Search Results (759)

In this study, a series of copolymers was synthesized using the promising biodegradable polymers Poly(L-lactic acid) (PLLA), Poly(lactic-co-glycolic acid) (PLGA), and Poly(ethylene adipate) (PEAd), known for their high potential. PEAd was synthesized through a two-step melt polycondensation process and then used to prepare copolymers with PLLA (PLLA-co-PEAd) and PLGA (PLGA-co-PEAd) at weight ratios of 90/10 and 75/25, respectively. The synthesized materials, along with the starting polymers, were extensively characterized for their structure, molecular weight, crystallinity, and thermal behavior. These novel systems exhibit single thermal transitions, e.g., glass transition. The incorporation of PEAd into the copolymers induced a plasticizing effect, evidenced by a consistent decrease in the glass transition temperature. Due to the latter effect in combination with the M_w drop, the facilitation of crystal nucleation was observed. Finally, the results by dielectric spectroscopy on the local and segmental molecular mobility provided additional proof for the homogeneity of the systems, as manifested, e.g., by the recording of single segmental relaxation processes. Overall, the findings indicate that the PLLA-co-PEAd and PLGA-co-PEAd copolymers hold significant potential, and the use of complementary experimental techniques offers valuable insights and indirect indications of their properties. Full article

Anthraquinone acid dyes are widely used in dyeing polyamide due to their good exhaustion and brightness. While ionic interactions primarily govern dye–fiber bonding, the molecular weight (Mw) of these dyes can significantly influence migration, apparent color strength, and fastness behavior. This study offers comparative insight into how the Mw of structurally similar anthraquinone acid dyes impacts their diffusion, fixation, and functional outcomes (e.g., UV protection) on polyamide 6 fabric, using Acid Blue 260 (Mw~564) and Acid Blue 127:1 (Mw~845) as representative low- and high-Mw dyes. The effects of dye concentration, pH, and temperature on color strength (K/S) were evaluated, migration index and zeta potential were measured, and UV protection factor (UPF) and FTIR analyses were used to assess fabric functionality. Results showed that the lower-Mw dye exhibited higher migration tendency, particularly at increased dye concentrations, while the higher-Mw dye demonstrated greater color strength and superior wash fastness. Additionally, improved UPF ratings were associated with higher-Mw dye due to enhanced light absorption. These findings offer practical insights for optimizing acid dye selection in polyamide coloration to balance color performance and functional attributes. Full article

This study investigated the immunonutritional potential of high-molecular-weight (Mw~85 kDa), non-degraded chitosan (NCS) and gamma-radiation-degraded, low-molecular-weight chitosan (RCS) incorporated into aquafeeds for Nile tilapia (Oreochromis niloticus). RCS was produced by γ-irradiation (10 kGy) in the presence of 0.25% (w/v) H₂O₂, yielding low-viscosity, colloidally stable nanoparticles with Mw ranging from 10 to 13 kDa. Five diets were formulated: a control, NCS at 0.50%, and RCS at 0.025%, 0.050%, and 0.075%. No adverse effects on growth were observed, confirming safety. Immune gene expression (e.g., ifng1, nfκb, tnf), antioxidant markers (e.g., reduced MDA, increased GSH and GR), and nonspecific humoral responses (lysozyme, IgM, and bactericidal activity) were significantly enhanced in the NCS-0.50, RCS-0.050, and RCS-0.075 groups. Notably, these benefits were achieved with RCS at 10-fold lower concentrations than NCS. Following challenge with Edwardsiella tarda, fish fed RCS-0.050 and RCS-0.075 diets exhibited the highest survival rates and relative percent survival, highlighting robust activation of innate and adaptive immunity alongside redox defense. These results support the use of low-Mw RCS as a biologically potent, cost-effective alternative to traditional high-Mw chitosan in functional aquafeeds. RCS-0.050 and RCS-0.075 show strong potential as immunonutritional agents to enhance fish health and disease resistance in aquaculture. Full article

