Surfactant Monomers Research Articles

Spotlight on reversible emulsification and demulsification of tetradecane-water mixtures using CO2/N2 switchable surfactants: Molecular dynamics (MD) simulation

CO2/N2 switchable surfactants have recently attracted significant attention in enhanced oil recovery. Their environmental and economic benefits are the main driving forces for their application in the oil and gas industry. This study evaluated mixtures of sodium dodecyl sulfate (SDS), C18 naphthalene sulfonate (C18PS), and CO2-switchable acetamidine surfactant N′-dodecyl-N, N-dimethylacetamidine (C12DMAA) in water/dodecane systems by using molecular dynamics (MD) simulation. The effects of the molecular structure of anionic surfactant and surfactant concentration on switchable emulsification and demulsification in an oil/water/SDS or C18PS/C12DMAA system triggered by CO2/N2 injection were investigated. The molecule mobility, hydration behavior, density field analysis, diffusion coefficient, radial distribution functions (RDFs), and the density profiles of various systems were thoroughly examined. Based on MD simulation outputs, increasing surfactant concentration can intensify a demulsification process and create a clear phase separation between water and tetradecane. On the other hand, during an emulsification process, adding more surfactant monomers improved a hydration layer around oil droplets and increased hydrogen bonds; however, the contribution of hydrogen bonds between water and N′-dodecyl-N, N-dimethylacetamidinium (C12DMAAH+) compared to SDS and C18PS is limited. MD simulations proved the switchability of SDS/C12DMAA and C18PS/C12DMAA for emulsification and demulsification processes. The results of the current study will be beneficial for developing and optimizing the switchable surfactant structures for further use in the oil and gas industry through surfactant injection.

Molecular interaction of lysozyme with therapeutic drug azithromycin: Effect of sodium dodecyl sulfate on binding profile

This paper describes an inclusive biophysical study elucidating the interaction of therapeutic drug azithromycin (Azith) with hen egg white lysozyme (HEWL). Spectroscopic and computational tools have been employed to study the interaction of Azith with HEWL at pH 7.4. The fluorescence quenching constant values (Ksv) exhibited a decrease with the increase in temperature which revealed the occurrence of static quenching mechanism between Azith and HEWL. The thermodynamic data demonstrated that hydrophobic interactions were predominantly involved in the Azith-HEWL interaction. The negative value of standard Gibbs free energy (ΔG°) stated that the Azith-HEWL complex formed via spontaneous molecular interactions. The effect of sodium dodecyl sulfate (SDS) surfactant monomers on the binding propensity of Azith with HEWL was insignificant at lower concentrations however the binding significantly decreased at increased concentrations of the former. Far-UV CD data revealed alteration in the secondary structure of HEWL in the presence of Azith and the overall HEWL conformation changed. Molecular docking results revealed that the binding of Azith with HEWL takes place through hydrophobic interactions and hydrogen bonds.

Study on wetting mechanism of nonionic silicone surfactant on coal dust

Coal dust disasters are serious in coal mining. The use of nonionic surfactants can effectively improve the wettability of coal dust and reduce the content of suspended coal dust in the air. For the problem of low wettability of ordinary surfactants, this paper selects silicone surfactants with high surface activity and low surface tension to improve the wetting ability of coal dust. To explore the wettability of nonionic silicone surfactants on coal dust, the effects of six nonionic silicone surfactants on the wettability of coal dust surfaces were studied by experiments. The test objects were four kinds of coal samples with different metamorphic degrees. The surface tension, wetting time, and contact angle experiments were carried out, and the critical micelle concentration and the expansion coefficient of the coal surface were calculated. The wetting time of the compound solution was measured to verify the synergistic effect of the compound solution. The results show that: 6 # has the best wetting effect on coal dust, followed by 4 # and 2 #; The order of surface tension is: 1 # < 3 # < 4 # < 6 # < 5 # < 2 #, the surface tension of 1 # is the lowest (19.962 mN/m); 1 # and 4 # are easier to spread on the surface of coal dust, the spreading coefficient of coking coal is the largest and the contact angle is the smallest, which is 18.8°. The 4 # and 6 # with a mass ratio of 8:2 were compounded. The compound surfactant solution had a significant synergistic effect. Compared with the monomer surfactant solution, the wettability of long-flame coal and coking coal increased by 15.14% and 10.00%, respectively. The results of this study can provide reference and experimental support for the development of high-efficiency dust suppressants based on silicone surfactants.

