Hydrophobic Tail Of Surfactant Research Articles

An emerging assay for rapid diagnosis of live Salmonella Typhimurium by exploiting aqueous/liquid crystal interface

The rapid and accurate identification of live pathogens with high proliferative ability is in great demand to mitigate foodborne infection outbreaks. Herein, we have developed an ultrasensitive image-based aptasensing array to directly detect live Salmonella typhimurium (S.T) cells. This method relies on the long-range orientation of surfactant-decorated liquid crystals (LCs) and the superiority of aptamers (aptST). The self-assembling of hydrophobic surfactant tails leads to a perpendicular/vertical ordered film at the aqueous/LC interface and signal-off response. The addition of aptST perturbed LCs’ ordering into a planar/tilted state at the aqueous phase due to electrostatic interactions between the surfactant with the aptST, and a signal-on response. Following the conformational switch of aptST in the presence of live S. typhimurium, a relative reversing signal-off response was observed upon the target concentration. This aptasensor could promptly confirm the presence of S. typhimurium without intricate DNA-extraction or pre-enrichment stats over a linear range of 1–1.1 × 106 CFU/mL and a detection limit of 1.2 CFU/mL within ∼30 min. These results were successfully validated using molecular and culture-based methods in spiked-milk samples, with a 92.61–104.61 % recovery value. Meanwhile, the flexibility of this portable sensing platform allows for its development and adoption for the precise detection of various pathogens in food and the environment.

Bioinspired simultaneous regulation in fluorescence of AIEgen-embedded hydrogels.

The development of stimuli-responsive functional fluorescent hydrogels is of great significance for the realization of artificial intelligence. In the present work, we design and synthesize a stimulus-responsive hydrogel embedded with an aggregation-induced emission (AIE) monomer, in which the fluorescence brightness and intensity can be tuned. The hydrogel embedded with tetraphenylethene-grafted-poly[3-sulfopropyl methacrylate potassium salt] (TPE-PSPMA) as the functional element is prepared by the radical polymerization method. Among them, the TPE core exhibits adaptive fluorescence ability through the AIE effect, while the PSPMA chain provides tunable hydrophilic properties under an external stimulus. The effect of different cationic surfactants with different lengths of hydrophobic tails on the fluorescence properties of TPE-PSPMA in solution is systematically investigated. With cationic surfactants, such as cetyltrimethylammonium bromide (CTAB), the fluorescence intensity is gradually tuned from 1059 to 4623. And the fluorescence intensities increase with the growth of hydrophobic tails of surfactants, which results from hydrophobicity-induced electrostatic interactions among surfactants and polymer chains. Furthermore, an obvious tunable fluorescence feature of hydrogel copolymerized TPE-PSPMA is realized, resulting from the change of brightness and the dynamic increase of fluorescence intensity (from 1031 to 3138) for the hydrogel immersed in CTAB solution with different soaking times. Such a typical fluorescence-regulated behavior can be attributed to the AIE of the TPE-PSPMA chain and the electrostatic interaction between the surfactant and the anionic polymer chain. The designed TPE-PSPMA-based hydrogel is responsive to stimuli, inspiring the development of intelligent systems such as soft robots and smart wearables.

Molecular dynamics study of “quasi-gemini” surfactant at n-decane/water interface: The synergistic effect of hydrophilic headgroups and hydrophobic tails of surfactants on the interface properties

