Higher Surfactant Concentrations Research Articles

Formation of N-nitrosamines by micelle-catalysed nitrosation of aliphatic secondary amines.

N-Nitrosamines are an important class of potent human carcinogens and mutagens that can be present in water and wastewater. For instance, N-nitrosamines can be formed by reaction of nitrosating agents such as NO+ or N2O3 formed from nitrite under acidic conditions with secondary amine precursors by an acid-catalysed nitrosation pathway. This study investigates the catalytic effect of cationic and anionic micelles on the nitrosation of secondary aliphatic amines in the presence of nitrite at different pH values. The results of this study demonstrate that the nitrosation of hydrophobic secondary amines (e.g., dipropylamine and dibutylamine) by nitrite was significantly enhanced in the presence of micelles of the cationic surfactant cetyltrimethylammonium chloride whereas anionic micelles formed by sodium dodecylsulfate did not significantly enhance the formation of N-nitrosamines. Rate enhancements of up to 100-fold were observed for the formation of N-nitrosodibutylamine in the presence of cetyltrimethylammonium chloride. The magnitude of the catalytic effect of cationic micelles on the nitrosation reaction depended mainly of the hydrophobicity of the amine precursors (i.e., alkyl chain length), the stability and the charge of the micelles and pH. One important enhancement factor is the lowering of the pKa of the precursor alkylammonium ion due to the electrical potential at the micelle-water interface by up to ∼2.5 pH units. These results suggest that cationic micelle-forming surfactants might play a role in the formation of N-nitrosamines in wastewater, consumer products and in industrial processes using high concentrations of cationic surfactants.

Hydrodynamic Signatures of Stationary Marangoni-Driven Surfactant Transport.

We experimentally study steady Marangoni-driven surfactant transport on the interface of a deep water layer. Using hydrodynamic measurements, and without using any knowledge of the surfactant physicochemical properties, we show that sodium dodecyl sulphate and Tergitol 15-S-9 introduced in low concentrations result in a flow driven by adsorbed surfactant. At higher surfactant concentration, the flow is dominated by the dissolved surfactant. Using camphoric acid, whose properties are apriori unknown, we demonstrate this method's efficacy by showing its spreading is adsorption dominated.

Confocal mapping of myelin figures with micro-Raman spectroscopy

We employ confocal micro-Raman spectroscopy (CMRS) with submicron spatial resolution to study the myelin structures (cylindrical lamellae) composed of nested surfactant C12E3 or lipid DMPC bilayers. The CMRS mapping indicates that for a straight C12E3 myelin, the surfactant concentration increases with the myelin width and is higher in the center region than in the peripheral region. For a curved C12E3 myelin, the convex side has a higher surfactant concentration than the corresponding concave side. The spectrum of DMPC myelins undergoes a qualitative change as the temperature increases above 60 °C, suggesting that the surfactant molecules may be damaged. Our work demonstrates the utility of CMRS in bio-soft material research.

Computer Simulations of Lipid Nanoparticles.

Lipid nanoparticles (LNP) are promising soft matter nanomaterials for drug delivery applications. In spite of their interest, little is known about the supramolecular organization of the components of these self-assembled nanoparticles. Here, we present a molecular dynamics simulation study, employing the Martini coarse-grain forcefield, of self-assembled LNPs made by tripalmitin lipid in water. We also study the adsorption of Tween 20 surfactant as a protective layer on top of the LNP. We show that, at 310 K (the temperature of interest in biological applications), the structure of the lipid nanoparticles is similar to that of a liquid droplet, in which the lipids show no nanostructuration and have high mobility. We show that, for large enough nanoparticles, the hydrophilic headgroups develop an interior surface in the NP core that stores liquid water. The surfactant is shown to organize in an inhomogeneous way at the LNP surface, with patches with high surfactant concentrations and surface patches not covered by surfactant.

A review of shampoo surfactant technology: consumer benefits, raw materials and recent developments.

