Wenlong Xu

Influence of Counterions on Lauric Acid Vesicles and Theoretical Consideration of Vesicle Stability

The counterions, including inorganic cations, Na(+) and Cs(+), and organic cation, (C(2)H(5))(4)N(+), influence the phase behavior and self-assembled structures of the lauric acid (LA) in water. Dissolving LA in NaOH, CsOH, and (C(2)H(5))(4)NOH (tetraethylammonium hydroxide, TeAOH) solutions, respectively, we observed that the three systems totally exhibited the same phase behavior, from birefringent L(α) phase/precipitates (P) → L(α) phase → L(α) phase/L(1) (micelles) → L(1). The temperature influence on phase behavior was investigated, and with an increase of temperature, we observed that less phase behavior change occurred in the systems of LA/CsOH/H(2)O and LA/TeAOH/H(2)O, while the phase behavior of the LA/NaOH/H(2)O system exhibited an obvious change. Cryogenic transmission electron microscopy (cryo-TEM) images demonstrated that the different microstructures of L(α) phase samples in the three systems existed. For the systems of LA/NaOH/H(2)O and LA/TeAOH/H(2)O, uni- and multilamellar vesicles coexist for L(α) phase samples, as both the morphology and size of these vesicles are polydisperse. The curvatures of the bilayer membranes of the two systems are considered to vary from positive, zero, and even negative. However, only spherically unilamellar vesicles exist in the system of LA/CsOH/H(2)O, indicating that the bilayers are more rigid than those in the LA/NaOH/H(2)O and LA/TeAOH/H(2)O systems. Through the combination of the Helfrich curvature energy theory and the mass-action model, the effective bending constant K = 0.5 k(B)T in the LA/CsOH/H(2)O system was obtained, demonstrating that the unilamellar vesicles are stabilized by thermal fluctuations. A primary discussion for the effect of the nature of counterions on the stability and deformation of the vesicles is presented.

Self-Assembled Peptide Nanofibers Encapsulated with Superfine Silver Nanoparticles via Ag⁺ Coordination.

We demonstrate that a glutanthione-based oligopeptide, Fmoc-GCE, could self-assemble into nanofibers induced by Ag(+) ions in NaOH solution. During the self-assembly process, the superfine silver nanoparticles were in situ produced on the nanofibers. On the basis of a series of characterizations, we proposed the possible mechanism of the self-assembly, for which the coordination interaction between Fmoc-GCE and Ag(+) ions as well as the π-π stacking of fluorenyl groups were the main driving forces of the self-assembled nanofibers. At appropriate compositions, the 3D networks of Fmoc-GCE/NaOH/Ag(+) nanofibers could further form metallogel, which was responsive to pyridine and melamine, which could coordination with Ag(+) ions. Moreover, the nanofibers encapsulated with superfine silver nanoparticles exhibited catalytic ability in degradation of the azo dye and the antibacterial properties to both Gram negative (E. coli) and Gram positive (S. aureus) bacteria.

CO2-Controllable Foaming and Emulsification Properties of the Stearic Acid Soap Systems

Fatty acids, as a typical example of stearic acid, are a kind of cheap surfactant and have important applications. The challenging problem of industrial applications is their solubility. Herein, three organic amines-ethanolamine (EA), diethanolamine (DEA), and triethanolamine (TEA)-were used as counterions to increase the solubility of stearic acid, and the phase behaviors were investigated systematically. The phase diagrams were delineated at 25 and 50 °C, respectively. The phase-transition temperature was measured by differential scanning calorimetry (DSC) measurements, and the microstructures were vesicles and planar sheets observed by cryogenic transmission electron microscopy (cryo-TEM) observations. The apparent viscosity of the samples was determined by rheological characterizations. The values, rcmc, for the three systems were less than 30 mN·m(-1). Typical samples of bilayers used as foaming agents and emulsifiers were investigated for the foaming and emulsification assays. CO2 was introduced to change the solubility of stearic acid, inducing the transition of their surface activity and further achieving the goal of defoaming and demulsification.

Transition of Phase Structures in Mixtures of Lysine and Fatty Acids.