Pectin is a multifunctional polysaccharide whose structural attributes, including degree of esterification (DE), molecular weight (MW), and branching, directly affect its gelling, emulsifying, and bioactive properties. Conventional pectin extraction relies on acid- or alkali-based methods that degrade the pectin structure, generate chemical waste, and alter its physicochemical and functional properties. Although novel methods such as ultrasound-assisted extraction (UAE), microwave-assisted extraction (MAE), and enzyme-assisted extraction (EAE) are recognized as environmentally friendly alternatives, they frequently use acids or alkalis as solvents. This review focuses on pectin extraction methods that do not involve acidic or alkaline solvents such as chelating agents, super/subcritical water, and deep eutectic solvents (DESs) composed of neutral components. This review also discusses how these alternative extraction methods can preserve or modify the key structural features of pectin, thereby influencing its monosaccharide composition, molecular conformation, and interactions with other biopolymers. Furthermore, the influence of these structural variations on the rheological properties, gelling behaviors, and potential applications of pectin in the food, pharmaceutical, and biomedical fields are discussed. This review provides insights into alternative strategies for obtaining structurally intact and functionally diverse pectin by examining the relationship between the extraction conditions and pectin functionality. Full article

A recently proposed method called “controlled swelling of monolithic films” was implemented to prepare ultra-high-molecular-weight polyethylene (UHMWPE) ultrafiltration membranes. For the first time, the effect of UHMWPE molecular weight (MW) on the structure and properties of the membranes prepared via this special case of thermally induced phase separation was studied in detail. The morphology and properties of the membranes were studied using SEM, DSC, liquid–liquid displacement porometry, and standard methods for the evaluation of mechanical properties, permeance, rejection, and abrasion resistance. High-quality membranes with a tensile strength of 5.0–17.8 MPa, a mean pore size of 25–50 nm, permeance of 17–107 L m⁻² h⁻¹ bar⁻¹, rejection of model contaminant (blue dextran) of 72–98%, and great abrasion resistance can be prepared only if the MW of the polymer in the initial monolithic film is sufficiently high. The properties of the membranes can effectively be controlled by changing the MW of the polymer and the mass fraction of the latter in the swollen film. Shrinkage is responsible for the variation in the membrane properties. The membranes prepared from a higher-MW polymer are more prone to shrinking after the removal of the solvent. Shrinkage decreases before rising again and minimizes with an increase in the polymer content in the swollen film. Full article

In this study, the ultrasonic-assisted extraction of deep eutectic solvents (UADES) for tea polysaccharides was optimized, and their physicochemical properties and antioxidant activities were analyzed. The optimal DES comprised choline chloride (CC) and ethylene glycol (EG) in a molar ratio of 1:3, with a water content of 40%. The optimized condition was an extraction temperature of 61 °C, an ultrasonic power of 480 W, and an extraction time of 60 min. The UADES extraction rate of polysaccharides (ERP) was 15.89 ± 0.13%, significantly exceeding that of hot water (HW) extraction. The polysaccharide content in the UADES-extracted tea polysaccharides (UADESTPs) was comparable to that of hot-water-extracted tea polysaccharides (HWTPs) (75.47 ± 1.35% vs. 74.08 ± 2.51%); the UADESTPs contained more uronic acid (8.35 ± 0.26%) and less protein (12.91%) than HWTP. Most of the UADESTPs (88.87%) had molecular weights (Mw) below 1.80 × 10³ Da. The UADESTPs contained trehalose, glucuronic acid, galactose, xylose, and glucose, with molar ratios of 8:16:1:10. The free radical scavenging rate and total reducing power of the UADESTPs were markedly superior to those of the HWTPs. Moreover, the UADESTPs had a better alleviating effect on H₂O₂-induced oxidative injury in HepG2 cells. This study develops an eco-friendly and efficient extraction method for tea polysaccharides, offering new insights for the development of tea polysaccharides. Full article

