Polysaccharides, Volume 3, Issue 3 (September 2022) – 11 articles

The photocatalytic Fenton process, which produces a strong oxidant in the form of hydroxyl radicals, is a useful method to degrade organic contaminants in water. The Fenton reaction uses hydrogen peroxide and Fe²⁺ ions under relatively acidic conditions (typically pH 2–3) to maintain solubility of the iron catalyst but is troublesome due to the large volumes of decontaminated yet highly acidic water generated. Starch-stabilized iron (Fe²⁺/Fe³⁺) oxide nanoparticles were synthesized to serve as a colloidal catalyst system as the hydrophilic starch effectively prevents precipitation of the nanoparticles under conditions closer to neutrality. To evaluate the usefulness of this catalyst system for the photo-Fenton degradation of methylene blue as a model dye, the preparation protocol used and the iron loading in the starch were varied. The photocatalytic Fenton reaction was investigated at pH values up to 4. Not only were the starch-stabilized catalysts able to decolorize the dye but also to mineralize it in part, that is, to degrade it to carbon dioxide and water. The catalysts could be reused in several degradation cycles. This demonstrates that starch is an efficient stabilizer for iron oxide nanoparticles in aqueous media, enabling their use as environmentally friendly and cost-effective photo-Fenton catalysts. These starch-stabilized iron nanoparticles may also be useful to degrade other dyes and pollutants in water, such as pesticides. Full article

Implantable drug delivery systems advocate a wide array of potential benefits, including effective administration of drugs at lower concentrations and fewer side-effects whilst increasing patient compliance. Amongst several polymers used for fabricating implants, biopolymers such as polysaccharides are known for modulating drug delivery attributes as desired. The review describes the strategies employed for the development of polysaccharide-based implants. A comprehensive understanding of several polysaccharide polymers such as starch, cellulose, alginate, chitosan, pullulan, carrageenan, dextran, hyaluronic acid, agar, pectin, gellan gum is presented. Moreover, biomedical applications of these polysaccharide-based implantable devices along with the recent advancements carried out in the development of these systems have been mentioned. Implants for the oral cavity, nasal cavity, bone, ocular use, and antiviral therapy have been discussed in detail. The regulatory considerations with respect to implantable drug delivery has also been emphasized in the present work. This article aims to provide insights into the developmental strategies for polysaccharide-based implants. Full article

The global demand for sustainable textile fibers is growing and has led to an increasing research interest from both academia and industry to find effective solutions. In this research, regenerated wood pulp fibers were functionalized with glycidyltrimethylammonium chloride (GTAC) to produce modified regenerated cellulose with cationic pending groups for improved dye uptake. The resultant cationic cellulose with a degree of substitution (DS) between 0.13 and 0.33 exhibited distinct morphologies and contact angles with water ranging from 65.7° to 82.5° for the fibers with DS values of 0.13 and 0.33, respectively. Furthermore, the thermal stability of the modified regenerated cellulose fibers, albeit lower than the pristine ones, reached temperatures up to 220 °C. Additionally, the modified fibers showed higher dye exhaustion and dye fixation values than the non-modified ones, attaining maxima values of 89.3% ± 0.9% and 80.6% ± 1.3%, respectively, for the cationic fibers with a DS of 0.13. These values of dye exhaustion and dye fixation are ca. 34% and 77% higher than those obtained for the non-modified fibers. Overall, regenerated wood pulp cellulose fibers can be used, after cationization, as textiles fiber with enhanced dye uptake performance that might offer new options for dyeing treatments. Full article

The purity and safety of water as a finite resource is highly important in order to meet current and future human needs. To address this issue, the usage of environmentally friendly and biodegradable adsorbers and flocculants is essential. Chitosan, as a biopolymer, features tremendous properties as an adsorber and flocculant for water treatment. For the application of chitosan as an adsorber under acidic aqueous conditions, such as acid mine drainage, chitosan has been modified with hydrophobic hexanoyl chloride (H-chitosan) to reduce the solubility at a lower pH. In order to investigate the influence of the substitution of the hexanoyl chloride on the adsorption properties of chitosan, two chitosans of different molecular weights and of three different functionalization degrees were analyzed for the adsorption of CdSO_4(aq) and Al₂(SO₄)_3(aq). Among biobased adsorbents, H-chitosan derived from the shorter Chitosan exhibited extraordinarily high maximum adsorption capacities of 1.74 mmol/g and 2.06 mmol/g for Cd²⁺ and sulfate, and 1.76 mmol/g and 2.60 mmol/g for Al³⁺ and sulfate, respectively. Full article

