Surface tension in biological systems - a common problem with a variety of solutions.

Water is of fundamental importance to living organisms, not only as a universal solvent to maintain metabolic activity but also due to the effects the physical properties of water have on different organismal structures. In this review, we explore some examples of how living organisms deal with surfaces covered with or in contact with water. While we do not intend to describe all possible forms of interactions in every minute detail, we would like to draw attention to this intriguing interdisciplinary subject and discuss the positive and negative effects of the interaction forces between water molecules and organisms. Topics explored include locomotion on water, wettability of surfaces, benefits of retaining a film of air while submerged (Salvinia effect), surface tension of water inhibiting air-breathing, accumulation of water in small tubes, surface tension in non-mammalian and mammalian respiratory systems. In each topic, we address the importance of interactions with water and the adaptations seen in an organism to solve the surface-related challenges, trying to explore the different selective pressures acting onto different organisms allowing exploring or compensating these surface-related interactions.

Biosurfactant Production from Pineapple Waste and Application of Experimental Design and Statistical Analysis.

The use of non-conventional carbon sources for biosurfactant-producing microorganisms is a promising alternative in fermentation to substitute costly substrates. So, the current research used pineapple peel as a cost-effective and renewable substrate because of its rich composition in minerals and sugars and high availability. Following a 22 full factorial design, a bacterial strain of Bacillus subtilis produced biosurfactants in fermentative media containing different concentrations of glucose and concentrated pineapple peel juice (CPPJ). The influence of these two independent variables was evaluated according to three different responses: surface tension reduction rate (STRR), emulsification index (EI24), and concentration of semi-purified biosurfactant (SPB). The maximum value for STRR (57.63%) was obtained in media containing 0.58% glucose (w/v) and 5.82% CPPJ (v/v), while the highest EI24 response (58.60%) was observed at 2% glucose (w/v) and 20% CPPJ (v/v) and maximum SPB (1.28 g/L) at 3.42% glucose (w/v) and 34.18% CPPJ (v/v). Statistical analysis indicated that the CPPJ variable mostly influenced the STRR and SPB responses, whereas the EI24 was significantly influenced by pineapple peel juice and glucose contents.

Characterization of biosurfactant produced in response to petroleum crude oil stress by Bacillus sp. WD22 in marine environment.

Bacillus sp. WD22, previously isolated from refinery effluent, degraded 71% of C8 hydrocarbons present in 1.0% v/v PCO in seawater (control medium), which reduced to 16.3%, on addition of yeast extract. The bacteria produced a biosurfactant in both media, whose surface was observed to be amorphous in nature under FESEM-EDAX analysis. The biosurfactant was characterized as a linear surfactin by LCMS and FT-IR analysis. The critical micelle concentration was observed as 50 mg/L and 60 mg/L at which the surface tension of water was reduced to 30 mN/m. Purified biosurfactant could emulsify petroleum-based oils and vegetable oils effectively and was stable at all tested conditions of pH, salinity and temperature up to 80 °C. The biosurfactant production was found to be mixed growth associated in control medium, while it was strictly growth associated in medium with yeast extract as studied by the Leudeking-Piret model.

Osmotic Method for Calculating Surface Pressure of Monolayers in Molecular Dynamics Simulations.

Surface pressure is a fundamental thermodynamic property related to the activity of molecules at interfaces. In molecular simulations, it is typically calculated from its definition: the difference between the surface tension of the air-water and air-surfactant interfaces. In this Letter, we show how to connect the surface pressure with a two-dimensional osmotic pressure and how to take advantage of this analogy to obtain a practical method of calculating surface pressure-area isotherms in molecular simulation. As a proof-of-concept, compression curves of zwitterionic and ionic surfactant monolayers were obtained using the osmotic approach and the curves were compared with the ones from the traditional pressure tensor-based scheme. The results shown an excellent agreement between both alternatives. Advantageously, the osmotic approach is simple to use and allows to obtain the surface pressure-area isotherm on the fly with a single simulation using equilibration stages.

Dynamical shapes of droplets of cyclodextrin-surfactant solutions.