Surfactants form the core of all shampoo formulations, and contribute to a wide range of different benefits, including cleansing, foaming, rheology control, skin mildness and the deposition of benefit agents to the hair and scalp. The purpose of this review was to assist the design of effective, modern, shampoo surfactant technologies. The mechanisms through which surfactants help deliver their effects are presented, along with the appraisal techniques through which surfactant options can be tested and screened for product development. The steps that should be taken to select the most appropriate blend of surfactants are described, and useful information on the most widely used surfactants is provided. The review concludes with an examination of recent developments in 'greener' surfactants, 'sulphate-free' technologies and structured liquid phases for novel sensory properties and for suspending benefit agents.

Colloidal Properties of Air, Oxygen, and Nitrogen Nanobubbles in Water: Effects of Ionic Strength, Natural Organic Matters, and Surfactants

Abstract Colloidal properties of nanobubbles (NBs) in liquid such as surface charge and surface tension influence stability (coalescence or size distribution), reactivity, and performance of applications (e.g., detergent-free cleaning, water treatment, and remediation) were studied. These colloidal properties are often effected by environmental factors such as pH, ionic strength, and the presence of natural organic matters (NOM). This work performed holistic investigations of colloidal properties of three types of NBs (pure air, oxygen, and nitrogen) in the presence of electrolytes, NOM, and surfactants, which are not reported elsewhere. Three different types of NBs exhibited different bubble size distribution (160–340 nm in water) and zeta potentials (approximately −27 to −45 mV at neutral pHs) presumably due to differences in their surface tension or charges. All tested NBs exhibited high stability against coalescence even under high ionic strength and surfactant concentrations. Soft particle extended D...

Crystallization of Nanodomains in Polyethylene Latexes

Semicrystalline polyethylene (PE) nanoparticles were obtained by free radical emulsion polymerization under mild conditions of pressure and temperature. At high surfactant concentration, the obtained anisotropic nanoparticles exhibit a strong degree of supercooling. This paper explores the relationship between the morphology of such particles and their high degree of supercooling. The shape anisotropy of the semicrystalline PE particles already observed by transmission electron microscopy was confirmed by dynamic light scattering with the autocorrelation function containing both translational and rotational diffusion coefficients as well as by in situ synchrotron small-angle and wide-angle X-ray scattering (SAXS/WAXS). Temperature-resolved synchrotron scattering was used to further characterize the evolution of particles morphology and crystallinity during cooling. Paying special attention to the role of the surfactant, we propose a novel mechanism which contributes to a better understanding of the crysta...

Toward Maximizing the Mechanical Property of Interconnected Macroporous Polystyrenes Made from High Internal Phase Emulsions.

Macroporous materials polymerized from high internal phase emulsions (PolyHIPEs) possess well-defined interconnected porous structures and tunable device shapes. This provides interesting property characteristics well-suited for a variety of applications. However, such materials also demonstrate poor mechanical performances, which limit their potential use. As will be demonstrated, this results from the high surfactant content required by PolyHIPEs. Herein, a new approach is introduced for designing a highly efficient polymeric surfactant, which generates interconnected pores in PolyHIPEs through designing an incompatible surfactant and skeleton material. The surfactant also possesses a hyperbranched topology, which combines the strong amphipathy of small molecular surfactants and the nanosphere structure of Pickering emulsifiers to provide an excellent colloidal stability to HIPEs. A hyperbranched polyethylene having pendant sodium sulfonate groups (HBPE-SO3Na) was thus designed and synthesized via chain walking copolymerization of ethylene and 2-trimethylsilyloxyethyl acrylate followed by sulfonation. Stable HIPEs of styrene/divinylbenzene and water at a weight ratio of 1 to 5 were obtained with using HBPE-SO3Na. The polymerization of HIPEs produced interconnected macroporous polystyrenes (PSs) at a substantially lower surfactant content, for example, 0.5 wt % HBPE-SO3Na. The compressive Young's moduli of PolyHIPEs reached 104-111 MPa with 0.5-2 wt % HBPE-SO3Na, which is the first reported case of a PS-based PolyHIPE achieving its theoretical modulus. The PolyHIPE was used to support Au nanoparticles and embed in a column for oxidation of dimethylphenylsilane. A complete conversion of dimethylphenylsilanol was achieved with low column back pressure in a 50 h continuous reaction with no degradation of PolyHIPE integrity and mechanical property.

