Self-assembly of surfactants and polymorphic transition in nanotubes

We study self-assembly and polymorphic transitions of surfactant molecules in water within a nanotube and the effect of water-nanotube interactions on the self-assembly morphologies. We present a simulation evidence of a cornucopia of polymorphic structures of surfactant assemblies--many of which have not been observed in bulk solutions--through adjusting the water-nanotube chemical interactions which range from hydrophilic to hydroneutral and to hydrophobic. The ability to control the morphologies of surfactant assemblies within nanoscale confinement can be used for patterning the interior surface of nanochannels for application in nanofluidics and nanomedical devices.     

Phase Behavior of Bicontinuous and Water/Diesel Fuel Microemulsions Using Nonionic Surfactants Combined with Hydrophilic Alcohol Ethoxylates

Bicontinuous and water-in-diesel microemulsions were formulated using single nonionic alkyl poly glycol ethers combined with hydrophilic alcohol ethoxylates. The phase behavior at temperatures ranging from 0°C to 50°C was investigated. Visual inspection as well as cross-polarizers were used to detect anisotropy. The fish phase diagrams were determined. The presence of the hydrophilic alcohol ethoxylates was necessary to initiate both types of microemulsions. Increasing the hydrophobic chain length of the surfactant led to a wider range of temperature stability at lower surfactant concentration. Meanwhile, increasing the ethylene oxide units in the headgroup by two units led to a phase diagram that is dominated by lyotropic liquid crystal. The formulated water in diesel microemulsions were tested experimentally in a 4-cylinder diesel engine. From this it is observed that the emissions of NO_x, soot, and CO₂ were reduced substantially compared to neat diesel, while for the CO the reduction occurs just at low load.      

Dilational Rheology at Air/Water Interface and Molecular Dynamics Simulation Research of Hydroxyl Sulfobetaine Surfactant

Hydroxyl sulfobetaines with hexadecyl-, octadecyl-hydrophobic chain and an industrial product hydroxyl sulfobetaine were synthesized from analytical-grade and industrial-grade tertiary amine, respectively. The dilational properties and surface tension of the three surfactants at the water-air interface were investigated by drop shape analysis and ring method. The influences of oscillating frequency and bulk concentration on dilational properties were explored. The experimental results show that the dilational module of octadecyl-hydroxyl sulfobetaine was higher than hexadecyl hydroxyl sulfobetaine and the dilational elastic component of the three surfactants were higher than dilational viscous component. Furthermore, the dilational elastic component of mixed surfactant system shows two maxima in a lower concentration than that of single surfactant system. As a result, the surface tension of mixed surfactant system reaches to minimum value in a lower concentration compared with single surfactant system. The simulation results show that the hydrophobic chains in the mixed betaine solution were more curled than in single-component betaine solution ascribed to stronger interaction among different hydrophobic chains, resulting to a more compact interfacial film.     

Molecular simulation study on the self-assembly behaviors of zwitterionic heterogemini surfactant in aqueous solution

The self-assembly behaviors of a series of zwitterionic heterogemini surfactants C_mH_2m+1-PO^4–(CH₂)₂-N⁺(CH₃)₂-C_nH_2n+1, abbreviated as C_m-P-N-C_n (m, n?=?9, 9; 9, 12; 9, 15; 9, 18; 12, 12; 12, 15; 12, 18; 15, 15; 15, 18; 18, 18), have been investigated in aqueous solution by the dissipative particle dynamics (DPD) method. Morphologies such as sphere (S), rod (R), planar grid (PG), lamella (L), honeycomb (H), one-, two-, and three-dimensional tunnels (1DT, 2DT, and 3DT) have been observed showing more diversities than those of the corresponding symmetric gemini surfactants C_m-N-N-C_m (m?=?9, 12, 15, 18). With the increase of surfactant concentration in the aqueous solution, a distinct transition path ‘‘S—R—PG—3DT—L—2DT—1DT’’ is proved to be common for all the C_m-P-N-C_n systems. Besides, the hydrophobic chain length has a significant influence on the self-assembly behaviors in the case of m?≠?n. Radial distribution function is an effective method to quantitatively evaluate the interaction and relationship between each functional group in the surfactant molecule and water. Results can provide a new insight into the self-assembly behaviors of zwitterionic heterogemini surfactants and the corresponding applications.     

