Low Surfactant Concentrations Research Articles

Binding dynamics of linear alkyl-sulfates of different chain lengths on a protein surface

Sulfate-based anionic surfactants, such as sodium dodecyl sulfate (SDS), are widely recognized for their ability to deactivate and denature proteins. Despite extensive research, the molecular mechanisms governing the preferential binding of surfactants to protein surfaces remain incompletely understood. This study employs molecular dynamics (MD) simulations to investigate interactions between subtilisin E (SubE) and two anionic surfactants: SDS and sodium hexyl sulfate (SHS), with SHS possessing alkyl chains half the length of SDS. Simulations conducted at a low surfactant concentration (0.5% w/v) reveal distinct binding dynamics and interaction preferences of these surfactants with the SubE protein surface. Results demonstrate that the presence of SDS and SHS does not induce significant alterations in the overall secondary structure of SubE compared to simulations in pure water. The residue-level analysis identifies SDS as having greater contact with surface residues than SHS, particularly in helical and turn regions of SubE. SDS exhibits persistent binding sites in proximity to active site residues, suggesting potential implications for the observed experimental reduction in enzymatic activity. Dynamic interaction analysis indicates rapid and sustained binding of nearly all surfactant molecules to the protein within the initial 10-25 ns, with SDS displaying more transient interactions compared to SHS. Specific interaction patterns are observed between SDS and catalytic triad residues Asp32, His64, and Ser221, as well as Asn155 in the oxyanion hole, contrasting with the minimal interaction observed with SHS. These findings offer insights into the molecular mechanisms underlying surfactant-protein interactions, underscoring opportunities for engineering protein stability and functionality in the presence of surfactants.

Optimisation of the carvacrol encapsulation method into PHBV nanoparticles

The need of sustainable food packaging preserving food from degradation conducted to increase research on active packaging using essential oil, as carvacrol, for their antimicrobial and antioxidant properties. The encapsulation of this kind of volatile molecules is necessary and nanoencapsulation into biopolymers, as poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) showed an increasing interest as a green solution, although this method again need to be improved. In this study, a full experimental design was developed to select the best method (nanoprecipitation and emulsification) and operating conditions (PHBV molecular weight, surfactant concentration, carvacrol/PHBV ratio and Aqueous/Organic phase volume ratios) to encapsulate carvacrol into PHBV. In this purpose, for each tested conditions, encapsulation efficiency (process efficiency, carvacrol recovery, PHBV recovery and loading capacity), as well as nanoparticles’ morphology and size were estimated, and statistically analysed. Carvacrol recovery and loading capacity were significatively highest (61 % and 100 % respectively) using emuslification method, low surfactant concentration, high carvacrol/PHBV ratio (for loading capacity) and low PHBV molecular weight (for carvacrol recovery). To the contrary, PHBV recovery increased (93 %) using the nanoprecipitation method, a high surfactant concentration and a low carvacrol/PHBV ratio, while process efficiency increased (73 %) with a low carvacrol/PHBV ratio and a low aqueous/organic phase volume ratio. Moreover, small spherical-shaped and separated nanoparticles were obtained using emulsification method, high surfactant concentration but low carvacrol/PHBV ratio. Therefore, including all the aspects of carvacrol nanoencapsulation into PHBV (shape and encapsulation efficiency) using emulsification method, with a low level for all parameters except the surfactant concentration are the most suitable strategy.

Enhancing the emulsification and demulsification efficiency of switchable surfactants through molecular dynamics simulation: The roles of surfactant concentration, salinity, and structure

This study aims to investigate the impacts of a surfactant structure, surfactant concentration, and salt content on switchable emulsification processes through molecular dynamics (MD) simulations. Specifically, we focus on assessing the properties and behaviors of water/tetradecane systems containing CO2-switchable acetamidine surfactant N’-dodecyl-N, N-dimethylacetamidine (C12DMAA) and C18 naphthalene sulfonate (C18PS), both of which are relevant to enhanced oil recovery processes. Utilizing MD simulations, we comprehensively explore the influence of the molecular composition of switchable surfactants, salinity, and surfactant concentration on the reversible processes of emulsification and demulsification in a complex oil/water/C18PS/C12DMAA system. This system can be activated through the injection of CO2 or N2 gas. Various analyses, including molecule mobility, hydration behavior, void volume analysis, a solvent accessible surface area (SASA), a diffusion coefficient, and relative concentration profiles, are employed to gain insights into the emulsification and demulsification processes. Our study reveals that lower surfactant concentrations result in the formation of partial emulsions, while the presence of salt disrupts surfactant hydration and weakens emulsification properties. Additionally, we observe that the impact of hydrogen bonding interactions is less pronounced at lower surfactant concentrations. Furthermore, the MD simulations provided insights into the interplay of a surfactant monomer number and alkyl phenyl introduction with a solvent-accessible surface area (SASA) and a void volume. Understanding these factors is crucial for designing and optimizing emulsion systems, particularly in oil recovery processes. The findings advance our understanding of CO2/N2-switchable surfactants, offering insights into their potential for sustainable development in the petroleum industry. This research contributes to the optimization of switchable surfactants, providing a foundation for improved emulsification processes in enhanced oil recovery applications.