Co-electrodeposited poly (3, 4-ethylenedioxythiophene) (PEDOT)-multiwall carbon nanotubes (MWCNT) hybrid electrodes based solid-state supercapacitors using ionic liquid gel electrolyte for energy storage with pulsed power capabilities

Electrochemical and energy storage properties of poly(styrene sulfonate) doped poly (3, 4-ethylenedioxythiophene) (PEDOT:PSS) conducting polymer hybridized with the multiwall carbon nanotubes (MWCNT) are studied as solid-state supercapacitor with anion-doped ionic liquid (IL) gel electrolyte. The PEDOT: PSS-MWCNT composite electrodes were formed by co-electrodeposition using sequential 4 mA cm−2 current density with 10 ms current pulses in an aqueous medium with highly dispersed MWCNTs using Na-dodecyl sulfate (SDS) surfactant, PSS dopant (10–20 %) and EDOT monomer. Raman spectral study confirms with ≤10%PSS, the MWCNTs are moored into PEDOT chains via covalent bonding with carbons at α and β-position as PEDOT grows over flexible graphite substrate. Specific capacitance of 138 F g−1 discerned from cyclic voltammetry in IL-gel electrolyte is higher than reported in liquid electrolytes and chemically polymerized electrodes. Electrical double layer (EDL) capacitance analysis shows high 71.2 mF cm−2 contribution originated from MWCNTs with 10 % PSS, and slightly lower 48.8 mF cm−2 with 20 % PSS. The performance optimized PEDOT: PSS (10 %)- MWCNT (1 mg) based supercapacitors show large (43 %) access to the electroactive nanoporous surface regions contributing to capacitive charge and 57 % electrode has access to charge storage via diffusion limited Faradaic process. Nyquist plots analyzed for Warburg coefficient show minimal charge transfer resistance unimpacted by ionic diffusion. From the frequency response of the real and imaginary impedances pulsed power is assessed as 6.33 kW kg−1 at energy density 3.43 Wh kg−1. Charge-discharge behavior of optimized supercapacitor over 0.05–2.0 A g−1 current densities is triangular, highly symmetrical. Ragone plot shows high energy density of 7.7 Wh kg−1 at specific power 5.3 kW kg−1 plateauing out to 4.4 Wh kg−1 at higher specific power of 11.5 kW kg−1. Charge-discharge cycle analysis shows merely 20 % loss of specific capacitance by ∼500 cycles largely stabilizing for over 2000 cycles while the Coulomb efficiency remaining invariant at 95 %.

DFT Calculation and MD Simulation Studies on Gemini Surfactant Corrosion Inhibitor in Acetic Acid Media.

Gemini surfactant corrosion inhibitor (CI) is one type of CI mainly used in mitigating corrosion in the complex system of oil/gas production industries. Computer modeling methods such as density functional theory (DFT) calculation and molecular dynamic (MD) simulation are required to develop new CI molecules focusing on their application condition as a prediction or screening process before the physical empirical assessment. In this work, the adsorption inhibition efficiencies of two monomer surfactants (2B and H) and their respective Gemini structures with the addition of different spacers (alkyl, benzene, ester, ether, and ketone) are investigated using DFT calculation and MD simulation method in 3% sodium chloride (NaCl), and 1500 ppm acetic acid solutions. In DFT calculation, 2B-benzene molecules are assumed to have the most promising inhibition efficiency based on their high reactivity and electron-donating ability at their electron-rich benzene ring region based on the lowest bandgap energy (0.765 eV) and highest HOMO energy value (-2.879 eV), respectively. DFT calculation results correlate with the adsorption energy calculated from MD simulation, where 2B-benzene is also assumed to work better as a CI molecule with the most adsorption strength towards Fe (110) metal with the highest negative adsorption energy value (-1837.33 kJ/mol at temperature 323 K). Further, diffusion coefficient and molecular aggregation analysis in different CI concentrations through MD simulation reveals that only a small amount of Gemini surfactant CI is needed in the inhibition application compared to its respective monomer. Computer simulation methods successfully predict and screen the Gemini surfactant CI molecules that can work better as a corrosion inhibitor in acetic acid media. The amount of Gemini surfactant CI that needs to be used is also predicted. The future planning or way forward from this study will be the development of the most promising Gemini surfactant CI based on the results from DFT calculation and MD simulations.

