Search Results (409)

In 2025, the oil and fat industry of the Republic of Kazakhstan showed steady growth, strengthening the country’s position as a major producer and exporter of vegetable oils. However, the production process generates large amounts of waste (up to 100 tons per day), and its recycling is an important part of the oil and fat industry’s economy. High-temperature processing of plant waste has proven to be a promising method for creating new materials for various industries. The aim of this study was to determine the influence of various technical parameters of carbonization (processing temperature and process environment) on the physical and chemical characteristics of materials obtained by carbonizing sunflower seed husks from the East Kazakhstan region at temperatures of 300, 400, 500, 600, 700 and 800 °C in an inert argon environment, as well as by processing the husks in an oxidizing environment at a temperature of 650 °C, for further use in elastomer compositions as new ingredients. Increasing the carbonization temperature in an inert environment led to an increase in the amorphous carbon content, surface porosity, and pH of the studied materials. Another parameter that showed a tendency to increase with increasing temperature in an inert environment was the BET specific surface area. In the case of using an oxidizing environment, the highest pH value was observed, and the formation of crystalline mineral phases was also observed. The differences in the phase states of the studied materials may play an important role in shaping the spatial stack of the polymer matrix when used in rubber compound formulations. Full article

Agricultural residues represent an abundant renewable resource for sustainable lignocellulosic biorefineries, offering opportunities to produce value-added biopolymers while mitigating the environmental impacts associated with conventional disposal. This study evaluated the technical feasibility of using sorghum stubble as a feedstock for the recovery of cellulose, hemicellulose, and lignin through an ethanol–water organosolv process. Specifically, the study aimed to separate the main structural polymers of sorghum stubble and evaluate the performance of the proposed fractionation system. The biomass was treated at 180 °C and approximately 30 bar, followed by chlorine-free peroxide bleaching. The hemicellulose fraction was obtained by extracting the holocellulose (Wise method) and precipitating the dissolved hemicellulose using a 3:1 (v/v) ethanol-to-liquor ratio. The lignin fraction was isolated from the black liquor through vacuum distillation and drying. This approach yielded a cellulose fraction (23.66 wt%), a hemicellulose fraction (36.22 wt%), and a lignin fraction (30.35 wt%), corresponding to an overall polymer recovery of approximately 90 wt%. Structural and physicochemical characterization (FTIR, SEM, XRD, and TGA) supported the fractionation of the lignocellulosic matrix and identified characteristic structural and physicochemical features of the recovered cellulose, hemicellulose, and lignin fractions. SEM revealed substantial structural breakdown following the organosolv treatment, while TGA demonstrated distinct degradation behaviors among the components. Notably, the crystallinity index increased from 38% in the raw material to 71% in the cellulose fraction, indicating effective removal of amorphous components. A preliminary mass–energy analysis showed that approximately 96% of the initial energetic content of the biomass was retained in the polymers. Furthermore, approximately 70% of the ethanol used was recycled, highlighting the potential for solvent reintegration under the evaluated laboratory conditions. Overall, these findings demonstrate the potential of sorghum stubble as a renewable feedstock for the recovery of lignocellulosic polymers and provide a technical basis for the future optimization of organosolv-based biorefineries. Full article

