Lingling Ge

Formation and Microstructure Transition of F127/TX-100 Complex†

Formation and structure transition of the complex composed of triblock copolymer F127 and nonionic surfactant TX-100 have been investigated by 1H NMR spectroscopy, dynamic light scattering (DLS), and isothermal titration calorimetry (ITC). Three TX-100 concentration regions are identified, within which TX-100/20 mg/mL F127 complex undergoes different temperature-induced structure transitions. In low concentration region (< 9.42 mM), F127 single molecular species (unimers) wrap around TX-100 micelles forming F127/TX-100 complex with TX-100 micelle as the skeleton at a lower temperature (5 degrees C), and the skeleton transfers to F127 micelle at higher temperature (40 degrees C); in intermediate TX-100 concentration region (9.42-94.85 mM), the skeleton of F127/TX-100 complex transfers from TX-100 micelle successively into F127 micelle and TX-100 micelle again upon heating. The interaction of F127 with TX-100 is saturated in high TX-100 concentration region (> 157.57 mM), and free TX-100 micelles coexist with larger clusters of F127/TX-100 complexes. In addition, TX-100-induced F127/TX-100 complex formation and structure transition are also investigated at constant temperatures. The results show that within 5-10 degrees C, F127 unimers mainly adsorb on the surface of TX-100 micelles just like normal water soluble polymers; in the temperature region of 15-25 degrees C, TX-100 micelles prompts F127 micelle formation. Within 30-40 degrees C, TX-100 inserts into F127 micelles leading to the breakdown of F127 aggregates at higher TX-100 concentrations, and the obtained unimers thread through TX-100 micelles forming complex with TX-100 micelle as skeleton.

Janus emulsions formed with a polymerizable monomer, silicone oil, and Tween 80 aqueous solution.

Janus emulsions of a polymerizable monomer tripropyleneglycol diacrylate (TP) combined with silicone oil (SO) as inner oil phases and Tween 80 aqueous solution as continuous phase are prepared in a one-step high energy mixing process. The dependence of droplet topology on the concentration of surfactant, TP/SO ratio, and the stirring speed during emulsification is investigated. The result shows that the volume ratio of two oils within an individual droplet changes correspondingly to the total composition of emulsion. Increasing the speed of stirring results in a significant reduction in the droplet size, i.e. a five times increase in the stirring speed produces a droplet size reduction from hundreds to a few microns. What is more important, the topology of Janus drops remains similar for the different preparations. These fundamental investigations illustrate the potential for future Janus particle synthesis in batch scale with a controllable particle topology.

Binding Characteristics between Poly(ethylene glycol) and Hydrophilic Modified Ibuprofen in Aqueous Solution

The solubility of ibuprofen, a nonsteroidal anti-inflammatory drug (NSAID), is enhanced by synthesizing ibuprofen ester with a water-soluble polymer, poly(ethylene glycol) (PEG), and the product obtained functions as a nonionic surfactant (IBF-PEG800, IP800). The morphology and aggregation behavior of IP800 micelles and IP800/PEG complexes in aqueous solution are investigated by (1)H NMR technology, dynamic light scattering (DLS), isothermal titration calorimetry (ITC), and fluorescence resonance energy transfer (FRET). The microstructure of IP800 micelles is strongly related to the concentration of IP800. IP800 monomers can form looser micelles at relatively low concentrations and much tighter micelles at high concentrations. And the binding model of PEG with looser IP800 micelles dramatically depends on the molecular weight and concentration of PEG: PEG with lower molecular weight (MW < or = 2000 Da) inserts to the interface of the hydrophilic corona and hydrophobic core of IP800 micelles; PEG with higher molecular weight (MW > 2000 Da) binds to the surface of IP800 micelles, and one long PEG chain (6000 < MW < or = 20000 Da) wraps several IP800 micelles. Besides, the ratio of short chain PEG400 to IP800 micelles of the IP800/PEG complex is about 15:1 at a fixed concentration of IP800 (0.05 mM), and for the long chain PEG20000 it is 1:3-1:4.