Surface tension behavior of superspreading and non-superspreading trisiloxane surfactants

One parameter frequently considered to be relevant for superspreading of trisiloxane surfactants is surface tension kinetics. In the scientific literature, some experimental results reported for trisiloxane surfactants are in contradiction with fundamental concepts of surfactant monomer diffusion. Therefore, maximum bubble pressure tensiometry has been used to determine dynamic surface tension (DST) of two types of trisiloxane surfactants: superspreader and non-superspreader. Results show that both surfactants behave similarly at concentrations below critical micelle concentration (CMC), as expected. The CMC curves, as determined by drop shape analysis, confirmed that the more hydrophilic non-superspreader has a higher CMC as compared to the more hydrophobic superspreader. Accordingly, the lower surfactant monomer concentration of the superspreader results in a higher DST than the non-superspreader at the same surface age. So, in contrary to claims in the literature, there is nothing mysterious or unexpected concerning the surface tension behavior of trisiloxane surfactants.Graphical

Characterization of Micelle Formation by the Single Amino Acid-Based Surfactants Undecanoic L-Isoleucine and Undecanoic L-Norleucine in the Presence of Diamine Counterions with Varying Chain Lengths

The binding of linear diamine counterions with different methylene chain lengths to the amino-acid-based surfactants undecanoic L-isoleucine (und-IL) and undecanoic L-norleucine (und-NL) was investigated with NMR spectroscopy. The counterions studied were 1,2-ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane. These counterions were all linear diamines with varying spacer chain lengths between the two amine functional groups. The sodium counterion was studied as well. Results showed that when the length of the counterion methylene chain was increased, the surfactants’ critical micelle concentrations (CMC) decreased. This decrease was attributed to diamines with longer methylene chains binding to multiple surfactant monomers below the CMC and thus acting as templating agents for the formation of micelles. The entropic hydrophobic effect and differences in diamine counterion charge also contributed to the size of the micelles and the surfactants’ CMCs in the solution. NMR diffusion measurements showed that the micelles formed by both surfactants were largest when 1,4-diaminobutane counterions were present in the solution. This amine also had the largest mole fraction of micelle-bound counterions. Finally, the und-NL micelles were larger than the und-IL micelles when 1,4-diaminobutane counterions were bound to the micelle surface. A model was proposed in which this surfactant formed non-spherical aggregates with both the surfactant molecules’ hydrocarbon chains and n-butyl amino acid side chains pointing toward the micelle core. The und-IL micelles, in contrast, were smaller and likely spherically shaped.

Constituent- and Composition-Dependent Surfactant Aggregation in (Lanthanide Salt + Urea) Deep Eutectic Solvents

Due to the ease of tailoring the physicochemical properties by simply changing a constituent or composition, deep eutectic solvents (DESs) possess widely varying capabilities for surfactant self-assembly that could depend on the surfactant headgroup charge. The self-aggregation process of three surfactants, sodium dodecylsulfate (SDS), cetyltrimethylammonium bromide (CTAB), and Triton X-100 (TX-100), dissolved in DESs composed of a lanthanide salt (Ln) and urea (U) is investigated. The role of the identity of the metal salt is assessed by using [La(NO3)3·6H2O] (La) and [Ce(NO3)3·6H2O] (Ce) and that of the composition is deciphered by systematically changing the mole ratio of the metal salt and urea in (La/U) DESs. The response to a fluorescence probe pyrene-1-carboxaldehyde along with electrical conductance and surface tension measurements is used to obtain the critical aggregation concentration (CAC). While the CACs in 1:3.5 (Ln/U) for SDS are significantly lower than that in water, the values are marginally higher for CTAB and TX-100. The CACs for all three surfactants are similar in 1:3.5 (La/U) and (Ce/U) DESs, implying that the identity of the metal in the salt is not so important. Increasing the urea composition in (La/U) DESs results in increased CAC for SDS and CTAB; however, a minimal decrease in CAC is observed for TX-100. From the temperature dependence of CAC, thermodynamic parameters, ΔGagg0, ΔHagg0, and ΔSagg0, of the surfactant self-aggregation process are estimated. These parameters reveal that while at a lower urea content, the SDS/CTAB self-assembly process is enthalpically driven, it becomes entropically favored at higher urea concentrations. The TX-100 self-aggregation in these DESs is found to be strongly enthalpically favored and entropically un-favored. These parameters are explained as a combination of passage of the solvophobic surfactant chain from the bulk DES to the aggregate pseudo-phase and differential orientation/organization of DES constituents around surfactant monomers and/or aggregates.

