Search Results (118)

In the field of enhanced oil recovery (EOR), particularly for water control in high-temperature reservoirs, there is a critical need for effective in-depth water shutoff and conformance control technologies. Polymer-based in situ-cross-linked gels are extensively employed for enhanced oil recovery (EOR), yet their short gelation time under high-temperature reservoir conditions (e.g., >120 °C) limits effective in-depth water shutoff and conformance control. To address this, we developed a hydrogel system via the in situ cross-linking of polyacrylamide (PAM) with phenolic resin (PR), reinforced by silica sol (SS) nanoparticles. We employed a variety of research methods, including bottle tests, viscosity and rheology measurements, scanning electron microscopy (SEM) scanning, density functional theory (DFT) calculations, differential scanning calorimetry (DSC) measurements, quartz crystal microbalance with dissipation (QCM-D) measurement, contact angle (CA) measurement, injectivity and temporary plugging performance evaluations, etc. The composite gel exhibits an exceptional gelation period of 72 h at 130 °C, surpassing conventional systems by more than 4.5 times in terms of duration. The gelation rate remains almost unchanged with the introduction of SS, due to the highly pre-dispersed silica nanoparticles that provide exceptional colloidal stability and the system’s pH changing slightly throughout the gelation process. DFT and SEM results reveal that synergistic interactions between organic (PAM-PR networks) and inorganic (SS) components create a stacked hybrid network, enhancing both mechanical strength and thermal stability. A core flooding experiment demonstrates that the gel system achieves 92.4% plugging efficiency. The tailored nanocomposite allows for the precise management of gelation kinetics and microstructure formation, effectively addressing water control and enhancing the plugging effect in high-temperature reservoirs. These findings advance the mechanistic understanding of organic–inorganic hybrid gel systems and provide a framework for developing next-generation EOR technologies under extreme reservoir conditions. Full article

Two recombinant cutinases, AfCutA and AfCutB, derived from Aspergillus fumigatus, were heterologously expressed in Pichia pastoris and systematically characterized for their biochemical properties and polyester-degrading capabilities. AfCutA demonstrated superior catalytic performance compared with AfCutB, displaying higher optimal pH (8.0–9.0 vs. 7.0–8.0), higher optimal temperature (60 °C vs. 50 °C), and greater thermostability. AfCutA exhibited increased hydrolytic activity toward p-nitrophenyl esters (C4–C16) and synthetic polyesters. Additionally, AfCutA released approximately 3.2-fold more acetic acid from polyvinyl acetate (PVAc) hydrolysis than AfCutB. Quartz crystal microbalance with dissipation monitoring (QCM-D) revealed rapid adsorption of both enzymes onto polyester films. However, their adsorption capacity on poly (ε-caprolactone) (PCL) films was significantly higher than on polybutylene succinate (PBS) films, and was influenced by pH. Comparative modeling of catalytic domains identified distinct structural differences between the two cutinases. AfCutA possesses a shallower substrate-binding cleft, fewer acidic residues, and more extensive hydrophobic regions around the active site, potentially explaining its enhanced interfacial activation and catalytic efficiency toward synthetic polyester substrates. The notably superior performance of AfCutA suggests its potential as a biocatalyst in industrial applications, particularly in polyester waste bioremediation and sustainable polymer processing. Full article

By monitoring the solidification of droplets of plant latices with a fast quartz crystal microbalance with dissipation monitoring (QCM-D), droplets from Campanula glomerata were found to solidify much faster than droplets from Euphorbia characias and also faster than droplets from all technical latices tested. A similar conclusion was drawn from optical videos, where the plants were injured and the milky fluid was stretched (sometimes forming fibers) after the cut. Rapid solidification cannot be explained with physical drying because physical drying is transport-limited and therefore is inherently slow. It can, however, be explained with coagulation being triggered by a sudden decrease in hydrostatic pressure. A mechanism based on a pressure drop is corroborated by optical videos of both plants being injured under water. While the liquid exuded by E. characias keeps streaming away, the liquid exuded by C. glomerata quickly forms a plug even under water. Presumably, the pressure drop causes an influx of serum into the laticifers. The serum, in turn, triggers a transition from a liquid–liquid phase separated state (an LLPS state) of a resin and hardener to a single-phase state. QCM measurements, optical videos, and cryo-SEM images suggest that LLPS plays a role in the solidification of C. glomerata. Full article

