Influence of chirality and sequence in lysine-rich lipopeptide biosurfactants and micellar model colloid systems.

Lipopeptides can self-assemble into diverse nanostructures which can be programmed to incorporate peptide sequences to achieve a remarkable range of bioactivities. Here, the influence of peptide sequence and chirality on micelle structure and interactions is investigated in a series of lipopeptides bearing two lysine or D-lysine residues and tyrosine or tryptophan residues, attached to a hexadecyl lipid chain. All molecules self-assemble into micelles above a critical micelle concentration (CMC). Small-angle x-ray scattering (SAXS) is used to probe micelle shape and structure from the form factor and to probe inter-micellar interactions via analysis of structure factor. The CMC is obtained consistently from surface tension and electrical conductivity measurements. We introduce a method to obtain the zeta potential from the SAXS structure factor which is in good agreement with directly measured values. Atomistic molecular dynamics simulations provide insights into molecular packing and conformation within the lipopeptide micelles which constitute model self-assembling colloidal systems and biomaterials.

Capillary adhesion of stick insects.

Scientific progress within the last few decades has revealed the functional morphology of an insect's sticky footpads-a compliant pad that secretes thin liquid films. However, the physico-chemical mechanisms underlying their adhesion remain elusive. Here, we explore these underlying mechanisms by simultaneously measuring adhesive force and contact geometry of the adhesive footpads of live, tethered Indian stick insects, Carausius morosus, spanning more than two orders of magnitude in body mass. We find that the adhesive force we measure is similar to the previous measurements that use a centrifuge. Our measurements afford us the opportunity to directly probe the adhesive stress in vivo and use existing theory on capillary adhesion to predict the surface tension of the secreted liquid and compare it to previous assumptions. From our predictions, we find that the surface tension required to generate the adhesive stresses we observed ranges between 0.68 and 12 mN m - 1 ${\rm m}^{-1}$ . The low surface tension of the liquid would enhance the wetting of the stick insect's footpads and promote their ability to conform to various substrates. Our insights may inform the biomimetic design of capillary-based, reversible adhesives and motivate future studies on the physico-chemical properties of the secreted liquid.

Framework for charged compact objects admitting conformal motion in higher dimension.

We propose a new framework for spherical charged compact objects admitting conformal motion in five-dimensional spacetime. The outer spacetime is considered as Reissner-Nordström to obtain matching conditions. The behavior of model characteristics like stress, pressure, and surface tension for the specific density profile is investigated by using Einstein's Maxwell field equations in a five-dimensional framework. For the proposed solution, all physical parameters behave very well even for variations in electric charge parameters. The existence of charged compact stars is also predicted by this study.

Simulating asymmetric membranes using P21 periodic boundary conditions.

Molecular dynamics (MD) simulations of symmetric lipid bilayers are now well established, while those of asymmetric ones are considerably less developed. This disjunction arises in part because the surface tensions of leaflets in asymmetric bilayers can differ (unlike those of symmetric ones), and there is no simple way to determine them without assumptions. This chapter describes the use of P21 periodic boundary conditions (PBC), which allow lipids to switch leaflets, to generate asymmetric bilayers under the assumption of equal chemical potentials of lipids in opposing leaflets. A series of examples, ranging from bilayers with one lipid type to those with peptides and proteins, provides a guide for the use of P21 PBC. Critical properties of asymmetric membranes, such as spontaneous curvature, are highly sensitive to differences in the leaflet surface tensions (or differential stress), and equilibration with P21 PBC substantially reduces differential stress of asymmetric bilayers assembled with surface area-based methods. Limitations of the method are discussed. Technically, the nonstandard unit cell is difficult to parallelize and to incorporate restraints. Inherently, the assumption of equal chemical potentials, and therefore the method itself, is not applicable to all target systems. Despite these limitations, it is argued that P21 simulations should be considered when designing equilibration protocols for MD studies of most asymmetric membranes.

Elucidating the roles of electrolytes and hydrogen bonding in the dewetting dynamics of the tear film.