Preparation of Organo-Montmorillonites and the Relationship Between Microstructure and Swellability

AbstractHydrophobicity, swellability, and dispersion are important properties for organo-montmorillonites (OMnt) and have yet to be fully characterized for all OMnt configurations. The purpose of the present work was to examine the preparation of OMnt from the reaction of Ca2+-montmorillonite (Ca2+-Mnt) with a high concentration of surfactant and to reveal the relevant properties of hydrophobicity and dispersion of the resultant OMnt. A series of OMnt samples were prepared using a small amount of water and cetyltrimethylammonium bromide (CTAB) with a concentration more than the CTAB critical micelle concentration (CMC). The relationship between OMnt microstructure and the hydrophobicity and swellability properties was investigated in detail. The resulting OMnt samples were characterized using powder X-ray diffraction patterns (XRD), Fourier-transform infrared (FTIR) spectroscopy, thermogravimetric and differential thermogravimetry (TG-DTG), water contact angle tests, swelling indices, and transmission electron microscopy (TEM). The addition of CTAB and water in the OMnt preparation affected the OMnt microstructure and properties. An increase in CTAB concentration led to a more ordered arrangement of cetyltrimethylammonium (CTA+) cations in the interlayer space of the OMnt and a large amount of CTA+ cations on the outer surfaces of the OMnt. The swelling indices and the water contact angles of OMnt samples depended on the distribution of the CTAB surfactant on OMnt and the orientation of the surfactant hydrophilic groups on the inner and on the outer surfaces of OMnt. A maximum swelling index of 39 mL/g in xylene was achieved with an average water contact angle of 62.0° ± 2.0° when the amount of CTAB added was 2 times the cation exchange capacity (CEC) of Mnt and the lowest water to dry Mnt mass ratio was 3 during the preparation of OMnt samples. The platelets of OMnt aggregated together in xylene by electrostatic attraction and by hydrophobic interactions.

Myoglobin and α-Lactalbumin Form Smaller Complexes with the Biosurfactant Rhamnolipid Than with SDS

Biosurfactants (BSs) attract increasing attention as sustainable alternatives to petroleum-derived surfactants. This necessitates structural insight into how BSs interact with proteins encountered by current chemical surfactants. Thus, small-angle x-ray scattering (SAXS) has been used for studying the structures of complexes made of the proteins α-Lactalbumin (αLA) and myoglobin (Mb) with the biosurfactant rhamnolipid (RL). For comparison, complexes between αLA and the chemical surfactant sodium dodecyl sulfate (SDS) were also investigated. The SAXS data for pure RL micelles can be described by prolate core-shell structures with a core radius of 7.7 Å and a shell thickness of 12 Å, giving an aggregation number of 11. The small core radius is attributed to RL’s complex hydrophobic tail. Data for the αLA-RL complex agree with a 12-molecule micelle with a single protein molecule in the shell. For Mb-RL, the analysis gives complexes of two connected micelles, each containing 10 RL and one protein in the shells. αLA-RL and Mb-RL form surfactant-saturated complexes above 5.6 and 4.7 mM RL, respectively, leaving the remaining RL in free micelles. The SAXS data for SDS agree with oblate-shaped micelles with a core of 20 Å, core eccentricity 0.7, and shell thickness of 5.45 Å, with an aggregation number of 74. The αLA-SDS complexes contain a prolate micelle with a core radius of 11−14 Å and a shell of 8−12 Å with up to 3 αLA per particle and up to 43 SDS per αLA, both considerably larger than for RL. Unlike the RL-protein complexes, the number of surfactant molecules in αLA-SDS complexes increases with surfactant concentration, and saturate at higher surfactant concentrations than αLA-RL complexes. The results highlight how RL and SDS follow similar overall rules of self-assembly and interactions with proteins, but that differences in the strength of protein-surfactant interactions affect the formed structures.