Chemical enhanced oil recovery (EOR), especially surfactant injection, has recently received a great deal of attention. Proper selection of the surfactant can lead to a high recovery from an oil reservoir by alternating the wettability and reducing interfacial tension. It is important to understand how the efficiency in reducing the interfacial tension is related to the structure of a surfactant. In this work, the aggregation behavior and the interfacial performance of a series of "quasi-gemini" nonylphenol-substituted dodecyl sulfonate surfactants denoted as n-C12S(NP) (n = 1, 2, 3, 4) at n-decane/water interface are explored in detail by employing the all-atomic molecular dynamics simulation. The influence of the substitution position of benzene ring on the interfacial performance is investigated by analyzing the interaction between headgroup and water and the interaction between the alkyl tails and n-decane. The interaction between headgroup and water and the interaction between the alkyl tails and n-decane are investigated by analyzing the density profiles, the radial distribution function, coordination number, the number of hydrogen bonds and the interface thickness. Simulation results suggest that a subtle structural variation in the headgroup and tails results in significant effects on limiting interface tensions at the fixed coverage: the interface properties of 3-C12S(NP) and 4-C12S(NP) are significantly better than those of 1-C12S(NP) and 2-C12S(NP). 3-C12S(NP) leads to the lowest interface tension and the largest interface formation energy by having the strongest interaction with water and decane. The results are useful for designing high performance surfactants for oil displacement.

Effects of catanionic surfactant mixture adsorption on the wettability of PTFE and PMMA

Surfactants can regulate the wettability of a liquid on a solid substrate as they adsorb to solid-liquid and gas-liquid interfaces. In the present work, a catanionic surfactant mixture, sodium dodecyl sulfate (SDS) and dodecyltrimethylammonium bromide (C12TAB) mixed at a molar ratio of 2:1, showed outstanding synergistic effect in improving the wettability of low energy substrates (PTFE and PMMA). The adsorption behaviors of the catanionic surfactant mixture on PTFE and PMMA substrates were studied. The surface tensions and contact angles of aqueous solutions of SDS, C12TAB, and their mixture on PTFE and PMMA were measured, and the adhesion tension and adhesion work were calculated. Compared to individual SDS and C12TAB, the SDS-C12TAB mixture formed a compactly arranged layer at the PTFE-aqueous interface, thereby leading to a more significant hydrophilic modification of PTFE. In the PMMA system, the SDS-C12TAB mixture adsorbed to the PMMA-aqueous interface through acid-base interactions between the positively charged surfactant headgroups and the basic groups at PMMA surface and increased the hydrophobicity of the PMMA substrate at low surfactant concentrations. When the surfactant concentration exceeded the critical micelle concentration (CMC), the surfactant started to adsorb to the PMMA-aqueous interface through hydrophobic interactions between the hydrophobic surfactant tails and the nonpolar sites at PMMA surface, which further improved the wettability of PMMA. Overall, the wettability of low energy substrates can be significantly improved under the strong synergistic effect of commercial anionic and cationic surfactants without need of complex synthesis of new amphiphiles. Therefore, the catanionic surfactant mixtures may be a very promising system for regulating wettability.

Manipulating membrane surface porosity via deep insight into surfactants during nonsolvent induced phase separation

Nonsolvent induced phase separation (NIPS) is a basic and classic method of preparing porous membranes. Surfactants have often been used to improve flux of porous membranes prepared by NIPS. However, not much have been reported on systematically using surfactants to control surface pore formation. Herein, the interface intermedia role of surfactants, a new understanding of the pore-making role of surfactants in NIPS, is used to tailor the surface pore of porous membrane. By controlling the known hydrophilic interaction between the hydrophilic head of surfactant and solvent, hydrophilic additive, etc., the hydrophobic interaction between hydrophobic polymer and surfactant can be varied with the hydrophobic tail of surfactant. We find that the hydrophobic interaction, represented by the compatibility between hydrophobic polymer and the hydrophobic tail of surfactant, has a vital effect on the NIPS process. As a result, this method greatly increases the surface porosity (up to 22%), optimizes the pore size distribution, and finally improves the pure water flux of polymer membranes (10-fold increase, maximally). More importantly, it has no obvious adverse effect on the mechanical strength of polymer membranes and can be extended to various polymer materials.

Phase transition and release kinetics of polyphenols encapsulated lyotropic liquid crystals.

