One Convenient Preparation and Characterization of a New Amphiphilic Cationic Cyclodextrin Derivative 2-O-(Hydroxypropyl-N,N-Dimethyl-N-Dodecylammonio)-β-Cyclodextrin

A new amphiphilic cyclodextrin derivative 2-O-(hydroxypropyl-N,N-dimethyl-N-dodecylammonio)-β-cyclodextrin (2-HPDMDA-β-CD) was prepared and characterized by surface tension, electrical conductivity, dynamic light scattering, transmission electron microscopy (TEM) and steady-state fluorescence. 2-HPDMDA-β-CD was found to be a fine surfactant with a smaller critical micelle concentration (1.21 mM) value than that of dodecyltrimethylammonium chloride. TEM showed that 2-HPDMDA-β-CD could form two kinds of spherical aggregates in solution. The smaller one showed little concentration dependence while the larger one showed relatively strong concentration dependence. 2-HPDMDA-β-CD could be a fine host compound in molecular recognition with two functional spaces of the cyclodextrin cavity and micelles.     

Synthesis and Evaluation of Some Schiff Base Surfactants for Treating Crude Oil Emulsions

Water soluble nonionic surfactants based on Schiff base monomers were prepared by their etherification with β,^` β- dichlorodiethylether and PEG 400 in presence of NaOH. The surface properties of the prepared surfactants were determined by measuring the surface tension at different temperatures. The prepared nonionic surfactants were evaluated as demulsifiers for synthetic water in crude-oil emulsions that were pronounced at different ratios of crude oil: water at 45°C and 60°C. The experimental results showed that the dehydration rate of the prepared demulsifiers reached 90% and 100% at some concentrations.     

Preparation of Helical Mesoporous Ethenylene-silica Nanofibers with Lamellar Mesopores on Their Surface

The morphologies and pore architectures of mesoporous ethenylene‐silica were controlled using cetyltrimethylammonium bromide (CTAB) as template and (S)‐β‐citronellol as a co‐structure‐directing agent under basic conditions. When the (S)‐β‐citronellol/CTAB molar ratios are in the range of 0.75–2.0, helical nanofibers were obtained. With increasing the (S)‐β‐citronellol/CTAB molar ratio, the lengths of the nanofibers increases. Lamellar mesopores were identified on the surfaces of the nanofibers prepared in the (S)‐β‐citronellol/CTAB molar ratio range of 1.5–2.0. At the (S)‐β‐citronellol/CTAB molar ratio of 2.5:1, nanoparticles with nanoflakes on the surfaces were obtained. The field emission scanning electron microscopy images taken after different reaction times indicated that the helical pitches of the nanofibers decreased with increasing the reaction time. Helical 1,4‐phenylene‐silica and methylene‐silica nanofibers were also prepared. The results indicated that the morphologies and pore architectures of the obtained organic‐inorganic hybrid silicas are also sensitive to the hybrid silica precursors. Helical ethenylene‐silica nanofibers with lamellar mesopores on their surfaces can be also prepared using the mixtures of CTAB and racemic citronellol within a narrower citronellol/CTAB molar ratio range.     

Cyclodextrins as Surfactants for Solubilization and Purification of Carbon Nanohorn Aggregates

Nano‐ to micrometer‐scale surface roughness contributes to the hydrophobicity of materials as discussed often in terms of superhydrophobicity. We report here that as little as 1 wt% of α, β, and γ‐cyclodextrins (CDs) can disperse carbon nanohorn aggregates (CNHa) as surfactants in water by binding on their pointed tips. The binding mode was visually demonstrated using single‐molecule atomic resolution real‐time electron microscopy (SMART‐EM). The SMART‐EM data provided an estimation of the equilibrium constant of the CD binding to be close to that of adamantane ammonium chloride to β‐CD. A qualitative study on the rate of decomplexation of α, β, and γ‐CDs from CNHa suggests a substantial mechanistic difference in their binding mode to the CNH tips. A sequence of α‐CD complexation and decomplexation allows us to purify CNHa by selectively removing graphitic ball‐shaped impurity (GB). Upon treatment with NaNH₂, the purified CNHa produce GB‐free amino‐CNHa where the tips are functionalized with NH₂ groups.     

