Macromol, Volume 6, Issue 1 (March 2026) – 19 articles

Among the most structurally diverse biomacromolecules, polysaccharides have attracted increased attention as nanocarriers for precision medicine due to their inherent biocompatibility and versatility in functionalization. Molecular features, such as monomer composition, glycosidic linkages, charge density, and chemical modification, essentially determine the nanoscale assembly process of these biopolymers, as well as their biological compatibility. This review highlights the role of these properties in the assembly process of polysaccharide-based nanocarriers leading to a variety of self-assembled nanostructures, such as polyelectrolyte complexes, protein–polysaccharide complexes, amphiphilic micelles, vesicles, hybrid systems, and nanogels, which are extensively discussed throughout the review. This review also focuses on the structure–property–function relationships of nanocarriers as applied to the rapidly developing area of precision medicine, emphasizing the problems of sustainability and reproducibility. By combining the principles of molecular engineering, supramolecular assembly, and measurable properties, this work aims to present a unified view of the molecular engineering of polysaccharide-based nanocarriers for enhanced translation potential, as well as to outline a coherent framework for the rational development of next-generation polysaccharide-based nanocarriers with improved clinical relevance. Full article

This work focused on the investigation of sulfonated lignin as a novel and sustainable reinforcing filler for polyamide 6 (PA6) composites. Different formulations were thus prepared by melt compounding, varying the lignin content (5, 10, and 20 wt%). The interaction between lignin and PA6 was systematically studied through rheological, structural, morphological, thermo-mechanical, and flammability tests. Rheological measurements showed an increase in the complex viscosity and viscoelastic moduli with increasing lignin content, suggesting restricted polymer chain mobility and the formation of strong physical interactions between the molten PA6 and the lignin particles. Microstructural observations through FESEM highlighted a good dispersion of lignin particles and efficient filler–matrix interfacial adhesion. Moreover, the addition of lignin significantly increased the tensile stiffness of the composites (up to 3.4 GPa), and a lignin content of 10 wt% enhanced the tensile strength up to 58.4 MPa (i.e., +45% compared to neat PA6) without compromising the ductility. Finally, UL-94 tests revealed an improvement in flame retardancy at higher lignin contents due to the intrinsic char-forming ability of this filler. These results demonstrated that lignin could be an effective multifunctional bio-based filler that can improve the thermo-mechanical performance of PA6 without the need for compatibilizing agents. Full article

This study investigates the efficacy of co-assembled, physically cross-linked nanocarriers comprising tannic acid (TA) and a P(DMAEMA-co-OEGMA) random/statistical double-hydrophilic copolymer for ovalbumin (OVA) encapsulation. TA-based nanocarriers, prepared at varying TA molar ratios (10% w/v and 20% w/v), exhibited nanoaggregates of different sizes, as revealed by dynamic light scattering, with Nanocarrier 1 system showing populations of 11 and 109 nm, while Nanocarrier 2 formed a single population of 75 nm in size. Notably, both colloidal systems demonstrated stability under thermal treatment and resilience to changes in salt concentrations higher than 0.15 M, but disassembly phenomena in basic media. Utilizing these nanocarriers for OVA loading via electrostatic interactions revealed strong positive charges (~30 mV) for all protein-loaded nanocarrier cases. In particular, they demonstrated sizes within the desired range (R_h = 96–118 nm) and considerable stability over 20 days and in the presence of serum proteins. Overall, this study underscores the importance of physical cross-linking as a viable strategy for the formation of tunable nanometric hydrocolloids for effective protein encapsulation, with significant implications for drug delivery systems. Full article