Synthesis and Characterization of Water-soluble Conjugates of Cabazitaxel Hemiesters-Dextran

Cabazitaxel (CTX) is a second- generation taxane derivative, a class of potent anticancer drugs with very low water solubility. CTX is used in patients with resistant prostate cancer unresponsive to the first generation taxane, docetaxel. Currently marketed formulations of CTX contain high concentrations of surfactant and ethanol, which cause severe hypersensitivity reactions in patients. In order to increase its solubility, two hemiester analogs; CTX-succinate and CTX-glutarate were synthesized and characterized. To improve the solubility of hemiesters even more, dextran as a biocompatible polymer was also conjugated to hemiester analogs. MTT assay was performed on MCF-7 cell line to evaluate the cytotoxicity effect of hemiesters and conjugates. Based on the results, hemiester analogs increased water solubility of the drug up to about 3 and 8 fold. Conjugation to dextran enhanced the CTX solubility to more than 1500 fold. These conjugates released the conjugated CTX in less than 24 hours in a pH dependent manner and showed proper hemocompatibility characteristics. The hemiesters had approximately similar cytotoxicity in comparison with CTX and the dextran conjugates showed higher cytotoxicity effect on MCF-7 cell line.

Application of micellar-enhanced ultrafiltration in the pre-treatment of seawater for boron removal

In this research, micellar enhanced ultrafiltration (MEUF) is tested as a seawater pre-treatment before entering RO. The experimental tests were performed by means of monotubular ceramic membranes of 210kDa and 1kDa. Boron is removed from the water flow using sodium dodecyl sulphate as a surfactant. The synthetic solutions contain 5mg/L of boron and SDS concentrations are equal to 1.15g/L and 2.88g/L, under and above the critical micellar concentration, respectively.Experimental data showed that MUEF is efficient in removing boron, with best performances obtained at low pressure, with a low or null surfactant concentration for 1kDa membrane and a high surfactant concentration for 210kDa membrane. Moreover, experimental results have been used to perform a preliminary process analysis for a hypothetic sea-water desalination plant, with MEUF as a pretreatment for the RO section. The results showed that the MEUF guarantees a boron concentration after RO below the allowed threshold, by using a single step osmosis; moreover, in this way it was possible to reduce the energy consumption thus resulting in an appreciable reduction of carbon footprint as well as of the unit cost of water.

Thermomechanical performance of blended metakaolin-GGBS alkali-activated foam concrete

This study aims to synthesize, at ambient temperature, blended metakaolin-ground granulated blast furnace slag (MK-GGBS) foam concrete (FC) presenting acceptable thermomechanical performance for use as self-bearing insulation material. First, a binder composition that could be used for MK-GGBS FC production was identified. Fourteen paste formulations were produced and analysed to determine the best proportions of MK, GGBS and activator to be used in an alkali-activated material (AAM) FC matrix. Certain requirements were specified for the fresh paste (initial setting time >180min) and solid materials (high compressive strength and moderate shrinkage) to be used for FC production. The optimized mix was then employed for AAM FC production by using an H2O2 blowing agent (gas-foaming method). The influence of two main parameters (H2O2 and surfactant contents) on AAM FC properties (density, porous structure, thermal conductivity and compressive strength) were investigated. FC density mostly depends on H2O2 content. The FC porous structure depends strongly on both H2O2 and surfactant contents. High surfactant content FCs have a thin homogenous porous structure. At constant density, FC compressive strength depends on the surfactant content. An optimized surfactant content maximizing FC compressive strength at constant density was identified.

Preparation of Magnetic Zinc Ferrite Nanoparticles and their Photocatalytic Performance

Zinc ferrites (ZnFe2O4) nanoparticles were successfully prepared by the simple co-precipitation method. The effects of calcination temperature and the amount of surfactant on the microstructure of zinc ferrite products were studied. The products were characterized with X-ray diffraction (XRD), Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and UV-Vis diffuse reflectance spectroscopy (DRS). The XRD results confirmed the formation of a cubic spinel structure in all samples. The SEM results revealed that surfactant molecules play a crucial role to control the microstructure of the samples. All samples showed extended absorptions in the visible region. The photocatalytic results indicated that ZnFe2O4 enhanced the photocatalytic activity with increased calcination temperature. In addition, the ZnFe2O4 prepared by addition of high concentrations of surfactant gave the highest photocatalytic activity. The synthesized ZnFe2O4 can be recovered by applying an external magnetic field.