Micellization behavior of the ionic liquid lauryl isoquinolinium bromide in aqueous solution

The micellization behavior of the ionic liquid lauryl isoquinolinium bromide ([C12iQuin]Br) in aqueous solution has been assessed using surface tension, electrical conductivity, and 1H nuclear magnetic resonance (NMR) measurements. The results reveal that the critical micelle concentration (CMC) and constant surfactant tension (γcac) are lower than that of butyl isoquinolinium bromide ([C4iQuin]Br), octyl isoquinolinium bromide ([C8iQuin]Br, and lauryl pyridinium bromide ([C12Pyr]Br). 1H NMR spectra show the evidence of paralleled π-stacking of adjacent isoquinoline rings. To elucidate the effect of the π–π interactions on the aggregation process, thermodynamic parameters such as the standard free energy, enthalpy, and entropy of aggregation have been discussed. These parameters are evaluated from the CMC with temperature by fitting these values to expressions derived from a micellization thermodynamic model. The enthalpy–entropy compensation phenomenon has been observed in the micellization process of [C12iQuin]Br in water, and the presence of isoquinoline cations is responsible for the decrease in the ΔHmic∗, compared with [C12Pyr]Br which has the same alkyl chain and counter-ion.

Aggregation of Double-Tailed Ionic Liquid 1,3-Dioctylimidazolium Bromide and the Interaction with Triblock Copolymer F127

The aggregation of ionic liquid-based double-tailed surfactant, 1,3-dioctylimidazolium bromide ([Doim]Br) and its interaction with pluronic copolymer F127 were systematically investigated by nuclear magnetic resonance (NMR), surface tension, dynamic light scattering (DLS), and isothermal titration calorimetry (ITC). It was found that the [Doim]Br aggregates are composed with the alkyl chains embedded in the micellar core and with the imidazolium rings parallel and staggered on the hydrophilic layer of micelles, which was generally different from the single-tailed IL [omim]Br. The hydrogen bonding between protons attached to the imidazolium rings and anion Br(-) was enhanced upon the aggregation of [Doim]Br. The aggregation of F127 was promoted by addition of [Doim]Br, which was more efficient than the single-tailed surfactant. At lower [Doim]Br content, [Doim]Br monomers embedded deeply into F127 micelle core. At higher [Doim]Br concentrations, the F127 micelles were disassociated, and then F127 chains penetrated into [Doim]Br micelle. In addition, the microstructure of F127/[Doim]Br complex can also be tuned by temperature.

Impact of Alkyl Chain Length on the Transition of Hexagonal Liquid Crystal–Wormlike Micelle–Gel in Ionic Liquid-Type Surfactant Aqueous Solutions without Any Additive

The search for functional supramolecular aggregations with different structure has attracted interest of chemists because they have the potential in industrial and technological application. Hydrophobic interaction has great influence on the formation of these aggregations, such as hexagonal liquid crystals, wormlike micelles, hydrogels, etc. So a systematical investigation was done to investigate the influence of alkyl chain length of surfactants on the aggregation behavior in water. The aggregation behavior of 1-hexadecyl-3-alkyl imidazolium bromide and water has been systematically investigated. These ionic liquid surfactants are denoted as C16-Cn (n = 2, 3, 4, 6, 8, 9, 10, 12, 14, 16). The rheological behavior and microstructure were characterized via a combination of rheology, cryo-etch scanning electron microscopy, polarization optical microscopy, and X-ray crystallography. The alkyl chain has great influence on the formation of surfactant aggregates in water at the molecular level. With increasing alkyl chain length, different aggregates, such as hexagonal liquid crystals, wormlike micelles, and hydrogels can be fabricated: C16-C2 aqueous solution only forms hexagonal liquid crystal; C16-C3 aqueous solution forms wormlike micelle and hexagonal liquid crystal; C16-C4, C16-C6 and C16-C8 aqueous solutions only form wormlike micelle; C16-C9 aqueous solution experiences a transition between wormlike micelle and hydrogel; C16-C10, C16-C12, C16-C14 and C16-C16 only form hydrogel. The mechanism of the transition of different aggregation with increasing alkyl chain length was also proposed.