Modelling and Optimization of Amphoteric Surfactant Concentration in Electroless Nickel Boron Coatings for Maximum Microhardness

In the electroless nickel-boron coating process, surfactant helps to minimize the surface tension between the substrate and the electrolyte in the bath. Despite, its high cost and the formation of micelles from monomeric surfactant molecules at its critical micelle concentration (CMC), it is essential to optimize the concentration while using in the bath. In this study, to solve this problem, mathematical models are developed using regression and artificial neural network (ANN) techniques to relate the concentration of amphoteric surfactant (0-0.162 g/L) as an independent variable and microhardness as a dependent variable. Then, the developed model was used to optimize microhardness at CMC using a genetic algorithm (GA). The goodness of fit of the models was evaluated using the coefficient of determination (R2). The ANN model was found to be the best fit with R2 = 0.99. The maximum microhardness of 852 HV was achieved at the CMC of 0.064 g/L, from the GA using the validated model as a fitness function.

Dye-surfactant interaction in aqueous premicellar and micellar environments in the alkaline fading of di-positive methyl green carbocation

The alkaline fading of di-positive methyl green carbocation (MeG2+) has been studied in different aqueous premicellar and micellar environments of anionic, cationic as well as non-ionic surfactants. Mono- and di-negative anions like halides and sulphate have been found to show an inhibiting effect on the fading reaction owing to the formation of dye-anion ion-pair adduct before hydrolysis. The binding strength of the dye-anion ion-pair adduct is in the order: SO42- > I- > Br- > Cl- which rationalizes the same order of inhibition of the rate. A substantial change in the electronic spectra of MeG2+ in the presence of anionic surfactants, sodium dodecyl sulfate (SDS) and dioctyl sodium sulfosuccinate (AOT), in the pre-CMC region indicates a change in the equilibrium distribution of the two stereo isomers of the dye owing to the formation of MeG2+-surfactant ion-pair and ion-pair micelle. The premicellar rate inhibition of the fading reaction by SDS and AOT occurs due to the formation of 1:1 MeG2+-surfactant ion-pair (where ≥ 85 % of MeG2+ remain associated) through electrostatic interaction before hydrolysis. The cationic surfactant cetyltrimethylammonium bromide (CTAB) shows a retarding effect in the post-micellar region as the HO- ion experiences both electrostatic repulsion and steric hindrance to approach the carbocation centre of the dye, embedded in the micelle. The polar hydroxyl group and the polyoxyethylene groups present in the moiety of the non-ionic surfactant Brij35 assist to increase the local concentration of HO- and MeG2+ in the palisade layer resulting in a catalyzing effect on the fading reaction in the post CMC region. Both pre- and post-micellar rate effects have been analyzed quantitatively by different established kinetic models. Detailed calculations have been made to find out different enthalpy and entropy of activation as well as of binding in order to establish the nature of interactions between the dye MeG2+ and monomeric surfactant(s) /micelles as well as solvent molecules. Results of spectrophotometric and tensiometric investigations strongly support the existence of different molecular interactions in different stages of the hydrolysis reaction in the presence of surfactants.

