Polysaccharides, Volume 4, Issue 3 (September 2023) – 6 articles

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

Calorimetric (from both isothermal micro-calorimetry and DSC), chiro-optical, viscometric and rheological data on aqueous solutions of pectic acid and low-methoxyl pectin (LMP), published over decades from different laboratories, have been comparatively revisited. The aim was to arrive at a consistent and detailed description of the behavior of galacturonan as a function of pH, i.e., of the degree of charging (as degree of dissociation, α) of the polyanion. The previously hypothesized pH-induced transition from a 3₁ to a 2₁ helix was definitely confirmed, but it has been shown, for the first time, that the transition is always coupled with loosening/tightening effects brought about by an increase in charge. The latter property has a twofold effect: the former effect is a purely physical one (polyelectrolytic), which is always a loosening one. However, in the very low range of pH and before the beginning of the transition, an increase in charge tightens the 3₁ helix by strengthening an intramolecular—but inter-residue—hydrogen bond. The value of the enthalpy change of 3₁ → 2₁ transition—+0.59 kcal·mol⁻¹—is bracketed by those provided by theoretical modeling, namely +0.3 and +0.8 kcal·mol⁻¹; the corresponding entropy value is also positive: +1.84 cal·mole r.u.⁻¹·K⁻¹. The enthalpic and the entropic changes in chain loosening amount only to about 23% of the corresponding 3₁ → 2₁ changes, respectively. Much like poly(galacturonic acid), the 3₁ conformation of LMP also stiffens on passing from pH = 2.5 to 3.0, to then start loosening and transforming into the 2₁ one on passing to pH = 4.0. Lowering the pH of a salt-free aqueous solution of LMP down to 1.6 brings about a substantial chain–chain association, which is at the root of the interchain junctions stabilizing the acid pH gels, in full agreement with the rheological results. A comparison of the enthalpic data reveals that, at 85 °C, LMP in acidic pH conditions has lost its initial order by about 2.3 times more than pectic acid brought from low charging to full neutralization (at α = 1.0) at 25 °C. A proper combination of experiments (enthalpic measurements) and theory (counterion condensation polyelectrolyte theory) succeeded in demonstrating, for the first time ever, a lyotropic/Hofmeister effect of the anion perchlorate in stabilizing the more disordered form of the 2₁ helix of galacturonan. The viscometric results in water showed that the 3₁ helix is capable of forming longer rheologically cooperative units compared with the 2₁ helix. Extrapolation to infinite ionic strength confirmed that, once all electrostatic interactions are cancelled, the elongation of the two helical forms is practically the same. At the same time, however, they indicated that the flexibility of the two-fold helix is more than fifteen times larger than that of the three-fold one. The result is nicely corroborated by a critical revisiting of ²³Na relaxation experiments. Full article

Lactic acid is a molecule used abundantly in the food, cosmetic, and pharmaceutical industries. It is also the building block for polylactic acid, a biodegradable polymer which has gained interest over the last decade. Seaweeds are fast growing, environmentally friendly, and economically beneficial. The Rhodophyta, Kappaphycus alvarezii, is a carrageenan-rich alga, which can be successfully fermented into lactic acid using lactic acid bacteria. Lactobacillus pentosus is a versatile and robust bacterium and an efficient producer of lactic acid from many different raw materials. Bioreactor strategies for lactic acid fermentation of K. alvarezii hydrolysate were tested in 2-L stirred-tank bioreactor fermentations, operating at 37 °C, pH 6, and 150 rpm. Productivity and yields were 1.37 g/(L.h) and 1.17 g/g for the pulse fed-batch, and 1.10 g/(L.h) and 1.04 g/g for extended fed-batch systems. A 3.57 g/(L.h) production rate and a 1.37 g/g yield for batch fermentation operating with an inoculum size of 0.6 g/L was recorded. When applying fed-batch strategies, fermentation products reached 91 g/L with pulse feed and 133 g/L with constant continuous feed. For control and comparison, a simple batch of synthetic galactose-rich Man-Sharpe-Rugosa (MRS) media was fermented at the same conditions. A short study of charcoal regenerability is shown. A scheme for a third-generation lactic acid biorefinery is proposed, envisioning a future sustainable large-scale production of this important organic acid. Full article

Adsorption processes, due to their technical simplicity and cost-effectiveness, have arisen as one of the most well-known, straightforward solutions to water pollution. In this context, polysaccharides, due to their abundance, biodegradability, and biocompatibility, are appealing raw materials for the design of adsorbents. Moreover, some of them, such as chitosan, can be obtained from organic waste products, and their use additionally contributes to solving another concerning problem: organic waste accumulation. Unfortunately, due to their low adsorption capacities and/or physicochemical properties, native polysaccharides are not suitable for this purpose. However, there are alternatives that can overcome these physical or chemical limitations, often taking advantage of the versatility of their polyhydroxylated structure. In this context, this review aims to present an overview of the advances from 2019 onwards in the design of new adsorbents for water treatment from cellulose, alginate, chitosan, and starch, addressing the two main strategies reported in the literature: the preparation of either polysaccharide-based composites or polysaccharide derivatives. It is important to point out that, herein, special emphasis is placed on the relationship between the chemical structure and the efficiency as adsorbents of the analyzed materials, in an attempt to contribute to the rational design of adsorbents obtained from polysaccharides. Full article

Mechanical, barrier, and thermal properties of films based on blends of corn starch and chitosan plasticized with ethylene glycol, glycerol, and sorbitol were investigated. Starch amylopectin variation was explored, and contents of 100% and 73% were employed to blend with chitosan and polyols. The findings showed that high amylopectin content has a significant effect (p < 0.05), resulting in films with lower tensile strength (TS) and reduced water vapor permeability (WVP). On the other hand, the incorporation of polyols showed a significantly high (p < 0.05) elongation at break (EB) for films plasticized with glycerol and sorbitol at high amylopectin content. For chitosan/73% amylopectin film, the addition of plasticizers exhibited no significant difference (p < 0.05) among the samples for TS and WVP results. The amylopectin content played no influence in the degradation stability of the films measured by thermogravimetry (TGA). However, amylopectin content influences the endothermic peak temperature observed by differential scanning calorimetry (DSC) analysis. A reduction of about 15 °C was noticed for the film prepared with high amylopectin content, a behavior correlated to its amorphous structure, capable of retaining more water than a crystalline region. Full article

Freeze-drying is often used as a final stage to produce three-dimensional porous matrices for medicine. Because a pure solvent crystallizes first during freezing, it acts as a pore-forming agent. The size of the solvent crystals primarily depends on the cooling rate and the composition of the material to be frozen. Ultrasonic treatment also affects the size of crystals and can be used to control the structure of a porous matrix. This article describes the effect of ultrasound (40 kHz, 50 W) applied at the preliminary freezing stage of polysaccharide solutions (alginate, chitosan, alginate–chitosan and alginate–gelatin) on the finished matrix properties. The most attention was paid to the effect of ultrasound on the size and shape of crystals formed during freezing, which leads to a change in the porous structure of the matrices after solvent sublimation. As a result of changes in the microstructure, a number of differences in the vibrational spectra of the molecules and the values of pore volume, sorption capacity, permeability and degradation of matrices were identified. Such changes in the structure of materials, as well as the emerging directionality of pores, together can affect the process of cell cultivation in these polysaccharide matrices, which can be useful in solving problems of tissue engineering. Full article