Polysaccharides

Natural fibers have been widely employed in different fields as composite materials. However, the thermal behavior of natural materials is not fully understood since the chemical components chemically interact with each other. Put simply, the thermal degradation kinetics of natural fibers are of crucial importance in the academic and industrial fields. This study objectively fully investigated the thermal behavior of different natural fibers using the thermal kinetic method criteria, as described by the ICTAC (International Committee of Thermal Analysis and Calorimetry). The kinetic triplet (activation energy, pre-exponential factor, and reaction mechanism) was determined as a function of the conversion degree. For all plant fibers, the results indicated an autocatalytic process with an average activation energy and pre-exponential factor of 200 kJ·mol⁻¹ and 40 s⁻¹, respectively. The activation energy can be mainly attributed to the cellulose component, while the pre-exponential factor is due to the possible compensation effect as a mathematical artifact of the Arrhenius-based equation. Finally, the lifetime prediction of the plant fibers was estimated using the pre-determined kinetic triplet parameters to estimate the plant fiber stability under isothermal conditions. Full article

In times of increasing demand for resources, processing various waste materials is becoming more economically and ecologically viable. Red mud is a waste material that originates from the bauxite process, also known as the Bayer process. Red mud, due to its high alkalinity and heavy metal content, is often stored in landfills, which can lead to accidents such as those in Brazil or Hungary, especially if the storage takes place above ground. Red mud contains not only iron and aluminum residues but also other economically valuable metals such as manganese, titanium, cadmium, or cobalt. Currently, only 4 million tons of the annual production of 150 million tons are utilized in various industries, which is a relatively small amount. Typically, only the iron content is further processed, leaving other potential resources untapped. Chitin has a high binding capacity for various trivalent and divalent metal ions, making it a suitable material for separating red mud into its components. It has been demonstrated that chitin can effectively remove aluminum, barium, cadmium, cobalt, copper, manganese, iron, nickel, lead, strontium, and various lanthanides from a red mud-like sludge. The elements bound to chitin can be easily removed using wet chemistry. Biologically compatible substances are predominantly used in this process, with few exceptions. The removal of elements from red sludge or other mining wastewater using chitin is a viable alternative to traditional mining methods. Full article

Polysaccharide-based nanoformulations with tailored hydrophobic properties have become a frontier in nanomedicine applications. Herein, highly hydrophobicized hydroxyethyl starch (HES) conjugates were synthesized by grafting stearic acid (SA) with HES via a carbodiimide-mediated reaction. A detailed NMR characterization of HES and the conjugates was studied to obtain structural information. The grafting ratio of the stearate-HES (St-HES) conjugates was determined from ¹H NMR spectra as 29.4% (St-HES29.4) and 60.3% (St-HES60.3). Thermal analyses and X-ray diffractograms suggested an entire transition from amorphous HES to a semicrystalline (St-HES60.3) character upon increasing the degree of grafting. Both conjugates, St-HES29.4 and St-HES60.3, were able to form self-assembled particles with a diameter of 130.7 nm and 152.5 nm, respectively. SEM images showed that the self-aggregates were mostly spherical in shape. These conjugates can be employed to entrap highly hydrophobic drugs with an increased encapsulation efficiency and loading capacity. Full article

The development of active food packaging is desirable for food safety and to avoid food loss and waste. In this work, we developed antioxidant bilayer films combining extrusion and electrospinning techniques. These films consisted of a first layer of thermoplastic cornstarch (TPS), incorporated with microcrystalline cellulose (MCC). The second layer consisted of gallic acid (GA) encapsulated at different concentrations in 1:1 chitosan/poly(ethylene-co-vinyl alcohol) (CS/EVOH) nanofibers. This layer was directly electrospun onto the TPS/MCC film. The morphological, structural, wettability, permeability to oxygen, and antioxidant properties were investigated for the first layer and the bilayer films. Water contact angle measurements revealed the hydrophobic nature of the first layer (θ₀ = 100.6°). The oxygen permeability (OP) was accessed through the peroxide value (PV) of canola oil, kept in containers covered by the films. PV varied from 66.6 meq/kg for the TPS/MCC layer to 60.5 meq/kg for a bilayer film. Intermolecular hydrogen bonds, mediated by GA, contributed slightly to improving the mechanical strength of the bilayer films. The bilayer film incorporated with GA at 15.0% reached a radical scavenging activity against the DPPH radical of (903.8 ± 62.2) μmol.L⁻¹.Eq. Trolox.g⁻¹. This result proved the effectiveness of the GA nanoencapsulation strategy. Full article