Equilibrium and Dynamic Surface Tension of Carboxymethylchitosan and Alkyl Trimethylammonium Bromide Mixtures

A water-soluble derivative of chitosan, carboxymethylchitosan (CMCH), was mixed with alkyltrimethylammoniumbromides (C_mTAB) and was studied on the adsorption at air/water interface using equilibrium and dynamic surface tension method. The effects of surfactant and polymer concentrations, surfactant chain length, as well as pH of solution were investigated. Addition of the surfactants remarkably promotes the polymer adsorption. Increasing any one of surfactant concentration, surfactant chain length, and pH will facilitate the adsorption of the mixture whereas little effects of polymer concentration were observed. The results are explained in terms of the interaction between CMCH and C_mTAB under different conditions.     

Formation of Vesicles from Amphiphilic Random Copolymers in Solution: A Dissipative Particle Dynamics Simulation Study

Five coarse-grained models were built for amphiphilic random copolymers. The self-assembly of amphiphilic random copolymers in selective solvent was investigated via dissipative particle dynamics simulations. The simulation results showed that the content of hydrophilic particles and the repulsive parameter between solvent and copolymer particles were two key factors of the vesicle formation. We report herein on how to control the self-assembled morphology evolution. The two mechanisms of vesicle formation from amphiphilic random copolymers are found through investigating the dynamic processes of vesicle formation, which is in accordance with the experiment and simulation results of amphiphilic block copolymer reported in the literature.      

Oleate Ester-Derived Nonionic Surfactants: Synthesis and Cloud Point Behavior Studies

The synthesis and cloud point behavior of high oleate ester-derived nonionic surfactants are now reported. The effect of various polyethoxylate chain lengths (polyethylene glycol with 7, 11, and 16 units of ethylene oxide (EO) monomer) as the surfactant's hydrophilic head on the cloud point was investigated. The effect of varying amounts of sodium chloride and five different ionic surfactants on the cloud points of the synthesized nonionic surfactants were also presented. When the chain length of polyethoxylate increased, the cloud point of the synthesized nonionic surfactant also increased, ranging from 16°C, 43°C, and 64°C for 7, 11, and 16 EO units, respectively. Increments in sodium chloride concentration depressed the cloud point values of the synthesized nonionic surfactants linearly. The addition of ionic surfactants elevated the cloud points of the synthesized nonionic surfactant. However, in the presence of sodium chloride, the cloud point of the mixed ionic-nonionic solution was suppressed and anincrease in ionic surfactant concentration was required to elevate the cloud point. It was also found that the cloud points of synthesized surfactants can be raised up to 95°C in the presence of 4wt% NaCl solution.     

Compositions and Physicochemical Properties of Tween Type Surfactants-Based Microemulsions

The compositions and physicochemical properties of the microemulsion systems consisting of Tween type surfactant (Tween 20, Tween 60, Tween 80)/butan-1-ol/dodecane/brine have been studied using ?-β fishlike phase diagram. From the ?-β fishlike phase diagram, solubility of the alcohol, composition of the interfacial layer, and solubilization ability of the microemulsion systems have been studied. The solubilization parameters of the microemulsion systems, SP* were in the order of magnitude Tween 60>Tween 80>Tween 20. The effects of different oils, alcohols, salinities and temperatures on the compositions and physicochemical properties have been investigated. The solubilization ability of the microemulsion systems increases with increasing salinities or decreasing temperatures. The effects of alcohols and alkanes display opposite patterns of change. By increasing the carbon chain length of the alkanol molecules, or decreasing the carbon chain length of the alkane molecules, the solubilization ability increases.     

Adsorption of SDBS and Its Effect on Rheology of Preformed Particle Gels

The adsorption of anionic surfactant sodium dodecylbenzenesulfonate (SDBS) onto preformed particle gels (PPGs) and the effect of SDBS on the swelling ratio and rheology of PPGs were investigated. SDBS molecules can adsorb onto PPGs because of the hydrophobic association with the chain of PPGs at low concentration and the association of the SDBS micelles with the chains of PPGs at high concentration. PPGs contract and the shear stress of PPGs decreases after adsorption of SDBS. In addition, the storage modulus decreases first and then increases with increasing SDBS concentration.     

Bulk Properties of Carboxymethylchitosan and Cationic Surfactant Mixtures: Fluorescence and Surface Tension Studies

The interactions between carboxymethylchitosan and alkyltrimethylammoniumbromides were studied in aqueous solution. The dependences of aggregation behavior on surfactant concentration, polyelectrolyte concentration, as well as surfactant chain length were investigated mainly using fluorescence spectroscopy method. The variation of I ₁/I ₃ of pyrene fully characterized the aggregation behavior of the polymer-surfactant complex. Meanwhile, based on that Nile red has the sensitivity to the environmental polarity different to pyrene, the changes of aggregates size and number can be reflected by the fluorescence spectroscopy of Nile red.     