Fabrication of carbon nanospheres by the pyrolysis of polyacrylonitrile-poly(methyl methacrylate) core-shell composite nanoparticles.

Carbon nanospheres with a high Brunauer–Emmett–Teller (BET) specific surface area were fabricated via the pyrolysis of polyacrylonitrile–poly(methyl methacrylate) (PAN–PMMA) core–shell nanoparticles. Firstly, PAN–PMMA nanoparticles at high concentration and low surfactant content were controllably synthesized by a two-stage azobisisobutyronitrile (AIBN)-initiated semicontinuous emulsion polymerization. The carbon nanospheres were obtained after the PAN core domain was converted into carbon and the PMMA shell was sacrificed via the subsequent heat treatment steps. The thickness of the PMMA shell can be easily adjusted by changing the feeding volume ratio (FVR) of methyl methacrylate (MMA) to acrylonitrile (AN). At an FVR of 1.6, the coarse PAN cores were completely buried in the PMMA shells, and the surface of the obtained PAN–PMMA nanoparticles became smooth. The thick PMMA shell can inhibit the adhesion between carbon nanospheres caused by cyclization reactions during heat treatment. The carbon nanospheres with a diameter of 35–65 nm and a high BET specific surface area of 612.8 m2/g were obtained from the PAN–PMMA nanoparticles synthesized at an FVR of 1.6. The carbon nanospheres exhibited a large adsorption capacity of 190.0 mg/g for methylene blue, thus making them excellent adsorbents for the removal of organic pollutants from water.

Effect of surfactant concentration to aggregations of nanogold particles

This research presents a study of aggregation of colloidal gold nanoparticles using 400 nm diameter gold nanoparticles mixed with a surfactant (Plantacare 2000) at various concentrations. When observed under a microscope, we found that the nanoparticles aggregated to form nearly spherical clusters at the beginning of the formation, and then sedimented to the bottom of the container. These clusters moved with Brownian’s motion and collided with each other in the horizontal plane, forming branch-like clusters in 2D. The appearance and size of the clusters were different depending on the concentration of surfactant. The clusters’ size and appearance were rarely changed after mixing with surfactant for 90 minutes, and we found that the cluster’s shapes were nearly spherical at low surfactant concentration (c = 0.25%). At surfactant concentration between 0.50% - 5.00%, the aggregates formed branch-like clusters with skinnier branches and smaller sizes at higher surfactant concentration. Moreover, we also found that, at surfactant concentrations between 2.50% - 5.00%, nanoparticles and aggregates stuck to the bottom of the glass container quickly and rarely moved after 10 minutes. At c = 0.25%, the 2D fractal dimension of the aggregates was measured to be D = 1.88 ± 0.04, since the aggregates were nearly spherical. The fractal dimension decreased to the minimum of D = 1.50 ± 0.12 at c = 1.50%, similar to D ∼ 1.45 found in diffusion-limited cluster aggregation (DLCA). At surfactant concentration above 1.50%, the fractal dimension increased until it reached the value of D ∼ 1.66 at c = 5.00%.

Synergistic stabilization of Pickering emulsions by in situ modification of kaolinite with non ionic surfactant

Synergistic stabilization of decane/water emulsions with a combination of kaolinite and non ionic surfactant SPAN-80 is explored. Pure kaolinite being charged and very hydrophilic is a poor stabilizer of emulsions even when sufficient quantity of salt is added to screen electrical double layer interactions. However, the hydrophobicity (via. contact angle) of kaolinite can be tuned with increasing concentration of SPAN-80 leading to very stable O/W emulsions when both kaolinite and SPAN-80 are used. This is due to increase in hydrophobicity of kaolinite particles due to surfactant adsorption which enables them to get adsorbed at oil/water interface more efficiently. Adsorption of kaolinite at emulsion droplets is demonstrated through fluorescently labeled kaolinite. Emulsions phase inverted from O/W to W/O at very high concentrations of surfactant. This phase inversion is due to competitive adsorption of excess unadsorbed surfactant. Other general features such as the effect of salt, pH, oil/water ratio on emulsion formation, stability, type and droplet size has been studied.