The development of sustainable, smart food packaging materials that simultaneously provide antimicrobial protection and real-time monitoring of food quality is a critical frontier in food safety. This study reports the fabrication of a multifunctional amphiphilic emulgel designed for the detection of pathogen-induced metabolic pH changes in food systems. The system utilizes Pomegranate-derived nitrogen-doped quasi-spherical carbon dots (QS-CDs) as fluorescent nanoprobes and Rosemary Essential Oil (REO) as a natural antimicrobial agent, both encapsulated within a polyelectrolyte complex of chitosan and sugarcane bagasse-derived carboxymethyl cellulose (CMC). A low degree of substitution (DS = 0.4) was specifically engineered for the CMC to ensure an amphiphilic character, enabling nanocomposite complex stabilization of the REO droplets without synthetic surfactants. Structural characterization via Transmission Electron Microscopy (TEM) revealed well-dispersed QS-CDs (4.71–6.62 nm) and stable oil droplets (~605.49 nm) anchored within a zipped polymer network. Thermal analysis (TGA/DSC) using the Coats–Redfern model revealed a significant synergistic effect: the smart-emulgel exhibits a distinct two-stage degradation profile, with the high-temperature stage requiring an activation energy (E_a) of 95.19 kJ/mol, a substantial increase over the corresponding stage in the CD-emulgel baseline (18.69 kJ/mol). This enhanced stability is complemented by a slight increase in crystallinity (X_c from 0.11 to 0.14). While the smart-emulgel remains predominantly amorphous, this shift suggests that the integration of REO and QS-CDs into the polymer network promotes the formation of localized, more ordered domains, contributing to a more robust and structurally integrated matrix. The emulgel demonstrated a dual-mode optical response (colorimetric and fluorometric) sensitive to the metabolic byproducts (e.g., organic acids, amines, other alkaline compounds) produced by Escherichia coli and Staphylococcus aureus. These findings were corroborated by Density Functional Theory (DFT) calculations, which confirmed the thermodynamic stability and optimized electronic energy gaps for pH-responsive sensing. This research provides a green, high-performance platform for the real-time monitoring of food freshness and the prevention of foodborne illnesses. Full article

Poly(methyl methacrylate) (PMMA) remains a clinically important denture base polymer because of its favorable processability, aesthetics, repairability and long-term prosthodontic use; however, its limited surface hardness and susceptibility to sliding-induced degradation constrain surface durability. This study establishes the structure–chemistry–microstructure–tribology relationships and composition-window predictive behavior of heat-polymerized PMMA reinforced with titanium diboride (TiB₂). PMMA/TiB₂ composites containing 1, 3 and 5 wt.% TiB₂ were prepared and compared with unreinforced PMMA. X-ray diffraction confirmed preservation of the broad amorphous/semi-amorphous PMMA response, while TiB₂-related crystalline features became increasingly detectable with reinforcement content. ATR-FTIR showed retention of the characteristic C–H, ester C=O and C–O/C–O–C vibrations. SEM/EDS demonstrated progressively greater particle-related surface contrast and local Ti/B-associated elemental signatures. Vickers microhardness increased from 20.0 ± 0.7 to 35.0 ± 1.39 HV0.03, corresponding to a 75.0% improvement at 5 wt.% TiB₂. After 1000 m of dry sliding, total mass loss decreased from 32.4 ± 0.5 to 14.9 ± 0.4 mg (54.0% reduction), overall coefficient of friction decreased from 0.58 to 0.35, and representative wear-track width decreased from 481.4 to 101.8 µm. A parsimonious distance–composition interaction model retained strong grouped leave-one-composition-out performance for cumulative wear (R² = 0.9622; RMSE = 1.53 mg), while a linear composition model provided the most robust hardness prediction (R² = 0.9317; RMSE = 1.50 HV0.03). More complex nonlinear models did not improve prediction for held-out compositions. Within the investigated 0–5 wt.% window, 5 wt.% TiB₂ provided the most effective combination of matrix preservation, surface hardening, wear suppression and frictional stabilization. Full article

