is dedicated to molecular imprinting polymers (MIPs) because of their great selectivity and affinity for the template molecules used in the imprinting technique. Focus is given to the understanding of the relationships between the chemical structure of these cross-linked polymers and their potential to bind bile salts. The synthetic pathways used in obtaining BASs and their in vitro and in vivo hypolipidemic activities are also introduced.

New Quaternary Ammonium Derivatives Based on Citrus Pectin.

New citrus pectin derivatives carrying pendant N,N-dimethyl-N-alkyl-N-(2-hydroxy propyl) ammonium chloride groups were achieved via polysaccharide derivatization with a mixture of N,N-dimethyl-N-alkyl amine (alkyl = ethyl, butyl, benzyl, octyl, dodecyl) and epichlorohydrin in aqueous solution. The structural characteristics of the polymers were examined via elemental analysis, conductometric titration, Fourier Transform Infrared spectroscopy (FTIR) and 1D (1H and 13C) nuclear magnetic resonance (NMR). Capillary viscosity measurements allowed for the study of viscometric behavior as well as the determination of viscosity-average molar mass for pristine polysaccharide and intrinsic viscosity ([η]) values for pectin and its derivatives. Dynamic light scattering measurements (DLS) showed that pectin-based polymers formed aggregates in aqueous solution with a unimodal distribution. Critical aggregation concentration (cac) for the hydrophobic pectin derivatives were determined using fluorescence spectroscopy. Atom force microscopy (AFM) images allowed for the investigation of the morphology of polymeric populations obtained in aqueous solution, consisting of flocs and aggregates for crude pectin and its hydrophilic derivatives and well-organized aggregates for lipophilic pectin derivatives. Antimicrobial activity, examined using the disc diffusion method, proved that all polymers were active against Staphylococcus aureus bacterium and Candida albicans yeast.

Insights on Some Polysaccharide Gel Type Materials and Their Structural Peculiarities.

Global resources have to be used in responsible ways to ensure the world's future need for advanced materials. Ecologically friendly functional materials based on biopolymers can be successfully obtained from renewable resources, and the most prominent example is cellulose, the well-known most abundant polysaccharide which is usually isolated from highly available biomass (wood and wooden waste, annual plants, cotton, etc.). Many other polysaccharides originating from various natural resources (plants, insects, algae, bacteria) proved to be valuable and versatile starting biopolymers for a wide array of materials with tunable properties, able to respond to different societal demands. Polysaccharides properties vary depending on various factors (origin, harvesting, storage and transportation, strategy of further modification), but they can be processed into materials with high added value, as in the case of gels. Modern approaches have been employed to prepare (e.g., the use of ionic liquids as "green solvents") and characterize (NMR and FTIR spectroscopy, X ray diffraction spectrometry, DSC, electronic and atomic force microscopy, optical rotation, circular dichroism, rheological investigations, computer modelling and optimization) polysaccharide gels. In the present paper, some of the most widely used polysaccharide gels will be briefly reviewed with emphasis on their structural peculiarities under various conditions.

Bile salts adsorption on dextran-based hydrogels.

Dextran-based gels bearing two types of pendant N, N-dimethyl-N-alkyl-N-(2-hydroxypropyl) ammonium chloride groups with different alkyl chain length substituents (C2 and C12/C16, respectively) at the quaternary nitrogen were synthesized and structural characteristics of the compounds were studied by elemental analysis, potentiometric titration, FTIR and NMR spectroscopy. The morphology and size of polymeric microspheres were examined by SEM and their swelling behavior in water was also investigated. The hydrogels were evaluated as sorbents for sodium cholate (NaCA) and sodium deoxycholate (NaDCA) in water and 10 mM NaCl solutions. Different isotherm models (nearest-neighbor-interaction, Langmuir, Freundlich, Dubinin-Raduskevich, Sips and Hill) were used to elucidate the adsorption mechanism and established the characteristics of the most efficient polymeric sorbent. The maximum adsorption capacity of the gels was highly controlled by gel hydrophobicity which enhanced gel-bile salt affinity but decreased binding cooperativity. Swelling porosity, ionic strength and ligand lipophilicity were other factors that also affected the adsorption process. The hydrogel having 25 mol% pendant dodecyl groups retained the maximum amount of bile salts (1051 mg NaCA/g and 1138 mg NaDCA/g). All hydrophobically modified hydrogels revealed a better affinity and strength of binding compared to commercial Cholestyramine®.

