Polysaccharides

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

Carbohydrates or polysaccharides are the main products derived from photosynthesis and carbon fixation in the Calvin cycle. Compared to other sources, polysaccharides derived from microalgae are safe, biocompatible, biodegradable, stable, and versatile. These polymeric macromolecules present complex biochemical structures according to each microalgal species. In addition, they exhibit emulsifying properties and biological characteristics that include antioxidant, anti-inflammatory, antitumor, and antimicrobial activities. Some microalgal species have a naturally high concentration of carbohydrates. Other species can adapt their metabolism to produce more sugars from changes in temperature and light, carbon source, macro and micronutrient limitations (mainly nitrogen), and saline stress. In addition to growing in adverse conditions, microalgae can use industrial effluents as an alternative source of nutrients. Microalgal polysaccharides are predominantly composed of pentose and hexose monosaccharide subunits with many glycosidic bonds. Microalgae polysaccharides can be structural constituents of the cell wall, energy stores, or protective polysaccharides and cell interaction. The industrial use of microalgae polysaccharides is on the rise. These microorganisms present rheological and biological properties, making them a promising candidate for application in the food industry and agriculture. Thus, microalgae polysaccharides are promising sustainable alternatives for potential applications in several sectors, and the choice of producing microalgal species depends on the required functional activity. In this context, this review article aims to provide an overview of microalgae technology for polysaccharide production, emphasizing its potential in the food, animal feed, and agriculture sector. Full article

The growing environmental concern with the inappropriate disposal of conventional plastics has driven the development of eco-friendly food packaging. However, the intrinsic characteristics of polymers of a renewable origin, e.g., poor mechanical properties, continue to render their practical application difficult. For this, the present work studied the influence of ionic strength (IS) from 0 to 500 mM to modulate the physicochemical properties of methylcellulose (MC). Moreover, for protection against biological risks, Nisin-Z was incorporated into MC’s polymeric matrices, providing an active function. The incorporation of salts (LiCl and MgCl₂) promoted an increase in the equilibrium moisture content in the polymer matrix, which in turn acted as a plasticizing agent. In this way, films with a hydrophobic surface (98°), high true strain (85%), and low stiffness (1.6 mPa) can be manufactured by addition of salts, modulating the IS to 500 mM. Furthermore, films with an IS of 500 mM, established with LiCl, catalyzed antibacterial activity against E. coli, conferring synergism and extending protection against biological hazards. Therefore, we demonstrated that the IS control of MC dispersion presents a new alternative to achieve films with the synergism of antibacterial activity against Gram-negative bacteria in addition to flexibility, elasticity, and hydrophobicity required in various applications in food packaging. Full article

In recent years, interest in the development of nanometric materials with specific characteristics has grown; however, there are few scientific contributions that associate encapsulation methodologies and matrices with the particle objective (metabolic directions, type of administration, biological impact, and biocompatibility). This review focuses on describing the benefits and disadvantages of different techniques for designing custom particles and alternatives for the biofunctionalization nanomaterials regarding the biological impact of a nanomaterial with potential use in foods known as nutraceuticals. The study of optical properties, physicochemical factors, and characteristics such as rheological can predict its stability in the application matrix; however, not only should the characterization of a nanocomposite with applications in food be considered, but also the biological impact that it may present. Full article

Orange bagasse (OB) could be considered a sustainable, renewable, and low-cost biomass for the extraction of cellulose. In this context, reactive extrusion can be considered an excellent, eco-friendly, alternative process for the extraction of cellulose from lignocellulosic materials. Thus, the present study aimed to obtain cellulose-based materials with a reactive extrusion process and also to investigate the impact of pectin on the delignification process. Two groups of samples (OB and depectinizated OB) were submitted to extrusion with sulfuric acid or sodium hydroxide in one-step processes. The cellulose content of extruded materials was highly affected by pectin content in the raw material; the thermal profile (TGA curves) and crystallinity also changed. The cellulose content of modified materials ranged from 18.8% to 58.4%, with a process yield of 30.6% to 79.2%. The alkaline reagent provided the highest cellulose content among all extrusion treatments tested, mainly for OB without pectin. The extrusion process was considered an efficient and promising process for extracting cellulose from citrus residue. Materials produced in this study can be used as sources of cellulose fiber for various products and processes, such as in the food industry, fermentation substrates, or refined applications after subsequent treatments. Full article

