Macromol, Volume 4, Issue 4 (December 2024) – 11 articles

The increasing industrial demand and the search for novel ingredients in food and non-food sectors have driven research efforts toward alternatives to traditional commercial starches, emphasizing sustainability and the valorization of native crops, thereby promoting income generation for small-scale farmers. The extraction of these starches through aqueous methods, employing reductive and/or alkaline agents, can impact their structure and technological properties. These starches exhibit distinct physicochemical, morphological, crystalline, thermal, and nutritional characteristics, influenced by factors such as botanical origin. Although certain limitations may exist in their technological applications, physical, chemical, and/or enzymatic modification methods, or a combination thereof, are employed to enhance these properties for specific uses. These alternative starch sources present potential applications across the food, pharmaceutical, paper, medicinal, and cosmetic industries, underscoring their versatility and unique advantages. Nonetheless, ongoing research is essential to fully explore their composition and potential applications. This review serves as a valuable resource for researchers and professionals interested in sustainable and innovative alternatives to conventional starches. Full article

Lipases and carboxylesterases are enzymes of biotechnological interest both for their reactions and their specificity. They have wide-ranging applications in the food, pharmaceuticals, biodiesel synthesis, and bioremediation industries. For that reason, the strain Neobacillus thermocopriae C255 was isolated from ash from Popocatepetl volcano and studied as a new source of lipolytic enzymes. It was identified using 16S ribosomal RNA and flagellar protein FliF sequence homology, yielding 100% identity. From the sequencing of its genome, an enzyme with lipolytic activity, classified as a monoacylglycerol lipase, and named Mgl-C255, was cloned in E. coli BL21, and then expressed, biochemically characterized, and tested via transesterification reactions with alcohols and monosaccharides. Based on its sequence and structure, it was placed within family V, having a catalytic triad of S90-D207-H237. Biochemical characterization showed its highest activity at 40 °C, pH 7.5 to 8.5, with C-2 length substrate preference. No metal ions or inhibitors influenced lipolytic activity, except for PMSF, SDS, Cu⁻², and Hg⁻². Mgl-C255 retained about 50% of its activity in non-polar solvents and showed synthetic activity in organic solvents, making it a good candidate for studying its catalytic potential and selectivity. Full article

The MALDI-TOF mass-spectrometry was employed to analyze the structure of the reaction products of limonene, a natural terpene, and elemental sulfur, with the objective of identifying the occurrence of side processes, such as oxidative dehydrogenation, aromatization, and the Diels–Alder reaction cascade. The MALDI-TOF mass-spectrometry was demonstrated to be effective for the analysis of high-sulfur polymers obtained by the inverse vulcanization reaction, allowing for the unambiguous separation of sulfur-containing and hydrocarbon molecular fragments and the detailed characterization of macromolecular structures. By varying the ratio of sulfur (S₈) and limonene in the initial reaction system, we were able to ascertain the limiting amount of sulfur that can be covalently bonded by terpene, as well as determine the average length of polysulfide chains under the assumption of equal reactivity and complete depletion of all double bonds. The side reaction of limonene aromatization, as indicated by the MALDI-TOF spectrum of the product resulting from its interaction with elemental sulfur, was corroborated by ¹H and ¹³C NMR spectroscopy. Consequently, the registration and interpretation of MALDI-TOF spectra of inverse vulcanization products, either independently or in conjunction with the application of ¹H and ¹³C NMR spectroscopy methods, as well as the determination of the limiting number of sulfur atoms that can be bound to one molecule of an unsaturated compound, paves the way for new avenues of investigation into the structure and side reactions involved in the synthesis of high-sulfur polymers. Full article