Self-assembly of dextran - b - deoxycholic acid polyester copolymers: Copolymer composition and self-assembly procedure tune the aggregate size and morphology.

Self-assembly potential of new amphiphilic block copolymers containing dextran (Mn 4500, 8000, 15,000) and a semi-rigid deoxycholic acid-oligoethyleneglycol polyester (Mn 2500-8800, 2 or 4 ethyleneglycol units), was evaluated as a function of copolymer composition and self-assembly procedure, using dynamic light scattering and transmission electron microscopy. Addition of copolymer solution to water provided small star-like micelles (∼ 100 nm), while addition of water to copolymer solution led to various morphologies and sizes (60-600 nm), depending on polymer composition. Worm-like micelles were obtained from a copolymer containing dextran with Mn 4500 and 66 wt% polyester, and vesicles were formed by copolymers prepared from dextran with Mn 8000 and containing 46 wt% polyester. Presence of a longer oligoethyleneglycol decreased the size of micelles and vesicles due to an enhanced flexibility of the polyester hydrophobic block. The results allow the selection of the most appropriate parameters to obtain the desired aggregate characteristics.

Novel amphiphilic dextran esters with antimicrobial activity.

New amphiphilic dextran esters were obtained by polysaccharide functionalization with different substituted 1,2,3-triazoles-4-carboxylic acid via in situ activation with N, N'-carbonyldiimidazole. Nitrogen-containing heterocyclic derivatives were achieved by copper(I)-catalyzed cycloaddition reaction between organic azides and ethyl propiolate. Structural characteristics of the compounds were studied by elemental analysis, Fourier transform infrared and nuclear magnetic resonance spectroscopy (1H and 13C-NMR). Thermogravimetric analysis, differential scanning calorimetry and wide-angle X-ray diffraction were used for esters characterization. Properties of polymeric self-associates, formed in aqueous solution, were studied by dynamic light scattering and transmission electron microscopy. The critical aggregation concentration values for dextran esters, determined by fluorescence spectroscopy, were in the range of 4.1-9.5 mg/dL. Antimicrobial activity, investigated for some of the polymers by disc-diffusion method, pointed out that polysaccharide esters were active.

Influence of dextran hydrogel characteristics on adsorption capacity for anionic dyes.

A series of cationic amphiphilic dextran hydrogels with pendent N, N-dimethyl-N-alkyl-N-(2-hydroxypropyl) ammonium chloride pendent groups was obtained with various molar ratios hydrophilic (alkyl = C2)/hydrophobic groups (alkyl = C12 or C16), total content in amino groups (50-68 mol%) and water swelling capacity (3-15 g water/g dry gel). Adsorption capacity for anionic dyes (Methyl Orange and Rose Bengal) was studied as a function of hydrogel characteristics. Adsorption kinetics was mainly influenced by swelling porosity and dye molecular weight. Equilibrium data showed that the maximum sorption capacity was strongly dependent on hydrophobic segment content, which enhanced the affinity dye-gel (increased Langmuir constant KL) and contribution of ion-exchange to adsorption mechanism, and significantly decreased the maximum uptake of Rose Bengal. The hydrophilic highly swollen hydrogel had the best adsorption capacity for Rose Bengal (1700 mg/g) at 25 °C, and more hydrophobic gels could adsorb 830-900 mg Methyl Orange/g, irrespective of the medium temperature.