This study explores the impact of electrostatic interactions and hydrogen bonding on tear film stability, a crucial factor for ocular surface health. While mucosal and meibomian layers have been extensively studied, the role of electrolytes in the aqueous phase remains unclear. Dry eye syndrome, characterized by insufficient tear quantity or quality, is associated with hyperosmolality, making electrolyte composition an important factor that might impact tear stability. Using a model buffer solution on a silica glass dome, we simulated physiologically relevant tear film conditions. Sodium chloride alone induced premature dewetting through salt crystal nucleation. In contrast, trace amounts of solutes with hydroxyl groups (sodium phosphate dibasic, potassium phosphate monobasic, and glucose) exhibited intriguing phenomena: quasi-stable films, solutal Marangoni-driven fluid influx increasing film thickness, and viscous fingering due to Saffman-Taylor instability. These observations are rationalized by the association of salt solutions with increased surface tension and the propensity of hydroxyl-group-containing solutes to engage in significant hydrogen bonding, altering local viscosity. This creates a viscosity contrast between the bulk buffer solution and the film region. Moreover, these solutes shield the glass dome, counteracting sodium chloride crystallization. These insights not only advance our understanding of tear film mechanics but also pave the way for predictive diagnostics in dry eye syndrome, offering a robust platform for personalized medical interventions based on individual tear film composition.

Enhancing the stability of O/W emulsions by the interactions of casein/carboxymethyl chitosan and its application in whole nutrient emulsions.

The influence of Carboxymethyl chitosan (CMCS) on the emulsification stability mechanism of casein (CN) and its effects on the stability of whole nutrient emulsions were investigated. The complex solutions of CN and CMCS were prepared and the turbidity, ultraviolet (UV) absorption spectrum, fluorescence spectrum, circular dichroism (CD) spectrum, Fourier transform infrared (FTIR) spectrum, interfacial tension and microstructural observations were used to study the inter-molecular interaction of CMCS and CN. The effects of CMCS on the emulsion stability of CN were further analyzed by particle size, ζ-potential, instability index and rheological properties. Moreover, the accelerated stability of whole nutrient emulsions prepared by CMCS and CN was evaluated. The results revealed that CN-CMCS complexes were mainly formed by hydrogen bonding. The stability of the CN-CMCS composite emulsions were improved, as evidenced by the interfacial tension decreasing from 165.96 mN/m to 158.49 mN/m, the particle size decreasing from 45.85 µm to 12.98 µm, and the absolute value of the potential increasing from 29.8 mV to 33.5 mV. The stability of whole nutrient emulsion was also significantly enhanced by the addition of CN-CMCS complexes. Therefore, CN-CMCS complex could be served as a novel emulsifier to improve the stability of O/W emulsions.

Dynamic interfacial adsorption and emulsifying performance of self-assembled coconut protein and fucoidan mixtures.

The functional properties of protein are affected by their aggregation behavior and morphology. In this study, the self-assembled coconut protein aggregates with specific morphology, including small amorphous aggregates (WLA), spherical-like aggregates (SLA) and rod-like aggregates (RLA), were regulated to form. The self-assembled process resulted in a decrease in fluorescence intensity and an increase in the surface hydrophobicity of coconut protein. Fucoidan was added to improve the stability of protein solutions, and the interfacial adsorption behavior was evaluated by dilatational rheology analysis. The results showed that the aggregation state of coconut protein affected its ability to reduce surface tension, and the interfacial layers mainly exhibited elastic property at oil-water interface (tanφ < 0.5). For macroscale analysis, the emulsions based on self-assembled coconut protein exhibited smaller droplet size, better rheological properties and centrifugal stability, especially WLA and RLA. This study may provide a reference to inspire the utilization of self-assembled coconut protein in the food industry.

Interfacial protein adsorption behavior can be connected across a wide range of timescales using the microfluidic EDGE (Edge-based droplet GEneration) tensiometer.