Aggregation behaviors of the mixtures of lysine and fatty acids (FAs) with different chain lengths in aqueous solutions were investigated, and the self-assembled structural transition was determined in detail. Aggregates including micelles, vesicles, sponge structures, and fibers were observed by varying the compositions and the chain length of fatty acids. The sponge phase found in mixtures of octanoic acid and lysine was determined by freeze fracture-transmission electron microscope (FF-TEM). Circular dichroism (CD) signals were detected in the self-assembled structures due to the chirality of lysine molecules. The rheological properties of samples consisting of different aggregates formed by mixtures of lysine and fatty acids were measured, which provided the controlling factor of the chain length. The combined effect of noncovalent interactions including electrostatic interactions, hydrogen bonding, and hydrophobicity is supposed to be responsible for the aggregation behaviors, in which the hydrogen bonding acts as the main driving force in the self-assembled process.

Chiroptical Vesicles and Disks That Originated from Achiral Molecules

We report a chiral gel of vesicles and disklike micelles that originated from achiral molecules. The supramolecular chirality was obtained via regulating pH, in which a sol-gel-sol transition in a colloidal system consisting of a gelator, 4,4-di(2,3-dicarboxylphenoxyl)azobenzene (AzoNa4), and a zwitterionic surfactant, tetradecyldimethylamine oxide (C14DMAO), happened. The supramolecular chirality was related to the state of aggregation, i.e., only the condensed gels show chiral sense and sols are chiral-silent. The coexistence of vesicles and disklike micelles was captured for the first time in supramolecular chiral hydrogels by cryo- and freeze-fracture transmission electron microscopy (cryo- and FF-TEM) observations. Ascribed to the photoisomerization of the azobenzene units, upon alternative UV/visible light irradiation, the gel chirality can be switched reversibly with the macroscopic changes between vesicles/disks and wormlike micelles. A pH- and light-dual-responsive chiroptical switch can be constructed, which may require understanding the regulating membrane permeability and reagent release of structural transformation through photoisomerization and also require understanding the origin of gelation-induced supramolecular chirality completely based on achiral molecules.

Modulating self-assembly behavior of a salt-free peptide amphiphile (PA) and zwitterionic surfactant mixed system

A salt-free surfactant system formed by a peptide amphiphile with short headgroup (PA,C16-GK-3) and a zwitterionic surfactant (dodecyldimethylamine oxide, C12DMAO) in water has been systematically investigated. The microstructures and properties of C16-GK-3/C12DMAO mixed system were characterized using a combination of microscopic, scattering and spectroscopic techniques, including transmission electron microscopy (TEM), field emission-scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), Fourier transform infrared (FT-IR), circular dichroism (CD) and rheological measurements. Rich phase transitions have been observed by adjusting the concentration of C16-GK-3. Investigation of the hydrogels of C16-GK-3/C12DMAO with TEM, SEM and AFM showed that all of these hydrogels form nanobelts. The nanobelt formation is performed in a hierarchical manner: β-sheet peptides and C12DMAO first interact each other to form small aggregates, which then arrange themselves to form one dimensional (1D) left-handed ribbons. The ribbons further aggregated into flat and rigid nanobelts. We proposed a mechanism to interpret the self-assembly process according to the specific peptide structure as well as multiple equilibria between the hydrogen bonding interactions between the headgroups of C16-GK-3, between C12DMAO molecules and the headgroups of C16-GK-3, chirality of the amino acid residues and hydrophobic interactions of the alkyl chains.

Bilayers at High pH in the Fatty Acid Soap Systems and the Applications for the Formation of Foams and Emulsions.

In our previous work, we reported bilayers at high pH in the stearic acid/CsOH/H2O system, which was against the traditional viewpoint that fatty acid (FA) bilayers must be formed at the pKa of the fatty acid. Herein, the microstructures at high pH of several fatty acid soap systems were investigated systematically. We found that palmitic acid/KOH/H2O, palmitic acid/CsOH/H2O, stearic acid/KOH/H2O, and stearic acid/CsOH/H2O systems can form bilayers at high pH. The bilayer structure was demonstrated by cryogenic transmission electron microscopy (cryo-TEM) and deuterium nuclear magnetic resonance ((2)H NMR), and molecular dynamics simulation was used to confirm the formation of bilayers. The influence of fatty acids with different chain lengths (n = 10, 12, 14, 16, and 18) and different counterions including Li(+), Na(+), K(+), Cs(+), (CH3)4N(+), (C2H5)4N(+), (C3H7)4N(+), and (C4H9)4N(+) on the formation of bilayers was discussed. The stability of foam and emulsification properties were compared between bilayers and micelles, drawing the conclusion that bilayer structures possess a much stronger ability to foam and stronger emulsification properties than micelles do.