Bead-free nanofibrous scaffolds composed of PVOH/keratin/chitosan were prepared using electrospinning after optimising the process parameters using a Box–Behnken experimental design. Two quadratic models were developed to optimise the fibre diameter and the diameter of fibre beads considering the voltage, flow rate, spinning distance, and amount of biopolymer as independent variables. All independent variables were found to be significant in determining responses, although not all interactions among these were significant. The models were highly effective in describing responses, with an R² of 98.58 and 99.67%. The optimum conditions were determined to be 15.82 kV voltage, 0.25 mL/h flow rate, 105 mm spinning distance, and 30% biopolymers. The accuracy of the models was verified and found to be within an acceptable range. The bead-free nanofibrous scaffold exhibited no cytotoxicity to Human Aneuploid Immortal Keratinocyte (HaCaT) and Normal Human Dermal Fibroblast (NHDF) cell lines, enabling cell adhesion and proliferation. Both cell lines remained attached with perfect cell morphology when co-cultured on the scaffold for 30 days, indicating the scaffold’s potential for biomedical applications. Full article

Hot spring (HS) waters manifest diverse positive effects on the skin due to their unique chemical compositions. Sodium hyaluronate acid (HA) comprises N-acetylglucosamine and D-glucuronic acid, and distinguishes itself with superior qualities in skin regeneration, providing moisturizing and anti-aging benefits. The combination of HA with HS water is widely applied across ophthalmology, pneumology, nutrition, and cosmetics. This study delved into the application of HA in cosmetology, with a focus on its interaction with HS water and its effects on moisture retention and promoting wound healing. In particular, with the alkaline pH levels of the Yumoto HS, HA molecules may undergo dissociation to be ionized resulting in a negatively charged polymer and interacting with positively charged ions in the HS water through electrostatic interactions. The shifted peaks in the FTIR result and zeta potential shifts to a less negative region in the case of HA-HS compared to HA-DI indicate an ionic interaction between HS water and HA. Moisture tests confirmed the sustained hydration when HA is dissolved in HS water, underscoring its potential to improve skin hydration at certain concentrations, specifically at 0.5% and 1%. Additionally, MTT assay results demonstrated that HS water stimulates the growth of fibroblast cells compared to distilled water, implying its potential beneficial effect in wound healing. These findings suggested the multifaceted benefits of HAHS in skincare, highlighting its role in enhancing skin hydration and potentially accelerating wound healing processes, thus presenting avenues for the development of advanced cosmeceutical formulations. Full article

Cellulose nanocrystals (CNCs) are bio-based materials able to be functionalized following different approaches, which expands their range of applications. One such approach is surface-initiated polymerization, which involves the attachment of an initiator to the CNC’s surface to initiate the growth of the polymer. This work reports the modification of CNCs using the described approach. First, a CNC-based film was prepared, on which an initiator (RAFT agent) was grafted, and then (trimethylaminoethyl methacrylate, a positively charged monomer, was polymerized using reversible addition–fragmentation chain-transfer (RAFT) polymerization. The CNC film was successfully modified and fully characterized. Different degrees of polymerization were targeted to emphasize the effect of the positively charged polymer and their chain length on the adsorption efficiency. The results showed that by increasing the chain length of the grafted polymer, up to 80% of both pollutants could be removed, with a faster adsorption of PFOS as compared to PFOA. Full article

In this study, chitosan-based surfactants were synthesized by epoxy–amine chemistry to stabilize concentrated O/W emulsions at pH7. Chitosan was first depolymerized by nitrous deamination to obtain chitooligosaccharides (COS) with degrees of polymerization of 10 (DP10) and 20 (DP20). Then, three different epoxidized fatty chains, i.e., octyl/decyl glycidyl ether (C9), hexadecyl glycidyl ether (C16) and epoxidized cardanol (card), were grafted onto the amine groups of chitosan to form six amphiphilic structures. NMR measurements revealed grafting efficiencies ranging from 1 to 30% while HLB values ranged from 13 to 20. The relationships between these surfactant structures and their adsorption properties were investigated by tensiometric measurements, highlighting the need for a short hydrophilic moiety and high grafting efficiency to obtain the best adsorption. Subsequently, concentrated O/W emulsions (66% of oil) at pH7 were produced using COS-based surfactants and the impact of stirring time and speed during the emulsification process was described through rheological, droplet size and microscopy measurements. Finally, emulsions were stored over 2 months in order to study the destabilization phenomenon into the mixture, i.e., coalescence and creaming, by using laser granulometry and Turbiscan. Results demonstrated that stability could be enhanced by increasing emulsion viscosity, reducing droplet size or optimizing the adsorption layer at the O/W interfaces. Full article