HYPOTHESIS: Our hypothesis is that dynamic interfacial tension values as measured by the partitioned-Edge-based Droplet GEneration (EDGE) tensiometry can be connected to those obtained with classical techniques, such as the automated drop tensiometer (ADT), expanding the range of timescales towards very short ones. EXPERIMENTS: Oil-water and air-water interfaces are studied, with whey protein isolate solutions (WPI, 2.5 - 10 wt%) as the continuous phase. The dispersed phase consists of pure hexadecane or air. The EDGE tensiometer and ADT are used to measure the interfacial (surface) tension at various timescales. A comparative assessment is carried out to identify differences between protein concentrations as well as between oil-water and air-water interfaces. FINDINGS: The EDGE tensiometer can measure at timescales down to a few milliseconds and up to around 10 s, while the ADT provides dynamic interfacial tension values after at least one second from droplet injection and typically is used to also cover hours. The interfacial tension values measured with both techniques exhibit overlap, implying that the techniques provide consistent and complementary information. Unlike the ADT, the EDGE tensiometer distinguishes differences in protein adsorption dynamics at protein concentrations as high as 10 wt% (which is the highest concentration tested) at both oil-water and air-water interfaces.

Droplet drinking in constrictions.

Droplets generated through microfluidics serve as a common platform for assembling artificial cells, which are feasibly tailored using microfluidic methodology. The ability of natural cells to undergo shape changes, such as phagocytosis, is a typical characteristic that researchers aim to mimic in artificial cells. However, simulating the deformation behavior of natural cells within droplets is exceptionally challenging. Here, this study reports a pinocytosis-like phenomenon observed in droplets, termed "droplet drinking". When droplets traverse a capillary with constrictions, the shear force from the continuous-phase fluid induces relative motion within the droplets, creating concave regions at the rear. These regions facilitate engulfing of the continuous-phase fluid, resulting in the formation of multiple emulsions. This behavior is influenced by the capillary number, and the size of the ingested droplets is governed by the interfacial tension between the two phases. The production of multicore or multi-shell emulsions can be easily accomplished by making slight adjustments to the constrictions. Furthermore, this method demonstrates the integration of reactants into pre-existing droplets, facilitating biochemical reactions. This study presents a convenient approach for generating complex emulsions and an innovative strategy for studying deformation behavior in droplet-based artificial cells.

Effect of surfactants on lactate dehydrogenase aqueous solutions: A comparative study of poloxamer 188, polysorbate 20 and 80.

The effect of three commonly used surfactants, poloxamer 188 (P188), polysorbate 20 and 80 (PS20 and PS80), on the stability of a model protein, lactate dehydrogenase (LDH), was compared in aqueous solutions. In the absence of a surfactant, protein solution revealed a gradual decrease in surface tension as a function of time. The addition of surfactant resulted in a rapid decrease in the surface tension. This suggested that the surface behavior was dictated by the surfactant. PS20 and PS80 were more effective than P188 in preventing LDH adsorption on the solution surface. The advantage of polysorbates over P188 was also evident from the higher LDH tetramer recovery after shaking (room temperature, 30 h), especially when the surfactants were used at concentrations ≤ 0.01% w/v. However, PS20 and PS80 accelerated protein unfolding during quiescent storage at 40 °C. Based on circular dichroism results, polysorbates perturbed the tertiary structure of LDH but not the secondary structure, while P188 did not impact the protein structure and stability. Polysorbates were more effective in stabilizing LDH against mechanical stress (shaking), but their adverse effects on protein conformational stability need to be carefully evaluated.

Dual function surfactants for pharmaceutical formulations: The case of surface active and antibacterial 1-tolyl alkyl biguanide derivatives.

One interesting field of research in the view of developing novel surfactants for pharmaceutical and cosmetic applications is the design of amphiphiles showing further bioactive properties in addition to those commonly displayed by surface-active compounds. We propose here the chemical synthesis, and characterization of 1-o-tolyl alkyl biguanide derivatives, having different lengths of the hydrocarbon chain (C3, C6, and C10), and showing surface active and antibacterial/disinfectant activities toward both Gram-positive and Gram-negative bacteria. Both surface active properties in terms of critical micelle concentration (CMC) and surface tension at CMC (γCMC), as well as the antimicrobial activity in terms of minimum inhibitory concentrations (MICs), were strongly dependent on the length of the hydrocarbon chain. Particularly, the C6 and C10 derivatives have a good ability to decrease surface tension (γCMC <40 mN/m) at low concentrations (CMC < 12 mM) and a satisfactory antibacterial effect (MIC values between 0.230 and 0.012 mM against S. aureus strains and between 0.910 and 0.190 against P.aeruginosa strains). Interestingly, these compounds showed a disinfectant activity at the tested concentrations that was comparable to that of the reference compound chlorhexidine digluconate. All these results support the possible use of these amphiphilic compounds as antibacterial agents and disinfectants in pharmaceutical or cosmetic formulations.