Comparative studies report inconsistent peptide yields, bioactivities, and sensory outcomes for Alcalase across substrates, creating uncertainty about when it should be favored over other proteases. This study mapped research on hydrolysis of food proteins with Alcalase to quantify scientific output, organize thematic trends, and identify gaps relevant to peptide-based functional foods. A bibliometric analysis of Web of Science records (2004–2024) was performed in R (bibliometrix), using co-occurrence networks, temporal overlays, and conceptual mapping. The dataset comprised 203 documents from 78 sources, exhibiting a 10.3% annual growth rate and a 36.9% international co-authorship rate. Themes clustered around antioxidant and angiotensin-converting enzyme (ACE) inhibitory peptides, particularly in dairy and marine matrices, are supported by workflows combining Alcalase hydrolysis with size-guided ultrafiltration, RP-HPLC (Reverse Phase High-Performance Liquid Chromatography), and, more recently, in silico analyses and encapsulation studies. Recurrent limitations were identified: heterogeneous hydrolysates and uneven reporting that hinder sequence–activity correlations, gastrointestinal degradation and bitterness affecting applicability, and scale-up and purification choices influencing feasibility. The mapping clarified where Alcalase enables bioactive peptide generation and highlighted practical priorities, including protocol standardization and enzyme benchmarking, the integration of peptidomics and machine learning with targeted assays, and formulation-focused validation (encapsulation, stability, and delivery) to bridge in vitro activity to real-world use. These directions support the production of reproducible, application-ready peptide ingredients. Full article

Waste lignin from the hydrolysis of lignocellulosic materials is an abundant but underused by-product of the pulp and biorefinery industries. Phenolic compounds derived from lignin, rich in aromatic structures, show strong antioxidant potential and can be applied in polymer stabilization, food, and medical fields. This study evaluated the radical-scavenging activity of phenolic fractions obtained from alkaline-treated waste lignin against DPPH● and ABTS•⁺, using Trolox as a reference. Both spectrophotometric and electrochemical techniques were employed, providing deeper insight into the underlying mechanisms. Depending on the assay, the phenolic extracts demonstrated substantial radical-scavenging capacity, in some cases matching or surpassing that of Trolox. This behavior was linked to electron/proton transfer pathways, radical reactivity, and solubility effects. The combined use of multiple antioxidant tests offered a comprehensive characterization of the bioactivity of lignin-derived phenolics and supports their potential as sustainable sources of antioxidant compounds within a circular economy framework. Furthermore, the study examined how toluene-extracted phenolics affect the thermo-oxidative stability of model polyurethane films. Incorporating small amounts (1%, 3%, 5%) into the polymer matrix showed that a 1% loading provides the most effective stabilization. At higher concentrations, however, additional oxidative processes seem to be activated, as indicated by FTIR measurements and thermogravimetric analysis. Full article

Quinoa (Chenopodium quinoa) is a promising source of plant proteins with the potential to produce bioactive peptides through enzymatic hydrolysis. This study aimed to extract quinoa protein and produce bioactive peptides using two microbial proteases: Alcalase (from Bacillus licheniformis) and Flavourzyme (from Aspergillus oryzae). The protein was extracted through alkaline solubilization and isoelectric precipitation, achieving a 72% yield. Hydrolysis was conducted for 4 h, and enzymatic activity was measured using the TNBS method to determine the degree of hydrolysis, while SDS-PAGE was used to analyze protein breakdown. The reaction was performed at controlled pH and temperature (Alcalase: 9.5 and 55 °C; Flavourzyme: 7 and 37 °C). Both enzymes achieved maximum hydrolysis at 60 min. Consequently, the separation and inhibitory capacity of angiotensin-converting enzyme (ACE-I) were tested at the first four time points (0, 20, 40, and 60 min). A wider variety and higher concentration of peptides smaller than 2 kDa were found in hydrolysates treated with Flavourzyme, which is associated with antihypertensive activity. The ACE-I assay showed greater activity at the end of hydrolysis. Inhibition percentages of 87.5 ± 2.11 were observed in hydrolysates with Flavourzyme, and 94.1 ± 1.11 in those with Alcalase. These findings indicate that quinoa protein, hydrolyzed with microbial proteases, is a feasible source of peptides with potential antihypertensive effects for use in functional foods and nutraceuticals. Full article