Crystallization can be exploited as an architecture-forming step for polymer membranes because it builds a load-bearing semicrystalline scaffold while simultaneously defining amorphous regions that later become transport pathways. Herein, we quantify how thermal history programs isotactic polystyrene (iPS) crystallization and translate the resulting microstructures into membrane-relevant design rules. Lux-calibrated digitally extracted pixel intensity (DPI) from polarized optical microscopy provides a quantitative, spatially resolved crystallinity proxy; benchmarking against differential scanning calorimetry confirms that the DPI proxy exhibits the same onset, peak, and completion signatures under matched temperature programs. The DPI–DSC agreement yielded R² = 0.98 under matched programs. We compared crystallization initiated from molten and glassy states across a wide range of melt pretreatments and crystallization temperatures. Molten-state pathways display pronounced melt-memory behavior: modest changes in melt pretreatment shift induction time and half-time and drive textures from dense, fine spherulitic fields to sparse, coarser morphologies. In contrast, glassy-state crystallization largely suppresses melt history, yielding overlapping sigmoidal crystallinity curves and stable kinetic parameters consistent with relaxation-mediated nucleation. Avrami analyses indicate three-dimensional growth in both routes but highlight the strong melt-history sensitivity of apparent rate constants in the molten state. The crystallization rate and half-life show bell-shaped temperature dependence. Finally, saturated nucleation density correlates with the melting response, providing a practical link between kinetic observables and morphology. The processing–morphology map provides membrane-relevant design rules by linking thermal history to nucleation density and scaffold texture, which are expected to influence transport and mechanical stability in downstream membrane fabrication. In this study, “membrane architecture” is used in a pre-fabrication sense to denote the crystallization-programmed semicrystalline scaffold expected to govern subsequent pore-generation behavior and mechanical stability. Accordingly, the present work establishes a quantitative process–structure map for iPS scaffold design. Full article

In this study, novel electrospun polymer mats based on biocompatible poly(lactic acid) (PLA) and hydrophilic poly(ethylene glycol) (PEG) were successfully fabricated for the co-delivery of two natural polyphenols, quercetin (QUE) and rosmarinic acid (RA). Scanning electron microscopy (SEM) revealed the formation of defect-free, continuous nanofibers with high interconnected porosity. By mimicking the structural features of the native extracellular matrix, these nanofibrous platforms facilitate pronounced combined antioxidant and anticancer action. X-ray diffraction (XRD) analysis confirmed that the rapid solvent evaporation during electrospinning induced a physical state transformation, converting both QUE and RA from their native crystalline structures into an amorphous dispersion within the polymer fibrous materials, thereby optimizing their potential bioavailability. The obtained hybrid fibrous materials possessed good mechanical properties. Moreover, the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging assay demonstrated that the incorporation of PEG enhanced matrix hydrophilicity, allowing the four-component PLA/PEG/QUE/RA mats to achieve the highest antioxidant efficiency (98.1%), suggesting an enhanced, complementary radical-neutralization pathway. Furthermore, in vitro biological assessments against human cervical carcinoma cell line (HeLa) and normal murine embryo fibroblasts BALB/3T3 demonstrated prominent anticancer activity, while noncancerous cells were significantly less affected. The dual-loaded PLA/PEG/QUE/RA fibrous mats induced significant cell shrinkage, chromatin condensation, and apoptotic cell death in HeLa cells, while normal BALB/3T3 fibroblasts retained cell membrane integrity and displayed higher resistance. Modeled after the native extracellular matrix, these bioinspired materials demonstrate significant antioxidant and anticancer activity, highlighting their potential for applications in localized cancer therapy, wound management, and tissue engineering. Full article

Polyethylene terephthalate (PET) is one of the most widely used plastics for single-use applications, with annual global production exceeding 80 Mt. Enzymatic degradation of PET has emerged as a promising and sustainable alternative to conventional recycling methods, enabling the hydrolysis of PET into its constituent monomers. While amorphous PET can be efficiently degraded by polyester hydrolases identified from environmental sources, crystalline PET remains highly recalcitrant to enzymatic attack and constitutes a major bottleneck for the industrial implementation of enzymatic PET recycling. Although physicochemical pretreatments can increase PET amorphicity, these approaches often require substantial energy input, thereby compromising the overall sustainability of the process. Consequently, the development of enzymes capable of directly degrading crystalline PET has long been sought; however, currently engineered enzymes exhibit insufficient catalytic activity toward highly crystalline PET owing to multiple factors, including limited substrate surface accessibility, highly ordered polymer morphology, incompatible binding-pocket geometries, restricted chain mobility, and unfavorable conformational energetics at the polymer–enzyme interface. This review aims to evaluate the factors limiting the enzymatic degradation of crystalline PET and to assess current strategies for overcoming low degradation rates. Specifically, it examines advances in substrate modification as well as enzyme- and process-engineering approaches designed to improve the depolymerization of crystalline PET. The advantages and limitations of these strategies are critically compared and discussed, highlighting the remaining challenges and future directions toward efficient and scalable biocatalytic PET recycling. Full article