We present a series of experiments with droplets of aqueous cyclodextrin-surfactant solutions, in which the volume is reduced after the equilibrium spherical shape is reached. The final shape of the drop after this perturbation is found to be dependent on the concentration of inclusion complexes in the bulk of the solution. These inclusion complexes are formed by two cyclodextrin molecules and one surfactat molecule. We propose a model to describe these dynamical processes. Dipole-dipole interactions on the surface of the drop trigger a competition between water surface tension and dipole-dipole interaction energies. The results of the model reproduce the spherical and rod-like shapes found in the experiments.

Actin protein inside DMPC GUVs and its mechanical response to AC electric fields.

Cells are dynamic systems with complex mechanical properties, regulated by the presence of different species of proteins capable to assemble (and disassemble) into filamentous forms as required by different cells functions. Giant unilamellar vesicles (GUVs) of DMPC (1,2-dimyristoyl-sn-glycero-3-phosphocholine) are systems frequently used as a simplified model of cells because they offer the possibility of assaying separately different stimuli, which is no possible in living cells. Here we present a study of the effect of acting protein on mechanical properties of GUVs, when the protein is inside the vesicles in either monomeric G-actin or filamentous F-actin. For this, rabbit skeletal muscle G-actin is introduced inside GUVs by the electroformation method. Protein polymerization inside the GUVs is promoted by adding to the solution MgCl2 and the ion carrier A23187 to allow the transport of Mg+2 ions into the GUVs. To determine how the presence of actin changes the mechanical properties of GUVs, the vesicles are deformed by the application of an AC electric field in both cases with G-actin and with polymerized F-actin. The changes in shape of the vesicles are characterized by optical microscopy and from them the bending stiffness of the membrane are determined. It is found that G-actin has no appreciable effect on the bending stiffness of DMPC GUVs, but the polymerized actin makes the vesicles more rigid and therefore more resistant to deformations. This result is supported by evidence that actin filaments tend to accumulate near the membrane.

Triglyceride Lenses at the Air-Water Interface as a Model System for Studying the Initial Stage in the Biogenesis of Lipid Droplets.

Lipid droplets (LD) are intracellular structures consisting of an apolar lipid core, composed mainly of triglycerides (TG) and steryl esters, coated by a lipid-protein mixed monolayer. The mechanisms underlying LD biogenesis at the endoplasmic reticulum membrane are a matter of many current investigations. Although models explaining the budding-off of protuberances of phase-segregated TG inside bilayers have been proposed recently, the assumption of such initial blisters needs further empirical support. Here, we study mixtures of egg phosphatidylcholine (EPC) and TG at the air-water interface in order to describe some physical properties and topographic stability of TG bulk structures in contact with interfaces. Brewster angle microscopy images revealed the appearance of microscopic collapsed structures (CS) with highly reproducible lateral size (∼1 µm lateral radius) not varying with lateral packing changes and being highly stable at surface pressures (π) beyond collapse. By surface spectral fluorescence microscopy, we were able to characterize the solvatochromism of Nile Red both in monolayers and inside CS. This allowed to conclude that CS corresponded to a phase of liquid TG and to characterize them as lenses forming a three-phase (oil-water-air) system. Thereby, the thicknesses of the lenses could be determined, observing that they were dramatically flattened when EPC was present (6-12 nm compared to 30-50 nm for lenses on EPC/TG and TG films, respectively). Considering the shape of lenses, the interfacial tensions, and the Neumann's triangle, this experimental approach allows one to estimate the oil-water interfacial tension acting at each individual microscopic lens and at varying compression states of the surrounding monolayer. Thus, lenses formed on air-water Langmuir films can serve to assess variables of relevance to the initial step of LD biogenesis, such as the degree of dispersion of excluded-TG phase and shape, spatial distribution, and oil-water interfacial tension of lenses.

A low-cost brewery waste as a carbon source in bio-surfactant production.

