Mengjun Chen

Self-Assembly and Rheological Properties of a Pseudogemini Surfactant Formed in a Salt-Free Catanionic Surfactant Mixture in Water

The surface and bulk properties of bola-type dicarboxylic acid (sebacic acid, SA) and zwitterionic surfactant tetradecyldimethylamine oxide (C14DMAO) mixtures in aqueous solutions were studied. Surface tension measurements indicate a pronounced synergistic effect between SA and C14DMAO. In bulk aqueous solutions, rich phase behavior was observed with a varied SA-to-C14DMAO ratio (ρ) and a total surfactant concentration. Typically at ρ = 0.5, a novel pseudogemini surfactant (C14-S-C14) forms, driven by electrostatic interaction and hydrogen bonding. The C14-S-C14/H2O system exhibits rich phase behavior induced by the transition of aggregates. With increasing concentration of C14-S-C14, one can observe a viscous L1 phase, an L1/Lα two-phase region where a birefringent Lα phase is on the top of an L1 phase, a single Lα phase, and finally a mixture of an Lα phase and a precipitate. Microstructures formed in the Lα phases were determined by freeze-fracture transmission electron microscopy (FF-TEM) and cryogenic-transmission electron microscopy (cryo-TEM) observations. Polymorphic aggregation behavior was observed with the formation of a variety of bilayer structures including unilamellar vesicles, onions, and open and hyperbranched bilayers. Rheological measurements showed that the Lα phases are viscoelastic and sensitive to temperature where a quick loss of viscoelasticity was observed at elevated temperature.

Robust onionlike structures with magnetic and photodynamic properties formed by a fullerene C60–POM hybrid

We report for the first time the synthesis of a covalently-linked fullerene C60-Dawson POM hybrid, which can form onionlike structures with rich magnetic, electrochemical and photodynamic properties.

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.

Tunable assembly and disassembly of responsive supramolecular polymer brushes

We report the synthesis and assembly of light-responsive supramolecular polymer brushes based on the host–guest interaction between β-cyclodextrin (β-CD) on star-like side chains and azobenzene groups on a polymer backbone. The fraction of the hydrophilic–hydrophobic units can be easily controlled via changing the ratio of host and guest molecules. The supramolecular polymer brushes can self-assemble into unimolecular micelles, multi-molecular micelles, and vesicles with tunable sizes from 28 to 300 nm in water, respectively, with the decrease of β-CD side chains. The assemblies of micelles or vesicles can be disassembled by the trigger of UV light irradiation due to the responsive azobenzene groups. In addition, the phase transition temperature of the supramolecular polymer brushes increases with the decrease of the side chains. The micelles or vesicles can further assemble into strawberry superstructures by increasing the temperature. Our work provides a platform for the generation of assemblies across a wide range of scales, from polymer brushes to micelles or vesicles and superstructures.

Properties and ionic self-assembled structures from mixture of a bola-type strong alkali dication and a branched phosphoric acid.

Ionic self-assembled structures have been prepared successfully between di-(2-ethylhexyl) phosphoric acid (DEHPA) and hexamethonium hydroxide (HMO(OH)2). The DEHPA/HMO(OH)2 complexes show good surface activity at a wide mixing molar ratio of DEHPA to HMO(OH)2 (ρ), within which the critical micellar concentration (cmc) is far below that of any single component. In bulk aqueous solutions, rich phase behavior was observed by varying cDEHPA and cHMO(OH)2. When the concentration of HMO(OH)2 is in the range of 10-100 mmol L(-1), isotropic L1 phases, birefringent Lα phases and a phase-separated region were successively observed with increasing cDEHPA. At high cHMO(OH)2 range (>78 mmol L(-1)), a narrow L1/Lα two-phase region with the Lα phase at the bottom was noticed between the single L1 and single Lα phase regions. The rheological properties of the samples in the single Lα phase region at 2.6 ⩽ ρ ⩽ 2.8 are quite similar. Cryo-TEM and freeze-fracture TEM (FF-TEM) observations revealed the presence of multilamellar vesicles with flexible and even branched bilayers. At 2.2 ⩽ ρ ⩽ 2.6, however, the rheological properties are highly sensitive to ρ due to the sophisticated self-assembly behavior as proved by imaging studies and (2)H NMR measurements. Closely-stacked flat structures which look like foams or cellular networks have been newly discovered. Interestingly, NaCl could arouse an L1 to Lα phase transition due to the suppression of the effective area of the hydrophilic headgroups of the ionic complexes, leading to an increase of the critical packing parameter p. The viscoelasticity properties of the salt-containing Lα phases decreased with increasing salinity. We hope our research can provide new ideas for the construction of supramolecular materials by surfactant ionic self-assembly (SISA) strategy.

Naphthalene-Functionalized, Photoluminescent Room Temperature Ionic Liquids Bearing Small Counterions.