Supported lipid bilayers (SLBs) that model neuronal membranes are needed to explore the role of membrane lipids in the misfolding and aggregation of amyloid proteins associated with neurodegenerative diseases, including Parkinson’s and Alzheimer’s disease. The neuronal membranes include not only phospholipids, but also significant amounts of cholesterol, sphingomyelin, and gangliosides, which are critical to its biological function. In this study, we explored the conditions for the formation of an SLB, for the five-component lipid mixture composed of zwitterionic 1,2-Dioleoyl-sn-glycero-3-phosphocholine (DOPC), anionic 1,2-dioleoyl- sn-glycero-3-phospho-L-serine (DOPS), nonionic cholesterol (Chol), zwitterionic sphingomyelin (SM), and anionic ganglioside (GM), using the quartz crystal microbalance with dissipation monitoring (QCM-D) technique, by varying experimental parameters such as pH, buffer type, temperature, vesicle size, and osmotic stress. SLB formation from this multicomponent lipid system was found challenging because the vesicles adsorbed intact on the quartz crystal and failed to rupture. For most of the variables tested, other than osmotic stress, we found no or only partial vesicle rupture leading to either a supported layer of vesicles or a partial SLB that included unruptured vesicles. When osmotic stress was applied to the vesicles already adsorbed on the surface, by having a different salt concentration in the rinse buffer that follows vesicle flow compared to that of the dilution buffer during vesicle flow and adsorption, vesicle rupture increased, but it remained incomplete. In contrast, when osmotic stress was applied during vesicle flow and adsorption on the surface, by having different salt concentrations in the dilution buffer in which vesicles flowed compared to the hydration buffer in which vesicles were prepared, complete vesicle rupture and successful formation of a rigid SLB was demonstrated. The robustness of this approach to form SLBs by applying osmotic stress during vesicle adsorption was found to be independent of the number of lipid components, as shown by SLB formation from the 1-, 2-, 3-, 4-, and 5-component lipid systems. Full article

Background: Silibinin (SLB), a flavonoid derived from milk thistle, exhibits promising therapeutic properties but faces significant clinical limitations due to poor solubility and bioavailability. Objectives: This study focuses on the development and characterization of SLB-loaded nanoemulsions designed for mucosal delivery. Methods: Nanoemulsions were prepared using the spontaneous emulsification method, guided by pseudoternary phase diagrams to determine selected component ratios. Comprehensive characterization included particle size, polydispersity index (PDI), zeta potential, encapsulation efficiency, rheological properties, and surface tension. Mucoadhesive properties were evaluated using quartz crystal microbalance with dissipation (QCM-D) to quantify interactions with mucin layers. Results: The combination of Capryol 90, Tween 80, and Transcutol in selected proportions yielded nanoemulsions with excellent stability and solubilization capacity, enhancing the solubility of silibinin by 625 times compared to its intrinsic solubility in water. The ternary phase diagram indicated that achieving nanoemulsions with particle sizes between 100 and 300 nm required higher concentrations of surfactants (60%), relative to oil (20%) and water (20%), with formulations predominantly composed of Smix (surfactant and cosurfactant mixture in a 1:1 ratio). Rheological analysis revealed Newtonian behavior, characterized by constant viscosity across varying shear rates and a linear torque response, ensuring ease of application and mechanical stability. QCM-D analysis confirmed strong mucoadhesive interactions, with significant frequency and dissipation shifts, indicative of prolonged retention and enhanced mucosal drug delivery. Furthermore, contact angle measurements showed a marked reduction in surface tension upon interaction with mucin, with the SLB-loaded nanoemulsion demonstrating superior wettability and strong mucoadhesive potential. Conclusions: These findings underscore the suitability of SLB-loaded nanoemulsions as a robust platform for effective mucosal drug delivery, addressing solubility and bioavailability challenges while enabling prolonged retention and controlled therapeutic release. Full article

This study examines the adsorption and bulk assembly behaviour of quaternized hydroxyethylcellulose ethoxylate (QHECE)–sodium dodecyl sulphate (SDS) complexes on negatively charged substrates. Due to its quaternized structure, QHECE, which is used in several industries, including cosmetics, exhibits enhanced electrostatic interactions. The phase behaviour and adsorption mechanisms of QHECE–SDS complexes are investigated using model substrates that mimic the wettability and surface charge of damaged hair fibres. Two preparation methodologies, high-concentration mixing and gradient-free mixing, were employed to examine their impact on the complex equilibrium, phase behaviour, and adsorption properties of the complexes. The measurements of turbidity, electrophoretic mobility, and conductivity demonstrate the existence of nonequilibrium dynamics during the mixing process, which exert a significant influence on the structural and functional characteristics of the complexes. The quartz crystal microbalance with dissipation monitoring (QCM-D) was employed to investigate the adsorption of the complexes onto the substrates. The results demonstrated the critical role of intermediate SDS concentrations in enhancing deposition. The findings emphasise the importance of formulation and preparation protocols in designing stable, high-performance cosmetic products. This research advances our understanding of polyelectrolyte–surfactant interactions and provides insights into optimising QHECE-based formulations. Full article