133Cs NMR and Molecular Dynamics Simulation on Bilayers of Cs+ Ion Binding to Aggregates of Fatty Acid Soap at High pH

Fatty acid bilayers are usually formed due to the hydrogen bonds between the protonated carboxyl (-COOH) and the deprotonated carboxylate (-COO(-)). Therefore, the formation of the bilayers must be at the pH around the pKa of the fatty acid, which is a narrow pH range (mostly about 7-9). Fatty acid bilayers can be used as cell membrane model but the narrow pH range largely limits their applications. Herein, fatty acid bilayers were first detected at high pH (>13) in the stearic acid (SA)/CsOH/H2O system, which is not consistent with the explanation of the traditional hydrogen bond theory for fatty acid bilayers around pH. Cryogenic transmission electron microscopy (cryo-TEM) images, X-ray diffraction (XRD) patterns, and deuterium nuclear magnetic resonance ((2)H NMR) spectra demonstrate the planar sheet bilayers. The pH, conductivity, and (133)Cs NMR data indicate the strong interaction between Cs(+) and the bilayers. Rheological characterizations reflect the viscoelasticity of the Lα phase sample of bilayers. Molecular dynamics simulation increases the reliability of our observations. The assumed growth process of the aggregates and the detailed arrangement of the Cs(+) on the bilayers were proposed according to the experimental data and the molecular dynamics simulation. This work will promote the application scope of fatty acid bilayers with wide pH range.

Self-Organization and Vesicle Formation of Amphiphilic Fulleromonodendrons Bearing Oligo(poly(ethylene oxide)) Chains

A new series of N-methylfulleropyrrolidines bearing oligo(poly(ethylene oxide))-appended Percec monodendrons (fulleromonodendrons, 4a-f) have been synthesized. The substituted position of the oligo(poly(ethylene oxide)) chain(s) on the phenyl group of the Percec monodendron for 4a-f was varied, which is at the 4-, 2,4-, 3,5-, 3,4,5-, 2,3,4- and 2,4,6- position, respectively. 4a-e are obtained as solids at 25 °C and can self-organize into lamellar phases as revealed by X-ray diffraction (XRD) and small-angle X-ray scattering (SAXS) measurements, while 4f appears as a viscous liquid. The substitution patterns of the oligo(poly(ethylene oxide)) chain(s) also significantly influence the solubility of 4a-f, especially in ethanol and water. Formation of self-organized supramolecular structures of 4d and 4e in water as well as 4d in ethanol is evidenced from UV-vis and dynamic light scattering (DLS) measurements. Further studies in water using various imaging techniques including transmission electron microscopy (TEM), freeze-fracture TEM (FF-TEM), cryo-TEM and atomic force microscopy (AFM) observations revealed the formation of well-defined vesicles for 4d and plate-like aggregates for 4e, indicating that the aggregation behavior of the fulleromonodendrons is highly dependent on their molecular structures. For 4d in ethanol, only irregular aggregates were noticed, indicating the solvent also plays a role on regulating the aggregation behavior. After functionalization with the Percec monodendrons, 4a-f can preserve the intriguing electrochemical properties of pristine C60 as revealed by cyclic voltammetries. The thermotropic properties of 4a-f have also been investigated. It was found that all of them show good thermal stability, but no mesophases were detected within the investigated temperature ranges.

Balance of coordination and hydrophobic interaction in the formation of bilayers in metal-coordinated surfactant mixtures.

Metal-ligand coordination and hydrophobic interaction are two significant driving forces in the aggregation of mixtures of M(n+) surfactants and alkyldimethylamine oxide (CnDMAO) in aqueous solutions. The coordinated systems exhibit rich aggregation behavior. This study investigated the effect of M(n+) ions (Zn(2+), Ca(2+), Ba(2+), Al(3+), Fe(3+), La(3+), Eu(3+), and Tb(3+)) and hydrophobic chains (hydrocarbon and fluorocarbon) on the formation of metal-coordinated bilayers. We found that fluorocarbon chains and branched hydrocarbon chains are preferable to the corresponding linear hydrocarbon chains for the formation of an Lα phase. Moreover, Lα phases formed by fluorocarbon chains exhibited higher viscoelasticity than ones formed by the hydrocarbons, and the bilayers formed by branched chains were rather flexible, revealing obvious undulation. The construction of bilayers was also strongly affected by metal ions due to their variable coordination ability with CnDMAO. Our results contribute to the understanding of the formation of metal-coordinated bilayers, which is driven by the interplay of noncovalent forces.