Surfactants can be utilized to improve oil recovery by changing the performance of reservoirs in rock pores. Kerogen is the primary organic matter in shale; however, high temperatures will affect the overall performance of this surfactant, resulting in a decrease in its activity or even failure. The effect of surfactants on kerogen pyrolysis has rarely been researched. Therefore, this study synthesized a polymeric surfactant (PS) with high temperature resistance and investigated its effect on kerogen pyrolysis under the friction of drill bits or pipes via molecular dynamics. The infrared spectra and thermogravimetric and molecular weight curves of the PS were researched, along with its surface tension, contact angle, and oil saturation measurements. The results showed that PS had a low molecular weight, with an MW value of 124,634, and good thermal stability, with a main degradation temperature of more than 300 °C. It could drop the surface tension of water to less than 25 mN·m⁻¹ at 25–150 °C, and the use of slats enhanced its surface activity. The PS also changed the contact angles from 127.96° to 57.59° on the surface of shale cores and reversed to a water-wet state. Additionally, PS reduced the saturated oil content of the shale core by half and promoted oil desorption, indicating a good cleaning effect on the shale oil reservoir. The kerogen molecules gradually broke down into smaller molecules and produced the final products, including methane and shale oil. The main reaction area in the system was the interface between kerogen and the surfactant, and the small molecules produced on the interface diffused to both ends. The kinetics of the reaction were controlled by two processes, namely, the step-by-step cleavage process of macromolecules and the side chain cleavage to produce smaller molecules in advance. PS could not only desorb oil in the core but also promote the pyrolysis of kerogen, suggesting that it has good potential for application in shale oil exploration and development. Full article

This study systematically investigates the impact of hydrolytic degradation on the crystallization kinetics and morphology of poly(butylene succinate-co-adipate) (PBSA). Gel Permeation Chromatography (GPC) confirmed extensive chain scission, significantly reducing the polymer’s weight-average molecular weight (M_w from ~103,000 to ~16,000 g/mol) and broadening its polydispersity index (PDI from ~2 to 7 after 64 days). Differential scanning calorimetry (DSC) analysis revealed that hydrolytic degradation dramatically accelerated crystallization rates, reducing crystallization time roughly 10-fold (e.g., from ~3000 s to ~300 s), and crystallinity increased from 34% to 63%. Multiple melting peaks suggested the presence of lamellae with varying thicknesses, consistent with the Gibbs–Thomson equation. Isothermal crystallization kinetics were evaluated using the Avrami equation (with n ≈ 3), reciprocal half-time of crystallization, and a novel inflection point slope method, all confirming accelerated crystallization; for instance, the slope increased from 0.00517 to 0.05203. Polarized optical microscopy (POM) revealed evolving spherulite morphologies, including hexagonal and flower-like dendritic spherulites with diamond-shape ends, while wide-angle X-ray diffraction (WAXD) showed a crystallization range shift to higher temperatures (e.g., from 72–61 °C to 82–71 °C) and a 14% increase in crystallite diameter, aligning with increased melting point and lamellar thickness and overall increased crystallinity. Full article

Anion exchange membranes (AEMs) are vital for electrochemical energy devices such as alkaline fuel cells and water electrolyzers, enabling the use of non-precious metal catalysts despite challenges from alkaline degradation. Hyperbranched polymers (hbPs) with their globular structure, high functional group density, and simple synthesis, offer a promising platform for enhancing transport and stability. In this study, multifunctional hbPs were synthesized from 4-vinylbenzyl chloride (VBC) and 2-hydroxyethyl methacrylate (HEMA) via atom transfer radical self-condensing vinyl polymerization (ATR-SCVP) and crosslinked into polyurethane-based AEMs. Characterization confirmed successful copolymerization and crosslinking, with excellent alkaline stability. Membranes crosslinked with higher molecular weight (MW) and VBC-richer hbPs (e.g., OH-hbP1-PU) exhibited high water uptake (75%) but low ion-exchange capacity (1.54 mmol/g) and conductivity (186 µS/cm), attributed to steric hindrance and insufficient ionic network connectivity. In contrast, OH-hbP2-PU exhibited optimal properties, with the highest OH⁻ conductivity (338 µS/cm) and IEC (2.64 mmol/g), highlighting a balanced structure for efficient ion transport. This work offers a tunable strategy for high-performance AEM development through tailored hbP architecture. Full article

Helianthus annuus L. (H. annuus) receptacles, a major agricultural by-product generated during seed processing, are currently underutilized. This study aimed to explore the valorization potential of this by-product by extracting H. annuus receptacles total polysaccharides (HRTP) and characterizing their potential as natural ingredients in ultraviolet (UV)-protective cosmetics. A new purified polysaccharide named H. annuus receptacles polysaccharide-1 (HRP-1) was isolated, likely exhibiting a backbone of alternating →4)-α-D-GalA-(1→ and →4)-α-D-GalA(6-OCH₃)-(1→ units, with a weight-average molecular weight (Mw) of 163 kDa. HRTP demonstrated significant protective effects against UV-induced damage in human immortalized keratinocyte (HaCaT) cells by suppressing intracellular reactive oxygen species (ROS) levels and downregulating MAPK-p38/ERK/JNK pathways, thereby inhibiting inflammatory cytokines (IL-1β, IL-6, IL-8, and TNF-α) and matrix metalloproteinases (MMP-1, MMP-3, and MMP-9). Additionally, HRTP exhibited moisturizing properties. These findings highlight H. annuus receptacle polysaccharides as sustainable, bioactive ingredients for eco-friendly sunscreen formulations, providing a practical approach to converting agricultural by-products into high-value industrial biomaterials. Full article