Effects of steaming on physicochemical and emulsification properties of gum arabic.

Gum arabic finds extensive application and typically undergoes sterilization prior to utilization in the food industry. This study explored the impact of steam sterilization temperature and duration on the physicochemical and emulsification characteristics of gum arabic, accompanied by proposed mechanisms elucidating observed effects. The results showed that when gum arabic was treated with high temperature sterilization (110 °C âˆ¼ 140 °C), the emulsion prepared turned unstable. The interfacial tension decreased from 8.26 mN/m to 6.77 mN/m after sterilization, while the elastic modulus decreased from 23.65 mN/m to 16.16 mN/m. Moreover, the circular dichroic chromatographic results indicated that the arabinogalactan protein (AGP) structure of gum arabic was more relaxed after high temperature treatment with ß-sheets content decreased from 36.2 % to 29.8 % and random coil content increased from 41.3 % to 51.8 %. Quartz crystal microbalance with dissipation (QCM-D) results demonstrated that emulsion surface film thickness and toughness decreased after sterilization treatment of gum arabic. The study indicates that high temperature sterilization may change protein structure in gum arabic and reduce the stability of prepared emulsions.

Mechanisms of Air Entraining of Proteins in Cementitious Materials.

While few prior studies examined the air-entraining properties of proteins in cementitious materials, the underlying mechanisms of proteins' air entraining and the interactions between proteins and cement have not been studied in the past. The significance of this article is to address this knowledge gap by investigating the effect of proteins on relevant factors that affect air entraining in cement paste and establishing an understanding of the mechanism of air entrainment with proteins. These factors include the surface tension of pore solution, protein adsorption on cement particles, cement paste hydrophobization, and flow of fresh paste. Thirteen different proteins were used to investigate the effect of a wide range of protein characteristics on air entraining. Proteins decreased the pore solution surface tension to different degrees. At low concentrations, the adsorption of proteins on cement particles slightly affected the pore solution surface tension. Protein adsorption on cement particles showed a wide range of adsorption isotherms. Proteins generally increased the flow of paste due to electrostatic repulsion between cement particles because of the adsorption of negatively charged proteins on cement particles, as well as the ball-bearing effect of bubbles in fresh paste. The surface hydrophobicity was increased in pastes with proteins. A detailed microcomputed tomography (micro-CT) analysis showed very different air void microstructures in pastes with various proteins. While a relatively strong correlation was observed between air void porosity and surface hydrophobicity, the correlation between air void porosity and the surface tension of pore solution was weak. This indicates that the accumulation of hydrophobized cement particles on the air bubble in the fresh paste, refered to as the Pickering effect, is the main mechanism of air entraining of proteins in the paste. It was shown that a high air void porosity occurs in an intermediate range of flow.

Evidence of Surface-Tension Lowering of Atmospheric Aerosols by Organics from Field Observations in an Urban Atmosphere: Relation to Particle Size and Chemical Composition.

Surface-active organics lower the aerosol surface tension (σs/a), leading to enhanced cloud condensation nuclei (CCN) activity and potentially exerting impacts on the climate. Quantification of σs/a is mainly limited to laboratory or modeling work for particles with selected sizes and known chemical compositions. Inferred values from ambient aerosol populations are deficient. In this study, we propose a new method to derive σs/a by combining field measurements made at an urban site in northern China with the κ-Köhler theory. The results present new evidence that organics remarkably lower the surface tension of aerosols in a polluted atmosphere. Particles sized around 40 nm have an averaged σs/a of 53.8 mN m-1, while particles sized up to 100 nm show σs/a values approaching that of pure water. The dependence curve of σs/a with the organic mass resembles the behavior of dicarboxylic acids, suggesting their critical role in reducing the surface tension. The study further reveals that neglecting the σs/a lowering effect would result in lowered ultrafine CCN (diameter <100 nm) concentrations by 6.8-42.1% at a typical range of supersaturations in clouds, demonstrating the significant impact of surface tension on the CCN concentrations of urban aerosols.