This work aims to produce bio-surfactant using a brewery waste (trub) as a strategy to reduce production costs related to the substrate, as well as to provide an eco-friendly destination for this residue. Trub is obtained during the boiling of the wort, being mainly composed of proteins and reducing sugars. To evaluate important process parameters on bio-surfactant production, a full factorial design (24) was elaborated, having agitation rate and concentrations of trub, yeast extract, and peptone as independent variables. The highest bio-surfactant concentration achieved was 100.76 mg L-1, where FTIR and Maldi-ToF-MS confirmed functional groups characteristic of peptides and isomers of surfactin in the bio-surfactant extract. Trub, agitation and yeast extract showed statistically significant effects on the response variable (surface tension), where an increase in the agitation rate and in the concentration of yeast extract demonstrated a positive impact on the production of bio-surfactant.

Fungal biosurfactants, from nature to biotechnological product: bioprospection, production and potential applications.

Biosurfactants are in demand by the global market as natural commodities that can be added to commercial products or use in environmental applications. These biomolecules reduce the surface/interfacial tension between fluid phases and exhibit superior stability to chemical surfactants under different physico-chemical conditions. Biotechnological production of biosurfactants is still emerging. Fungi are promising producers of these molecules with unique chemical structures, such as sophorolipids, mannosylerythritol lipids, cellobiose lipids, xylolipids, polyol lipids and hydrophobins. In this review, we aimed to contextualize concepts related to fungal biosurfactant production and its application in industry and the environment. Concepts related to the thermodynamic and physico-chemical properties of biosurfactants are presented, which allows detailed analysis of their structural and application. Promising niches for isolating biosurfactant-producing fungi are presented, as well as screening methodologies are discussed. Finally, strategies related to process parameters and variables, simultaneous production, process optimization through statistical and genetic tools, downstream processing and some aspects of commercial products formulations are presented.

Impact of electrostatic potential on microcapsule-formation and physicochemical analysis of surface structure: Implications for therapeutic cell-microencapsulation.

Cell-encapsulation is used for preventing therapeutic cells from being rejected by the host. The technology to encapsulate cells in immunoprotective biomaterials, such as alginate, commonly involves application of an electrostatic droplet generator for reproducible manufacturing droplets of similar size and with similar surface properties. As many factors influencing droplet formation are still unknown, we investigated the impact of several parameters and fitted them to equations to make procedures more reproducible and allow optimal control of capsule size and properties. We demonstrate that droplet size is dependent on an interplay between the critical electric potential (Uc,), the needle size, and the distance between the needle and the gelation bath, and that it can be predicted with the equations proposed. The droplet formation was meticulously studied and followed by a high-speed camera. The X-ray photoelectron analysis demonstrated optimal gelation and substitution of sodium with calcium on alginate surfaces while the atomic force microscopy analysis demonstrated a low but considerable variation in surface roughness and low surface stiffness. Our study shows the importance of documenting critical parameters to guarantee reproducible manufacturing of beads with constant and adequate size and preventing batch-to-batch variations.

SGTPy: A Python Code for Calculating the Interfacial Properties of Fluids Based on the Square Gradient Theory Using the SAFT-VR Mie Equation of State.

In this work, we showcase SGTPy, a Python open-source code developed to calculate interfacial properties (interfacial concentration profiles and interfacial or surface tension) for pure fluids and fluid mixtures. SGTPy employs the Square Gradient Theory (SGT) coupled to the Statistical Associating Fluid Theory of Variable Range employing a Mie potential (SAFT-VR-Mie). SGTPy uses standard Python numerical packages (i.e., NumPy, SciPy) and can be used under Jupyter notebooks. Its features are the calculation of phase stability, phase equilibria, interfacial properties, and the optimization of the SGT and SAFT parameters for vapor-liquid, liquid-liquid and vapor-liquid-liquid equilibria for pure fluids and multicomponent mixtures. Phase equilibrium calculations include two-phase and multiphase flash, bubble and dew points, and the tangent plane distance. For the computation of interfacial properties, SGTPy incorporates several options to solve the interfacial concentration, such as the path technique, an auxiliary time function, and orthogonal collocation. Additionally, the SGTPy code allows the inclusion of subroutines from other languages (e.g., Fortran, and C++) through Cython and f2py Python tools, which opens the possibility for future extensions or recycling tested and optimized subroutines from other codes. Supporting Information includes a review of the theoretical expressions required to couple SAFT-VR-Mie equation of state with the SGT. The use and capabilities of SGTPy are illustrated through step by step examples written on Jupyter notebooks for the cases of pure fluids and binary and ternary mixtures in bi- and three- phasic equilibria. The SGTPy code can be downloaded from https://github.com/gustavochm/SGTPy.