Charge-Transfer Chromatographic Study on the Interaction of Nonhomologous Series of Nonionic Surfactants with Heptakis(2,6-di-O-methyl)-β-cyclodextrin

Abstract

The interaction of 38 nonionic surfactants containing various hydrophobic moieties with dimethyl-β-cyclodextrin (DIMEB) was studied by charge transfer chromatography. DIMED modified the retention behaviour of each surfactant, however, the strength of interaction varied considerably. Both the lipophilicity and specific hydrophobic surface area of surfactants significantly influenced the strength of interaction. The presence of ester bond and double bond in the hydrophobic moiety of surfactants has impact on the complex formation.     

Demulsification of Crude Oil Emulsions Using Some New Water-Soluble Schiff Base Surfactant Blends

Six new surfactant blends were prepared by mixing one Schiff base non ionic surfactant prepared by etherification of Schiff base monomer with β, ^` β-dichlorodiethylether and PEG 400 in presence of NaOH with six water-soluble Schiff base nonionic surfactants prepared in the same way but etherified with PEG 2000. The mixing process was based on the high dehydration rates given by the PEG 400 Schiff base surfactant compared to the other PEG 2000 surfactants. The experimental results of this study indicate that the demulsification rates of these blends are higher than those of the PEG 400 surfactant. Demulsification process was carried out on an emulsion of w/o ratio 50:50 and studied at 60°C at two different concentrations of the demulsifiers (200 and 240 ppm). The dehydration rates of the six prepared blends reached 100%. The total dehydration time varied from 50 minutes up to 2 hours.     

Biosurfactants—An Overview

The large structural and functional variety of bio-surfactants (BS), which are produced by microorganisms, leads to the use of several methods to study these amphiphilic molecules. This review seeks to consolidate information on various surface-active product extraction techniques, microbiological screening methodologies, and analytical terminologies utilized in this sector. The potential benefits and drawbacks of various approaches for studying cell biomass or microbial culture broth for the generation of surface-reactive chemicals are also discussed. Additionally, the most popular techniques for detection, structural characterization, and purification of a variety of BS are introduced. A number of straightforward techniques are described in detail, including dialysis, ion exchange, solvent extraction, ultrafiltration, lyophilization, and thin layer chromatography (TLC). In addition to more sophisticated techniques like nuclear magnetic resonance (NMR), fast atom bombardment mass spectroscopy (FAB-MS), gas chromatography-mass spectroscopy (GC-MS), high-pressure liquid chromatography (HPLC), and infrared (IR), proteolysis and sequencing of amino acid are also explained. In this field of study, it is quite necessary to combine several analytical techniques, and it often takes multiple iterations to purify, isolate, and characterize different surface-active substances. The numerous approaches that are essential for researching bio-surfactants are covered in this review.     

Synthesis,chemistry, physicochemical properties and industrial applications of amino acid surfactants: A review

Surfactant use throughout mankind is extensive, from their initial applications as detergents extending to use in medicine, lubricant, cosmetics and even enhanced oil recovery. However, the image of surfactant use has in the past been tarnished by issues with low biodegradability and their synthesis from nonsustainable resources. Amino acid–based surfactants are a class of surfactants derived from a hydrophobe source coupled with simple amino acids, mixed amino acids from synthesis or from protein hydrolysates, and as such can be derived solely from renewable resources. There are several pathways for their synthesis and this allows for extensive structural diversity in this class of surfactants, resulting in widespread tuneable functionality in their physiochemical properties. This review includes the details of most of the available routes of synthesis for amino acid surfactants (AASs) and the impact of the diverse routes on their final physiochemical properties, including solubility, dispersability, toxicity and biodegradability. The diversity offered by the structural variation in AASs offers many exciting commercial opportunities for this ever-growing class of surfactants. It also includes a discussion on current and future potential uses of AASs.     