The essential role of aggregation for the emulsifying ability of a fungal CYS-rich protein.

Biosurfactants are in demand by the global market as natural commodities suitable for incorporation into commercial products or utilization in environmental applications. Fungi are promising producers of these molecules and have garnered interest also for their metabolic capabilities in efficiently utilizing recalcitrant and complex substrates, like hydrocarbons, plastic, etc. Within this framework, biosurfactants produced by two Fusarium solani fungal strains, isolated from plastic waste-contaminated landfill soils, were analyzed. Mycelia of these fungi were grown in the presence of 5% olive oil to drive biosurfactant production. The characterization of the emulsifying and surfactant capacity of these extracts highlighted that two different components are involved. A protein was purified and identified as a CFEM (common in fungal extracellular membrane) containing domain, revealing a good propensity to stabilize emulsions only in its aggregate form. On the other hand, an unidentified cationic smaller molecule exhibits the ability to reduce surface tension. Based on the 3D structural model of the protein, a plausible mechanism for the formation of very stable aggregates, endowed with the emulsifying ability, is proposed. KEY POINTS: • Two Fusarium solani strains are analyzed for their surfactant production. • A cationic surfactant is produced, exhibiting the ability to remarkably reduce surface tension. • An identified protein reveals a good propensity to stabilize emulsions only in its aggregate form.

Evaluation of surface tensions and root-dentin surface contact angles of different endodontic irrigation solutions.

BACKGROUND: Surface tension and contact angle properties, which play a crucial role in determining the effectiveness of irrigation solutions in penetrating dentin surfaces and dentin tubules, are highly important for the development of new irrigation solutions and their preferences. The aim of the current study was to compare the surface tension and contact angle properties of different irrigation solutions used in endodontics, both on the dentin surface and within dentin tubules. METHODS: In this study, the contact angles and surface tensions of 5.25% sodium hypochlorite (NaOCl), 17% ethylenediaminetetraacetic acid (EDTA), 2% chlorhexidine (CHX), 5% boric acid (BA), 0.02% hypochlorous acid (HOCl), 0.2% chlorine dioxide (ClO2), Biopure MTAD, QMix solutions, and distilled water (control group) were measured. Measurements were conducted using a goniometer device (Attension Theta Lite Tensiometer, Biolin Scientific, USA), employing the sessile drop method for contact angle measurements on pre-prepared dentin surfaces, and the pendant drop method for surface tension. RESULTS: Contact angle measurements revealed no statistically significant differences between the contact angle values of MTAD, ClO2, and CHX or between NaOCl, QMix, BA, and HOCl (p > 0.05). However, EDTA exhibited a significantly greater contact angle than did MTAD, ClO2, CHX, NaOCl, QMix, BA, and HOCl (p < 0.05). Furthermore, the contact angle of dentin with distilled water was greater than that with all other solutions tested (p < 0.05). Surface tension measurements revealed that the surface tension values of QMix and MTAD were statistically similar (p > 0.05). CHX exhibited lower surface tension than distilled water and HOCl (p < 0.05), and it also had lower surface tension than ClO2, NaOCl, and BA (p < 0.05). Additionally, the surface tension of the samples treated with EDTA was greater than that of all other solutions tested (p < 0.05). CONCLUSION: The direct linear relationship between the surface tension of liquids and contact angles on different surfaces may not always hold true, and these values should be considered independently for each solution on various surfaces. Considering the contact angles and surface tension properties of irrigation solutions with root canal dentin, it can be suggested for clinical use that ClO2 could be recommended over NaOCl, and similarly, BA could be recommended over EDTA.