Enhanced stability and reduced irritation of 4-n-butylresorcinol via nanoemulsion formulation: Implications for skin pigmentation treatment

4-n-butylresorcinol (4-nBR) is a valuable ingredient to lighten skin and reduce pigmentation, contributing to an even skin tone and a more youthful appearance. However, its poor solubility, low stability, and strong irritation to the skin limit its application. In this study, 4-nBR was prepared into 4-n-butylresorcinol nanoemulsion (4-nBR-NE) for the first time, enhancing the solubility and stability of 4-nBR while greatly reducing its skin irritation. The relationship between the viscosity of nanoemulsion and the formulation process, as well as the impact of surfactant ratio on the formability of 4-nBR-NE were further studied. This led to the successful development of a nanoemulsion with adjustable viscosity (AV-NE) and with a low surfactant content. The particle size of 4-nBR-NE was 13.34 ± 0.16 nm with a PDI of 0.0853 ± 0.0191, indicating a uniform particle size distribution. The encapsulation rate of 4-nBR-NE was determined to be 80.05 ± 0.75 % via UV–Vis spectrophotometry. In addition, 4-nBR-NE demonstrated excellent stability over several months, with negligible changes in particle size. Cellular and transdermal evaluations confirmed that the preparation of 4-nBR-NE effectively reduced the original irritation cause by 4-nBR on cells and skin. Then, 4-nBR-NE was incorporated into an essence. This advancement enhances the applicability of 4-nBR in treating pigmentation disorders such as melasma and freckles, thereby increasing its applicability in pharmaceutical and cosmetic industries.

Synthesis and Physicochemical Stability of a Copaiba Balsam Oil (Copaifera sp.) Nanoemulsion and Prospecting of Toxicological Effects on the Nematode Caenorhabditis elegans.

Nanoemulsions are dispersions of oil-in-water (O/W) and water-in-oil (W/O) immiscible liquids. Thus, our main goal was to formulate a nanoemulsion with low surfactant concentrations and outstanding stability using Copaiba balsam oil (Copaifera sp.). The high-energy cavitation homogenization with low Tween 80 levels was employed. Then, electrophoretic and physical mobility properties were assessed, in addition to a one- and two-year physicochemical characterization studies assessment. Copaiba balsam oil and nanoemulsions obtained caryophyllene as a major constituent. The nanoemulsions stored at 4 ± 2 °C exhibited better physical stability. Two years after formulation, the nanoemulsion showed a reduction in the particle size. The size underwent changes in gastric, intestinal, and blood pH, and the PdI was not changed. In FTIR, characteristic bands of sesquiterpenes and overlapping bands were detected. When subjected to freezing and heating cycles, nanoemulsions did not show macroscopic changes in higher concentrations. Nanoemulsions subjected to centrifuge force by 1000 rpm do not show macroscopic instability and phase inversion or destabilization characteristics when diluted. Therefore, the nanoemulsion showed stability for long-term storage. The nematode Caenorhabditis elegans was used to assess the potential toxicity of nanoemulsions. The nanoemulsion did not cause toxicity in the animal model, except in the highest concentration tested, which decreased the defecation cycle interval and body length. The toxicity and stability outcomes reinforce the nanoemulsions' potential for future studies to explore pharmacological mechanisms in superior experimental designs.

Effect of Surfactants on Eliminating Stable Ultrafine Chalcopyrite Froth.