Amidst population growth and challenges with existing fertilizers, the development of smart and environmentally friendly agrochemicals is imperative. While 3D printing is widespread, its potential in slow-release agrochemicals remains unexplored. This proof-of-concept study employed solvent casting and 3D printing to develop agar–urea structures. These structures, comprising 2.5% (w/w) agar, incorporated either 7% (w/w) or 13% (w/w) urea as nitrogen nutrients. Rheological, mechanical, and morphological properties and sorption capabilities were explored. Rheological analysis revealed a substantial impact of urea, enhancing material resistance to deformation. In mechanical tests, inclusion of urea showed no significant impact on compressive strength. SEM analysis confirmed the successful entrapment of urea within the agar matrix. The inclusion of urea resulted in a diminished water sorption capacity, attributed to the urea–water interactions disrupting the hydrogen bonding ability of agar. Agar–urea inks were employed in 3D printing utilizing the direct-ink writing technique, and the nitrogen release behavior was investigated. Results revealed nearly complete urea release in the positive control within 48 h. In contrast, agar–urea formulations with 7% (w/w) and 13% (w/w) achieved nitrogen release rates of 88.8% and 94.4%, respectively, suggesting potential for 3D-printed agar formulations to modify the immediate release behavior seen in conventional urea fertilizers. Full article

Origanum dictamnus L. (Lamiaceae), a local endemic plant of Crete (Greece), creates polysaccharide-containing subcuticular compartments presenting biological activity against phytopathogenic fungi, and, among others, significantly affects the fungal cell wall polysaccharides. This field study introduces a fertilization scheme for O. dictamnus, which was developed and refined to optimize the yield as well as critical herbal quality aspects. Five fertilization schemes were investigated, based on a polysaccharide-based Integrated Nutrient Management (INM), a mixture of conventional inorganic fertilizers (ChF) and two biostimulants (not algae) via foliar and soil application. Plant growth, together with leaf chlorophyll fluorescence and color (SPAD meter, DA meter, Chroma Meter) were determined. The leaf content of chlorophyll, three critical antioxidant compounds (carotenoids, flavonoids, phenols) and nutrients were also assessed. Considering all three antioxidants together, the enhanced efficiency, non-toxic, water-soluble, polysaccharide-based INM by foliar application was the most stimulatory scheme, playing an important role in plant growth and development. The present field study provides, for the first time, baseline fertilization data improving key herbal quality features in O. dictamnus and unravels the attainment of high antioxidant properties. The latter may be exploited in favor of its further utilization as a raw material for tea preparation, medicinal purposes, natural food flavoring and/or food preservative. Full article

Rice hulls have a high-value potential, and the lignocellulose components are underutilized compared to other biomass resources. Pretreatments such as carboxymethylation of the degree of substitutions (DS) are used to prepare lignocellulose nanofibril (LCNF) from desilicated rice hull (DSRH). High-pressure homogenization (HPH) and grinding are used to process nano fibrillation. The composition of LCNF DS of desilicated rice hull was identified using ¹H NMR for polysaccharide composition and DS determination, acetone and hot water extraction to evaluate extractives, and Klason lignin for lignin content. LCNF was prepared using various DS from 0.2 until DS 0.4. The results showed that LCNF DS has a more than −30 mV zeta potential, suitable for stable nanoemulsion formulations. The particle size of LCNF DS decreases with an increasing carboxyl content in the hydrogel and an increasing number of passes through grinding and high-pressure homogenization, of which LCNF DS 0.4 had the smallest width and length. Mechanical processes further reduced the size. Full article