In this work, glucose oxidase (GOx) has been immobilized onto graphite rod electrodes through an assisted-chitosan adsorption reaching an enzyme coverage of 4 nmol/cm². The direct and irreversible single adsorption of the Flavine Adenine Dinucleotide (FAD) cofactor has been minimized by electrode incubation in a chitosan (CH) solution containing the enzyme GOx. Chitosan keeps the enzyme structure and conformation due to electrostatic interactions preventing FAD dissociation from the protein envelope. Using chitosan, both the redox cofactor FAD and the protein envelope remain in the active form as demonstrated by the electrochemistry studies and the enzymatic activity in the electrochemical oxidation of glucose up to a concentration of 20 mM. The application of the modified electrodes for energy harvesting delivered a power density of 119 µW/cm² with a cell voltage of 0.3 V. Thus, chitosan presents a stabilizing effect for the enzyme conformation promoted by the confinement effect in the chitosan solution by electrostatic interactions. Additionally, it facilitated the electron transfer from the enzyme to the electrode due to the presence of embedded chitosan in the enzyme structure acting as an electrical wiring between the electrode and the enzyme (electron transfer rate constant 2.2 s⁻¹). This method involves advantages compared with previously reported chitosan immobilization methods, not only due to good stability of the enzyme, but also to the simplicity of the procedure that can be carried out even for not qualified technicians which enable their easy implementation in industry. Full article

Fruit and vegetable-based materials, rich in phenolic pigments, and especially anthocyanins, have attracted attention as promising sources for bio-based antioxidant coating polymers, being a non-toxic, natural, ecofriendly, and green label solution to lower oxidation degradation in oil-water emulsion food, such as cheeses. However, could their pomaces also be used in such materials? This work has investigated the use of jabuticaba peels and red cabbage stir pomace extracts as antioxidant additives for cheese coating polymers. The antioxidant capacity of the jabuticaba-red cabbage pomace cassava-based polymer was evaluated in vitro (total phenolic, total anthocyanin content and DPPH scavenging %) and in vivo (by coating Minas Frescal cheeses and monitoring their peroxide index increase during a 9-day shelf life, at 10 °C). An in vitro characterization has indicated a high antioxidant capacity for both pomace extracts, with a higher capacity observed for the jabuticaba peels. In vivo investigations indicated that the pomace-starch coatings have protected cheeses up to 8.5 times against oxidation when compared to the control, with a synergistic protector effect among pomaces. Physical–chemical characterizations (pH, acidity, total solids, ash, total protein, fat content and syneresis) have indicated no coating interference on the cheese’s development. Full article

The human-made pollution of surface and ground waters is becoming an inevitable and persistently urgent problem for humankind and life in general, as these pollutants are also distributed by their natural circulation. For example, from mining activities and metallurgy, toxic heavy metals pollute the environment and present material risk for human health and the environment. Bioadsorbers are an intriguing way to efficiently capture and eliminate these hazards, as they are environmentally friendly, cheap, abundant, and efficient. In this study, we present brewers’ spent grain (BSG) as an efficient adsorber for toxic heavy metal ions, based on the examples of iron, manganese, cadmium, and nickel ions. We uncover the adsorption properties of two different BSGs and investigate thoroughly their chemical and physical properties as well as their efficiency as adsorbers for simulated and real surface waters. As a result, we found that the adsorption behavior of BSG types differs despite almost identical chemistry. Elemental mapping reveals that all components of BSG contribute to the adsorption. Further, both types are not only able to purify water to reach acceptable levels of cleanness, but also yield outstanding adsorption performance for iron ions of 0.2 mmol/g and for manganese, cadmium, and nickel ions of 0.1 mmol/g. Full article

Electrostatic complexes based on chitosan, lecithin, and sodium tripolyphosphate were produced and evaluated with respect to their encapsulation capacity and cytotoxicity. Physical chemical properties were determined by zeta potential values and size distributions. For encapsulation assays, the emulsification method was followed, and Citrus senensis peel oil was utilized as volatile compound model. Morphology of complexes with oil incorporated was observed by scanning electron microscopy. The cytotoxicity of complexes was related to cell viability of zebrafish hepatocytes. The complexes produced presented positive Zeta potential values and size distributions dependent on the mass ratio between compounds. Higher concentrations of sodium tripolyphosphate promote significant changes (p < 0.05) in zeta values, which did not occur at smaller concentrations of the crosslinking agent. These complexes were able to encapsulate Citrus sinensis peel oil, with encapsulation efficiency higher than 50%. Cytotoxicity profiles showed that in a range of concentrations (0.1–100 μg/mL) studied, they did not promote cellular damage in zebrafish liver cells, being potential materials for food and pharmaceutical applications. Full article