Chalcopyrite is a primary source of copper in nature. However, with the increasing need to process low-grade and complex chalcopyrite ores, overly stable froth is becoming more and more common and poses operational and safety challenges. No reliable strategy has been developed to address the issue. As a new initiative, this study investigated three different structured surfactants, sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), and pentadecafluorooctanoic acid (PFOA), which vary in hydrophobic group, aiming to modify the surfaces of ultrafine chalcopyrite particles and adjust the interfacial tension at the gas-liquid interface to eliminate stable ultrafine chalcopyrite froth. The fundamental hypothesis was that an ideal surfactant structure could adjust the particle surface wettability and interfacial tension to eliminate overly stable froth. Based on contact angle measurements and interfacial tension measurements using a Theta Flow tensiometer by the pendant drop method and the sessile drop method, it was demonstrated that the contact angle played a dominant role in defoaming, while the reduction of gas-liquid interfacial tension had an adverse effect. Additionally, defoaming tests indicated that SDBS had lower defoaming effectiveness than SDS at low surfactant concentrations due to the steric hindrance in its structure, whereas the addition of SDBS could achieve a froth reduction efficiency as high as 93.75% at higher surfactant concentrations due to its stronger hydrophobicity and adsorption capacity to chalcopyrite particles, which could reduce the contact angle from 70 to 37.62°. However, PFOA exhibited lower defoaming effectiveness than both SDS and SDBS due to its lipophobic fluorocarbon tail of PFOA and weaker adsorption capacity to chalcopyrite particles, making it unsuitable for eliminating stable ultrafine chalcopyrite froth.

Association in Like-Charged Surfactant-Nanoparticle Systems: Interfacial and Bulk Effects.

The association of similarly charged surfactant molecules and nanoparticles in an aqueous solution remains unresolved, and the understandings reported in the literature are conflicting. To address this issue, we undertake a fundamental study to investigate bulk and interfacial phenomena in binary mixtures of (i) positively charged nanoparticles and cationic surfactants and (ii) negatively charged nanoparticles and anionic surfactants. We find that the surfactant molecules adsorb on the surface of the nanoparticle despite similar charge, leading to supercharging of particles and simultaneously driving more surfactant molecules to the air-dispersion interface. Hence, the properties of the dispersed species, such as the size and zeta potential, and the interfacial properties, such as the surface tension and surface excess concentration, change significantly. This effect is more pronounced at a low surfactant concentration and is observed irrespective of the size of nanoparticles and surfactant-particle combination. Further, we elucidate the important role of electrostatic interactions in the surfactant-particle complexation process by varying the pH of the dispersions. Contrary to changes in the properties of the dispersed species and interface, the presence of particles does not appreciably change the bulk property, such as the critical micelle concentration.

Pyranine Interaction with Amines in Micelles.

The fluorescence behavior of pyranine in anionic micellar system of sodium dodecyl sulphate was studied in the presence of selected amines. The amines included cyclopropylamine (CPA), ethylenediamine (EDA), benzylamine (BA), dibutylamine (DBA), cyclohexylamine (CHA), and polyethylenediamine (PEDA). All the studied amines quenched the intensity of pyranine. Study was performed in 0.05M and 0.1M SDS. The thermodynamic parameters were determined in order to understand the quenching of pyranine by the studied amines. Change in Gibbs free energy and quenching was found higher in 0.05M SDS concentration and was found lower when SDS concentration was increased to 0.1M SDS. Pyranine quenching by the amines studied were treated with an extended Stern-Volmer equation that produced the Stern-Volmer constant ([Formula: see text]). Binding constant (Kb), number of binding stoichiometry (n) and Gibbs free energy change (ΔGbinding) were found higher for lower surfactant concentration as compare to higher surfactant concentration. More negative (-ve) the Gibbs free energies more will be the quenching, higher will be the sensitivity and vice versa. The Gibbs free energies for all the studied amines were found in the order as cyclopropylamine > ethylenediamine > benzylamine > dibutylamine > cyclohexylamine > polyethylenediamine. Fluorescence quenching of pyranine by amines in aqueous SDS is reproducible and is useful for the determination of amines in environmental samples.

Impact of Surfactants on Cumulative Trypsin Activity in Bottom-Up Proteome Analysis.