两亲性含糖三嵌段共聚物的合成与自组装研究

以二(2-溴异丁酸)4,4′-联苯酯(BiBBP)为引发剂,采用顺序加料的方法,用原子转移自由基聚合法(ATRP)合成了一系列窄分子量分布的甲基丙烯酸甲酯(MMA)和6-O-甲基丙烯酰基-1,2;3,4-双-O-亚异丙基-α-D-吡喃半乳糖苷(MAIPGal)的三嵌段共聚物.用GPC和1H-NMR表征了聚合物的相对分子量和链段组成.结果表明,通过改变投料顺序可以合成ABA和BAB型2种三嵌段共聚物,改变投料比和控制单体的转化率可以调控聚合物的链段组成.聚合物脱保护后得到两亲性含糖共聚物.用TEM考察了聚合物在水溶液中的自组装行为,表明具有不同链段组成的共聚物可以形成不同形态的聚集体,含糖段组成高的聚合物易于形成大尺寸的胶团,含糖段组成低的聚合物易于形成结构清晰的囊泡、胶束,其中,含糖段在两边的BAB型共聚物易于形成囊泡,含糖段在中央的ABA型共聚物易于形成胶束.     

MODULAR SYNTHESIS OF AMPHIPHILIC MOLECULES - 7 NEW ROUTE TO LONG CHAIN N-ALKYLBETAINES STUDY OF THEIR ADSORPTION ONTO WOOL FIBERS

Anionic and cationic surfactants have formed the subject of numerous physicochemical investigations, but few studies have been devoted to amphoteric amphiphilic agents. In a series of investigations on new synthetic routes to novel surfactants, we devised a simple method for the preparation of N-alkylbetaïnes with different chain lengths:

In addition, we investigated the adsorption of these compounds onto wool fibers in aqueous media. The effects of pH, temperature and chain length on the adsorption isotherms were investigated. A relationship between the behavior of the surfactant at the solid/liquid interface and its behavior in solution was detected. Maximum adsorption was observed for values close to the critical micellar concentration.     

Unique Micellization and CMC Aspects of Gemini Surfactant: An Overview

Critical micelle concentration (CMC) is an essential fundamental property of surfactant molecules, as the CMC value provides significant information regarding the surfactant for industrial use. The industrial efficacy of surfactant molecules totally depends on its CMC value. Without a complete perceptive approach of CMC, it is impractical to employ surfactant molecules efficiently. This article provides an elaborate discussion of dimeric gemini surfactant and pays particular attention to the aggregation behavior, that is, micelle formation, CMC, and thermodynamics of micellization. Micelles structures, packing parameters, and properties of the micelles are summarized. The principles and techniques involved in the determination of CMC are discussed. Thermodynamics of micellization of dimeric surfactants including free energy, enthalpy, and entropy is successively reviewed. Superiority of gemini surfactant in respect of their CMC values is interpreted.     

Studies of Synergism in Binary Alkylbenzene Sulfonate Mixtures for Producing Low Interfacial Tensions at Oil/Water Interface

In order to study the synergism between alkybenzene sulfonate and alkybenzene sulfonate, five di-n-alkylbenzene sulfonates were used and the interfacial tensions of single sulfonates and their binary mixtures against a series of alkane homologues were measured. The effects of hydrophilic-lipophilic abilities of sulfonates and mixing ratio on synergism were discussed. It is revealed that the synergistic mechanism derives from the amelioration of the hydrophilic-lipophilic ability of the surfactant system, and the method to achieve synergism is adding the hydrophilic alkybenzene sulfonate to the lipophilic alkylbenzene sulfonate, and ultralow interfacial tensions can be obtained in proper mixing ratios. The results are useful for enhanced oil recovery.      

表面活性剂对污泥脱水性能影响的机理研究:Gemini表面活性剂与聚电解质相互作用的分子动力学模拟

表面活性剂可以与污泥表面的胞外聚合物(EPS)吸附形成胶束,释放出自由水和结合水,从而达到改善污泥脱水性能的目的.本文采用粗粒化的分子动力学模拟方法,研究了Gemini表面活性剂与EPS形成复合物的过程和结构.聚电解质链的亲疏水性对吸附过程有显著影响,亲水聚电解质链与Gemini表面活性剂吸附的主要驱动力为静电吸引,Gemini表面活性剂头基吸附在链上,尾链朝向溶剂;疏水聚电解质链与Gemini表面活性剂吸附过程由静电作用与疏水作用共同促进,Gemini表面活性剂以平行于聚电解质链的构型存在.Gemini表面活性剂联结基团长度对吸附过程的影响甚微;聚电解质链的电荷密度对亲水聚电解质链的吸附产生协同作用,对疏水聚电解质链的吸附不产生作用.