Synergistic Behavior of Binary Mixed Micellar Solution

Conductivity measurement has been used to study the properties of aqueous solutions of the nonionic polyoxyethylene sorbitan(20)monooleate (T₈₀) and the cationic 1,1′ lauryl amido propyl ammonium chloride (LAPACl) and their mixtures in the presence of 0.1 M HCl and at 303 K. The values of the critical micelle concentration (CMC) of the individual surfactants and their mixtures were determined from the conductometric measurements. Based on Rubingh's theory (approximation of the theory of regular solutions), the compositions of micelles (X₁), and the parameters of interaction between the molecules of cationic and nonionic surfactants (β) were calculated for mixture of systems LAPACl+α T₈₀ and T₈₀+α LAPACl. The mixture LAPACl+α T₈₀ showed synergistic interactions up to α=0.2 whereas those of T₈₀+α LAPACl registered antagonistic behavior. The study disclosed that for cationic/nonionic surfactants mixtures, the priority is for mixtures of cationic base with small mole fraction of nonionic surfactant and not the reverse.     

Mixed micellization and surface properties of non-ionic/cationic surfactants

We investigate the surface properties of aqueous binary mixtures of our cationic surfactant O-dodecyl-N,N′-diisopropylisourea hydrochloride (ISO-DIC C₁₂) with commercially available nonionic surfactant polyoxyethylene p-(1,1,3,3-tetramethylbutyl)phenyl ether (TritonX-100) at different temperatures (288 to 303?K). The micellization behavior of the binary systems is studied by determining the surface tension and other important physicochemical parameters, such as the critical micelle concentration (CMC), surface tension at the CMC(γ_cmc), Krafft Temperature (T_K), maximum excess concentration (Γ_max), minimum surface area per molecule (A_min), surface pressure at the CMC (П_cmc), and the adsorption efficiency (pC20) at the air/water interface. The study has additionally covered the calculation of thermodynamic parameters of micellization, including the standard Gibbs free energy, the standard enthalpy, the standard entropy, the free energy, and the Gibbs free energy of adsorption at air/water interface. The CMC values of the binary systems determined by experimental data are used to evaluate the micellar composition in the mixed micelle, the interaction parameter β and the activity coefficients f₁(ISO-DIC C₁₂) and f₂ (polyoxyethylene p-(1,1,3,3-tetramethylbutyl)phenyl ether) using the theoretical treatment proposed by Clint and Rubingh. Our results reveal that the proposed binary systems possess enhanced surface activity compared to those of the individual surfactants.     

Separation and sweeping of flavonoids by microemulsion electrokinetic chromatography using mixed anionic and cationic surfactants

In this report, a novel means for the separation and sweeping of flavonoids (quercetin, rutin, calycosin, ononin and calycosin-7-O-β-d-glucoside) by microemulsion electrokinetic chromatography using mixed anionic and cationic surfactants as modified pseudostationary phase was presented. The optimized background electrolyte consisted of 0.5% (w/v) ethyl acetate, 2.0% (w/v) SDS, 9 mM DTAC, 4.0% (w/v) 1-butanol and 10 mM sodium borate or 25 mM phosphoric acid. We systematically investigated the separation and preconcentration conditions, including the concentrations of surfactant, types of sweeping, sample matrix, the effect of high salt or acetonitrile, and sample injection volume. It was found that the use of mixed surfactants significantly enhanced the separation efficiency through the change of the efficient electrophoretic mobility of analytes. Compared with normal sample injection, 185-508-fold sensitivity enhancement in terms of limit of detection was achieved through effective sweeping of large sample volume at 50 mbar pressure (up to 45% capillary length). At last, the proposed method was suitable for the determination of Radix Astragali sample.     

Determination of Anionic Surfactant Turkey Red Oil by Capillary Electrophoresis with Direct UV Detection

A method using capillary electrophoresis with direct UV detection has been developed and validated for the determination of Turkey Red Oil (sulfonated castor oil). The highest performance with respect to separation efficiency and analysis time was achieved with 30 mM Tris (pH 8.0) buffer containing 7.5 mM HP-β-CD. The feasibility of the proposed CE method for the analysis of Turkey Red Oil surfactant in industrial water samples is demonstrated. Spiking of real samples gave recoveries between 90 and 106%. The CE results were compared with that obtained by GC-MS. It was concluded that CE can be a good alternative for fast determination of Turkey Red Oil component distribution in industrial process waters with no sample preparation other than dilution. However, the method sensitivity is not satisfactory for monitoring surfactant level in a waste effluent stream.     