Trypsin digestion plays a pivotal role in successful bottom-up peptide characterization and quantitation. While denaturants are often incorporated to enhance protein solubility, surfactants are recognized to inhibit enzyme activity. However, several reports have suggested that incorporating surfactants or other solvent additives may enhance digestion and MS detection. Here, we assess the impacts of ionic surfactants on cumulative trypsin activity and subsequently evaluate the total digestion efficiency of a proteome mixture by quantitative MS. Although low surfactant concentrations, such as 0.01% SDS or 0.2% SDC, significantly enhanced the initial trypsin activity (by 14 or 42%, respectively), time course assays revealed accelerated enzyme deactivation, evident by 10- or 40-fold reductions in trypsin activity half-life at these respective surfactant concentrations. Despite enhanced initial tryptic activity, quantitative MS analysis of a common liver proteome extract, digested with various surfactants (0.01 or 0.1% SDS, 0.5% SDC), consistently revealed decreased peptide counts and signal intensity, indicative of a lower digestion efficiency compared to a nonsurfactant control. Furthermore, including detergents for digestion did not improve the detection of membrane proteins, nor hydrophobic peptides. These results stress the importance of assessing cumulative enzyme activity when optimizing the digestion of a proteome mixture, particularly in the presence of denaturants.

Pore analysis of dendritic mesoporous silica nanoparticles by STEM tomography and nitrogen sorption

Dendritic mesoporous silica nanoparticles (DMSN) provide a high diversity and complexity regarding their pore structure. Herein, we present results related to electron tomographic reconstruction and nitrogen sorption analysis of DMSNs with different pore structures obtained through variation of the surfactant concentration in the synthesis. The tomograms revealed that at all DMSNs exhibit a highly porous shell structure and a denser porous core with smaller pores. The shell generally consists of dendritic silica walls forming a disordered pore system of center radially aligned mesopores. At the highest surfactant concentration these mesopores had a roughly conical geometry, providing a highly accessible pore network. Nitrogen sorption revealed a broad pore size distribution, in agreement with this conical mesopore shape. The mesopore dimensions obtained through reconstruction were in good agreement with the pore size distribution obtained by nitrogen sorption. For intermediate and low surfactant concentrations, different pore geometries were observed in the reconstruction with increasing restriction of the pore volume towards the outer surface of the particles by branching of large pores into smaller ones. Nitrogen sorption analyses support these observations by featuring an increasing hysteresis with decreasing surfactant concentration in the synthesis, which indicates that the accessible pore volume is restricted by smaller mesopores towards the rim of the particles.

Insecticidal Activity of Allium sativum Essential Oil-Based Nanoemulsion against Spodoptera littoralis.

Spodoptera littoralis, commonly known as the Egyptian or African cotton leafworm, is a significant agricultural threat. It is widely distributed in Africa, Mediterranean Europe, and Middle Eastern countries. This polyphagous pest infests numerous crop plants across 44 families, including cotton, soybeans, alfalfa, sweet potato, pepper, eggplant, tomato, maize, lettuce, strawberry, wheat, and hibiscus. The damage caused by S. littoralis on different plant organs, such as young leaves, shoots, stalks, bolls, buds, and fruits, often determines substantial product losses. Current control strategies predominantly rely on synthetic insecticides, which, despite their efficacy, have notable drawbacks, including insecticide resistance, environmental contamination, consumer concerns, and adverse effects on non-target organisms and beneficial insects. In response to these challenges, in this study, we developed and evaluated a garlic EO-based nanoemulsion with a high EO concentration (15%) and low surfactant content to mitigate the possible negative impact on plants and to enhance efficacy against S. littoralis larvae. Laboratory bioassays demonstrated promising larvicidal activity and reduced larval feeding, although some phytotoxicity symptoms were observed. This study underscores the potential of botanical insecticides as sustainable alternatives to synthetic chemicals, emphasizing the importance of balancing efficacy with environmental and ecological considerations in pest management strategies.

Microfluidic Stress Device to Decouple the Synergistic Effect of Shear and Interfaces on Antibody Aggregation

Protein denaturation and aggregation resulting from the effects of interfacial stress, often enhanced by flow and shear stress, pose significant challenges in the production of therapeutic proteins and monoclonal antibodies. The influence of flow on protein stability is closely intertwined with interfacial effects. In this study, we have developed a microfluidic device capable of exposing low volume (< 320 µL) protein solutions to highly uniform shear. To disentangle the synergistic impact of flow and interfaces on protein aggregation, we fabricated two devices composed of different materials, namely poly(methyl methacrylate) (PMMA) and stainless steel. Upon application of shear, we observed formation of protein particles in the micron-size range. Notably, The number of particles generated in the steel devices was ∼ 3.5 fold lower than in the PMMA device, hinting at an interface-mediated effect. With increasing the protein concentration from 1 to 50 mg/mL we observed a saturation in the amount of aggregates, further confirming the key role of solid-liquid interfaces in inducing particle formation. Introduction of non-ionic surfactants prevented protein aggregation, even at the highest tested protein concentration and low surfactant concentrations of 0.05 mg/mL. Overall, our findings corroborate the synergistic impact of shear and interface effects on protein aggregation. The device developed in this study offers a small-scale platform for assessing the stability of antibody formulations throughout various stages of the development and manufacturing process.