In this paper, the lyotropic liquid crystals formed in SL/IP/H2O system were prepared as a drug carrier system to encapsulate polyphenols. The components and introduction of drug had influences in the structure and rheological properties of lyotropic liquid crystals. The structure underwent a phase transition from lamellar phase (Lα) to Lα + HII (reverse hexagonal phase) mixed phases and micelle by increasing its IP/H2O mass ratio from 5/35 to 20/20 and 35/5, consistent with the transition from solid-like properties to viscous fluid properties. For the Lα + HII phase, the loading of DMY induced the structural transition to the HII phase, confirmed by SAXS results. This may be due to the penetration of DMY into the hydrophobic tails of surfactants. The in vitro release kinetic resulted that the release of drug in Lα was associated with diffusional mass transport and matrix swelling. While the release behavior of DMY in HII phase was predominantly controlled by concentration diffusion. These relationships among structure, rheology and release kinetics should be conductive to further design the drug sustained carrier system formed by lyotropic liquid crystals.

Controlled Formation of Hydrated Micelles by the Intervention of Cyclodextrins.

The interaction between surfactants and cyclodextrins (CDs) is well known. Studies have focused mainly on destruction of micelles with CDs to release the encapsulated drugs. However, less emphasis has been given on understanding the formation of micelles with the CD encapsulated surfactants. We have used fluorescence spectroscopy to study the impact of CDs on micelles using a fluorophore that has been tactically designed as a reporter. This molecule has a pyrene moiety on one end and a cationic head group on the other so that the orientation of the compound can be prefixed on micelle formation in aqueous environment. We have observed that the CD encapsulated surfactants can form "hydrated micelles" that allow extensive penetration of water molecules toward the core. The mechanism for such a process involves inclusion of the hydrophobic surfactant tails within the CD core and participation of these inclusion complexes in micelle formation. The process could be controlled by tuning the concentration of CD. The degree of hydration varies as the micelles get more opened up due to the residence of the CDs inside them.

Multiscale Modeling of the Effects of Salt and Perfume Raw Materials on the Rheological Properties of Commercial Threadlike Micellar Solutions

We link micellar structures to their rheological properties for two surfactant body-wash formulations at various concentrations of salts and perfume raw materials (PRMs) using molecular simulations and micellar-scale modeling, as well as traditional surfactant packing arguments. The two body washes, namely, BW-1EO and BW-3EO, are composed of sodium lauryl ethylene glycol ether sulfate (SLEnS, where n is the average number of ethylene glycol repeat units), cocamidopropyl betaine (CAPB), ACCORD (which is a mixture of six PRMs), and NaCl salt. BW-3EO is an SLE3S-based body wash, whereas BW-1EO is an SLE1S-based body wash. Additional PRMs are also added into the body washes. The effects of temperature, salt, and added PRMs on micellar lengths, breakage times, end-cap free energies, and other properties are obtained from fits of the rheological data to predictions of the "Pointer Algorithm" [ Zou , W. ; Larson , R.G. J. Rheol. 2014 , 58 , 1 - 41 ], which is a simulation method based on the Cates model of micellar dynamics. Changes in these micellar properties are interpreted using the Israelachvili surfactant packing argument. From coarse-grained molecular simulations, we infer how salt modifies the micellar properties by changing the packing between the surfactant head groups, with the micellar radius remaining nearly constant. PRMs do so by partitioning to different locations within the micelles according to their octanol/water partition coefficient POW and chemical structures, adjusting the packing of the head and/or tail groups, and by changing the micelle radius, in the case of a large hydrophobic PRM. We find that relatively hydrophilic PRMs with log POW < 2 partition primarily to the head group region and shrink micellar length, decreasing viscosity substantially, whereas more hydrophobic PRMs, with log POW between 2 and 4, mix with the hydrophobic surfactant tails within the micellar core and slightly enhance the viscosity and micelle length, which is consistent with the packing argument. Large and very hydrophobic PRMs, with log POW > 4, are isolated deep inside the micelle, separating from the tails and swelling the radius of the micelle, leading to shorter micelles and much lower viscosities, leading eventually to swollen-droplet micelles.