Chitosan films with potential application in triboelectric nanogenerators (TENGs) represent a promising approach to replace non-biobased materials in these innovative devices. In the present work, chitosan with varying molecular weights (MW) and degrees of deacetylation was dissolved in aqueous acetic acid (AA) at different acid concentrations. It was observed that the MW had a greater influence on the viscosity of the solution compared to either the acid concentration or deacetylation degree. Gel formation occurred in high-MW chitosan solutions prepared with low AA concentration. Films prepared from chitosan solutions, through solvent-casting, were used to prepare TENGs. The power output of the TENGs increased with higher concentrations of AA used in the chitosan dissolution process. Similarly, the residual AA content in the dried films also increased with higher initial AA concentrations. Additionally, hot-pressing of the films significantly improves the TENG power output due to the decrease in morphological defects of the films. It was demonstrated that a good selection of the acid concentration not only facilitates the dissolution of chitosan but also plays a key role in defining the properties of the resulting solutions and films, thereby directly impacting the performance of the TENGs. Full article

Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P(3HB-co-3HHx)) is a representative PHA copolymer that can improve the mechanical limitations of polyhydroxybutyrate (P(3HB)). Although genetic engineering can facilitate 3HHx incorporation, it often compromises cell growth and reduces polymer molecular weight owing to metabolic disruptions caused by the deletion of acetoacetyl coenzyme A (acetyl-CoA) reductase (PhaB). To address this issue, native strains capable of producing high levels of 3HHx were identified via oil-based Cupriavidus screening. Eight PHA-producing strains were isolated from various samples and Cupriavidus sp. Oh_1 exhibited the highest polyhydroxybutyrate (PHB) production at 15.23 g/L from 17.2 g/L of biomass using soybean oil. Moreover, Oh_1/phaC_RaJ_Pa, containing enoyl-CoA hydratase (phaJ) and PHA synthetase (phaC), was identified as the most effective novel strain producing the highest 3HHx mole fraction, 48.93 g/L of PHA from 52.3 g/L of biomass and achieving a maximum 3HHx accumulation of 27.2 mol%. The resulting P(3HB-co-3HHx) showed a higher Mw (12.3 × 10⁵) compared with P(3HB-co-3HHx) produced by the phaB-deleted strain (14.6 × 10⁴). Higher production of 3HHx was attributed to the higher expression of phaC_Ra and phaJ_Pa in Oh_1, with log2 fold changes of 2.94 and 8.2, respectively, as well as the upregulation of certain β-oxidation encoding operons. Collectively, these findings highlight a strain capable of synthesizing a substantial 3HHx fraction without requiring gene deletions or extensive genetic modifications. Full article

Background/Objectives: Gingipains produced by P. gingivalis have been shown to be directly related to periodontal tissue degradation and are significant molecular targets in therapy of periodontitis. Blocking the activity of these enzymes should reduce survival of this pathogen and mitigate the effects of inflammation in periodontitis. Therefore, gingipains inhibitors and specific antibodies could be recommended in the treatment of periodontitis. Cysteine peptidase inhibitors can be obtained by chemical synthesis, or isolated from natural raw materials. This research has the following aims: 1. to analyze in vitro the inhibition of cysteine protease activity in the gingival crevicular fluid (GCF) and 2. to compare the toxicity of natural raw inhibitors (obtained from Fallopia japonica plant and egg white) with chlorhexidine (CHX) using an MTS viability test. Methods: Samples of GCF were collected from healthy (N = 17) individuals and (N = 65) periodontal patients. Cysteine peptidase activity was inhibited by adding a solution of cystatin from egg white (with 20% glycerol), or cystatin from knotweed, or low molecular weight inhibitors (MW < 3 kDa) from egg white and knotweed against Nα-Benzoyl-DL-arginine 4-nitroanilide hydrochloride. Results: There was a statistically significant difference between the inhibition means of cysteine protease activity for the five groups (p < 0.001). Means for the four groups of patients with periodontitis were not statistically significant different from each other (p = 0.320). The inhibition rates were higher in periodontitis patients. The toxicity of knotweed cystatin inhibitor was several times lower than the toxicity of E-64d, and of CHX. Conclusion: Cysteine protease inhibitors isolated from egg or plants were non-toxic, effectively inhibited the activity of cysteine proteases in GCF, and may be a promising alternative to more toxic standard antimicrobials (CHX) in preventing periodontal tissue breakdown. Full article

