Polysaccharides, Volume 2, Issue 4 (December 2021) – 8 articles

Starch is one of the biopolymers that has been recognized as promising for its application as an eco-friendly substitute for conventional polymers due to its biodegradable nature, low cost, and considerable abundance from renewable vegetal-type resources. In particular, the use of cassava starch as raw material in the manufacture of packaging materials has increased in recent years. Consequently, the analytical study of the quality and features of starch and its derivatives throughout their entire life cycle have gained importance, with non-destructive sample methods being of particular interest. Among these, spectroscopic methods stand out. The aim of this study was evaluated using spectroscopic techniques (i.e., mid-infrared spectroscopy (MIRS) and functional-enhanced derivative spectroscopy (FEDS)) for the monitoring of the effect of the thermal stress of starch in conjunction with computational tools such as density-functional theory (DFT). It is concluded that the FEDS technique in conjunction with DFT calculations can be a useful tool for the high-precision spectral analysis of polymers subjected to small thermal perturbations. In addition, it is demonstrated that small changes produced by thermal stress can be monitored by infrared spectroscopy in conjunction with FEDS at wavenumber range between 3800 and 3000 cm⁻¹, which would allow for the implementation of spectral techniques instead of thermal techniques for out-lab evaluations and for the study of the thermal stress of biomaterials. Full article

The complexity of the substituent distribution in polysaccharide derivatives is discussed and defined. The challenges regarding analytical characterization that results from various interrelated categories of distributions, including molecular weight, chemical composition, and microstructure, are outlined. Due to these convoluted levels of complexity, results should always be interpreted with carefulness. Various analytical approaches which have been applied to starch and cellulose derivatives are recapped, including enzymatic, mass spectrometric, and chromatographic methods. The relation of heterogeneities of first and second order among and along the polysaccharide chains is addressed. Finally, examples of own analytical work on cellulose ethers are presented, including the MS analysis of methyl cellulose (MC) blends and fractionation studies of fully esterified MC, especially its 4-methoxybenzoates by gradient HPLC on normal phase. Preparative fractionation according to the degree of substitution (DS) allows follow-up analysis in order to get more detailed information on the substituent distribution in such sub-fractions. Full article

Cyclodextrins (CDs) have been used by the pharmaceutical and food industries since the 1970s. Their cavities allow the accommodation of several hydrophobic molecules, leading to the formation of inclusion complexes (ICs) increasing the guest molecules’ stability, allowing their controlled release, enhancing their water solubility and biodisponibility. Due to these, CDs and their ICs have been proposed to be used as potential allies in food packaging, especially in active packaging. In this review, we present the many ways in which the CDs can be applied in food packaging, being incorporated into the polymer matrix or as a constituent of sachets and/or pads aiming for food preservation, as well as the diverse polymer matrices investigated. The different types of CDs, natives and derivatives, and the several types of compounds that can be used as guest molecules are also discussed. Full article

Lipopolysaccharides (LPS) are cell wall components from Gram-negative bacteria and are composed of three covalently linked regions: the O-antigen, the core oligosaccharide, and the lipid A moiety, which carries most of their endotoxic activity. The objective of this study was to isolate and compare the lipid A structures from ruminal LPS derived from total mixed ration (TMR)- and pasture-fed cows, by using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). Ruminal bacteria were collected from two rumen-cannulated Holstein cows; one fed a TMR (60:40, forage–concentrate) and the other pasture fed. The representativeness of each sample was validated by comparing the rumen microbiome from the cows in our study to the core rumen microbiome from the previous literature. Lipopolysaccharides from each respective sample were extracted with a phenol–water extraction procedure and purified via ultracentrifugation. To isolate lipid A from the core and O-antigen, pure ruminal LPS samples were hydrolyzed with acetic acid. Lipid A derived from the TMR-fed cow potentially exhibited a tetra-acylated structure, whereas lipid A derived from the pasture-fed cow potentially exhibited a penta-acylated lipid A structure. Both samples were quantified using limulus amebocyte lysate (LAL) assay and exhibited low endotoxic activity, consistent with the MALDI-TOF MS observations. Results indicate that the lipid A acylation pattern differs between diets, and that ruminal bacteria express solely under-acylated lipid A structures contrary to hexa-acylated lipid A, typically expressed by bacteria such as E. coli. Full article