In response to the environmental and health concerns associated with high-sodium brine disposal and the sodium content in table olives, this study proposes a novel, sustainable preservation method that completely replaces traditional brine with chitosan solutions. Three food-grade chitosan solutions were formulated using acetic acid, vinegar, and vinegar neutralized with baking soda as alternative liquid media for preserving Kalamata olives. Over a five-month storage period with a one-year endpoint, these solutions were evaluated against a conventional 8% NaCl brine control. The chitosan-based systems demonstrated effective microbial control, maintaining significantly lower total viable counts for most of the storage period, while yeast and mold populations were comparable to or slightly higher than the control over extended storage. Notably, they reduced the medium’s salinity by 75–85%, directly addressing the issue of high sodium content. The chitosan solutions also provided superior pH stability and color maintenance in the olives. A key finding was the distinct nature of the interaction between the olives and the chitosan medium compared to brine: while antioxidant activity within the olive flesh declined, the chitosan solutions themselves exhibited high and stable intrinsic antioxidant capacity (>78%), acting as an active antioxidant reservoir—a dynamic not observed with traditional brine. This research successfully validates chitosan solution as a viable, low-sodium, brine-free preservation medium, offering a novel strategy for sustainable olive processing that valorizes seafood waste and aligns with circular economy principles. Full article

Ionic liquids (ILs) and deep eutectic solvents (DESs) have emerged as effective solvents for poorly soluble materials such as natural polysaccharides, including chitin. This review describes recently developed efficient chitin derivatization methods that harness the solubilizing power of ILs and DESs. It covers chitin acylation approaches, including acylation and mixed ester formation, as well as chitin etherification protocols. For example, the ILs 1-allyl-3-methylimidazolium bromide (AMIMBr) and 1-allyl-2,3-dimethylimidazolium bromide serve as effective media for chitin acylation and etherification, respectively, yielding single esters and benzyl derivatives with high degrees of substitution (DS). The use of DESs comprising AMIM chloride (AMIMCl) as a hydrogen bond acceptor and several hydrogen bond donors for chitin acylation are presented. In an optimized system, acylation using acyl chlorides proceeded smoothly without additives, such as a base/catalyst, in a DES comprising AMIMCl and 1,1,3,3-tetramethylguanidine, affording high-DS ester derivatives. The method was extended to the synthesis of mixed chitin esters bearing both long and bulky acyl substituents at appropriate substitution ratios, which exhibit thermoplasticity. Full article

This study presents the first characterization of the globulin fraction from a newly registered chickpea cultivar, which represents the first desi-type cultivar (GB Cappuccino) released in Brazil. Although desi chickpeas are widely consumed in other countries, they have not been part of the Brazilian dietary pattern, and this introduction may represent an opportunity for changing this scenario. Characterizing its proteins is essential, given that legumes are recognized as important protein sources. In this study, globulins were confirmed as the predominant protein fraction, with the legumin-like fraction accounting for more than 80% of the total globulins. Its electrophoretic and amino acid profiles were highly distinctive and strongly influenced by this major fraction. In addition to the expected solubilization in saline solution, under in vitro pepsin–pancreatin digestion conditions designed to assess maximum hydrolysis potential, the globulin fraction was partially hydrolyzed, indicating a degree of protein digestibility while simultaneously releasing peptides that exhibited antioxidant activity and angiotensin-converting enzyme (ACE) inhibitory potential. Overall, these results highlight the nutritional relevance of this new cultivar and, based on the preliminary bioactivity screening performed, suggest that its globulin-rich protein composition may represent a promising source of bioactive peptides. Full article

Research on tannin-based foams has shown promising results. However, all developments in this field have not been addressed from different perspectives, in a systematic way, and with an emphasis on sustainability. This work discusses different formulations, emphasizing their bio-based components and how modifications influence key properties. It examines life cycle assessment (LCA) studies through a sustainability lens and identifies major commercial phenolic products to highlight the practical use of tannin foams for thermal insulation. The type of tannins, as well as their sources, influences the key properties of these foams. The replacement of formaldehyde, a crosslinking agent known for its health risks, is possible, particularly through more sustainable alternatives that allow for foams with better properties than those obtained with formaldehyde. Substitution of diethyl ether with less hazardous alternatives results in foams with improved thermal and mechanical performance. The elimination of the blowing agent—the green alternative—also leads to foams with good performance. The presence of additives (surfactants, plasticizers, and fillers), some of which are sustainable, improves the mechanical properties of the foams. The performance in fire-related applications, already promising, is also enhanced by the presence of additives. An increase in understanding, combined with the sustainable nature of the various alternatives, makes tannin-based foams promising candidates for next-generation insulation and structural materials in construction. Full article