Nowadays, the scientific interest is focused more and more on the development of new strategies in recycling of waste products as well as on the development of clean technologies due to the increased environmental pollution. In this work we studied the valorization of an expired cheese-tomato flavor corn snack, which is polysaccharide food product, by producing advanced hybrid magnetic materials for environmental remediation purposes. The carbonization-chemical activation of this snack using potassium hydroxide leads to a microporous activated carbon with high surface area (S_gBET ~800 m²/g). The magnetic hybrid material was synthesized via an in-situ technique using iron acetate complex as the precursor to produce iron based magnetic nanoparticles. The resulting material retains a fraction of the microporous structure with surface area S_gBET ~500 m²/g. Such material consists, of homogenously dispersed magnetic isolated zero valent iron nanoparticles and of iron carbides (Fe₃C), into the carbon matrix. The magnetic carbon exhibited high adsorption capacity in Cr(VI) removal applications following a pseudosecond order kinetic model. The maximum adsorption capacity was 88.382 mg_Cr(VI)/g_AC at pH = 3. Finally, oxidation experiments, in combination with FT-IR, Mössbauer, and VSM measurements indicated that the possible Cr⁶⁺ removal mechanism involves oxidation of iron phases and reduction of Cr⁶⁺ to Cr³⁺. Full article

In the aquaculture sector, the biofunctionalization of biomaterials is discussed using materials from algae and analyzed as a possible potential strategy to overcome the challenges that hinder the future development of the application of endolysins in this field. Derived from years of analysis, endolysins have recently been considered as potential alternative therapeutic antibacterial agents, due to their attributes and ability to combat multi-resistant bacterial cells when applied externally. On the other hand, although the aquaculture sector has been characterized by its high production rates, serious infectious diseases have led to significant economic losses that persist to this day. Although there are currently interesting data from studies under in vitro conditions on the application of endolysins in this sector, there is little or no information on in vivo studies. This lack of analysis can be attributed to the relatively low stability of endolysins in marine conditions and to the complex gastrointestinal conditions of the organisms. This review provides updated information regarding the application of endolysins against multi-resistant bacteria of clinical and nutritional interest, previously addressing their important characteristics (structure, properties and stability). In addition, regarding the aquaculture sector, the biofunctionalization of biomaterials is discussed using materials from algae and analyzed as a possible potential strategy to overcome the challenges that hinder the future development of the application of endolysins in this field. Full article

Cellulose is a natural, unbranched, and fibrous homopolymer that is a major component in several agroindustrial residues. The aim of this study was to extract cellulose from oat hulls and then to modify it using a green route to obtain esterified cellulose through reaction with organic acids employing the reactive extrusion process, which is a process that presents some advantages, including low effluent generation, short reaction times, and it is scalable for large scale use. Citric (CA) and succinic (SA) acids were employed as esterifying agents in different concentrations (0, 5, 12.5, and 20%). Modified cellulose samples were characterized by their degree of substitution (DS), Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (DRX), scanning electron microscopy (SEM), wettability, oil and water absorption capacities, and thermal stability. DS of modified samples ranged from 2.28 to 3.00, and FTIR results showed that the esterification occurred in all samples for both acids by observation of important bands at 1720 and 1737 cm⁻¹ for samples modified with CA and SA, respectively. All modified samples presented increased hydrophobicity. The modification did not have an influence on the morphological structure or crystallinity pattern of all samples. This study proved to be possible to modify cellulose using a simple and ecofriendly process based on reactive extrusion with organic acids. Full article

The obtainment of new materials with distinct properties by mixing two or more polymers is a potential strategy in sustainable packaging research. In the present work, a blend of cellulose acetate (CA) and zein (60:40 wt/wt CA:zein) was manufactured by adding glycerol or tributyrin as plasticizers (30% wt/wt), and garlic essential oil (GEO), complexed (IC) or not with β-cyclodextrin (βCD), to produce active packaging. Blends plasticized with tributyrin exhibited a more homogeneous surface than those containing glycerol, which showed major defects. The blends underperformed compared with the CA films regarding mechanical properties and water vapor permeability. The presence of IC also impaired the films’ performance. However, the blends were more flexible than zein brittle films. The films added with GEO presented in vitro activity against Listeria innocua and Staphylococcus aureus. The IC addition into films, however, did not ensure antibacterial action, albeit that IC, when tested alone, showed activity against both bacteria. These findings suggest that the mixture of CA and plasticizers could increase the range of application of zein as a sustainable packaging component, while essential oils act as a natural bioactive to produce active packaging. Full article

Microalgae are used in flocculation processes because biopolymers are released into the culture medium. Microalgal cell growth under specific conditions (temperature, pH, luminosity, nutrients, and salinity) provides the production and release of exopolysaccharides (EPS). These biopolymers can be recovered from the medium for application as bioflocculants or used directly in cultivation as microalgae autoflocculants. The optimization of nutritional parameters, the control of process conditions, and the possibility of scaling up allow the production and industrial application of microalgal EPS. Therefore, this review addresses the potential use of EPS produced by microalgae in bioflocculation. The recovery, determination, and quantification techniques for these biopolymers are also addressed. Moreover, other technological applications of EPS are highlighted. Full article