Examples of labeling polysaccharides at hydroxyl groups are described in this paper, which are especially in demand for molecules with a blocked reducing end. The protocols presented are suitable for the microscale synthesis of labeled polysaccharides that do not require a chromatography step for isolation. Examples of hydroxyl labeling include (1) direct modification with fluorescein isothiocyanate; (2) reaction with a fluorescein-dichlorotriazine derivative; (3) reaction with biotin-dichlorotriazine; (4) indirect two-step modification (given for glycosphingolipid) with glutaric anhydride followed by amidation with aminospacered BODIPY or SuCy5. The labeling of carboxyl groups of hyaluronic acid with BODIPY is also described. The staining of plant tissue sections with biotinylated polysaccharide versus being fluorescein labeled is compared. Full article

This study has investigated the influence of cellulose nanocrystals (CNCs) with partially acetylated surfaces on the formation, stability, rheology and biodegradability of the Pickering emulsion in a crude oil/water (co/w) system. In all investigated systems, it was observed that the CNC concentrations of 7 mg/mL led to the emulsions showing stability over time. It was also noticed that the increase in concentration of background electrolyte (NaCl) leds to the droplets of emulsions becoming smaller. It was demonstrated that the rheology of the o/w emulsions of the oil products and crude oil stabilized by CNCs depends, to a large extent, on the colloid chemical properties of nanocellulose particles. Calculations and experimental methods were used to study the changes in the acid–base properties of CNCs on the surface of emulsion droplets, depending on a type of hydrophobic components (crude oil and liquid paraffin). The formation of Pickering emulsions leads to the oxidation of oil by Rhodococcus egvi in aerobic conditions becoming more effective, provided that the environment includes mineral salts of nitrogen, potassium and phosphorus. The results obtained present a scientific basis for the development of technologies for the disposal of oil spills on water surfaces. Full article

Within the domain of starch modification, the study delved into cationization of wheat starch through a laboratory-scale twin-screw extruder, exploring various processing conditions. Cationic starch, a crucial component for enhancing paper attributes like dry strength and printability, took center stage. The focus shifted towards integration into papermaking, investigating the transformative potential of reactive extrusion. By contrasting it with conventional dry-process methodology, innovative strides were unveiled. The study extended to pilot-scale extrusion, bridging the gap between laboratory experimentation and potential industrial implementation. Infused with scientific rigor, the investigation navigated the benefits brought about by reactive extrusion. Empirical insights highlighted a significant reduction in the intrinsic viscosity of extruded starch, decreasing from 170 mL·g⁻¹ (native starch) to 100 mL·g⁻¹ at a specific mechanical energy (SME) input of 800 kWh·t⁻¹, demonstrating remarkable stability despite increased mechanical treatment. Moreover, beyond the critical threshold of 220 kWh·t⁻¹, retention efficiency reached a stable plateau at 78%. The study revealed that utilizing a larger extruder slightly improved the mechanical properties of the paper, emphasizing the advantage of scaling up the production process and the consistency of results across different extruder sizes. Full article

The use of natural polymers has increased due to concern about environmental pollution caused by plastics and emerging pollutants from fossil fuels. In this context, polysaccharides from macroalgae and microalgae arise as natural and abundant resources for various biological, biomedical, and food applications. Different nanomaterials are produced from these polysaccharides to act as effective carriers in the food and pharmaceutical industry: drug and nutrient carriers, active compound encapsulation, and delivery of therapeutic agents to tumor tissues. Polysaccharides-based nanomaterials applied as functional ingredients incorporated into foods can improve texture properties and decrease the caloric density of food products. These nanostructures also present the potential for developing food packaging with antioxidant and antimicrobial properties. In addition, polysaccharides-based nanomaterials are biocompatible, biodegradable, and safe for medical practices to prevent and manage various chronic diseases, such as diabetes, obesity, and cardiovascular disease. In this sense, this review article addresses the use of algal polysaccharides for manufacturing nanomaterials and their potential applications in food and biomedical areas. In addition, the paper discusses the general aspects of algae as a source of polysaccharides, the nanomaterials produced from these polymers, as well as recent studies and the potential use of algal polysaccharides for industries. Full article