Addressing the interaction of stem bromelain with different anionic surfactants, below, at and above the critical micelle concentration (cmc) in phosphate buffer at pH 7: Physicochemical, spectroscopic, & molecular docking study

The structural stability and therapeutic activity of Stem Bromelain (BM) have been explored by unravelling the interaction of stem BM in presence of two different types of anionic surfactants namely, bile salts, NaC and NaDC and the conventional anionic surfactants, SDDS and SDBS, below, at and above the critical micelle concentration (cmc) in aqueous phosphate buffer of pH 7. Different physicochemical parameters like, surface excess (Γcmc), minimum area of surfactants at air water interface (Amin) etc. are calculated from tensiometry both in absence and presence of BM. Several inflection points (C1, C2 and C3) have been found in tensiometry profile of surfactants in presence of BM due to the conformational change of BM assisted by surfactants. Similar observation also found in isothermal titration calorimetry (ITC) profiles where the enthalpy of micellization (ΔH0obs) of surfactants in absence and presence of BM have calculated. Further, steady state absorption and fluorescence spectra monitoring the tryptophan (Trp) emission of free BM and in presence of all the surfactants at three different temperatures (288.15 K, 298.15 K, and 308.15 K) reveal the nature of fluorescence quenching of BM in presence of bile salts/surfactants. Time resolved fluorescence studies at room temperature also support to determine the several quenching parameters. The binding constant (Kb) of BM with all the surfactants and free energy of binding (∆G0 of bile salts/surfactants with BM at different temperatures have been calculated exploiting steady state fluorescence technique. It is observed that, the binding of NaC with BM is greater as compared to other surfactants while Stern-Volmer quenching constant (KSV) is found greater in presence of SDBS as compared with others which supports the surface tension and ITC data with the fact that surface activity of surfactant(s) is decreasing with the binding of the surfactants at the core or binding pocket of BM. Circular Dichroism (CD) study shows the stability of secondary structure of BM in presence of NaC and NaDC below C3, while BM lost its structural stability even at very low surfactant concentration of SDDS and SDBS which also supports the more involvement of bile salts in binding rather than surfactants. The molecular docking studies have also been substantiated for better understanding the several experimental investigations interaction of BM with the bile salts/surfactants.

Enhanced electrochemical properties of cobalt oxide nanoparticle electrode modified with low concentration of cationic surfactant

Metal oxides are proficient electrode materials for supercapacitors because of their physiochemical properties, especially their wide range of oxidation states that facilitate charge transfer in redox reactions and compatibility with electrolytes. Their performances can be further improved by adding surfactants, which also help with controlled synthesis, inhibit aggregation, and alter surface characteristics. The functional groups present in the surfactant molecule can undergo chemical bonding with the surface of the metal oxide, thereby modifying their surface chemistry and electronic characteristics. Recent research has focused on increasing the specific capacitance of cobalt oxide owing to its large surface area and size. The surfactants help to control the surface modification as a size-reducing agent and improve the electrochemical properties. Herein, A facile co-precipitation method is employed in synthesising cobalt oxide without cationic surfactant cetyltrimethylammonium bromide (CTAB) and with different concentrations of CTAB, followed by calcination. Herein, we compare the electrochemical properties with varying concentrations of surfactant-assisted Co3O4. The modified Co3O4 electrode with a low surfactant concentration (CO 1) exhibits a highly specific capacitance of 531F/g at 5 mV/s with a potential window of 0.7 V. The CO 1 electrode is suitable for supercapacitor devices with a specific capacitance of 296F/g at 0.8 A/g. Moreover, the asymmetric supercapacitor composed of CO1//AC demonstrated a remarkable energy density of 46.2 Wh/Kg and a robust power density of 800 W/kg. These results indicate that the hierarchical porous structure accelerates electron and ion movement, lowers charge transfer resistance, and improves hybrid electrode capacitive properties.