This study examines the nature of enzymatic degradation of polyethylene terephthalate (PET) films mediated by a novel recombinant LCC^ICCG PETase enzyme preparation based on P. verruculosum fungus. The investigation was conducted using amorphous PET samples and PET samples with varying degrees of crystallinity as substrates for PETase-catalyzed hydrolysis under different temperature and pH conditions. Mechanical testing revealed that enzymatic treatment reduced the yield stress by 20–25%, tensile strength by approximately twofold, and elongation at break by 5–10 times, while the deformation mechanism remained unchanged. Enzymatic degradation under acidic conditions was ineffective, whereas increasing the pH to 9–10 markedly accelerated PET degradation and the associated deterioration of mechanical properties. Thermal analysis (TGA, DSC) and microscopy (optical and scanning electron microscopy) demonstrated that degradation was localized at the polymer surface, leading to the formation of cavities, cracks, and submicron-sized pores rather than bulk material disintegration. An inverse correlation was observed between PET crystallinity and susceptibility to enzymatic degradation: samples with crystallinity below 13% could be almost completely degraded, whereas samples with crystallinity above 30% exhibited little or no measurable weight loss over the same period. Low-crystallinity PET underwent rapid degradation accompanied by a transient increase in crystallinity, while highly crystalline PET primarily accumulated surface defects that nevertheless caused a substantial loss of mechanical strength. Consequently, the experimental data obtained in this study provide useful information for understanding PET degradation and for future studies on enzymatic PET recycling. The systematization of feedstock characteristics and the elucidated patterns of enzymatic degradation will enable optimization of pretreatment, enzymatic hydrolysis, and monomer recovery process parameters, thereby facilitating the eventual production of secondary raw materials. Full article

The valorization of lignocellulosic residues into bioactive and biodegradable materials offers a sustainable route for functional food packaging. In this study, hazelnut shells were exploited through an integrated process enabling the integrated recovery of polyphenols and cellulose. Polyphenols were extracted via hot water, liquid–liquid partitioning, and column chromatography, yielding a purified bioactive fraction. The residual biomass after polyphenol recovery was used for cellulose extraction (approximately 23% w/w) and converted into carboxymethyl cellulose (CMC) with a degree of substitution (DS) of 0.77. Active CMC films incorporating polyphenolic extracts exhibited improved mechanical performance, reaching tensile strengths of about 78 MPa and elongation at break values above 20%, while reducing water solubility to approximately 31%. The addition of carnauba wax further enhanced water resistance while modulating flexibility and stiffness. Attenuated Total Reflectance-Fourier Transform Infrared spectroscopy (ATR-FTIR) and scanning electron microscopy (SEM) analyses confirmed the conversion of crystalline cellulose into amorphous CMC and the successful incorporation of additives within the polymer matrix. The resulting films showed tunable mechanical, optical, and barrier properties, along with UV-blocking and antioxidant activity. These findings demonstrate that hazelnut shell-derived CMC films enriched with polyphenols and carnauba wax represent promising candidates for a sustainable platform for active food packaging applications, supporting a circular waste-to-value approach. Full article

Single-use polypropylene (PP) food containers represent a rapidly growing waste stream characterized by compositional heterogeneity and microstructural defects. Conventional reactive compatibilization using isotactic maleic anhydride-grafted PP (iPP-g-MA) provides rigid crystalline anchoring but lacks the interfacial flexibility to accommodate complex micro-defects. Herein, we propose a defect-tolerant compatibilization strategy by developing a binary iPP-g-MA/aPP-g-MA masterbatch for real post-consumer rPP derived from food-service containers. The amorphous aPP-g-MA component is proposed to provide a compliant interfacial environment that accommodates stress concentrations associated with microscale defects, whereas the iPP-g-MA component contributes crystalline anchoring with the recycled PP matrix. This soft/hard interfacial architecture is supported by grafting-degree analysis, GPC, XRD, DSC crystallization behavior, and SEM fracture morphology. The 1:1 mass-ratio binary formulation shows a marked improvement in elongation at break to 200%, representing a 203% increase relative to the single-component iMA system. The notched Charpy impact strength is enhanced to 8.98 kJ m⁻², while tensile strength is retained at 20.9 MPa within the typical strength–ductility trade-off of polymer toughening. TGA shows no premature degradation within the melt-processing window, indicating adequate thermal stability for melt reprocessing. This study provides a compositionally tunable, data-supported route for high-value upcycling of heterogeneous post-consumer polyolefins. From an application viewpoint, the improved ductility-impact balance makes the material relevant to injection-moulded semi-structural products such as storage crates, appliance housings, and automotive interior panels. Full article