Effects of nonionic sugar surfactants on the phase transition of DPPC membranes

The influence of newly synthesized N-alkanoyl-N-methyllactitolamines (decanoyl [C₁₀MELA], lauoroyl [C₁₂MELA] and miristoyl [C₁₄MELA]) on the thermotropic phase transition of phosphatidylcholine bilayer was compared with common sugar-based surfactants N-dodecyl-β-d-glucopyranoside [C12G1] and decanoyl-N-methyl glucamide [MEGA-10]. The results indicate that C_nMELA are very active at the membrane surface and disturb the phospholipid bilayer structure less than commercially used MEGA-10 and C12G1.     

Supramolecular Systems Based on Novel Mono‐ and Dicationic Pyrimidinic Amphiphiles and Oligonucleotides: A Self‐Organization and Complexation Study

Novel mono‐ and dicationic pyrimidinic surfactants are synthesized and their aggregation behavior is studied by methods of tensiometry and nuclear magnetic resonance (NMR) self‐diffusion. To estimate their potentiality as gene delivery agents, the complexation with oligonucleotides (ONus) is explored by dynamic light scattering (DLS) and zeta‐potential titration methods and ethidium bromide exclusion experiments. Bola‐type pyrimidinic amphiphile (BPM) demonstrates rather a weak affinity to ONus. Although it induces mixed associations with ONus, only slight charge compensation changes occur at a large excess of bola, with no recharging reached. Similarly, the ethydium bromide exclusion study reveals a slow increase in the binding capacity toward an ONu with an increment in BPM concentration. The monocationic pyrimidinic surfactant (MPM) and its gemini analogue (GPM‐1) are ranked as intermediates in both their aggregative activity and complexing properties toward ONus. They both form mixed associates with ONus well below the critical micelle concentrations (cmcs) of 2 and 15 mM respectively. However, GPM‐1 has a much lower isoelectric point at the molar ratio surfactant/ONu r～1 compared to r～3 for MPM. This probably indicates a larger electrostatic contribution to the ONu complexation in the case of GPM‐1. The most hydrophobic pyrimidinic surfactant (GPM‐2), bearing three alkyl tails, demonstrates enhanced aggregative activity and binding capacity toward ONus as compared to former pyrimidinic surfactants. Due to effective aggregative (low cmc of 0.04 mM ) plus binding properties (fraction of bound ONu β=0.76 at r=2.5), GPM‐2 may be ranked as a promising agent for wider biological applications.     

Synergistic interactions between zwitterionic surfactants derived from olive oil and an anionic surfactant

Abstract

The surface properties of the mixtures of zwitterionic surfactants derived from olive oil (carboxylbetaine-OCB and sulfobetaine-OSB) and anionic surfactant-sodium dodecylbenzene sulfonate (SDBS) at different mole fractions were investigated by surface tension measurement. The influences of the addition of inorganic salts (NaCl, MgCl₂) on the surface activities in OCB/SDBS and OSB/SDBS systems were also studied. The result shows that the two mixed systems possess lower CMC values and higher surface activities over all mole fractions studied than their individual components. Meanwhile, the noticeable synergistic interactions of OCB/SDBS and OSB/SDBS were determined by the micelle interaction parameter (β^m) according to regular solution theory. It is observed that the mixed OCB/SDBS system at α_OCB?=?0.6 and the mixed OSB/SDBS system at α_OSB?=?0.6 exhibit the strongest synergism. In addition, the binary surfactant mixtures performed better surface activities upon addition of inorganic salts and the different valence state of mental ions of the inorganic salts had different surface ability effect on the mixed system: Mg²⁺?>?Na⁺.     

Hydrogenated and fluorinated host-guest surfactants: complexes of cyclodextrins with alkanes and fluoroalkyl-grafted alkanes

A novel type of surfactants named "host-guest surfactants" were designed and synthesized. The headgroup and hydrophobic tail of the new surfactants are connected by supramolecular interactions rather than covalent bonds. The inclusion complexes of a series of cyclodextrins (CDs) and alkanes/fluoroalkyl-grafted alkanes were synthesized and measured by surface tension, XRD, XPS, TGA, and NMR spectroscopy. The methyl-β-CD/hexadecane complex showed surface activity relative to those conventional hydrogenated surfactants. For the inclusion complex of hydroxypropyl-α-CD/C(8)F(17)SO(2)NHC(8)H(17), the structure was locked by subtle intermolecular recognition, which ensured the surprising surface activity similar to common excellent fluorinated surfactants. This surfactant, which was fabricated from nonsurface-active even insoluble components, showed the prospect that its surface activity might also be destroyed by introducing appropriate small species to extrude the guest from the cavity.     