Edible mushrooms are an underexplored source of industrial proteases, whose synthesis is highly dependent on the cultivation substrate. This study investigated the effect of nine culture media on the proteolytic profiles of Auricularia sp., Lentinus sp., Macrocybe sp., and Grifola frondosa. Fungi were cultivated on diverse media (e.g., Czapek, Malt, Soy Flour). We analyzed total protein, specific activities (total, cysteine, serine proteases) using a biochemical assay, and protein secondary structure via FTIR, with metabolic patterns identified by PCA. A dissociation was found between total protein yield (highest in MFI/Casein media) and specific activity (highest in maltose media), suggesting catabolite repression. Distinct metabolic strategies emerged: Grifola frondosa specialized in serine protease production in the minimal Czapek medium (catabolic derepression), while Macrocybe sp. maximized cysteine protease production on soy flour (substrate induction). FTIR confirmed this, revealing a β-sheet-dominant (75.5%) structure for Grifola extract versus a random-coil-dominant (60.8%) structure for Macrocybe. This study provides a framework for mechanism-based bioprocess design, enabling the tailored production of serine proteases from G. frondosa (Czapek medium) or cysteine proteases from Macrocybe sp. (soy medium) for customized biotechnological applications. Full article

Optical frames are used worldwide to correct visual impairments, protect from UV damage, or simply for fashion purposes. Optical frames are often made of poorly biodegradable and fossil-based materials, with designs not targeted to everyone’s tastes and requirements. Additive manufacturing processes allow personalisation of optical frames and the use of new sustainable biomaterials to replace fossil-based ones. This comprehensive review combines an extensive survey of the scientific literature, market trends, and information from other relevant sources, analysing the biomaterials currently used in additive manufacturing and identifying biomaterials (biopolymers, natural fibres, and natural additives) with the potential to be developed into biocomposites for printing optical frames. Requirements for optical devices were carefully considered, such as standards, regulations, and demands for manufacturing materials. By comparing with fossil-based analogues and by discussing the chemical, physical, and mechanical properties of each biomaterial, it was found that combining various materials in biocomposites is promising for achieving the desirable properties for printing optical frames. The advantages of the various techniques of this cutting-edge technology were also analysed and discussed for optical industry applications. This study aims to answer the central research question: which biopolymers and biocomposite constituents (natural fibres, plasticisers, and additives) have the ideal mechanical, thermal, physical, and chemical properties for combining into a biomaterial suitable for producing sustainable, customisable, and inclusive optical frames on demand, using additive manufacturing techniques. Full article

Poly(L-lactide-co-ε-caprolactones) (PLCL) are promising biodegradable polymers with tunable properties for various biomedical applications. Along with the composition, the microstructure of PLCL chain is an important factor affecting its properties, crystallinity, and degradation profile. In this study, to find effective ways for tailoring the microstructure of PLCL chain, kinetic patterns of L-lactide/ε-caprolactone (75:25) ring-opening copolymerization in the presence of two different catalysts were evaluated. The kinetic studies, accompanied by the assessment of the evolution of PLCL microstructure over the reaction course, provided the optimal regimes for synthesis of PLCL with a fixed composition (LA:CL = 75:25) and different chain microstructure. This was achieved by employing two types of catalysts (tin(II) 2-ethylhexanoate and zirconium(IV) acetylacetonate) and delayed co-monomer addition approach. The control of average LA block length (l_LA) was achieved in a wide range from 4 to 14 monomeric units. Differential scanning calorimetry and wide-angle X-ray scattering revealed a pronounced effect of l_LA on glass transition temperature, melting temperature, and crystallinity. Full article