Using the framework of an investigation of the stimuli-responsive behavior of peptide assembly on a solid surface, this study on the behavior of a chemisorbed peptide on a gold surface was performed. The studied peptide is a dimeric form of the antimicrobial peptide Trichogin GAIV, which was also modified by substituting the glycine with lysine residues, while the N-terminus octanoyl group was replaced by a lipoic one that was able to bind to the gold surface. In this way, a chemically linked peptide assembly that is pH-responsive was obtained because of the protonation/deprotonation of the sidechains of the Lys residues. Information about the effect of protonation/deprotonation equilibria switching the pH from acid (pH = 3) to basic (pH = 11) conditions was obtained macroscopically by performing Quartz crystal microbalance with dissipation monitoring (QCM-D), Surface Plasmon Resonance (SPR), Nanoplasmonic Sensing (NPS), and FTIR techniques. Using molecular dynamics (MD) simulations, it is possible to explain, at the molecular level, our main experimental results: (1) pH changes induce a squeezing behavior in the system, consisting in thickness and mass variations in the peptide layer, which are mainly due to the pH-driven hydrophilic/hydrophobic character of the lysine residues, and (2) the observed hysteresis is due to small conformational rearrangements from helix to beta sheets occurring mainly on the first half of the peptide, closer to the surface, while the second half remains almost unaffected. The latter result, together with the evidence that the layer thickness is not simply double the assembly of the monomeric analog, indicates that the dimeric peptide does not behave as a double monomer, but assumes very peculiar features. Full article

The unique structure of G4.0 PAMAM dendrimers allows a drug to be enclosed in internal spaces or immobilized on the surface. In the conducted research, the conditions for the formation of the active G4.0 PAMAM complex with doxorubicin hydrochloride (DOX) were optimized. The physicochemical properties of the system were monitored using dynamic light scattering (DLS), circular dichroism (CD), and fluorescence spectroscopy. The Quartz Crystal Microbalance with Dissipation Monitoring (QCM-D) method was chosen to determine the preferential conditions for the complex formation. The highest binding efficiency of the drug to the cationic dendrimer was observed under basic conditions when the DOX molecule was deprotonated. The decrease in the zeta potential of the complex confirms that DOX immobilizes through electrostatic interaction with the carrier’s surface amine groups. The binding constants were determined from the fluorescence quenching of the DOX molecule in the presence of G4.0 PAMAM. The two-fold way of binding doxorubicin in the structure of dendrimers was visible in the Isothermal calorimetry (ITC) isotherm. Fluorescence spectra and release curves identified the reversible binding of DOX to the nanocarrier. Among the selected cancer cells, the most promising anticancer activity of the G4.0-DOX complex was observed in A375 malignant melanoma cells. Moreover, the preferred intracellular location of the complexes concerning the free drug was found, which is essential from a therapeutic point of view. Full article

Coupling spectroscopic ellipsometry (SE), quartz crystal microbalance with dissipation (QCM-D), X-ray photoemission spectroscopy (XPS), and atomic force microscopy (AFM), we developed a multi-technique approach to characterize the surface immobilization of probe DNA strands, as a tool for the design of a DNA-based biosensor for the detection of disease-related oligonucleotide strands [...] Full article