Two sides of the coin. Part 1. Lipid and surfactant self-assembly revisited

Hofmeister, specific ion effects, hydration and van der Waals forces at and between interfaces are factors that determine curvature and microstructure in self assembled aggregates of surfactants and lipids; and in microemulsions. Lipid and surfactant head group interactions and between aggregates vary enormously and are highly specific. They act on the hydrophilic side of a bilayer, micelle or other self assembled aggregate. It is only over the last three decades that the origin of Hofmeister effects has become generally understood. Knowledge of their systematics now provides much flexibility in designing nanostructured fluids.The other side of the coin involves equally specific forces. These (opposing) forces work on the hydrophobic side of amphiphilic interfaces. They are due to the interaction of hydrocarbons and other “oils” with hydrophobic tails of surfactants and lipids. The specificity of oleophilic solutes in microemulsions and lipid membranes provides a counterpoint to Hofmeister effects and hydration. Together with global packing constraints these effects determine microstructure.Another factor that has hardly been recognised is the role of dissolved gas. This introduces further, qualitative changes in forces that prescribe microstructure.The systematics of these effects and their interplay are elucidated.Awareness of these competing factors facilitates formulation of self assembled nanostructured fluids.New and predictable geometries that emerge naturally provide insights into a variety of biological phenomena like anaesthetic and pheromone action and transmission of the nervous impulse (see Part 2).

Probing the Microstructure of Nonionic Microemulsions with Ethyl Oleate by Viscosity, ROESY, DLS, SANS, and Cyclic Voltammetry

Microemulsions are important formulations in cosmetics and pharmaceutics and one peculiarity lies in the so-called "phase inversion" that takes place at a given water-to-oil concentration ratio and where the average curvature of the surfactant film is zero. In that context, we investigated the structural transitions occurring in Brij 96-based microemulsions with the cosmetic oil ethyl oleate and studied the influence of the short chain alcohol butanol on their structure and properties as a function of water addition. The characterization has been carried out by means of transport properties, spectroscopy, DLS, SANS, and electrochemical methods. The results confirm that the nonionic Brij 96 in combination with butanol as cosurfactant forms a U-type microemulsion that upon addition of water undergoes a continuous transition from swollen reverse micelles to oil-in-water (O/W) microemulsion via a bicontinuous region. After determining the structural transition through viscosity and surface tension, the 2D-ROESY studies give an insight into the microstructure, i.e., the oil component ethyl oleate mainly is located at the hydrophobic tails of surfactant while butanol molecules reside preferentially in the interface. SANS experiments show a continuous increase of the size of the structural units with increasing water content. The DLS results are more complex and show the presence of two relaxation modes in these microemulsions for low water content and a single diffusive mode only for the O/W microemulsion droplets. The fast relaxation reflects the size of the structural units while the slower one is attributed to the formation of a network of percolated microemulsion aggregates. Electrochemical studies using ferrocene have been carried out and successfully elucidated the structural transformations with the help of diffusion coefficients. An unusual behavior of ferrocene has been observed in the present microheterogeneous medium, giving a deeper insight into ferrocene electrochemistry. NMR-ROESY experiments give information regarding the internal organization of the microemulsion droplets. In general, one finds a continuous structural transition from a W/O over a bicontinuous to an O/W microemulsion, however with a peculiar network formation over an extended concentration range, which is attributed to the somewhat amphiphilic oil ethyl oleate. The detailed knowledge of the structural behavior of this type of system might be important for their future applications.