Microbial biosurfactants (mBSs) are bioactive molecules with diverse applications, notably as antimicrobial agents against antibiotic-resistant pathogens. Produced by bacteria and yeasts, mBSs are classified as glycolipids, lipopeptides, polymeric, and particulate types. The global rise in multidrug-resistant organisms, such as Escherichia coli, Klebsiella pneumoniae, Salmonella typhimurium, Pseudomonas aeruginosa, and Acinetobacter baumannii, underscores the urgent need for new antimicrobial strategies. mBSs disrupt microbial growth by interacting with the lipid components of pathogens, offering promising alternatives to conventional antibiotics. This review highlights the sources, chemical structures, and properties of mBSs, their antimicrobial activities, synergistic effects with antibiotics, and structure–activity relationships. Special emphasis is placed on surfactant modification, where targeted changes—such as valine substitution in surfactin—significantly lower critical micelle concentrations (CMC) and enhance antimicrobial potency. Such rational engineering demonstrates how biosurfactants can be tailored for improved biomedical performance while minimizing cytotoxicity. In parallel, artificial intelligence (AI) algorithms, including artificial neural networks and genetic algorithms, optimize yields, predict substrate suitability from agricultural residues, and guide microbial strain engineering. AI models can predict interfacial behavior and synchronize fermentation with purification. Advancing the understanding of mBS interactions with microbial membranes, combined with modification strategies and AI-guided optimization, is essential for developing targeted therapies against resistant infections. Future research should integrate these approaches to engineer novel derivatives, reduce costs, and validate clinical potential through comprehensive in vivo studies. Full article

Fibrous polycaprolactone-based composite materials with the addition of hardystonite (1, 3, and 5 wt.%) were developed using the electrospinning method. The obtained PCL and PCL-HT nonwovens were evaluated in terms of their physiochemical properties (SEM, EDS, BET, and zeta potential). Furthermore, the antioxidant potential [measured by thiobarbituric acid reactive substance (TBARS) levels], blood plasma coagulation parameters, and cyto- and genotoxicity towards PBM and Hs68 cells were assessed to determine the biochemical activity of the composites. The conducted experiments confirmed that hardystonite was successfully incorporated into the PCL matrix. No substantial changes in the fibres’ surface morphology and the structure of the composites were observed. Similarly, the specific surface area, total pore volume, and average pore size did not change significantly. The addition of hardystonite to the polymer solution resulted in a shift in zeta potential toward less negative values. With regard to plasma coagulation parameters, no significant changes were observed in the aPTT, PT, or TT, likely due to the counterbalancing effect of Zn²⁺ and Ca²⁺ ions. Furthermore, the PCL-HT composites exhibited a lowered TBARS level, suggesting antioxidant properties, which could be attributed to the presence of zinc in hardystonite. The PCL and PCL-HT composites demonstrated no cytotoxic or genotoxic effects on the tested blood or skin cell types, suggesting their safety. Full article

Agave lechuguilla fibers exhibit high tensile strength, low density and durability, but their use in natural rubber composites is underexplored. This study investigates alkaline-treated fibers (149–180 µm) as reinforcements for natural latex. Fibers were pretreated with a methanol–acetone mixture, followed by immersion in 10% NaOH at 70 °C for 1 h, removing lignin and hemicellulose as confirmed by FTIR and SEM. Thermogravimetric analysis showed three weight-loss stages: moisture/volatiles (9.4%), hemicellulose (peak at 341 °C), and cellulose/lignin (peak at 482 °C), with <3% residue above 500 °C. Treated composites exhibited enhanced tensile strength (4.68 ± 1.2 MPa vs. 1.3 ± 0.8 MPa for untreated) and elongation at break (530 ± 51% vs. 452 ± 32%). Hardness increased from 21.8 (neat latex) to 30.3, and compression resistance was improved. Optical microscopy revealed strong fiber–matrix adhesion with uniform dispersion. Alkaline treatment enhances interfacial bonding and mechanical performance, making A. lechuguilla fibers a sustainable reinforcement for eco-friendly composites in automotive, construction, and packaging sectors. Full article