Edible films of three high methoxy pectins (DE: 70–75%) in the presence of dittany and anise infusions were studied. Apart from a commercial one, two more pectins, selected by their yield and DE from preliminary experiments on pectin extraction from orange peels using ultrasound- and microwave-assisted extraction or a combination of both, were used. Extracted pectins were darker, less surface active and had lower [η] and absolute zeta values. All three pectin solutions were Newtonian. Furthermore, all films had statistically the same thickness (~40 μm) and moisture content (~25.2%). For the same herbal infusion, all pectins resulted in films with the same density (~1.01 and ~1.19 g/cm³ for dittany and anise films, respectively). Values of 2–4.65 N and 76.62–191.80 kPa, for maximum force and modulus, respectively, were reported. The commercial pectin film with anise was the stronger, whereas that with dittany, the stiffer. Total phenolics content (TPC) and antioxidant activity (SA) were also measured for films and film-forming solutions (FFS). TPC values ranged from 0.035 to 0.157 mg GAE/0.5 mL and SA from ~62 to 91%. Films had greater TPC but lower SA than their FFS. The presence of both pectin and herbal infusions were significant for our observations. Full article

The adsorption of heavy metal ions from surface water with ecologically safe and biodegradable biopolymers is increasingly becoming an appealing research challenge. Starch as a biopolymer is exceptionally attractive to solve this problem for its low cost and abundant availability in nature. To expel Ni²⁺, Fe^2+/3+, and Mn²⁺ from water, we analyzed two native and two oxidized starches, namely potato and corn starch, as bio-adsorbers. The morphology and the surface property of the different starches were studied using SEM. To assess the effectiveness of adsorption onto the starches, we tested three realistic concentrations based on German drinking water ordinance values that were 10-fold, 100-fold, and 1000-fold the limits for Mn²⁺, Fe²⁺, and Ni²⁺, respectively. The concentration of the different ions was measured using the ICP-OES. Furthermore, from subsequent investigations of the adsorption isotherms, we evaluated the adsorption capacities and mechanisms. The adsorption isotherms were fitted using the Langmuir, Sips, and Dubinin–Radushkevich models, whereby Sips showed the highest correlation. Oxidized potato starch achieved viable adsorption capacities of 77 µmol Fe²⁺/g, 84 µmol Mn^2+/g, and 118 µmol Ni^2+/g. Investigating the influence of initial swelling in water on the adsorption performance, we found that especially the percentage removal with oxidized starches decreased significantly due to the formation of hydrogen bonds with water molecules at their binding sites with prior swelling. Full article

This review examines the immobilization of A. pullulans cells for production of the fungal polysaccharide pullulan. Pullulan is a water-soluble gum that exists structurally as a glucan consisting primarily of maltotriose units, which has a variety of food, non-food and biomedical applications. Cells can be immobilized by carrier-binding or entrapment techniques. The number of studies utilizing carrier-binding as a method to immobilize A. pullulans cells appears to outnumber the investigations using cell entrapment. A variety of solid supports, including polyurethane foam, sponge, diatomaceous earth, ion-exchanger, zeolite and plastic composite, have been employed to immobilize pullulan-producing A. pullulans cells. The most effective solid support that was used to adsorb the fungal cells was polyurethane foam which produced polysaccharide after 18 cycles of use. To entrap pullulan-producing fungal cells, agents such as polyurethane foam, polyvinyl alcohol, calcium alginate, agar, agarose, carrageenan and chitosan were investigated. Polysaccharide production by cells entrapped in polyurethane foam, polyvinyl alcohol or calcium alginate was highest and the immobilized cells could be reutilized for several cycles. It was shown that the pullulan content of the polysaccharide synthesized by cells entrapped in calcium alginate beads was low, which limits the method’s usefulness for pullulan production. Further, many of the entrapped fungal cells synthesized polysaccharide with a low pullulan content. It was concluded that carrier-binding techniques may be more effective than entrapment techniques for A. pullulans cell immobilization, since carrier-binding is less likely to affect the pullulan content of the polysaccharide being synthesized. Full article

There is strong adsorption of metal ions and their complexes to chitin, which depends on both the oxidation and complexation states of many of the said elements (whereas others display chemical reactions detectable via electrochemical methods while being retained by chitin); thus, ad- and desorption at ambient water concentrations (often in the nMol/L range) are controlled by the presence and photochemical properties (concerning Eu and probably U and Ag) of mainly biogenic organic matter (both DOC and POC, and DON). With chitin forming the outer hull of mobile organisms (animals), this biopolymer is expected to take part in metal distribution in aquatic (limnetic and riverine) ecosystems. Having studied the attachment of many different elements to both crayfish and grafted (marine shrimp) chitin, with the highest accumulations observed in Bi, V, Ni, and LREEs, one should consider secondary biochemical transformations which take place at different water and sediment levels. After chitin had been embedded into sediment, methanogenesis (which requires Ni), Bi, and Sb biomethylations and photodesorption in the illuminated water column will occur if there are appropriate organics, causing the vertical separation of Eu from other REEs, at least during the daytime. Eutrophication will enhance both the production and especially the photooxidation rates of organics in water because phosphorylated sugars and lipids are formed quantitatively within min P, which enter water and undergo Eu-mediated photooxidation much more readily. Another biopolymer, gelatin, acts as an inert matrix-enhancing organic photooxidation product via Eu, producing chemical waves, indicating autocatalysis upon light impact. From the redox-related photodesorption of metal analytes from chitin, both sensors and devices for (light-assisted) electrochemical energy conversion are being developed by our workgroup. The electrochemical determination of adsorption thermodynamics on chitin is thus directly linked to its applications in environmental monitoring and technology. Full article