The microstructure of semicrystalline bioresorbable polymers is central to their biomedical performance because the crystalline content influences both the mechanical stability and the degradation behaviour. Experimental studies have shown that crystallinity evolves concurrently with mass loss during enzymatic degradation. However, most existing models represent the material as a single homogeneous structure, preventing them from capturing this microstructural evolution or the state-selective mechanisms that drive it. We present a one-dimensional partial differential equation model for the enzymatic degradation of thin films, which treats the crystalline and amorphous states as distinct reactive components. Calibrated to poly($\epsilon$-caprolactone) (PCL) degraded by Candida antarctica lipase in vitro, the model accurately reproduces both the observed weight-loss profile and the concurrent decline in crystallinity. Parameter uncertainty analysis indicates that while there are varying degrees of confidence in individual parameter values, the overall model predictive uncertainty is well constrained. Parameter sensitivity analysis shows that the amorphous catalytic rate (the rate at which the enzyme degrades the amorphous region) is the dominant driver of degradation dynamics. The identified model parameters are used to explore the role of film thickness on the rates of mass and crystallinity loss. It was found that thin films remain largely reaction-limited, whereas thicker specimens become increasingly transport-influenced, with slower degradation and delayed structural evolution in the material interior. The model provides a useful tool to explore the effect of changing PCL film thickness on degradation rate and crystallinity-related properties without extensive experimentation. Full article

Architected polymer composites use spatially organized phases to achieve targeted property combinations. Shape forming elements (SFEs) are modular coextrusion die inserts that impose internal architectures by reshaping multiple melt streams. This study evaluates three SFE designs (Jacks, I-Beam, and Barn Door) that position a liquid crystalline polymer (LCP) and an amorphous polyamide (APA) in distinct core–shell configurations. Polymer clay prototyping and ANSYS Polyflow simulations were used to screen flow behavior, followed by extrusion at two puller speeds and characterization via optical microscopy and tensile testing. Microscopy revealed that abrupt area transitions and viscosity contrast disrupt encapsulation and distort designed features. Regression analysis showed that LCP content governs stiffness and strength, while higher puller speed enhances reinforcement through molecular orientation. Cross sectional geometries were quantified using interfacial perimeter, moments of inertia, and polar dispersion ratios, and correlated to tensile performance. Increased interfacial length reduced modulus, strength, and ductility. Modulus improved with LCP orientation and confinement, strength increased when LCP was placed at vertical extremities, and elongation was maximized by horizontally distributing LCP within a thick APA shell. These results demonstrate that SFEs enable tunable tradeoffs between stiffness, strength, and ductility. Full article