Arabinoxylans (AXs) extracted from distillers dried grains with solubles (DDGSs) were treated with amylase, amyloglucosidase, and protease, to evaluate their effect on the polysaccharide capability to form covalent electro-sprayed nanoparticles. Enzymatically treated arabinoxylans (AXPPs) presented a significant decrease in protein content and molecular weight (31 and 37%, respectively), while the ferulic acid content and the arabinose-to-xylose ratio (A/X) were not statistically modified. The Fourier transform infrared spectra of the AXPPs showed a diminution in the intensity of amide I and amide II bands concerning AXs. The AXPP gels (1% w/v) induced via laccase registered a slight increase in the dimers of ferulic acid cross-linking content (9%) and the G’ value (27%) about the AX gels. The electro-sprayed nanoparticles of AXs and AXPPs (NAXs and NAXPPs, respectively) revealed a spherical and regular morphology via transmission electron microscopy. The nanoparticle diameter was not different for the NAXs and NAXPPs, while the NAXPPs show a significant reduction in Z potential value compared to NAXs. Confocal laser microscopy observations were conducted, to analyze the protein content in the AX network, and a decrease in illuminated areas was observed in the AXPP gels and the NAXPPs. These results indicate that the enzymatical treatment of an AX improves the polysaccharide gelling capability, but does not influence the fabrication of electro-sprayed covalent nanoparticles. NAXs and NAXPPs could be attractive biomaterials for diverse pharmaceutical and biomedical applications. Full article

The aim of this work was to investigate the physico-chemical and biological properties of cyclodextrin-based polymers by the example of interaction with human serum albumin, erythrocytes, and bacteria to understand the prospects of their application as drug delivery systems. We synthesized polymers based on one of cyclodextrin derivatives with nonpolar (-CH₃) or polar (-CH₂CH(OH)CH₃) substituents by crosslinking with 1,6-hexamethylene diisocyanate or succinic anhydride. The polymers form particles with an average size of ~200 nm in the aqueous solutions; their structures were confirmed by FTIR and ¹H NMR. Cyclodextrin derivatives and their polymers did not affect the secondary structure content of human serum albumin, which might mean a mild effect on the structural and functional properties of the main blood plasma protein. Polymers extract drug molecules from albumin + drug complex by 8–10%, which was demonstrated using ibuprofen and bromophenol blue as model bioactive molecules for site I and site II in protein; thus, the nanoparticles might slightly change the drug’s pharmacokinetics. Using the hemolysis test, we found that polymers interact with red blood cells and can be assigned to non-hemolytic and slightly hemolytic groups as biocompatible materials, which are safe for in vivo use. The cyclodextrins and their polymers did not extract proteins from bacterial cell walls and did not demonstrate any antibacterial activity against Gram-positive and Gram-negative strains. Thus, the cyclodextrin-based polymers possess variable properties depending on the substituent in the monomer and linker type; demonstrated biocompatibility, biodegradability, and negligible toxicity that opens up prospects for their application in biomedicine and ecology. Full article

Providing safe drinking water free of heavy metal ions like iron and oxyanions like sulfate has become a worldwide issue. Starch, as one of the widely cheapest and available biomaterials, has demonstrated its capability to adsorb heavy metal ions from water in various scientific research, but in low adsorption rates. Therefore, this paper aims to prepare a biopolymer based on a starch–chitosan blend to raise the adsorption efficiency of starch. Two types of chitosan were used to modify potato starch (ps): low molecular chitosan (ch60) and high molecular chitosan (ch4000). Nano potato starch (n.ps) was prepared from potato starch and was also modified with both chitosans. The surface property, the morphology, the particle size, and the structure of the samples were analyzed. Moreover, the investigation of the samples by the zeta potential and charge density were evaluated to determine the charge of the adsorbents’ surface. Furthermore, the pseudo first order (PFO) and pseudo second order (PSO) were employed to examine the adsorption kinetic. The adsorption isotherms of Fe^2+/3+ and SO₄²⁻ were fitted employing Langmuir, Sips, and Dubinin-Radushkevich adsorption models. The maximum achieved sorption capacities from the FeSO₄ solution for Fe^2+/3+ were as follows: 115 mg/g for n.ps & ch4000, 90 mg/g for ps & ch4000, 80 mg/g for n.ps & ch60, and 61 mg/g for ps & ch60. Similarly, for SO₄²⁻, it was 192 mg/g for n.ps & ch4000, 155 mg/g for n.ps & ch60, 137 mg/g for ps & ch4000, and 97 mg/g for ps & ch60. Full article