Coalescence stability of water-in-oil drops: Effects of drop size and surfactant concentration

We study the effects of (1) drop size; (2) surfactant chain-length and concentration; and (3) viscosity of the oil phase on the stability of water drops, pressed by gravity towards planar oil-water interface. The experimental results show that at low surfactant concentrations (around and below the CMC) the drop lifetime is controlled by the drainage time of the oily film, viz. by the time for reaching the critical film thickness at which this film ruptures. The small drops coalesce before the formation of a planar film with the large interface and, as a consequence, their lifetime rapidly decreases with the increase of drop diameter. In contrast, the bigger drops coalesce after formation of a plane-parallel film and their lifetime increases with the drop diameter. Therefore, the drop lifetime passes through a minimum when varying the drop diameter. The obtained results at low surfactant concentrations and for small drops are described well by theoretical models, available in the literature. The lifetime of the respective larger drops is shorter, as compared to the theoretical predictions, due to the faster thinning of the oil films which are with uneven thickness. The increase of surfactant concentration above the CMC leads to a significant increase in the stability of the small drops. Interestingly, the stability of the intermediate in size drops remains low for all surfactants and oils studied. At higher surfactant concentrations, the stability of the large water drops increases significantly when Span 80 is used, while it remains rather low for drops stabilized by Span 20. The results obtained with single water drops are in a good agreement with the stability of the respective batch water-in-oil emulsions.

Preparation of lipid nanoparticles with high loading capacity and exceptional gastrointestinal stability for potential oral delivery applications

Exploitation of lipid nanoparticles for oral delivery of nutrients and drugs is limited by their poor stability under gastrointestinal tract and low loading capacity, unless a high concentration of synthetic surfactants is formulated. The main objective of present study is to design a series of new formulations for solid lipid nanoparticles (SLN) and nanostructured lipid carriers (NLC) that are suitable for potential oral delivery applications, using natural biopolymers, i.e. sodium caseinate (NaCas) as emulsifier and pectin as coating, with minimal addition of a synthetic surfactant, Tween 80. Effects of pectin coating, concentration of Tween 80, thermal treatment (80°C for 30min), as well as two chemical cross-linkers on the particulate characteristics, stability, encapsulation efficiency, controlled release and drying feasibility were comprehensively investigated. The intermolecular interactions and cross-linking reactions were studied using Fourier transform infrared spectroscopy. Tween 80 at 0.15% (w/v) together with 0.15% (w/v) NaCas was proved effective to obtain stable cross-linked pectin-coated SLN (PSLN) under 200nm with high loading capacity for curcumin, while NLC prepared under the same condition failed to pass storage stability test. The 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) cross-linked PSLN exhibited superior characteristics than glutaradehyde (GA) cross-linked PSLN, especially for the stability and controlled release under simulated gastrointestinal conditions, with curcumin studied as a model compound. The feasibility of both nano spray drying and freeze-drying technologies were both investigated to transform of colloidal lipid nanoparticles into dry powders. Our results demonstrated a novel strategy to prepare small and homogenous SLN with exceptional GI stability and high loading capacity as a potential oral delivery system.

Experimental Investigation of the Mechanism of Foaming Agent Concentration Affecting Foam Stability

AbstractWith the aim of determining the effect of foaming agent concentration (FAC) on foam stability, the half‐life of a selection of typical foaming agents was investigated at different concentrations using the FoamScan® instrument. The surface tension of the bulk solution after foaming was tested using a surface tension meter. The FAC had a significant effect on foam stability at concentrations <1%, and a weak relationship at concentrations >1%. A significant turning point in the plot of foam stability versus FAC indicated maximum foam stability. The concentration at this point was defined as the optimal stability concentration, which is a guide in foam application. The micelles were thermodynamically unstable at low concentrations and degraded into surfactant solution, but were extremely stable at high surfactant concentrations that did not affect the stability of the foam. A turning point was also observed in the plot of surface tension versus FAC, beyond which the surface tension remained constant; the concentration at this point was defined as the no spherical micelle concentration. The influence of FAC on foam stability is explained in terms of mean bubble diameter (dmb) and bubble size distribution.