Cancer is one of the major causes of death worldwide. Chemotherapeutic drugs have become a popular choice as anticancer agents. Despite the therapeutic benefits of chemotherapeutic drugs, patients often experience side effects and drug resistance. Biopolymers could be used to overcome some of the limitations of chemotherapeutic drugs, as well as be used either as anticancer agents or drug delivery vehicles. Chitosan is a biocompatible polymer derived from chitin. Chitosan, chitosan derivatives, or chitosan nanoparticles have shown their promise as an anticancer agent. Additionally, functionally modified chitosan can be used to deliver nucleic acids, chemotherapeutic drugs, and anticancer agents. More importantly, chitosan-based drug delivery systems improved the efficacy, potency, cytotoxicity, or biocompatibility of these anticancer agents. In this review, we will investigate the properties of chitosan and chemically tuned chitosan derivatives, and their application in cancer therapy. Full article

Chitin is an effective sorbent which can be used in environmental monitoring, beyond obvious applications in withholding metal-containing pollutants from wastewater- or nuclear fuel reprocessing flows, since background levels in (purified) chitin are very low except for a few metals (Fe, Cu, Al, Ti, and Zn). Since retention of M^x+ and their complexes on chitin depend on an oxidation state, and to a lesser extent the presence of possible ligands or co-ligands, partition between chitin samples exposed to sediment and those exposed to water can be changed by environmental factors such as local biota producing or absorbing/metabolizing effective ligands such as citrate or oxalate and by changes of redox potential. Thermodynamics are studied via log P, using calibration functions log P vs. 1/r or log P vs. Σσ (sum of Hammett parameters of ligand donor groups) for di- and trivalent elements not involved in biochemical activity (not even indirectly) and thus measuring “deviations” from expected values. These “deviations” can be due to input as a pollutant, biochemical use of certain elements, precipitation or (bio-induced reduction of SO₄²⁻ or CO₂) dissolution of solids in sediment. Biochemical processes which occur deep in sediment can be detected due to this effect. Data from grafted chitin (saturation within ≤ 10 min) and from outer surfaces of arthropods caught at the same site do agree well. Log P is more telling than total amounts retrieved. Future applications of these features of chitin are outlined. Full article

Microalgae and cyanobacteria are photosynthetic microorganisms capable of synthesizing several biocompounds, including polysaccharides with antioxidant, antibacterial, and antiviral properties. At the same time that the accumulation of biomolecules occurs, microalgae can use wastewater and gaseous effluents for their growth, mitigating these pollutants. The increase in the production of polysaccharides by microalgae can be achieved mainly through nutritional limitations, stressful conditions, and/or adverse conditions. These compounds are of commercial interest due to their biological and rheological properties, which allow their application in various sectors, such as pharmaceuticals and foods. Thus, to increase the productivity and competitiveness of microalgal polysaccharides with commercial hydrocolloids, the cultivation parameters and extraction/purification processes have been optimized. In this context, this review addresses an overview of the production, characterization, and potential applications of polysaccharides obtained by microalgae and cyanobacteria. Moreover, the main opportunities and challenges in relation to obtaining these compounds are highlighted. Full article

Edible insects have gained attention due to their impressive nutritional composition, as well as their efficient use of natural resources. However, a research gap remains on the applications of insect chitosan, especially as it relates to their potential use as food packaging material. Chitosan from two reared cricket species (Acheta domesticus and Gryllodes sigillatus) was evaluated for use as food packaging material. Cricket chitosan films (CCF) were structurally similar to commercial shrimp chitosan films (SCF) at controlled glycerol levels, as seen by shared spectral peaks in FT-IR analyses. Mechanical properties of CCF showed they had equal or greater tensile strength when compared to commercial SCF, although flexibility was lower. Scanning electron microscopy showed increased roughness of microstructure, likely increasing the tortuosity. As a result, CCF had improved water vapor permeability compared to commercial SCF. Melanin complexes present in cricket chitin and chitosan increased hydrophobicity and decreased light transmittance. This study also revealed that intrinsic species differences, which occur during insect and crustacean exoskeleton development, could have effects on the functionality of chitosan packaging materials. Overall, CCF were found to be as effective as commercial SCF, while providing additional advantages. CCF derived from reared crickets have good mechanical and barrier properties, and improved water resistance and light barrier characteristics. Edible cricket chitosan has the potential to be used as bio-based packaging material for food and pharmaceutical applications. Full article