Hydroxypropyl-β-cyclodextrin (HPβCD) is a derivatized cyclodextrin in which several H atoms on the hydroxyls of the glucose rings are substituted by 2-hydroxypropyl groups. The cyclic structure of HPβCD creates a cavity capable of totally or partially enclosing different molecules (inclusion complexes), and this capacity makes it useful in the pharmaceutical industry. Rifampicin is an antibiotic commonly used to treat tuberculosis; however, some of its properties such as its low solubility and variable bioavailability need to be improved by encapsulating it in systems such as HPβCD. The inclusion complexes formed by twelve structures of HPβCD and rifampicin with various polar and non-polar solvents are studied using molecular simulation. Diverse solvents are simulated using the zwitterionic or neutral configuration of rifampicin, and different values of relative permittivity in the electrostatic contribution to the total energy. The latter constant has little effect on the formation of inclusion complexes, whereas the type of rifampicin essentially determines the energies and configurations of the complexes. The zwitterion is located near the primary rim of HPβCD and the neutral form of rifampicin is near the secondary one. In both cases, the piperazine tail is incorporated into higher-energy complexes inside the host. Full article

Plant-derived phenolic compounds are recognized to provide several health benefits for humans, including anticancer, anti-inflammatory, and antioxidant proprieties. Their bioavailability in the human body has a significant impact on these outcomes. Their bioaccessibility and bioavailability are highly dependent on the structure and manner in which phenolics enter into the organism, through a complex food matrix, for instance, or as pure isolates. Furthermore, the bioaccessibility of phenolic compounds in the body is greatly impacted by interactions with a broad range of other macromolecules (such as proteins, lipids, dietary fibers, and polysaccharides) in food or during digestion. Encapsulation is a process that can improve bioaccessibility and bioavailability by guaranteeing coating of the active ingredients, controlled release, and targeted distribution to specific parts of the digestive system. However, this field has not yet received enough attention, due to the complex mechanisms through which phenolics act in the body. This review attempts to shed light on the results of research that has been performed on the potential and therapeutic benefits of encapsulated polyphenols in both health and disease. Full article

Agrochemical residues, including pesticides and herbicides, pose significant environmental and health risks when present in water sources. Conventional water treatment methods often fall short in effectively removing these persistent pollutants, necessitating innovative solutions. This review explores the use of polysaccharides and composite adsorbents as sustainable alternatives for agrochemical residue removal from water. Biopolymers such as chitosan, alginate, and cellulose are highlighted for their biodegradability, biocompatibility, and ability to be functionalized for enhanced adsorption performance. Recent advances in the development of composite materials incorporating nanomaterials, such as graphene, oxide, and metal oxides, have shown significant promise in enhancing the efficiency and selectivity of agrochemical adsorption. The review also addresses the fundamental mechanism of adsorption, such as electrostatic interactions, hydrogen bonding, and hydrophobic forces, that contribute to the effectiveness of these materials. Challenges associated with scalability, regeneration, and real-world applications are discussed, as well as future opportunities for integrating emerging technologies like 3D printing and machine learning into adsorbent design. Overall, polysaccharides and composites offer a promising pathway toward achieving efficient and sustainable agrochemical residue removal, with ongoing research needed to overcome current limitations and optimize their practical application in water treatment. Full article

Biopolymer blends of polylactic acid (PLA) and polybutylene adipate-co-terephthalate (PBAT) are extruded into flexible monolayer films. These blends are excellent candidates for the realization of environmentally friendly packaging applications. A necessary pre-requisite for that are appropriate tribological properties under mechanical contact. Reasonable wear resistance allows good protection of packed goods, and low friction forces reduce difficulties in stacking. In this research, mechanical embossment under high loads at room temperature was used for the modification of polymer surfaces to exhibit a significant friction reduction under dry conditions. The results particularly show a systematic decrease in the coefficient of friction for biopolymer blends containing 30 wt% and 40 wt% PBAT. FTIR was used to analyze the change in surface composition after mechanical embossing. A sophisticated FTIR calibration method revealed that the blend with 30 wt% PBAT shows a modified distribution of PBAT and PLA at the surface due to mechanical embossment. This leads to a controlled and long-lasting modification of the surface properties without a substantial change in the chemical composition of the polymer in bulk. Without the use of additional coatings, biodegradable packaging foils with improved characteristics are accessible. Full article