Background: Sulfated chitosan (ChS) is a chemically modified polysaccharide derived from chitin that mimics heparan sulfate (HS) structures and has emerged as a promising antimicrobial biomaterial. Piscirickettsia salmonis, the etiological agent of Salmonid Rickettsial Septicemia (SRS), represents the main driver of antibiotic use in Chilean aquaculture. Objective: In this study, the in vitro antibacterial activity of ChS against P. salmonis was evaluated. Methods: Elemental characterization by SEM-EDS and FTIR analysis confirmed successful sulfation of the polymer, with a degree of sulfation ranging from 0.92 to 0.95. Additionally, X-ray diffraction (XRD) analysis revealed a reduction in polymer crystallinity, indicating a transition toward a more amorphous structure associated with increased molecular flexibility and functional group accessibility. Results: Antibacterial assays revealed a minimum inhibitory concentration (MIC) of 1500 µg/mL and a minimum bactericidal concentration (MBC ≥ 1500 µg/mL). LIVE/DEAD™ fluorescence imaging showed the formation of bacterial aggregates with increasing size, frequency, and red fluorescence compared to controls over the exposure to ChS, indicating progressive membrane damage. This was supported by a reduction (p < 0.05) in the Green/Red fluorescence ratio of 37–46% between 5 h and 96 h of exposure, corresponding to alteration of the cell membrane. Scanning electron microscopy revealed pronounced morphological alterations by ChS, including surface disruption and loss of cellular integrity. This was more severe compared to commercial chitosan (ChC). Also, ChS reduced (p < 0.05) biofilm formation (>50% at day 6 and 34.8% at day 8). Conclusions: These results demonstrated that ChS disrupts the cell membrane and reduces biofilm formation in P. salmonis, thereby affecting viability. This is the first report of the antibacterial effect of ChS, an HS analogue, against P. salmonis. Full article

Background: Amorphous drug formulations are commonly used to improve the solubility and bioavailability of poorly soluble molecular pharmaceuticals, yet less is known about their molecular conformations and local bonding interactions than their crystalline phases. Methods: High-energy X-ray diffraction structure factor measurements have been made on liquid and glassy nifedipine (NIF), felodipine (FEL), NIF 1:3 polyvinylpyrrolidone (PVP), and FEL 1:3 PVP wt.% mixtures. The corresponding X-ray pair distribution functions have been interpreted using empirical potential structure refinement using different models and density functional theory conformer calculations. Results: In both NIF and FEL, the NH···O inter-molecular hydrogen bonds between the pyridyl nitrogen and ester carbonyls are found to be considerably weaker than those observed in the crystalline polymorphs. For nifedipine, it is proposed that either inter-molecular NH…ON nitro bonds are present and/or a fraction (<20%) of conformational changes, with the aryl ring flipped, occur in the liquid state. For felodipine, the models indicate significant disorder associated with the methyl and ethyl side chains in the liquid state, with the main peak intensity at 3.0 Å arising from intra-molecular Cl-Cl atom pairs. When nifedipine molecules are incorporated into PVP, our models show they possess stronger NH···O bonds to the PVP polymer than felodipine molecules, which have stronger affinity for bonding to the polymer than to other felodipine molecules. Conclusions: The amorphous forms of both NIF and FEL show much weaker hydrogen bonding than found in their crystalline phases. Liquid NIF also exhibits configurations which are not observed in the crystal phases. Full article

Recently, more sustainable and biodegradable packaging materials have begun to attract attention in food packaging due to major, rising concerns related to plastic usage. This study aims to develop and characterize biodegradable food packaging materials, namely poly(lactic acid) (PLA) and poly(ε-caprolactone) (PCL) enriched with pomegranate peel extract (PoPE). Firstly, the optimal extract selected was a 24 h maceration of PoPE with 60% ethanol, after production with different solvents and methods. PLA- and PCL-based films were produced via melt compounding with the addition of PoPE at different concentrations (1, 3, 5 and 10%, w/w). FTIR confirmed that the PoPE did not modify the chemical backbones of PLA or PCL, with only a more pronounced O–H band in PCL, suggesting mainly non-covalent/physical interactions. UV–Vis spectroscopy showed tunable warm coloration and strong UV shielding with reduced transparency; for PLA ~3–5 wt.%, PoPE enabled near-complete UV blocking, while PCL achieved very high UV protection even at low loadings. PoPE improved toughness in PLA (3–5 wt.%) and maintained ductility in PCL (1–10 wt.%). PoPE-added PLA and PCL films maintained thermal stability up to 10 wt.% according to TGA results. DSC/XRD indicated a matrix-dependent crystallization response. PLA remained largely amorphous, whereas PoPE promoted PCL crystallinity without changing polymer crystal polymorphs. SEM images revealed homogenous dispersion of PoPE in the films. Full article