Evaluation of biosurfactant production potential of Lysinibacillus fusiformis MK559526 isolated from automobile-mechanic-workshop soil.

BACKGROUND: Biosurfactants are amphipathic biological compounds with surface active potential and are produced by many microorganisms. Biosurfactant production by Lysinibacillus fusiformis MK559526 isolated from automobile-mechanic-shop soil was investigated with a view to assessing its potential for production and potential for optimization. MATERIALS AND METHODS: Effects of carbon and nitrogen sources, pH, temperature and incubation periods on biosurfactant production were evaluated with a view to optimizing the processes. Fourier Transform Infra-Red absorption peaks and Gas chromatography mass spectrometry were used to determine the functional groups of the chemical make-up and the chemical profile of the biosurfactant respectively. RESULTS: Lysinibacillus fusiformis surfactant had emulsification index of 65.15 ± 0.35 %, oil displacement of 2.7 ± 0.26 mm, zone of haemolysis of 7.3 ± 0.16 mm and a positive drop collapse test. Optimized culture conditions for biosurfactant production: temperature, 35 ºC; pH, 7.0; starch solution, 40 g/L and urea, 1.5 g/L showed a reduction in surface tension to 28.46 ± 1.11 mN/m and increased emulsification index to 93.80 ± 0.41 %. Maximum biosurfactant production of 2.92 ± 0.04 g/L was obtained after 72 h. The biosurfactant contained peptides and fatty acids. The predominant fatty acid was 9-Octadecenoic acid (80.80%). CONCLUSIONS: The above results showing high emulsification potential and remarkable reduction in the surface tension are good biosurfactant attributes. Consequently, Lysinibacillus fusiformis MK559526 is a good candidate for biosurfactant production.

Biosurfactant production of Piper hispidum endophytic fungi.

AIMS: To evaluate the production of biosurfactants by fungi isolated from the Amazonian species Piper hispidum (Piperaceae), and to determine the physico-chemical properties of the crude biosurfactant obtained from the most promising fungi. METHODS AND RESULTS: A total of 117 endophytic fungi were isolated, and 50 were used to verify the production of biosurfactants. Of these, eight presented positive results in the drop collapse test, and emulsification index ranging from 20 to 78%. The most promising fungi, Ph III 23L and Ph II 22S (identified as Aspergillus niger and Glomerella cingulata, respectively) were recultivated for extraction and analysis of the biosurfactant's physico-chemical characteristics. The cultivation broth that presented the greatest decrease in surface tension (36%) was that of the A. niger, which reduced it from 68·0 to 44·0 mN m-1 . The lowest critical micellar concentration value was found for the same endophyte (14·93 mg ml-1 ). CONCLUSIONS: Endophytes of P. hispidum proved to be interesting producers of biosurfactants and presented promising physico-chemical characteristics for applications in diverse industrial sectors. SIGNIFICANCE AND IMPACT OF THE STUDY: Piper hispidum endophytic fungi can be used as a new source of biosurfactants, as these molecules present a significant market due to their wide industrial applications.

Interactions of ß-carotene with WPI/Tween 80 mixture and oil phase: Effect on the behavior of O/W emulsions during in vitro digestion.