Polysaccharides are formed by a long chain of monosaccharides, with the main function of promoting energetic and structural reserves for plants and animals. They can be applied as a base of electrolytes, using ionic liquids (ILs) as a solvent base. The study of electrolytes is an emerging field, as they are applied as secondary batteries, fuel cells, solar cells, supercapacitors and chemical sensors. They operate stably under extreme conditions, maintaining their high thermal stability. Furthermore, their low cost and environmentally safe character, compared to conventional electrolytes, have attracted considerable attention in the scientific field. ILs are composed entirely of ions and could be potentially applied as solvents. As electrolytes, ILs are environmentally friendly, and their use in combination with polysaccharides leads to a synergic effect. In the present study, a systematic review was performed of all papers published from 2014 to 2022 regarding ILs and polysaccharides through a search of three databases. Due to the large number of results found, only papers about electrolytes were considered and the main findings described. This study allows for easy identification of the most relevant fields of study with respect to ILs and polysaccharides, as well as the main gaps to be explored in the literature. Full article

Biodegradable films emerge as alternative biomaterials to conventional packaging from fossil sources, which, in addition to offering protection and increasing the shelf life of food products, are ecologically sustainable. The materials mostly used in their formulation are based on natural polysaccharides, plasticizing agents, and bioactive components (e.g., antimicrobial agents or antioxidants). The formulation of biodegradable films from polysaccharides and various plasticizers represents an alternative for primary packaging that can be assigned to specific food products, which opens the possibility of having multiple options of biodegradable films for the same product. This review describes the main characteristics of the most abundant polysaccharides in nature and highlights their role in the formulation of biodegradable films. The compilation and discussion emphasize studies that report on the mechanical and barrier properties of biodegradable films when made from pure polysaccharides and when mixed with other polysaccharides and plasticizing agents. Full article

Methyl cellulose and its derivatives are widely used in the food industry, cosmetics, and as construction materials. The properties of methyl celluloses (MC) strongly depend on their degrees and positions of substitution. In order to generate MCs with uncommon blocky substitution, we apply fully protected O-benzyl-O-methyl celluloses (BnMC). Such complex polysaccharide derivatives could not be deprotected completely and without shift of the composition by methods usually applied to mono- and oligosaccharides. Therefore, a facile debenzylation method was developed based on photo-initiated free-radical bromination in the presence of hydrobromic acid scavengers followed by alkaline treatment. The reaction proceeds under homogeneous conditions and without the aid of any catalyst. There is no need for expensive equipment, materials, anhydrous reagents, or running the reaction under anhydrous conditions. Reaction parameters were investigated and optimized for successful debenzylation of completely protected BnMC with degrees of methyl substitution (DS_Me) around 1.9 (and DS_Bn around 1.1). Side-product-free and almost complete debenzylation was achieved when 1,2-epoxybutane (0.5 eq./eq. N-bromosuccinimide) and 2,6-di-tert-butylpyridine (0.5 eq./eq. N-bromosuccinimide) were used in the reaction. Furthermore, ATR-IR and ¹H NMR spectroscopy confirmed the successful removal of benzyl ether groups. The method was developed to monitor the transglycosylation reaction of the BnMC with permethylated cellulose, for which the deprotection of many small samples in parallel is required. This comprises the determination of the methyl pattern in the glucosyl units by gas-liquid chromatography (GLC), as well as oligosaccharide analysis by liquid chromatography mass spectrometry (LC-MS) after perdeuteromethylation and partial hydrolysis to determine the methyl pattern in the chains. The unavoidable partial chain degradation during debenzylation does not interfere with this analytical application, but, most importantly, the DS and the methyl pattern were almost congruent for the debenzylated product and the original MC, indicating the full success of this approach The presented method provides an unprecedented opportunity for high throughput and parallel debenzylation of complicated glucans, such as BnMC (as a model compound), for analytical purposes. For comparison, debenzylation using Na/NH₃ was applied to BnMC and resulted in a completely debenzylated product with a remarkably high recovery yield of 99 mol% and is, thus, the method of choice for synthetic applications, e.g., for the transglycosylation product prepared under the selected conditions in a preparative scale. Full article