Obtaining π-conjugated room temperature ionic liquids (RTILs) is difficult because of the relatively strong π-π interaction among the π-moieties. Existing strategies by using bulky counterions greatly hindered further property optimization and potential applications of these intriguing functional fluids through simple ion exchange. Herein, four naphthalene-functionalized, π-conjugated RTILs with small counterions (Br(-) ) have been facilely synthesized with high yields. Our strategy is to attach branched alkyl chains to the cationic backbone of the target compounds (2 a-d), which effectively tune inter- and intramolecular interactions. Compounds 2 a-d have satisfactory thermal stability (up to 300 °C) and low melting points (<-19 °C). Rheological measurements revealed the fluid character of 2 a-d, whose viscosity decrease with the increase of the alkyl chain length and temperature. The presence of the π-conjugated naphthalene moiety imparts 2 a-d photoluminescent properties in bulk solutions. Moreover, the absence of strong π-π stacking among the naphthalene units in solvent-free states enables them to be used as a new generation of photoluminescent inks.

Ferrofluids of Thermotropic Liquid Crystals by DNA–Lipid Hybrids

Here is the first report the creation of ferrofluids of thermotropic liquid crystals in the absence of any solvent or nanoparticle. These ferrofluids were prepared by the electrostatic coupling of single-strand (ss) DNA with paramagnetic lipids. DNA molecules, as rigid parts, offer the orientational anisotropy and lipids (surfactants) due to the flexible hydrocarbon chains suppress crystallization, hybrids with DNA significantly increase the Cure temperature (Tc) of the lipids. The ferrofluids possess good fluidity and low viscosity. They serve as excellent solvents for both hydrophilic and lipophilic compounds. Their strong magnetism further allows the solutes to be controlled by external magnetic force. The DNA-lipid hybrid ferrofluids show liquid crystal (LC) behavior at low temperatures, and the LC phase is made of ordered multilamellar structures. Compared with conventional magnetic nanoparticle dispersions, the solvent-free lipoplex ferrofluids provide potential applications for nanotechnology, material science, and biotechnology.

Aggregation-Induced Emission of EuIII Complexes Balanced with Bulky and Amphiphilic Imidazolium Cations in Ethanol/Water Binary Mixtures

A series of EuIII complexes with thenoyltrifluoroacetone (tta) as the ligands were synthesized, which are balanced with imidazolium cations bearing naphthyl and branched alkyl chains. The complex with the longest alkyl chain (1Eu(tta)4 ) shows aggregation behavior in ethanol and water mixtures. It exists as individuals at low water percentages (VH2O ), and form particles with solid interiors at VH2O ≥50 % the sizes of which decrease with the increase of VH2O . At VH2O =90 %, vesicles were observed. The aggregation of 1Eu(tta)4 in ethanol and water binary mixtures induced changes of the photoluminescence (PL) properties where an abrupt increase in PL intensity, quantum yield, and lifetime were noticed above VH2O =50 %. This PL enhancement can be explained by the encapsulation of 1Eu(tta)4 inside the aggregates, preventing it from quenching by the active hydroxyls of water molecules. Contrary to the aggregation-induced emission (AIE) of the Eu complex, the naphthyl group in the imidazolium cation exhibited an aggregation-caused quenching (ACQ) effect. When the length of the alkyl chain in the imidazolium cation is reduced, no PL enhancement can be observed owing to the difficulty in forming the aggregates.

Metal-Organic Gels of Catechol-Based Ligands with Ni(II) Acetate for Dye Adsorption

Metal organic gels (MOGs) are a class of supramolecular complexes, which have attracted widespread interest because of the coupled advantages of inorganic and organic building blocks. A new compound terminated with catechol was synthesized. This new compound can be used to coordinate with Ni2+ to form MOGs. These MOGs show favorable viscoelasticity and wormhole-shaped porous structures, which were confirmed by transmission electron microscope and scanning electronic microscope images. Taking the benefits of porosity into account, the xerogel could serve as an adsorbent to adsorb dye molecules from the aqueous media. The experimental results indicate that xerogels possess good adsorption effect both on anionic and cationic dyes. Exhaustive research has been performed on the adsorption kinetics and isotherms, revealing that the adsorption process accords with the pseudo-second-order model and the Langmuir model.

Photoluminescent and pH-Responsive Supramolecular Structures from Co-assembly of Carbon Quantum Dots and Zwitterionic Surfactant Micelles

The co-assembly of negatively charged carbon quantum dots (CQDs) and a zwitterionic surfactant (tetradecyldimethylamine oxide, C14DMAO) in water has been investigated, which results in the formation of a new class of photoluminescent and pH-responsive self-assemblies. Instead of a direct binding mode, the surfactant unimers self-associate into micelles before interacting with the CQDs. Each of the micelles carries a small amount of positive charge due to the partial protonation of C14DMAO (C14DMAO + H+ = C14DMAOH+). For aqueous solutions containing 0.1 mg mL-1 CQDs, two types of structures have been confirmed upon the addition of C14DMAO, i.e., supramolecular polymers and vesicles. Between them, a variety of intermediate structures are observed, including ribbons, oligomers of vesicles and helixes. Due to the reversible protonation/deprotonation of the zwitterionic surfactant, both the supramolecular polymers and vesicles exhibit reversible changes toward the variation of pH, providing opportunities to facilely adjust their properties wherever necessary. As the CQDs evenly distribute in the micelle matrix, the self-quenching of the CQDs has been significantly suppressed and their photoluminescence has been well preserved. The supramolecular polymers have been further selected as hosts to accommodate rhodamine 6G, which is used as a model drug, and the controlled release stimulated by pH has been realized.