Grape processing residues are a good source of bioactive and nutritional compounds. The incorporation of grape pomace extract (GPE) in starch films can be a strategy for the elaboration of new food packaging products for applications such as edible films or fruit strips. In this context, the objective of this research was to analyze the effect of incorporation and variation of concentration of GPE (0, 20, 30, and 40% mass/mass starch solids) on the physical chemical properties of arrowroot starch edible films created by casting. The GPE was characterized for moisture content, pH, total titratable acidity, total soluble solids, and anthocyanin content. Starch films with and without GPE were evaluated by analyzing their visual appearance, water activity, water content, thickness, water solubility, and water vapor permeability. The GPE had high water content, acidity, and anthocyanins content. The films with GPE showed a noticeable reddish color, similar to observed for the GPE. Increasing the concentration of GPE in the film resulted in significantly increased (p < 0.05) thickness (from 0.060 to 0.106 mm), water content (from 8.17 to 12.48%), solubility in water (from 13.33 to 33.32%), and water vapor permeability (from 3.72 to 6.65 g.mm/m² day kPa). GPE increased the hydrophilic portion of the film, in addition to acting as a plasticizer, decreasing the molecular interactions of the polymer chain, and favoring its solubilization, which is desirable for applications such as edible films. The elaboration of arrowroot starch films with the incorporation of grape pomace is a good alternative for the reduction of by-products of grape processing. Full article

In this study, chitosan and collagen (Ch: Col)-based materials containing curcumin (Cur) as a bioactive compound were developed for wound-healing purposes. The effects of incorporating curcumin and increasing its concentration on both the rheological properties of the formed solutions and the morphological and thermal properties of the three-dimensional scaffolds obtained from them were evaluated. Rheology showed that the presence of curcumin resulted in solutions with a solid-like behavior (G’ > G″), higher collagen denaturation temperatures, and higher viscosities, favoring their use as biomaterials for wound healing. A greater cross-linking effect was observed at higher curcumin concentrations, possibly between the amino groups from both polymers and the hydroxyl and keto groups from the polyphenol. Such cross-linking was responsible for the delay in the onset of degradation of the scaffolds by 5 °C, as revealed by thermogravimetric analysis. Moreover, the pore diameter distribution profile of the scaffolds changed with increasing curcumin concentration; a greater number of pores with diameters between 40 and 60 µm was observed for the scaffold with the highest curcumin content (50 mg), which would be the most suitable for the proposed application. Thus, the materials developed in this study are presented as promising biomaterials for their biological evaluation in tissue regeneration. Full article

The interest in the development of biobased adhesives has increased due to environmental concerns. Moreover, as the production of engineered wood products (EWPs) is expected to grow, the wood adhesives market needs to transit toward formaldehyde-free products. Cellulose nanoparticles (CNPs) are a material with unique properties and advantages for producing hybrid materials as biobased wood adhesives. Besides their traditional use as reinforcing additives, CNPs can be incorporated at the beginning of the polymerization reaction to form in situ polymerized hybrid adhesives with better mechanical and physicochemical properties than the neat adhesive. Despite their outstanding characteristics, CNPs are still an emerging nanomaterial in the wood adhesive field, and the studies are incipient. This review explores the utilization of CNPs in heterogeneous polymerization for the production of polyvinyl acetate, polymeric isocyanates, waterborne polyurethane systems, and other waterborne polymer latexes. The main challenges are discussed, and some recommendations are set down for the manufacture of these novel hybrid nanocomposites. Full article

Cardamom essential oil (EO) is a rare oil of high scientific and economic interest due to its biofunctionality. This work aims to stabilize the EO by Pickering emulsions with nanocellulose, in the form of nanocrystals (CNC) or nanofibers (CNF), and to investigate the stability and chemical and physical interactions involved in the process. The emulsions were characterized by droplet size, morphology, stability, surface charges, Fourier transform infrared spectroscopy, FT-Raman, nuclear magnetic resonance, and scanning electron microscopy. Stable emulsions were prepared with cellulose morphologies and CNCs resulted in a 34% creaming index, while CNFs do not show instability. Emulsions indicate a possible interaction between nanocellulose, α-terpinyl acetate, and 1,8-cineole active essential oil compounds, where α-terpinyl acetate would be inside the drop and 1,8-cineole is more available to interact with cellulose. The interaction intensity depended on the morphology, which might be due to the nanocellulose’s self-assembly around oil droplets and influence on oil availability and future application. This work provides a systematic picture of cardamomum derived essential oil Pickering emulsion containing nanocellulose stabilizers’ formation and stability, which can further be extended to other value-added oils and can be an alternative for the delivery of cardamom essential oil for biomedical, food, cosmetics, and other industries. Full article