Model of inverse “dry” micelles with coexisting spherical, globular and cylindrical aggregates

A new statistical thermodynamic model of inverse nonionic aggregates of surfactant molecules in nonpolar solvents is considered. This model admits the fluctuation coexistence of inverse spherical, globular, and spherocylindrical aggregates without activation barriers between them. The model is based on the assumption of a uniform bulk density of the number of molecular groups inside the core of an aggregate that can continuously transform into a sphere, a globule, and a spherocylinder. In this model, for any aggregation numbers, the work of aggregation depends not only on the aggregation numbers and the concentration of surfactant monomers, but also on two independent geometric parameters characterizing, at the same aggregation numbers, the deviation from the spherical form of the aggregate towards globular and spherocylindrical forms. Even in the range of small aggregation numbers, this fact leads to a significant difference between the equilibrium distribution function of aggregates, which depends on the aggregation number and two form parameters, and the one-dimensional distribution function in terms of aggregation numbers. It is shown that the optimal values of the form parameters, which minimize the work of aggregation, are in good agreement for spherocylindrical aggregates with the predictions of a purely geometric model of such aggregates under the additional assumption of a uniform surface density of molecular groups at the micelle core. The predictions of a new molecular thermodynamic model for the degrees of surfactant micellization in inverse aggregates of various forms at different surfactant concentrations are considered.

Diffusion of surfactant from a micellar solution to a bare interface. 1. Absorbing boundary

We analyze dynamic adsorption of surfactant from a micellar solution to a rapidly created surface that acts as an absorbing boundary for surfactant monomers (single molecules), along which the monomer concentration vanishes, with no direct micelle adsorption. This somewhat idealized situation is analyzed as a prototype for situations in which strong suppression of monomer concentration accelerates micelle dissociation, and will be used as a starting point for analysis of more realistic boundary conditions in subsequent work. We present scaling arguments and approximate models for particular time and parameter regimes and compare the resulting predictions to numerical simulations of the reaction–diffusion equations for a polydisperse system containing surfactant monomers and clusters of arbitrary aggregation number. The model considered here exhibits an initial period of rapid shrinkage and ultimate dissociation of micelles within a narrow region near the interface. This opens a micelle-free region near the interface after some time τe, the width of which increases as t1/2 at times t≫τe. In systems that exhibit disparate fast and slow bulk relaxation times τ1 and τ2 in response to small perturbations, τe is usually comparable to or greater than τ1 but much less than τ2. Such systems exhibit a wide intermediate time regime τe<t<τ2 in which the remaining micellar region reaches a state of partial local equilibrium, followed by a final stage t≫τ2 in which full local equilibrium is established.

Enhancement of the wettability of a coal seam during water injection: effect and mechanism of surfactant concentrations above the CMC.

This paper determines the optimal surfactant concentration for enhancing coal's wettability and explores the wetting mechanism at surfactant concentrations above the critical micelle concentration (CMC) during coal seam water injection. In this study, laboratory experiments and field tests were used to investigate the influence of monomeric surfactants and compound surfactants at various concentrations on coal's wettability. The results showed that when the surfactant solution concentration was greater than the CMC, the coal's wettability was significantly enhanced as the surfactant concentration increased. However, the coal's wettability did not monotonically increase with the concentration, and the maximum value was reached in the range of 0.5-3 wt.%. Increasing the surfactant adsorption density and changing the adsorption state on the coal surface were the essential reasons surfactants continued improving the coal's wettability at concentrations above the CMC. The Marangoni flow effect and changes in the viscosity of the surfactant solution with concentration were also important factors that affected the coal's wettability.

The partitioning of primary alcohols into the aggregates of gemini amphiphiles determined from diffusion NMR experiments.

The partition constants (p-values) of primary alcohols in solutions containing aggregates of symmetric gemini surfactants of the family N,N'-dimethyl, N-dialkyl-α,ω-alkanediammonium dibromide (m-s-m = symmetric gemini surfactants) have been computed from the measured values of their diffusion coefficients obtained from NMR-diffusion experiments. From the p-values, both mole-fraction and concentration-based partition coefficients and Gibbs energies of transfer for the alcohols from the bulk D2O phase to the gemini aggregate phase have been calculated. As expected, the Gibbs energy of transfer decreased linearly with an increase in the alcohol carbon length for each of the primary alcohol/gemini amphiphile series studied. The Gibbs transfer energy increment per CH2 for the alcohols was consistent for all the alcohol/gemini amphiphile series and was in excellent agreement with the values measured for the same primary alcohol series in conventional single-headed, single-tailed surfactants. Surprisingly, the partition coefficients of the alcohols in the symmetric gemini aggregates exhibited little, if any, dependence on the spacer length of the gemini amphiphiles and were remarkably consistent as the length of the main surfactant chain increased at constant spacer length. When these results are compared to the partition coefficients of the same alcohols in corresponding monomeric surfactants, we observe little difference in the thermodynamic driving forces governing the transfer of alcohols from water to the aggregates of either monomeric or symmetric gemini surfactants.

