Lijuan Shi

Aggregation Behavior of Long-Chain N-Aryl Imidazolium Bromide in Aqueous Solution

The aggregation behavior of three long-chain N-aryl imidazolium ionic liquids (ILs), 1-(2,4,6-trimethylphenyl)-3-alkylimidazolium bromide [C(n)pim]Br (n = 10, 12, and 14), in aqueous solutions was systematically explored by surface tension, electrical conductivity, and (1)H NMR. A lower critical micelle concentration (cmc) for the N-aryl imidazolium ILs is observed compared with that for 1,3-dialkylimidazolium ILs [C(n)mim]Br, indicating that the incorporation of the 2,4,6-trimethylphenyl group into a headgroup favors micellization. The enhanced π-π interactions among the adjacent 2,4,6-trimethylphenyl groups weaken the steric hindrance of headgroups and thus lead to a dense arrangement of [C(n)pim]Br molecules at the air-water interface. An analysis of the (1)H NMR spectra revealed that the introduced 2,4,6-trimethylphenyl group may slightly bend into the hydrophobic regions upon micellization. The micelle formation process for [C(n)pim]Br (n = 10, 12, and 14) was found to be enthalpy-driven in the investigated temperature range, which is attributed to the strong electrostatic self-repulsion of the headgroups and the counterions as well as the π-π interactions among headgroups. Strong, stable fluorescence properties are presented by the new N-aryl imidazolium ILs, indicating their potential application in the field of photochemistry.

Aggregation behavior of 1-dodecyl-3-methylimidazolium bromide in aqueous solution: effect of ionic liquids with aromatic anions.

The effects of ionic liquids (ILs), 1-butyl-3-methylimidazolium methylsulfonate (bmimMsa), 1-butyl-3-methylimidazolium benzenesulfonate (bmimBsa), and 1-butyl-3-methylimidazolium 2-naphthalenesulfonate (bmimNsa), on the aggregation behavior of 1-dodecyl-3-methylimidazolium bromide (C12mimBr) in aqueous solution were investigated by surface tension, dynamic light scattering measurements, and (1)H NMR spectroscopy. The ability to promote the surfactant aggregation is in the order bmimNsa > bmimBsa > bmimMsa. Nevertheless, only bmimNsa distinctly reduces both the CMC value and the surface tension at CMC. Due to the penetration of C10H7SO3(-)anions into the surfactant aggregate, bmimNsa is found to induce a phase transition from micelles to vesicles, whereas the other ILs only slightly increase the sizes of micelles. The combined effect of intermolecular interactions, such as hydrophobic effect, electrostatic attractions, and π-π stacking interactions, is supposed to be responsible for this structural transformation, in which π-π stacking plays an important role.

Photoresponsive Self-Assembly of Surface Active Ionic Liquid

A novel photoresponsive surface active ionic liquid (SAIL) 1-(4-methyl azobenzene)-3-tetradecylimidazolium bromide ([C14mimAzo]Br) with azobenzene located in the headgroup was designed. Reversible vesicle formation and rupture can be finely controlled by photostimuli without any additives in the aqueous solution of the single-tailed ionic liquid. The photoisomerization of the azobenzene derivative was investigated by (1)H NMR and UV-vis spectroscopy. Density functional theory (DFT) calculations further demonstrate that trans-[C14mimAzo]Br has less negative interaction energy, which is beneficial to aggregate formation in water. The incorporation of trans-azobenzene group increases the hydrophobicity of the headgroup and reduces the electrostatic repulsion by delocalization of charge, which are beneficial to the formation of vesicles. However, the bend of cis-azobenzene makes the cis-isomers have no ability to accumulate tightly, which induces the rupture of vesicles. Our work paves a convenient way to achieve controlled topologies and self-assembly of single SAIL.

Supramolecular interactions via hydrogen bonding contributing to citric-acid derived carbon dots with high quantum yield and sensitive photoluminescence

Herein, we report the characterization of highly fluorescent citric-acid derived carbon dots (CACDs) synthesized by hydrothermal treatment of citric acid and diethylenetriamine below 200 °C. After being purified using a gel permeation chromatography cleanup system, the complexity and chemical composition of the CACDs were evaluated by liquid chromatography coupled with high-resolution Fourier transform ion cyclotron resonance mass spectrometry. The fluorophores consisted of five-membered ring fused 2-pyridones identified as the photoluminescence origin. M06-2X density functional calculations, surface tension and morphological studies suggested DETA@5CA serves as the main building block to fabricate supramolecular aggregates. Then we proposed that the dimeric and trimeric fluorophores coupled with DETA@5CA led to “dot” topologies in the CACDs solution under the effect of hydrogen bonding. In aqueous solution, the CACDs exhibited narrowly dispersed optical properties and a high fluorescent quantum yield (∼98%). Moreover, the supramolecular interaction induced CACDs have high sensitivity under various ambient conditions, such as pH, organic solvents and metal ions.