This study investigated the impact of adding ß-carotene on the structure of fresh O/W emulsions with different oil phase (sunflower oil-LCT or NEOBEE®1053-MCT) and emulsifiers (WPI, Tween 80 - T80 or WPI/T80 mixture). In this sense, the behavior of emulsions through the gastrointestinal tract, the stability and bioaccessibility of ß-carotene were also assessed. The ß-carotene reduced the interfacial tension of the LCT/MCT-water systems. The addition of ß-carotene promoted an increase of viscoelasticity of LCT/MCT-T80 (0.5%WPI/0.5%T80 and 1%T80 w/w) interfaces, but an increase of WPI content reduced the viscoelasticity of interfacial layers (LCT/MCT-1% WPI). These changes in the interface properties influenced the mean droplet size and ζ-potential of the fresh emulsions. LCT systems presented similar bioaccessibility/stability of ß-carotene. However, ß-carotene entrapped within protein-coated MCT droplets was more stable than within T80-MCT systems. Our results show that ß-carotene interacted with other ingredients of emulsions changing their properties and behavior under gastrointestinal tract as well as the stability/bioaccessibility of ß-carotene.

Physicochemical properties, droplet size and volatility of dicamba with herbicides and adjuvants on tank-mixture.

The adoption of dicamba-tolerant soybean varieties has increased the concern and demand for new drift and volatility reduction technologies. Potential spray nozzles and adjuvants should be studied to determine its effects on drift and volatility of dicamba tank-mixtures. The objective of this study was to evaluate physicochemical characteristics of spray solutions containing dicamba; to analyze droplet size effect with air induction nozzles; and to assess dicamba volatilization on soybean plants with a proposed methodology. Treatments included dicamba only and mixtures with herbicides and adjuvants. Dicamba mixed with lecithin + methyl soybean oil + ethoxylated alcohol adjuvant had the greatest efficacy potential among treatments considering tank-mixture pH, surface tension, contact angle and droplet size. The MUG11003 nozzle produced the coarsest droplet size and was better suited for drift management among nozzle types. The proposed volatilization methodology successfully indicated dicamba volatilization in exposed soybean plants and among the evaluated treatments, it showed greater volatilization for dicamba with glyphosate + lecithin + propionic acid adjuvant.

Physicochemical and functional properties of native and modified agave fructans by acylation.

Native agave fructans were modified by an acylation reaction with lauric acid. Native and modified fructans were characterized using NMR, FTIR and various physicochemical and functional properties at different pHs were evaluated. NMR and FTIR spectra demonstrated the incorporation of lauric acid in the molecular structure of fructans. Modified agave fructans exhibited a color, moisture and water activity similar to native fructans, but properties such as solubility, swelling capacity, emulsifying activity and foam capacity were significantly modified by the acylation reaction mainly when the samples were analyzed at different pHs. The thermogram of the acylated fructans evidenced significant changes in thermal properties when compared with native fructans and acylated fructans were able to form micellar aggregates. In general, modified fructans showed improved functional properties in comparison with native fructans representing an important opportunity to improve the functionality of the foods in which it is incorporated.

Development of chitosan nanocapsules containing essential oil of Matricaria chamomilla L. for the treatment of cutaneous leishmaniasis.

Matricaria chamomilla L. has been used for centuries in many applications, including antiparasitic activity. Leishmaniasis is a parasitic disease, with limited treatments, due to high cost and toxicity. Thus, there is a need to develop new treatments, and in this context, natural products are targets of these researches. We report the development of chitosan nanocapsules containing essential oil of M. chamomilla (CEO) from oil-in-water emulsions using chitosan modified with tetradecyl chains as biocompatible shell material. The nanocapsules of CEO (NCEO) were analyzed by optical microscopy and dynamic light scattering, which revealed spherical shape and an average size of 800 nm. Successful encapsulation of CEO was further confirmed by fluorescence microscopy observations taking advantage of the autofluorescence properties of CEO. The encapsulation efficiency was around 90%. The entrapment of CEO reduced its cytotoxicity towards normal cells. On the other hand, the CEO was active against promastigotes and intracellular amastigotes, exhibiting IC50 of 3.33 µg/mL and 14.56 µg/mL, respectively, while NCEO showed IC50 for promastigotes of 7.18 µg/mL and for intracellular amastigotes of 14.29 µg/mL. These results demonstrate that encapsulation of CEO in nanocapsules using an alkylated chitosan biosurfactant as a "green" stabilizer is a promising therapeutic strategy to treat leishmaniasis.