Comparative studies on the aggregate formation of synthesized zwitterionic gemini and monomeric surfactants in the presence of the amphiphilic antipsychotic drug chlorpromazine hydrochloride in aqueous solution: an experimental and theoretical approach.

The formation of aggregates, which are widely used in the field of biochemistry and the medical industry, was studied with different compositions of alkyl betaine gemini surfactant (C14Ab) in conjugation with chlorpromazine hydrochloride (CPZ). The results were compared with those of a single-chain zwitterionic surfactant (C12DmCB) of the same type with CPZ. Dynamic light scattering (DLS), confocal laser scanning microscopy (CLSM), and transmission electron microscopy (TEM) methods were used to distinguish the aggregates for the CPZ/C14Ab system in aqueous solutions above a certain mole fraction of the drug CPZ (αCPZ = 0.2). Time-resolved fluorescence decay measurements of acridine orange revealed relative polarity near the head group regions of mixed micelle (CPZ/C14Ab and CPZ/C12DmCB) systems. The hydrophilic environment around the head group regions of the CPZ/C14Ab system was different from that in the case of the CPZ/C12DmCB system. On the other hand, several theoretical models were employed (Clint, Rubingh, Motomura, and SPB) for mixed micellar systems to elucidate the different interaction parameters. Such a systematic study of a zwitterionic gemini amphiphile and its interaction with other amphiphiles and an amphiphilic drug molecule is rare in the literature.

Objective Criteria for Estimation of Initial Parameters for the Modeling of Micelle and Liposome Structures from Small-Angle X-ray Scattering Data

The structures of hydrophobic membrane proteins are studied using matrices, which serve as models of cell membranes and are formed by the appropriate amphiphilic molecules, e.g., by surfactant or lipid molecules. To study the structure of a protein incorporated into an artificial membrane, first of all it is necessary to determine the structure of the membrane. The ELLLIP and ELLMIC algorithms were previously developed to address this issue by small-angle X-ray scattering. These algorithms allow the construction of models of ellipsoidal vesicles based on the atomic structure of a lipid or surfactant monomer. However, the results of modeling depend, to a large extent, on the subjective assessment of the initial values of the structural parameters of the matrices and may be wrong due to the ambiguity in the solution of such problems. Here, we present an independent approach to the determination of the initial sizes of model membranes for their subsequent structural modeling, which is based on the analysis of the pair-distance distribution functions derived directly from the small-angle X-ray scattering curve.

Wetting effect of branched anionic Gemini surfactant aqueous solution on PMMA surface.

In this paper, the adsorption behaviour and wetting modification ability of the sodium salts of bis-octadecenoyl succinate (GeminiC3, GeminiC6) and monomers on polymethyl methacrylate (PMMA) surfaces were investigated. The difference in spacer length led to slightly different behaviour of surfactant molecules in solution. The large molecular structure and short flexible spacer of GeminiC3 led to a complex self-aggregation behaviour in solution, forming micelles at low concentrations, leading to a rapid decrease in surface tension and subsequent transition to monolayer or multilayer vesicles. In GeminiC6, the longer flexible spacer groups act as spatial structure modifiers that hinder the formation of vesicles. The adsorption behaviour of the gas-liquid interface was analysed in three stages for the peculiar inflection points where surface tension appears. Combining contact angle measurements, adhesion tension and interfacial tension data showed that GeminiC3 and C6 formed a saturated monolayer on the adsorbed PMMA surface at low concentrations and a bilayer structure at high concentrations. Due to the low resistance of molecular space sites, the monomers adsorbed heavily on the PMMA surface, forming semi-colloidal aggregates with the lowest contact angle of monomeric surfactant solutions reaching 38° on the PMMA surface. Also, the monomer and GeminiC3 and C6 surfactants in this paper have a very high hydrophilic modification ability on the PMMA surface compared to other literature.

Electrochemical behavior, antimicrobial activities, and effect of temperature on micellization of imidazolium monomeric surfactants.