Aggregation behavior of zwitterionic surface active ionic liquids with different counterions, cations, and alkyl chains

A group of zwitterionic surface active ionic liquids (SAILs) with different counterions, cations and alkyl chains, 3-(1-alkyl-3-imidazolio)propanesulfonate β-naphthalene sulfonate, (CnIPS-Nsa, n = 12, 14), 3-(1-dodecyl-3-imidazolio)propanesulfonate benzenesulfonate (C12IPS-Bsa), and dodecyl-N,N-dimethylammonio-3-propane sulfonate β-naphthalene sulfonate (SB-12-Nsa), were synthesized. Their aggregation behaviors in aqueous solutions were systematically investigated by surface tension, dynamic light scattering (DLS) and 1H NMR spectroscopy. Surface tension and DLS results illustrated that the surface properties, micelle size, and micellization behavior of zwitterionic SAILs in aqueous solutions are significantly affected by the anion type, anionic structure and the hydrophobicity of the alkyl chain. The SAILs with more hydrophobic anions and long alkyl chains are expected to favor the micellization. The steric hindrance and hydrophobicity of the cations, as well as the binding strength of the cations with the anions, also play important roles in the aggregation of zwitterionic SAILs. Additionally, the micelle formation mechanism was acquired by detailed analysis of the 1H NMR spectra. The existence of π–π stacking between imidazolium and counterions was proved. The enhanced π–π stacking and hydrophobic effect of Nsa− can promote the aggregation of zwitterionic SAILs. Density functional theory (DFT) calculations illustrated that the negative interaction energy of the complexes were C12IPS-Bsa/H2O > SB-12-Nsa/H2O > C12IPS-Nsa/H2O > C14IPS-Nsa/H2O. It is more difficult to form micelles in complexes with more negative interaction energy. The counterion electronegativity of Nsa− is smaller than that of Bsa−, which favors the formation of micelles.

Controllable hierarchical self-assembly of gemini supra-amphiphiles: the effect of spacer length

Gemini supra-amphiphiles with different spacer lengths, [M-n-M]2+@2[DBS]- (n = 2, 6, 10), were easily constructed. The conformational flexibility and hydrophobicity of the spacer group can be effectively tailored through regulating the spacer length, leading to the fine control of the topologies and subsequent hierarchical self-assemblies of [M-n-M]2+@2[DBS]-. Vesicles are primarily fabricated by [M-n-M]2+@2[DBS]-, and then successively fused into vesicle clusters, nanotubes, and planar bilayers, whose bilayer curvatures are gradually decreased, with increasing spacer length. Coating [M-10-M]2+ with β-CD can reduce the flexibility and hydrophobicity of the decyl spacer, resulting in the reversion from planar bilayers to vesicles. Furthermore, stable aqueous two-phase systems (ATPSs) that spontaneously formed via vesicle fusion in the solutions of [M-n-M]2+@2[DBS]- (n = 6, 10) can act as functional supramolecular systems in the isolation and purification of oil-soluble biomaterials.

Multiple-Responsive Hierarchical Self-Assemblies of a Smart Supramolecular Complex: Regulation of Noncovalent Interactions

We herein report a smart amphiphilic supramolecular complex ([MimA-EDA-MimA]@[DBS]2) with stimuli-responsive self-assembly, constructed by 3-(3-formyl-4-hydroxybenzyl)-1-methylimidazolium chloride (MimACl), sodium dodecyl benzene sulfonate (SDBS), and ethylenediamine (EDA). The self-assembly of [MimA-EDA-MimA]@[DBS]2 shows triple-sensitivities in response to pH, concentration, and salt. At a low pH, only micelles are formed, which can transform into vesicles spontaneously when the pH increases to 11.8. Vesicles can gradually fuse into vesicle clusters and elongated assemblies with increasing concentration of [MimA-EDA-MimA]@[DBS]2. Chainlike aggregates, ringlike aggregates, or giant vesicles can be formed by adding inorganic salts (i.e., NaCl and NaNO3), which could be derived from the membrane fusion of vesicles. The noncovalent interactions, including π-π stacking, hydrogen bonding, and electrostatic interactions, were found to be responsible for the topology evolution of assemblies. Thus, it provides an opportunity to construct smart materials through the regulation of the role of noncovalent interactions in self-assembly.