The Nature of the Sodium Dodecylsulfate Micellar Pseudophase as Studied by Reaction Kinetics

The nature of the rate-retarding effects of anionic micelles of sodium dodecyl sulfate (SDS) on the water-catalyzed hydrolysis of a series of substituted 1-benzoyl-1,2,4-triazoles (1a-f) has been studied. We show that medium effects in the micellar Stern region of SDS can be reproduced by simple aqueous model solutions containing small-molecule mimics for the surfactant headgroups and tails, namely sodium methyl sulfate (NMS) and 1-propanol, in line with our previous kinetic studies for cationic surfactants ( Buurma et al. J. Org. Chem. 2004 , 69 , 3899 - 3906 ). We have improved our mathematical description leading to the model solution, which has made the identification of appropriate model solutions more efficient. For the Stern region of SDS, the model solution consists of a mixture of 35.3 mol dm(-3) H(2)O, corresponding to an effective water concentration of 37.0 mol dm(-3), 3.5 mol dm(-3) sodium methylsulfate (NMS) mimicking the SDS headgroups, and 1.8 mol dm(-3) 1-propanol mimicking the backfolding hydrophobic tails. This model solution quantitatively reproduces the rate-retarding effects of SDS micelles found for the hydrolytic probes 1a-f. In addition, the model solution accurately predicts the micropolarity of the micellar Stern region as reported by the E(T)(30) solvatochromic probe. The model solution also allows the separation of the individual contributions of local water concentration (water activity), polarity and hydrophobic interactions, ionic strength and ionic interactions, and local charge to the observed local medium effects. For all of our hydrolytic probes, the dominant rate-retarding effect is caused by interactions with the surfactant headgroups, whereas the local polarity as reported by the solvatochromic E(T)(30) probe and the Hammett ρ value for hydrolysis of 1a-f in the Stern region of SDS micelles is mainly the result of interactions with the hydrophobic surfactant tails. Our results indicate that both a mimic for the surfactant tails (NMS) and a mimic for the surfactant headgroups (1-propanol) are required in a model solution for the micellar pseudophase to reproduce all medium effects experienced by a variety of different probes.

Study of the interaction between a diblock polyelectrolyte PDMA- b-PAA and a gemini surfactant 12- 6-12 in basic media

The interactions between negatively charged diblock polyelectrolyte PDMA 71- b-PAA 59 and oppositely charged gemini surfactant hexylene-1,6-bis(dodecyldimethylammonium bromide) (12- 6-12) in basic media were studied using dynamic light scattering, fluorescence spectroscopy, surface tension, and 1H NMR. With increased addition of surfactant, the conformation of polyelectrolyte experienced changes from the initial unimer with open-extended PAA block, to the nano-scaled aggregates/complexes with a maximum hydrodynamic diameter ( D h ), and finally to the stable complexes with a smaller D h . Accordingly, the value of D h during the whole process of increasing the surfactant concentration changed from 14–17 nm, to 184 nm, and to the final 70 nm, respectively. This transformation was driven by the electrostatic attractive/repulsive interactions, the hydrophobic interaction between hydrophobic surfactant tails, and the hydrophilicity of PDMA block.

Intercalation of methylene blue in n-alkanethiolated self-assembled monolayers: Versatile electrochemical platforms for characterizing surfactant adsorption on hydrophobic surfaces

A versatile electrochemical platform for characterizing the adsorption of neutral and positively charged surfactants on hydrophobic surfaces was established using methylene blue (MB) as the probe. As a rigid, planar and electroactive species, MB can intercalate inside the regular self-assembled monolayers (SAMs) of n-hexanethiol and exhibit well-defined electrochemical responses. The adsorption of surfactants on the hydrophobic SAMs through the intercalation interaction between the hydrophobic tails of surfactants and the SAMs might change the density of the SAMs and influence the electrochemical behaviors of MB, providing a simple but effective approach for characterizing surfactant adsorption on hydrophobic surfaces. As an example, the adsorptive behaviors of cetyltrimethylammonium bromide (CTAB), a positively charged surfactant, and Triton X-100, a neutral surfactant, on hydrophobic surfaces were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The results showed that these surfactants generally experienced three different adsorptive behaviors: the monomer adsorption at low concentrations, the loose monolayer adsorption at intermediate concentrations and the dense monolayer adsorption at high concentrations. In the case of CTAB, a new additional submonolayer adsorptive behavior between the monomer and the loose monolayer adsorption was observed for the first time, due to its rather long hydrophobic tail.