In the present study, we herein report the conductance behavior, effect of temperature, and chain-length of two environmentally friendly imidazolium cationic capric and stearic surfactants. The conductance behavior has been carried out in aqueous solvent (H2O) at four different temperatures such as 24 °C, 29 °C, 34 °C, and 39 °C. The normal micelles were formed in an aqueous solvent and critical micelle concentration (CMC) can be estimated through conductivity parameters. The expected dependency of the CMC on the alkyl chain length of the 3-(2-(decanoyloxy)ethyl)-1-methyl-1H-imidazol-3-ium-bromide and 3-(2-(octadecanoyloxy)ethyl)-1-methyl-1H-imidazol-3-ium-bromide was demonstrated. It was observed that the graphs of molar conduct activity v/s square root were not linear, which specifies that the synthesized surfactants behave as weak electrolytes in the dilute solutions. The electrochemical characterization of capric and stearic surfactant modified SPCE was studied in 1mM K3FeCN6 solution. The CS/SPCE and SS/SPCE were shown elevated sensitivity, high stability, and excellent conductivity. Moreover, the antimicrobial behaviors of the synthesized imidazolium cationic surfactants versus various microbial strains were evaluated. Results showed that capric surfactant demonstrated high antibacterial activity against Escherichia coli (MIC > 31.5 μg/mL).

Probing Surfactant Bilayer Interactions by Tracking Optically Trapped Single Nanoparticles

AbstractSingle‐particle tracking and optical tweezers are powerful techniques for studying diverse processes at the microscopic scale. The stochastic behavior of a microscopic particle contains information about its interaction with surrounding molecules, and an optical tweezer can further facilitate this observation with its ability to constrain the particle to an area of interest. Although these techniques found their initial applications in biology, they can also shed new light on microscopic interface phenomena by unveiling nanoscale morphologies and molecular‐level interactions in real time, which are obscured in traditional ensemble analysis. Here, the application of single‐particle tracking and optical tweezers are demonstrated for studying molecular interactions at solid–liquid interfaces. Specifically, the surfactant behaviors at the water–glass interface are investigated by tracing gold nanoparticles that are optically trapped on these molecules. The underlying mechanisms governing the particle motion, which can be explained by hydrophobic interactions, disruptions, and rearrangements among surfactant monomers at the interfaces, are discovered. These interpretations are further supported by statistical analysis of an individual trajectory and comparison with theoretical predictions. The findings provide new insights into the surfactant dynamics and also illustrate the promise of single‐particle tracking and optical manipulation for studying nanoscale physics and chemistry of surfaces and interfaces.

Interactions of Surfactants with the Bacterial Cell Wall and Inner Membrane: Revealing the Link between Aggregation and Antimicrobial Activity.

Surfactants with their intrinsic ability to solubilize lipid membranes are widely used as antibacterial agents, and their interactions with the bacterial cell envelope are complicated by their differential aggregation tendencies. We present a combined experimental and molecular dynamics investigation to unravel the molecular basis for the superior antimicrobial activity and faster kill kinetics of shorter-chain fatty acid surfactant, laurate, when compared with the longer-chain surfactants studied in contact time assays with live Escherichia coli (E. coli). From all-atom molecular dynamics simulations, translocation events across peptidoglycan were the highest for laurate followed by sodium dodecyl sulfate, myristate, palmitate, oleate, and stearate. The translocation kinetics were positively correlated with the critical micellar concentration, which determined the free monomer surfactant concentration available for translocation across peptidoglycan. Interestingly, aggregates showed a lower propensity to translocate across the peptidoglycan layer and longer translocation times were observed for oleate, thereby revealing an intrinsic sieving property of the bacterial cell wall. Molecular dynamics simulations with surfactant-incorporated bacterial inner membranes revealed the greatest hydrophobic mismatch and membrane thinning in the presence of laurate when compared with the other surfactants. The enhanced antimicrobial efficacy of laurate over oleate was further verified by experiments with giant unilamellar vesicles, and electroporation molecular dynamics simulations revealed greater inner membrane poration tendency in the presence of laurate when compared with the longer-chain surfactants. Our study provides molecular insights into surfactant translocation across peptidoglycan and chain length-induced structural disruption of the inner membrane, which correlate with contact time kill efficacies observed as a function of chain length with E. coli. The insights gained from our study uncover unexplored barrier properties of the bacterial cell envelope to rationalize the development of antimicrobial formulations and therapeutics.