Bacterial quorum sensing (QS) is a critical communication process that regulates gene expression in response to population density, influencing activities such as biofilm formation, virulence, and antibiotic resistance. This study investigates the inhibitory effects of five phytochemicals—apigenin, carnosol, chlorogenic acid, quercetin, and rosmarinic acid—on the S-ribosylhomocysteinase (LuxS) enzyme, a key player in AI-2 signaling across both Gram-positive and Gram-negative bacteria. Using molecular docking studies, we identified that these phytochemicals interact with the LuxS enzyme, with apigenin, carnosol, chlorogenic acid, and rosmarinic acid binding within the substrate-binding pocket and exhibiting binding scores below −7.0 kcal/mol. Subsequent in vitro assays demonstrated that these compounds inhibited AI-2 signaling and biofilm formation in Escherichia coli MG1655 in a concentration-dependent manner. Notably, carnosol and chlorogenic acid showed the most potent effects, with IC₅₀ values of approximately 60 μM. These findings suggest that these phytochemicals may serve as potential QS inhibitors, providing a foundation for developing new anti-pathogenic agents to combat bacterial infections without promoting antibiotic resistance. Further studies are warranted to explore the therapeutic applications of these compounds in both clinical and agricultural settings. Full article

During the manufacturing of wooden musical instruments, offcut wood pieces are inevitably generated. This study explores the potential of utilizing three types of these small offcut wood pieces, mahogany, maple, and rosewood, by converting them into polyurea through liquefied wood technology by proposing a novel approach to synthesizing bio-based polyurea. This polyurea is a durable polymer, offering long-term carbon fixation and thereby contributing to environmental sustainability. In this study, various liquefaction conditions as parameters, including the temperature, sulfuric acid content, mix solvent ratio, and liquefaction time, were investigated in relation to polyurea film properties. The relationship between the mechanical and thermal properties of the resulting films and the characteristics of the liquefied product was investigated. Notably, when the hydroxyl value of the liquefied product exceeded 300, the resulting polyurea derived from the liquefied product exhibited a high tensile strength of 25 MPa. In contrast, when the hydroxyl value was below 300, the polyurea derived from the liquefied product displayed a strain value of up to 150%, alongside an increased thermal decomposition temperature. These findings suggest that the properties of polyurea can be effectively tuned by manipulating the characteristics of the liquefied product, offering a promising approach to enhancing the value of offcut wood in instrument manufacturing. Full article

Natural fiber composites have gained increasing attention due to sustainability considerations. One often neglected aspect is the potential for the mechanical recycling of such materials. In this work, we compounded injection-molded polypropylene (PP) and polylactic acid (PLA) short cellulose fiber composites with fiber shares up to 40 percent by weight. Both matrix materials were reinforced by the addition of the fibers. We investigated a trifold full recycling process, where we subjected the materials produced in the first place to compounding, injection molding, testing, and shredding, and then repeated the process. Although the materials’ properties assigned to degradation were found to decrease with progressive recycling, attractive mechanical properties could be preserved even after the third reprocessing cycle. Full article

The development and characterization of agricultural byproduct-based biocomposites are an important part of green chemistry. In this work, four-ingredient blends were formulated with the melt blending method. The set of composites (named as CSO series) was made with poly(lactic acid) (PLA) as the major matrix, washed cottonseed meal (WCSM) as a filler, cottonseed oil (CSO) as a compatibilizer, and glycerol (GLY) as a plasticizer. The morphological analysis showed the homogenous dispersion of the cottonseed byproducts into the PLA matrix to some extent. The thermogravimetric analysis revealed that thermal stability was impacted by the ingredient’s addition. The functional group analysis of the sample and simulation by Fourier transform infrared spectra confirmed the chemical interactions of PLA with WCSM in the blend products. CSO was most likely subjected to physical blending into the products. The mechanical strengths of those composites were affected by the ratios of PLA-CSO. Generally, the tensile strengths were in the range of 0.74–2.1 MPa, which indicate its suitability for low-strength biodegradable plant container development. The blend products had a lower water absorption during the water soaking test. This work shows the feasibility of incorporating cottonseed WCSM and CSO into a PLA composite for sustainable agricultural applications. Full article