Kefiran, the extracellular polysaccharide produced by Generally Recognized as Safe (GRAS) bacteria found in kefir grains, is a promising biopolymer with multiple applications in agri-food and biomedical fields. Besides its characteristics and potential applications, the factors that affect its production remain a prime subject of interest. Lactic acid bacteria synthesize polysaccharides to protect their cells from adverse conditions. Therefore, low-temperature storage (4 °C) of kefir grains inoculated into Ultra-High-Temperature (UHT) milk at two different concentrations (5% and 30%) was studied as a factor for increasing kefiran production in the medium. The cryoprotectant disaccharide trehalose, which comprises a carbon and energy source for many microorganisms, was also evaluated for its effectiveness in enhancing kefiran production. The pH, the increase in kefir grain mass, the amount of kefiran produced, and the rheological properties of the acidified milk were determined during two distinct storage periods, depending on kefir grain concentration. For comparison, kefir grains were also fermented at 25 °C and 30 °C. Low-temperature storage at a kefir grain concentration of 30% resulted in an increase in the amount of polysaccharide produced beyond that obtained through fermentation. Fermentation of a 5% grain inoculum at 30 °C resulted in the lowest kefiran production. In the presence of trehalose, prolonged low-temperature storage favored an increase in the biosynthesis of kefiran, especially at a 30% kefir grain inoculum. Trehalose, however, was not a significant factor in the fermentation experiments. Proper selection of low-temperature storage time is required to avoid a reduction in kefiran concentration due to the metabolic activity of the microorganisms in kefir grains. The acidified milk (low-temperature storage) and kefir (fermentation) samples both exhibited increased elasticity and apparent viscosity with increasing kefir grain concentration. However, the rheological behavior of acidified milk was greatly affected by protein degradation during low-temperature storage. As shown by the findings of the present study, low-temperature storage (4 °C) of a 30% kefir grain inoculum in the presence of trehalose (3% w/w) until a final pH of 4.2 proves to favor kefiran production in the medium the most. Full article

Protein-based films are attractive candidates for biodegradable packaging, yet their performance is often compromised by phase separation when combining components with contrasting hydrophilicity. In this study, gelatin/zein films were used as a model system to elucidate how phase separation governs multifunctional properties. FTIR, XRD, TGA, and SEM analyses confirmed heterogeneous domains arising from immiscibility, which strongly influenced mechanical, heat-sealing, barrier, and optical behaviors. Zein incorporation improved tensile strength, water resistance, and UV-blocking capacity, while it simultaneously compromised heat-sealing strength, transparency, and gas barrier uniformity. To rationalize these trade-offs, a Multi-Criteria Decision-Making (MCDM) framework integrating the Analytic Hierarchy Process (AHP) and Technique for Order of Preference by Similarity to the Ideal Solution (TOPSIS) was applied, revealing that gelatin/zein blends performed worse overall than pure films. These findings demonstrate that phase separation can improve individual attributes without generating synergistic effects, emphasizing the importance of compatibility control and holistic evaluation in the rational design of biodegradable packaging materials. Full article

The stability of physical and mechanical properties of highly filled swelling rubbers in polar and nonpolar liquids (oil, mineralized water) was studied. Nitrile butadiene rubber of BNKS-28 AMN grade served as the elastomer matrix, with sodium salt of carboxymethylcellulose (NaCMC) as the swelling filler. Oxal T-92, a mixture of dioxane alcohols (10–50 phr, step 10 phr), was used as a plasticizer due to its good thermodynamic miscibility with rubber (confirmed by Scatchard–Hildebrand calculations). Adding Oxal T-92 to NaCMC-filled compounds markedly reduced Mooney viscosity, improving processing through increased macromolecule mobility, without significantly affecting vulcanization kinetics—indicating chemical inertness toward crosslinking centers. Increasing Oxal T-92 from 10 to 50 phr reduced tensile strength from 4.1 MPa to 2.9 MPa. Swelling in aqueous solutions of varying mineralization was evaluated via volume and mass change. The optimal plasticizer content for high swelling with acceptable strength is 20–30 phr. After 3 days in oil and formation water, NaCMC-filled rubbers retained stable physical and mechanical properties. Full article