Spontaneous emulsification between incompatible aqueous solutions in the water/ethanol/benzene system.

Two aqueous solutions on the de-mixing line in the water/benzene/ethanol system formed an O/W emulsion, when mixed. Contacting the solutions without mixing gave a slow spontaneous emulsification over several hours. The emulsion in question was found exclusively in the solution of greater water fraction and the dimension of the emulsion layer expanded as the square root of time. The reduction in the volume fraction the solution with less water was divided by the volume fraction of the emulsion, giving an - albeit exaggerated - measure of the volume fraction of the dispersed phase in the emulsion. It reached 0.6 after 1h, after which it remained constant for 3h. The composition change from the initial stage to the final equilibrium was calculated using a combination of the phase diagram features and earlier diffusion flux calculations in a similar system to estimate the fraction of the compounds transferred between the layers. These transfers were unexpectedly clear-cut, 95 wt% of the water in the less water solution was transferred into the water rich solution as was 80% of the ethanol. In the same manner 95% of the benzene in the water rich solution was relocated into the water poor solution.

Some experiments on complex spontaneous emulsification in the system water–benzene–ethanol

The system water–benzene–ethanol was used to illustrate the complexity of spontaneous emulsification, when water-poor emulsions are brought in contact with water. In the first case, an O/W emulsion located close to the plait point in the system was used. The aqueous phase in the emulsion was incompatible with water, and a strong spontaneous emulsification to an O/W between the two liquids took place in the water layer close to the interface between layers. In the second case, a W/O emulsion, also close to the plait point, was brought in contact with water. Now, the spontaneous emulsification between the water and the oil phase of the original emulsion to an O/W emulsion also took place in the water layer forming a distinct emulsion layer beneath the interface.

Improvement in lubricating properties of TritonX-100/n-C 10 H 21 OH/H 2 O lamellar liquid crystals with the amphiphilic ionic liquid 1-alkyl-3-methylimidazolium hexafluorophosphate

The applications of ionic liquids (ILs)/lamellar liquid crystals (LLCs) have great potential in nanotribology because they could be used where conventional oils could not work. To clarify the lubricating mechanism, herein, ILs/LLCs lubricants were prepared by addition of amphiphilic 1-alkyl-3-methylimidazolium hexafluorophosphate (CnmimPF6, n = 8, 12) into TritonX-100/n-C10H21OH/H2O LLCs with different concentration. The influence of alkyl chain lengths of ILs on the microstructures and the tribological properties of LLCs were investigated. The phase structure parameters and the tribological properties of the LLCs in the presence of CnmimPF6 were analyzed via freeze-fracture transmission electron microscopy (FF-TEM), the small-angle X-ray scattering (SAXS) technique, oscillating reciprocating friction and wear tester. Compared with the LLCs without CnmimPF6, 4.5 wt% CnmimPF6 /LLCs can reduce the friction and wear of sliding pairs. The better lubricating property and antiwear capability of the CnmimPF6/LLCs may be attributed to the increasing of the interlayer thickness d and the decreasing of the bilayer thickness d0 in microstructures. This work provides a better understanding of the relationship between the microstructures and friction wear performances of ILs/LLCs.

Viscosity Variation During Evaporation of a Vegetable Oil Emulsion Stabilized by Tween 80R

The viscosity during evaporation was determined for emulsions in the system water, vegetable oil, a commercial surfactant, Tween 80R, and the results related to the phases of the emulsion according to the phase diagram. The correlation between the viscosity and the fraction of liquid crystal in the emulsion was pronounced for the emulsions with the oil as the dispersed phase. For the emulsions with oil as the major phase, the effect was significantly less.