Mechanics of human embryo compaction.

The shaping of human embryos begins with compaction, during which cells come into close contact1,2. Assisted reproductive technology studies indicate that human embryos fail compaction primarily because of defective adhesion3,4. On the basis of our current understanding of animal morphogenesis5,6, other morphogenetic engines, such as cell contractility, could be involved in shaping human embryos. However, the molecular, cellular and physical mechanisms driving human embryo morphogenesis remain uncharacterized. Using micropipette aspiration on human embryos donated to research, we have mapped cell surface tensions during compaction. This shows a fourfold increase of tension at the cell-medium interface whereas cell-cell contacts keep a steady tension. Therefore, increased tension at the cell-medium interface drives human embryo compaction, which is qualitatively similar to compaction in mouse embryos7. Further comparison between human and mouse shows qualitatively similar but quantitively different mechanical strategies, with human embryos being mechanically least efficient. Inhibition of cell contractility and cell-cell adhesion in human embryos shows that, whereas both cellular processes are required for compaction, only contractility controls the surface tensions responsible for compaction. Cell contractility and cell-cell adhesion exhibit distinct mechanical signatures when faulty. Analysing the mechanical signature of naturally failing embryos, we find evidence that non-compacting or partially compacting embryos containing excluded cells have defective contractility. Together, our study shows that an evolutionarily conserved increase in cell contractility is required to generate the forces driving the first morphogenetic movement shaping the human body.

Investigating the mechanism of interfacial tension reduction through the combination of low-salinity water and bacteria.

In the enhanced oil recovery (EOR) process, interfacial tension (IFT) has become a crucial factor because of its impact on the recovery of residual oil. The use of surfactants and biosurfactants can reduce IFT and enhance oil recovery by decreasing it. Asphaltene in crude oil has the structural ability to act as a surface-active material. In microbial-enhanced oil recovery (MEOR), biosurfactant production, even in small amounts, is a significant mechanism that reduces IFT. This study aimed to investigate fluid/fluid interaction by combining low biosurfactant values and low-salinity water using NaCl, MgCl2, and CaCl2 salts at concentrations of 0, 1000, and 5000 ppm, along with Geobacillus stearothermophilus. By evaluating the IFT, this study investigated different percentages of 0, 1, and 5 wt.% of varying asphaltene with aqueous bulk containing low-salinity water and its combination with bacteria. The results indicated G. Stearothermophilus led to the formation of biosurfactants, resulting in a reduction in IFT for both acidic and basic asphaltene. Moreover, the interaction between asphaltene and G. Stearothermophilus with higher asphaltene percentages showed a decrease in IFT under both acidic and basic conditions. Additionally, the study found that the interaction between acidic asphaltene and G. stearothermophilus, in the presence of CaCl2, NaCl, and MgCl2 salts, resulted in a higher formation of biosurfactants and intrinsic surfactants at the interface of the two phases, in contrast to the interaction involving basic asphaltene. These findings emphasize the dependence of the interactions between asphaltene and G. Stearothermophilus, salt, and bacteria on the specific type and concentration of asphaltene.

Surface activity of Lupinus angustifolius (blue lupine) seed extracts.

Surface tension (γeq) of the seed extracts of four lupine cultivars showed values in the range 44.9-46.4 mN/m. The surface compression elasticity (E') of the adsorbed layers and foaming capacity (FC) also showed similar values (E' âˆ¼ 30 mN/m, FC âˆ¼ 100%). The effect of defatting prior to extraction at pH 8.5 depends on the solvent employed - hexane and dichloromethane improved the subsequent protein extraction yield, while ethanol reduced it. The effect of defatting on surface tension could be positive (for hexane and ethanol) or negative (for dichloromethane). Generally, defatting improved the surface compression rheological and foaming parameters. On the other hand, fractionation of the extracts obtained at pH 8.5 from hexane-defatted seeds did not improve significantly the surface activity parameters. Some improvement with respect to the unfractionated extracts was observed only for the extracts of undefatted seeds. γeq, E', E" and FC isotherms confirm the surfactant-like behavior of the lupine seed extracts.