Bacterial lipopolysaccharides (LPSs) are important indicators of a bacteria presence in any samples. They can therefore be used for the detection of microbiological contamination in food and dairy products. We performed a comparative analysis of different bacterial models by the application of liposomes containing LPS from Salmonella enterica serotype typhimurium on the surface of an 11-mercaptoundecanoic acid (MUA) monolayer chemisorbed on the gold surface of quartz crystal. Using quartz crystal microbalance with dissipation monitoring (QCM-D), we were able to monitor the formation of the lectin, concanavalin A (ConA), layer on the MUA surface. We determined the optimal concentration of the ConA for the layer formation. ConA of 0.3 mg/mL was selected as the most suitable adsorption of liposomes containing LPS. Using the Sauerbrey equation, we calculated that approximately 1.13 × 10¹² ConA molecules per cm² was adsorbed on the MUA surface, which closely corresponds to the 1.19 × 10¹² molecules per cm² by theoretical models. Later, mixed LPS liposomes containing dipalmitoyl phosphatidyl choline (DPPC), dipalmitoyl phosphatidyl ethanolamine (DPPE) and cholesterol successfully interacted with the ConA layer, which resulted in a decrease in the resonant frequency and an increase in dissipation. We compared the adsorption of liposomes with different fractions of LPS and containing LPS from different bacteria. Lack of any LPS in liposomes caused weaker adsorption on the ConA layer. Liposomes containing 50% LPS caused the most prominent adsorption and were suitable for interaction with DNA aptamers specific to certain LPS. The addition of the aptamers to the surface of ConA covered by LPS-containing liposomes resulted in a decrease in resonant frequency and an increase in the dissipation. Using the Kelvin–Voigt viscoelastic model and multiharmonic response of acoustic sensors, we also determined changes in viscoelastic values of the molecular films during interaction with liposomes and the ConA layer. Full article

Quartz Crystal Microbalances (QCMs) are versatile sensors employed in various fields, from environmental monitoring to biomedical applications, owing mainly to their very high sensitivity. However, the assessment of their metrological performance, including the impact of conditioning circuits, digital processing algorithms, and working conditions, is a complex and novel area of study. The purpose of this work is to investigate and understand the measurement errors associated with different QCM measurement techniques, specifically focusing on the influence of conditioning electronic circuits. Through a tailored and novel experimental setup, two measurement architectures—a Quartz Crystal Microbalance with dissipation monitoring (QCM-D) system and an oscillator-based QCM-R system—were compared under the same mechanical load conditions. Through rigorous experimentation and signal processing techniques, the study elucidated the complexities of accurately assessing QCM parameters, especially in liquid environments and under large mechanical loads. The comparison between the two different techniques allows for highlighting the critical aspects of the measurement techniques. The experimental results were discussed and interpreted based on models allowing for a deep understanding of the measurement problems encountered with QCM-based measurement systems. The performance of the different techniques was derived, showing that while the QCM-D technique exhibited higher accuracy, the QCM-R technique offered greater precision with a simpler design. This research advances our understanding of QCM-based measurements, providing insights for designing robust measurement systems adaptable to diverse conditions, thus enhancing their effectiveness in various applications. Full article

Biosensors play an important role in numerous research fields. Quartz crystal microbalances with dissipation monitoring (QCM-Ds) are sensitive devices, and binding events can be observed in real-time. In combination with aptamers, they have great potential for selective and label-free detection of various targets. In this study, an alternative surface functionalization for a QCM-D-based aptasensor was developed, which mimics an artificial cell membrane and thus creates a physiologically close environment for the binding of the target to the sensor. Vesicle spreading was used to form a supported lipid bilayer (SLB) of 1-palmitoyl-2-oleoyl-glycero-3-phosphocholine (POPC) and 1,2-dipalmitoyl-sn-glycero-3-phosphethanolamine-N-(cap biotinyl) (biotin-PE). The SLB was then coated with streptavidin followed by applying a biotinylated aptamer against thrombin. SLB formation was investigated in terms of temperature and composition. Temperatures of 25 °C and below led to incomplete SLB formation, whereas a full bilayer was built at higher temperatures. We observed only a small influence of the content of biotinylated lipids in the mixture on the further binding of streptavidin. The functionalization of the sensor surface with the thrombin aptamer and the subsequent thrombin binding were investigated at different concentrations. The sensor could be reconstituted by incubation with a 5 M urea solution, which resulted in the release of the thrombin from the sensor surface. Thereafter, it was possible to rebind thrombin. Thrombin in spiked samples of human serum was successfully detected. The developed system can be easily applied to other target analytes using the desired aptamers. Full article