Efficiency of single pharmaceutical surfactants to mimic intestinal biorelevant media solubilization and dissolution of etravirine: Comparison of intrinsic and film dissolution models

We understand that quality control dissolution media may best anticipate in vivo product performance by mimicking in vivo media, but preferably involve at most a single pharmaceutical surfactant for routine laboratory use. The objective here was to estimate the concentrations of six pharmaceutical surfactants to mimic etravirine solubility and intrinsic dissolution rate, as well as dissolution rate from a film model, in each Fed State Simulated Intestinal Fluid Version 2 (FeSSIF-V2) and Fasted State Simulated Intestinal Fluid Version 2 (FaSSIF-V2). Solubility studies and colloid sizing measurements were conducted. Results indicate that all six surfactants were more efficient than FeSSIF-V2 or FaSSIF-V2 at solubilizing drug, and also exhibited higher micelle diffusivities than FeSSIF-V2 and FaSSIF-V2 mixed-micelles. The rank-order potency (on mM basis) of the six pharmaceutical surfactants to mimic etravirine solubility in each FeSSIF-V2 and FaSSIF-V2 was: polysorbate 80 (PS80) > polysorbate 20 (PS20) > polyoxyethylene(23) lauryl ether (POE23) > POE10 > hexadecyltrimethylammonium bromide (HEX) > sodium lauryl sulfate (SLS). This rank-order potency was almost the same to mimic drug dissolution rate into each FeSSIF-V2 and FaSSIF-V2, except POE10 > POE23. For the most potent surfactant, PS80, 0.461 mM and 0.140 mM PS80 was estimated to mimic etravirine's solubility and dissolution rate into FeSSIF-V2, respectively, using the intrinsic dissolution model. The low PS80 concentration to mimic dissolution rate reflects the relatively high diffusivity of PS80 micelles, compared to FeSSIF-V2 mixed-micelle diffusivity, which was the case for all six pharmaceutical surfactants. Results are also presented in terms of a film dissolution model for surfactant-mediated dissolution, where dissolution enhancement was less than that in the intrinsic dissolution model, and the film model required lower surfactant concentration than in intrinsic dissolution model to mimic FeSSIF-V2-enhanced dissolution. Findings have promised to identify single pharmaceutical surfactant concentrations that mimic key performance attributes of biorelevant media.

Charge Regulation at the Nanoscale as Evidenced from Light-Responsive Nanoemulsions.

Emulsions are indispensable in everyday life, and the demand for emulsions' diversity and control of properties is therefore substantial. As emulsions possess a high internal surface area, an understanding of the oil/water (o/w) interfaces at the molecular level is fundamental but often impaired by experimental limitations to probe emulsion interfaces in situ. Here, we have used light-responsive surfactants (butyl-AAP) that can photoisomerize between E and Z isomers by visible and UV light irradiation to tune the emulsion interfaces. This causes massive changes in the interface tension at the extended o/w interfaces in macroemulsions and a drastic shift in the surfactants' critical micelle concentration, which we show can be used to control both the stability and phase separation. Strikingly different from macroemulsions are nanoemulsions (RH ∼90 nm) as these are not susceptible to E/Z photoisomerization of the surfactants in terms of changes in their droplet size or ζ-potential. However, in situ second-harmonic scattering and pulsed-field gradient nuclear magnetic resonance (NMR) experiments show dramatic and reversible changes in the surface excess of surfactants at the nanoscopic interfaces. The apparent differences in ζ-potentials and surface excess provide evidence for a fixed charge to particle size ratio and the need for counterion condensation to renormalize the particle charge to a critical charge, which is markedly different compared to the behavior of very large particles in macroemulsions. Thus, our findings may have broader implications as the electrostatic stabilization of nanoparticles requires much lower surfactant concentrations, allowing for a more sustainable use of surfactants.