Background/Objectives: This research focuses on the development and optimization of polymer–lipid hybrid nanoparticles (PLHNs) using two grades of mPEG-PCL co-polymers in combination with DPPC and lecithin to address the biopharmaceutical challenges of acalabrutinib (ACP), a selective treatment for different hematological malignancies. Methods: Variations in the mPEG-to-ε-caprolactone ratio influenced both the molecular weight (Mw) of the synthesized co-polymers and their aqueous phase affinity. The ACP-loaded PLHNs (ACP-PLHNs) were optimized using a circumscribed central composite design. The in vivo studies were performed in Wistar rats. Results: The lipophilic mPEG-PCL (Mw = 9817.67 Da) resulted in PLHNs with a particle size of 155.91 nm and 40.08% drug loading, while the hydrophilic mPEG-PCL (Mw = 23,615.84 Da) yielded PLHNs with a relatively larger size (223.46 nm) and relatively higher drug loading (46.59%). The drug release profiles were polymer-grade dependent: lipophilic ACP-PLHNs (lACP-PLHNs) sustained release up to 30 h in pH 7.2 buffer, while hydrophilic ACP-PLHNs (hACP-PLHNs) completed release within 24 h. Stability studies showed greater stability for lACP-PLHNs, likely due to reduced molecular rearrangement from the chemically stable lipophilic co-polymer. Conclusions: Oral administration of both formulations exhibited a 2-fold (p < 0.001) improvement in the C_max and AUC_0-tlast and a 3.9-fold (p < 0.001) increase in the relatively oral bioavailability compared to the conventional ACP suspension in male wistar rats. Full article

The focus of this work was to perform a preliminary study on the suitability of commercially available nanofiltration (NF) and reverse osmosis (RO) membranes for the separation of 1,3-propanediol (1,3-PD) post-fermentation solutions. The experiments were conducted with the use of AFC30 and AFC99 (PCI Membrane System Inc., Milford, OH, USA) as well as BW30 membranes (Dow FilmTec Co., Midland, MI, USA) and various feed solutions: selected compounds of fermentation broths, and synthetic and real fermentation broths. Firstly, it was found that for pure water, the AFC30 membrane was characterized by the highest performance. It clearly indicated that the membrane is the most open membrane and is characterized by a more porous structure. In turn, the lowest flux was noted for the AFC99 membrane. Studies performed with the use of synthetic broth found that for the BW30 membrane, the order in which the rejection coefficient (R) was obtained was glycerol~lactic acid > 1,3-propanediol > acetic acid. It clearly confirmed that the R increased with the molecular weight (MW) of the solution compounds. With regard to ions, it was found that SO₄²⁻ and PO₄³⁻ is characterized by higher R than Cl⁻ and NO₃⁻ ions. Multivalent ions are characterized by higher charge density, hydrated radius, hydration energy and MW. Finally, experiments performed with the use of the AFC30 membrane and real broths showed that the membrane ensured almost complete separation of 1,3-PD. With regard to organic acid, the separation performance was as follows: succinic acid > lactic acid > butyric acid > acetic acid > formic acid. It has been documented that the AFC30 membrane can be successfully used to concentrate the following ions: SO₄²⁻, PO₄³⁻, NO₃⁻ and Na⁺. Hence, most of the medium used for the fermentation process was retained by the membrane and may be reused, which is crucial for the scaling up of the process and reducing the total technology cost. With regard to the obtained permeate, it can be subsequently purified by other methods, such as distillation or ion exchange. For further development of the tested process, determining the retention degree for 1,3-PD and other solutes during long-term separation of real broth is necessary. Full article