Comparison of mono-rhamnolipids and di-rhamnolipids on microbial enhanced oil recovery (MEOR) applications.

Rhamnolipids (RMLs) have more effectiveness for specific uses according to their homologue proportions. Thus, the novelty of this work was to compare mono-RMLs and di-RMLs physicochemical properties on microbial enhanced oil recovery (MEOR) applications. For this, RML produced by three strains of Pseudomonas aeruginosa containing different homologues proportion were used: a mainly mono-RMLs producer (mono-RMLs); a mainly di-RMLs producer (di-RMLs), and the other one that produces relatively balanced amounts of mono-RML and di-RML homologues (mono/di-RML). For mono-RML, the most abundant molecules were Rha-C10 C10 (m/z 503.3), for di-RML were RhaRha-C10 C10 (m/z 649.4) and for Mono/di-RML were Rha-C10 C10 (m/z 503.3) and RhaRha-C10 C10 (m/z 649.4). All RMLs types presented robustness under high temperature and variation of salinity and pH, and high ability for oil displacement, foam stability, wettability reversal and were classified as safe for environment according to the European Union Directive No. 67/548/EEC. For all these properties, it was observed a highlight for mono-RML. Mono-RML presented the lowest surface tension (26.40 mN/m), interfacial tension (1.14 mN/m), and critical micellar concentration (CMC 27.04 mg/L), the highest emulsification index (EI24 100%) and the best wettability reversal (100% with 25 ppm). In addition, mono-RML showed the best acute toxicity value (454 mg/L), making its application potential even more attractive. Based on the results, it was concluded that all RMLs homologues studied have potential for MEOR applications. However, results showed that mono-RML stood out and have the best mechanism of oil incorporation in micelles due their most effective surface-active physicochemical features.

The dynamics of shapes of vesicle membranes with time dependent spontaneous curvature.

We study the time evolution of the shape of a vesicle membrane under time-dependent spontaneous curvature by means of phase-field model. We introduce the variation in time of the spontaneous curvature via a second field which represents the concentration of a substance that anchors with the lipid bilayer thus changing the local curvature and producing constriction. This constriction is mediated by the action on the membrane of an structure resembling the role of a Z ring. Our phase-field model is able to reproduce a number of different shapes that have been experimentally observed. Different shapes are associated with different constraints imposed upon the model regarding conservation of membrane area. In particular, we show that if area is conserved our model reproduces the so-called L-form shape. By contrast, if the area of the membrane is allowed to grow, our model reproduces the formation of a septum in the vicinity of the constriction. Furthermore, we propose a new term in the free energy which allows the membrane to evolve towards eventual pinching.

The stabilizing effect of cellulose crystals in O/W emulsions obtained by ultrasound process.

The encapsulation of lipophilic bioactive compounds, such as flaxseed oil, is usually done using O/W emulsions as carrier matrix. The aim of this study was to understand the stabilization mechanism of micro-nano cellulose crystals produced from acid hydrolysis in O/W emulsion. Effects of emulsification process conditions using ultrasound on the cellulose particles properties were evaluated varying the proportion of oil-cellulose particles in the emulsion formulation. Cellulose structure did not change using different conditions of emulsification and X-ray diffraction showed major presence of cellulose I. Particle size distribution of cellulose was bimodal and mean particle size reduced after hydrolysis. Emulsions stabilized by cellulose were opaque, homogeneous and showed good kinetic stability. The largest microcrystals were displayed between the oil droplets, preventing the flocculation of the droplets while smaller particles were adsorbed on the oil-water interface. The mechanism of droplets stabilization was not associated to the reduction of interfacial tension. Stabilization was associated to significant effect of electrostatic repulsion and increase in viscosity. Moreover, the flaxseed oil droplets were completely surrounded by cellulose nanocrystals, showing also Pickering-type stabilization. Therefore, emulsions with cellulose crystals were stabilized by different mechanisms and have interesting properties and characteristics for the protection of lipophilic compounds that could be applied in food and cosmetics products.