Conductometric and spectral analyses of dye-surfactant interactions between indigo carmine and N-alkyltrimethylammonium chloride

The electrical conductivity technique was used to investigate the critical micelle concentration (CMC) of cationic surfactants N-alkyltrimethylammonium chloride (CnTAC; n = 12, 14, 16, and 18). Meanwhile, the interaction between CnTAC and indigo carmine (IC, an anionic dye) was studied using spectrophotometry. Employing the Benesi-Hildebrand and Scott equations, the binding constant (Kb) of IC to the cationic micelles was determined. Calculation of the Gibbs free energy (ΔG) revealed the tendency of IC to bind to micelles. The association between IC and CnTAC clearly depends on the CnTAC concentration: a lower surfactant concentration disrupts the IC-CnTAC complex and decreases IC adsorption, while a higher surfactant concentration has the opposite effect. The alkyl chain length of CnTAC was also found to affect the CMC, Kb, and thermodynamic parameters. A longer alkyl chain reduces the CMC and ΔG and increases Kb, leading to increased solubilization and high spontaneity of the dye. The binding of IC to micelles is ranked as C12TAC < C14TAC < C16TAC < C18TAC.

Mass Transfer in Emulsion Polymerization: High Solids Content Latex and Mixing Effects

AbstractThe impact of different agitator configurations used during the emulsion polymerization of vinylidene fluoride (VDF) is studied with the goal of achieving a solids content of 55 wt% while minimizing particle coagulation and maintaining low levels of surfactant. The design and number of impellers, their spacing and the agitation speed are shown to have a strong influence on the transfer of gaseous monomer to the aqueous phase, and thus the rate of polymerization. Increasing the number of impellers on the central shaft, and decreasing the spacing of the impellers close to the latex surface has a strong influence on the ability to incorporate gaseous monomer, so the solids content and the latex level in the reactor increased. Furthermore, it is found that changes in the agitation rate during the reaction is necessary at high solids content to avoid destabilizing the particles in view of the low surfactant concentrations used.

Impact of the Amphoteric Nature of a Chelating Surfactant on its Interaction with an Anionic Surfactant: A Surface Tension and Neutron Reflectivity Study of Binary Mixed Solutions.

2-Dodecyldiethylenetriaminepentaacetic acid (C12-DTPA) is a chelating, amphoteric surfactant with a bulky headgroup containing eight pH-responsive groups. The hypothesis was that the amphoteric nature of the chelating surfactant would affect the interaction with another surfactant and, consequently, also the composition of mixed surface layers. Binary mixed monolayers of C12-DTPA and the anionic surfactant sodium dodecyl sulfate (SDS) were examined using neutron reflection and surface tension measurements. The experiments were conducted at pH 5, where the C12-DTPA monomers carried a net negative charge. Surface excess calculations at low total surfactant concentration revealed that the chelating surfactant dominated the surface composition. However, as the concentration was raised, the surface composition shifted toward an SDS-dominant state. This phenomenon was attributed to the increased ionic strength at increased concentrations, which altered the balance between competing entropic forces in the system. Interaction parameters for mixed monolayer formation were calculated, following a framework based on regular solution theory. In accordance with the hypothesis, the chelating surfactant's ability to modulate its charge and mitigate repulsive interactions in the surface layer resulted in favorable interactions between the anionic SDS and negatively charged C12-DTPA monomers. These interactions were found to be concentration-dependent, which was consistent with the observed shift in the surface layer composition.

Effect of linear anionic surfactant (sodium dodecyl sulfate) dosage on nitrogen removal performance of an anammox reactor

AbstractThe impact of sodium dodecyl sulfate (SDS, as model linear anionic surfactant) dosage on overall nitrogen removal performance of anammox reactor alongside its microbial population and sludge properties was investigated. In this study (day 136), an anmmox sequencing batch biofilm reactor was subjected to gradual dosage of SDS from 0 to 20 mg L−1. Intriguingly, results revealed that SDS at ≥7.5 mg L−1 prompted sludge disintegration, evidenced by increased protein and polysaccharide content in the effluent. Nevertheless, reactor's average total nitrogen removal efficiency slightly improved from 83.12% (0 mg L−1) to 86.3% (20 mg L−1). The 16S rRNA gene sequencing revealed that SDS dosing significantly suppressed the unwanted and unavoidable nitrite oxidizing bacteria (NOBs) in the reactor as the abundance of genus Nitrospira declined from 40.68% (day 1) to 19.15% (day 136). The abundance of anammox genus Candidatus Kuenenia significantly improved from 1.86% (day 1) to 40.02% (day 136) as a result of NOB suppression. This study revealed that low concentration of surfactants in wastewater does not affect the anammox bacteria in a biofilm reactor. Furthermore, adding low concentrations of SDS (≥7.5 to 20 mg L−1) to wastewater may effectively suppress notorious NOBs in biofilm‐based anammox systems.