Cloud point variation of amphiphilic drug promethazine hydrochloride with added surfactants

In this paper we report clouding phenomenon occurring in an amphiphilic phenothiazine drug promethazine hydrochloride (PMT) in presence of surfactants. Cationic and nonionic surfactants increase the CP of 75 mM PMT solutions (prepared in 10 mM sodium phosphate buffer). These surfactants form mixed micelles with PMT. Anionic surfactants also form mixed micelles with the drug but the CP behavior is different by showing a peaked behavior. At low concentrations, anionic surfactants hinder micelle formation by forming ion-pairs whereas the usual CP decreasing effect at higher concentrations is due to mixed micellization. The CP behavior of 75 mM PMT+50 mM TBAB+surfactant systems is also explored which is found similar to PMT+surfactant systems with the difference only in magnitude of the clouding temperature.     

Synthesis and Aqueous Solution Properties of Polyoxyethylene Surfactants with Ultra-Long Unsaturated Hydrophobic Chains

Methoxypolyethylene glycols (M _n = 750, 1000, 2000, and 5000 g/mol) were hydrophobically modified by transestification with mono-unsaturated alkyl chains (UC18, UC22, and UC24), and the obtained ultra-long-chain nonionic surfactants were characterized by ¹H NMR, FTIR and gel permeation chromatographic, respectively. Aqueous solution properties of all these surfactants, including cloud point, surface activities, viscosifying ability, and phase diagrams were examined. It was found that all these ultra-long-chain polyoxyethylene surfactants exhibit good water solubility and typical Newtonian rheological behavior. For the surfactants with the same hydrophobic length, the CP, equilibrium surface tension (γ_cmc), as well as zero-shear viscosity (η₀) increase with increasing their hydrophilic length; for those with same hydrophilic head group, the critical micellar concentration and η₀ increase while the γ_CMC decreases with increasing hydrophobic tail length. Moreover, a decrease in the critical overlap concentration and an increase in the critical temperature were observed in phase diagrams of all these ultra-long-chain polyoxyethylene surfactants. (Supplemental materials are available for this article. Go to the publisher's online edition of the Journal of Dispersion Science and Technology to view the free supplemental file.)     

Microcolumn chromatography for the analysis of detergents and lubricants. Part 1: High temperature capillary gas chromatography (HT-CGC) and capillary supercritical fluid chromatography (CSFC)

High Temperature Capillary GC and Capillary SFC have been applied to the analysis of non-ionic lubricants, i.e. alkylphenol polyethoxylates (APnEO), ethoxylated alcohols (nEOAIc), polyethylene glycols (PEG), and ethoxylated triethanolamines (nEOEA); to the analysis of anionic lubricants, i.e. alkylbenzene-sulfonates (ABS), alkylsulfonates (AS), and ethoxylated phosphoric acids (nEOPhA); and to the analysis of cationic lubricants, i.e. quaternary ammonium salts (Quats). Both techniques are compared in terms of resolution and analysis time. The importance of derivatization in HT-CGC and CSFC is illustrated.     

Mixtures of branched non-ionic oligo-oxyethylene surfactants in aqueous solutions — the effect of molecular geometry on LC phase behaviour 4

The LC phase behavior of ternary mixtures of the two corresponding branched non-ionic surfactants 1,3-bis-(methoxy-tetraoxyethylene)-2-propoxy-tetradecane (Y-surfactant) and 1,3-bis-(heptyloxy)-2-propoxyoctaoxyethylene mono-methyl ether (V-surfactant) and water were studied by polarizing microscopy. The two branched surfactants, which have different molecular geometries but nearly the same hydrophilic-lipophilic volume ratio, exhibit extremely different phase behavior in binary surfactant/water systems. For the ternary mixtures of Y- and V-surfactant and water we found-according to established packing models-a continuous stabilization of the cubic and hexagonal phases and a destabilization of the lamellar phase with increasing amount of Y-surfactant. On the other hand, we observed a thermal stabilization of the lamellar phase. The maximal transition temperatures of the lamellar phase pass a maximum with increasing amount of Y-surfactant.