Peri-implantitis is a growing pathological concern for dental implants which aggravates the occurrence of revision surgeries. This increases the burden on both hospitals and the patients themselves. Research is now focused on the development of materials and accompanying implants designed to resist biofilm formation. To enhance this endeavor, a smart method of biofilm inhibition coupled with limiting toxicity to the host cells is crucial. Therefore, this research aims to establish a proof-of-concept for the pH-triggered release of chlorhexidine (CHX), an antiseptic commonly used in mouth rinses, from a titanium (Ti) substrate to inhibit biofilm formation on its surface. To this end, a macroporous Ti matrix is filled with mesoporous silica (together referred to as Ti/SiO₂), which acts as a diffusion barrier for CHX from the CHX feed side to the release side. To limit release to acidic conditions, the release side of Ti/SiO₂ is coated with crosslinked chitosan (CS), a pH-responsive and antimicrobial natural polymer. Scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM/EDX) and Fourier transform infrared (FTIR) spectroscopy confirmed successful CS film formation and crosslinking on the Ti/SiO₂ disks. The presence of the CS coating reduced CHX release by 33% as compared to non-coated Ti/SiO₂ disks, thus reducing the antiseptic exposure to the environment in normal conditions. Simultaneous differential scanning calorimetry and thermogravimetric analyzer (SDT) results highlighted the thermal stability of the crosslinked CS films. Quartz crystal microbalance with dissipation monitoring (QCM-D) indicated a clear pH response for crosslinked CS coatings in an acidic medium. This pH response also influenced CHX release through a Ti/SiO₂/CS disk where the CHX release was higher than the average trend in the neutral medium. Finally, the antimicrobial study revealed a significant reduction in biofilm formation for the CS-coated samples compared to the control sample using viability quantitative polymerase chain reaction (v-qPCR) measurements, which were also corroborated using SEM imaging. Overall, this study investigates the smart triggered release of pharmaceutical agents aimed at inhibiting biofilm formation, with potential applicability to implant-like structures. Full article

Single-chain lipid amphiphiles such as fatty acids and monoglycerides are promising antimicrobial alternatives to replace industrial surfactants for membrane-enveloped pathogen inhibition. Biomimetic lipid membrane platforms in combination with label-free biosensing techniques offer a promising route to compare the membrane-disruptive properties of different fatty acids and monoglycerides individually and within mixtures. Until recently, most related studies have utilized planar model membrane platforms, and there is an outstanding need to investigate how antimicrobial lipid mixtures disrupt curved model membrane platforms such as intact vesicle adlayers that are within the size range of membrane-enveloped virus particles. This need is especially evident because certain surfactants that completely disrupt planar/low-curvature membranes are appreciably less active against high-curvature membranes. Herein, we conducted quartz crystal microbalance–dissipation (QCM-D) measurements to investigate the membrane-disruptive properties of glycerol monolaurate (GML) monoglyceride and lauric acid (LA) fatty acid mixtures to rupture high-curvature, ~75 nm diameter lipid vesicle adlayers. We identified that the vesicle rupture activity of GML/LA mixtures mainly occurred above the respective critical micelle concentration (CMC) of each mixture, and that 25/75 mol% GML/LA micelles exhibited the greatest degree of vesicle rupture activity with ~100% efficiency that exceeded the rupture activity of other tested mixtures, individual compounds, and past reported values with industrial surfactants. Importantly, 25/75 GML/LA micelles outperformed 50/50 GML/LA micelles, which were previously reported to have the greatest membrane-disruptive activity towards planar model membranes. We discuss the mechanistic principles behind how antimicrobial lipid engineering can influence membrane-disruptive activity in terms of optimizing the balance between competitive membrane remodeling processes and inducing anisotropic vs. isotropic spontaneous curvature in lipid membrane systems. Full article

Curcumin exhibits antioxidant and antitumor properties, but its poor chemical stability limits its application. Insoluble peptide precipitates formed by proteolysis of rice glutelin are usually discarded, resulting in resource waste. The coupled treatment of heat-assisted pH shifting and compounded chitosan (CS) was used to fabricate rice peptide aggregate–chitosan complexes (RPA–CS). The structure, interfacial behavior, emulsion properties, and digestibility of curcumin-loaded RPA–CS Pickering emulsions were investigated. Increasing the CS concentration led to lower interfacial tension but larger particle size, and the three-phase contact angle of the RPA–CS complexes approached 90°. Quartz crystal microbalance with dissipation (QCM–D) indicated that RPA–CS complexes with 6 g·kg⁻¹ of CS (RPA–CS₆) had the highest K₁ (0.592 × 10⁶ Hz⁻¹) and K₄ (0.487 × 10⁶ Hz⁻¹), suggesting that the softest interfacial layers were formed. The solid–liquid balance of RPA–RPA–CS emulsions was lower than 0.5, declaring that they had more elastic behavior than that of RPA emulsions. RPA–RPA–CS₄-and RPA–CS₆ emulsions had better storage stability, lower FFA release (79.8% and 76.3%, respectively), and higher curcumin bioaccessibility (65.2% and 68.2%, respectively) than RPA emulsions. This study showed that a low-value insoluble rice peptide precipitate could be used as a valuable emulsifier in foods, which may increase the economics and sustainability of the food supply. Full article