Effect of alcohol addition to the aqueous phase on the thermal effects of micellization of cationic benzyldimethyldodecylammonium bromide and its adsorption onto porous and nonporous silicas

Titration calorimetry has been used to study the effect of the addition of two primary alcohols, 1-butanol and 1-heptanol, to the aqueous phase on the thermal effects of micellization of benzyldimethyldodecylammonium bromide (BDDAB) as well as its adsorption onto nonporous Spherosil XO15M and onto porous aluminosilicate SiAl32 d 22 possessing uniformly sized mesopores. A linear decrease of the critical micelle concentration (CMC) of the cationic surfactant with the additive content was inferred from the specific conductivity measurements. All adsorption and calorimetry experiments were carried out at 298 K and at a fixed alcohol content (0.01 mol kg −1) either in deionized water or in a 0.01 mol kg −1 NaBr solution. Dilution calorimetry measurements allowed determination of the cumulative molar enthalpy changes and a new analysis of these data was proposed to calculate easily the enthalpy of micellization per mole of BDDAB, Δ mic h, and the CMC value. The alcohol addition was shown to render the micellization phenomenon more exothermic, the effect being larger as the chain length of alcohol increased. These effects were attributed to the location of alcohol molecules between the surfactant units, their hydroxyl groups close to the surfactant head-groups, in competition with the surfactant counterions. The individual isotherms of alcohol and surfactant adsorption onto XO15M and SiAl32 d 22 were determined. The plots of the pseudo-differential molar enthalpy of displacement, Δ dpl h, against the surface coverage by the surfactant cation, Θ BDDA+, were derived from the titration calorimetry data. The formation of surface-bound aggregates was thought to be a prerequisite for alcohol coadsorption at the solid–solution interface. At least two different types of adsolubilization sites were postulated, one of the sites being the same as in micelles and the other related to the contact area between the hydrophobic surfactant tails and the equilibrium bulk solution. Coadsorption (adsolubilization) of alcohol molecules at such sites was found to increase the exothermic contribution to the enthalpy of displacement per mole of the BDDA + adsorbed.

A new approach towards redispersable polyelectrolyte-surfactant complex nanoparticles

Redispersable and weakly cross-linked block copolymer particles with a core–shell structure were prepared by the use of a macroinitiator. Subsequent sulfonation of the polystyrene core and complex formation with a variety of cationic surfactants led to sterically stabilized, redispersable polyelectrolyte–surfactant complex particles with spherical shape and diameters of about 400 nm. Spontaneous microphase separation of the hydrophobic surfactant tails and the hydrophilic entities of the polyelectrolyte and the surfactant headgroups induces mesostructure formation within the particle cores. The characteristic lengths of the mesostructures formed depend mainly on the chain lengths of the surfactants and vary between 2 and 4 nm. For the first time, preformed nanoparticles were used as constrained nanogeometries for polyelectrolyte–surfactant complex formation.

DSC spectra as thermal fingerprints of percolative microemulsions

Three component percolative W/O microemulsions were studied by differential scanning calorimetry. Water-AOT-Decane, D2O-AOT-Decane, Water-AOT-Isooctane and Water-Ca(AOT)2-Decane systems were analyzed. Thus by changing, in the order, the dispersed phase, the dispersing medium, and by modifying the interphase region. The thermal history of the samples was monitored by a suitable thermal program. Following the latter, first order phase transitions associated with the freezing and/or melting of the two massive phases were obtained, as well as the higher order phase transition associated with the percolation process. From the melting spectra an estimate of the amount of water bound to the hydrophilic groups of the AOT as well as of that of oil bound to the hydrophobic surfactant tails was obtained. The latter result shows a difference in the behaviour of the continuous oily phase at the O/W interphase. From the freezing spectra, the percolative character of the microemulsion was evidenced by the exotherms associated with the freezing of the water phase.