Shangyang Li

Self-assembled vesicles prepared from amphiphilic cyclodextrins as drug carriers.

Controlled self-assembly of amphiphilic cyclodextrin is always a challenging topic in the field of supramolecular chemistry, since it provides the spontaneous generation of well-defined aggregation with functional host sites with great potential applications in drug-carrier systems. β-Cyclodextrin modified with an anthraquinone moiety (1) was successfully synthesized. In the aqueous solution, 1 was found able to self-assemble into vesicles, which was characterized in detail by TEM, SEM, EFM, and DLS. The formation mechanism of the vesicles was suggested based on the 2D ROESY and UV-vis results, and further verified by the MD simulation. Subsequently, the stimuli response property of the vesicles, including to Cu(2+) and H(+), was also studied. The vesicles can efficiently load Paclitaxel inside the membrane with functional macrocyclic cavities available, which can further carry small molecules, such as ferrocene. The vesicles loading with Paclitaxel have remarkable anticancer effects. This work will provide new strategy in drug-carrier systems and tumor treatment methods.

Hybrid Gels Assembled from Fmoc–Amino Acid and Graphene Oxide with Controllable Properties

A supramolecular gel is obtained from the self-assembly of an ultralow-molecular-weight gelator (N-fluorenyl-9-methoxycarbonyl glutamic acid) in good and poor solvents. The gelators can self-assemble into a lamellar structure, which can further form twisted fibers and nanotubes in the gel phase. Rheological studies show that the gels are robust and rigid, and are able to rapidly self-recover to a gel after being destroyed by shear force. Fluorescence experiments reveal the aggregation-induced emission effects of the gel system; the fluorescence intensity is significantly enhanced by gel formation. Graphene oxide (GO) is introduced into the system efficiently to give a hybrid material, and the interaction between gelators-GO sheets is studied. Rheological and fluorescent studies imply that the mechanical properties and the fluorescent emission of the hybrid materials can be fine-tuned by controlling the addition of GO.

Influence of measuring conditions on the thixotropy of hydrotalcite-like/montmorillonite suspension

Abstract The influence of the measuring conditions on the thixotropy of suspensions, which were made up of hydrotalcite-like compounds (HTlc) and Na-montmorillonite (MT), was studied. Usually, the structure recovery at rest after preshear is considered the fundamental thixotropic process. And the recovery process was performed under the steady shear experiments, then the thixotropic type can be judged according to the recovery process. In this paper, the influence of rest time (ts) and the shear rate ( γ ) on the recovery process was studied. Three kinds of HTlc/MT suspension were studied, their mass ratios of HTlc to MT, which were signed as R (e.g. R=WHTlc/WMT), were 0.013, 0.051, 0.091, respectively. It is found the HTlc/MT suspension with R=0.013 showed positive thixotropy at ts=0, but it changed to negative one with the increase of ts. The suspension with R=0.051 transformed from complex thixotropy at low γ or positive thixotropy at high γ into negative one with the increase of ts. The suspension with R=0.091 behaved as complex thixotropy when γ is 1022 s−1, and it behaved as negative thixotropy when γ is 10 s−1. Whereas, the suspension transformed from negative thixotropy to the weak complex one as the increase of ts when γ is 170 or 341 s−1. For all the systems, the equilibrium viscosity decreased gradually with ts at the low γ , but the equilibrium viscosity increased with ts at high γ because of the memory effect. The mechanism has been discussed.

Melamine as an Effective Supramolecular Modifier and Stabilizer in a Nanotube-Constituted Supergel

Self-assembly of N-fluorenyl-9-methoxycarbonyl glutamic acid (Fmoc-Glu) in water generates metastable single-wall nanotubes. These nanotubes entangle and bundle together to form unstable gels that shrink with time and finally result in lamellar crystalline precipitates. Melamine (Mm) was employed as a supramolecular modifier and stabilizer to improve the stability of the nanotubes. Mm interacts with the carboxyl-rich surfaces of the nanotubes via H-bonds and static electronic forces to diminish the high affinity of individual nanotubes and facilitate Fmoc-Glu supergelation (critical gelation concentration <0.1 wt %). Although the basic process of nanotube formation is not disturbed, Mm inverts the supramolecular helicity of nanotubes from P to M.

Switchable and orthogonal self-assemblies of anisotropic fibers

Anisotropic and well-defined β-cyclodextrin (β-CD) and sodium laurate (SL) gel fibers, with tetragonal and lamellar packing modes respectively, were combined to generate orthogonal and switchable assemblies for the first time. Through controlling the inclusion–exclusion processes between β-CD and SL by changing external stimuli, β-CD gel fibers, SL gel fibers and their coexistence states can be easily tailored. Different assembled states exhibited versatile morphologies and microstructures, which were detected by microscopy and X-ray scattering measurements. Furthermore, controllable assemblies provide facile ways to control the mechanical properties of the hybrid gels. The orthogonal self-assembly with self-sorting properties would enable this system to attract interest in material science.

Tuning of gel morphology with supramolecular chirality amplification using a solvent strategy based on an Fmoc-amino acid building block

Gel formation by an N-fluorenyl-9-methoxycarbonyl (Fmoc)-based molecule was investigated and the chirality amplification observed during the self-assembly process could be switched on and off by controlling the solvent environment. The molecules could form gel in mixed solvents of water and dimethyl sulfoxide (DMSO) at either a high water fraction to afford flat nanofibers or a low water fraction to generate nanofibers with supramolecular chirality. At a moderate fraction of water, the molecules self-assemble into a precipitate composed of nanosheets. Furthermore, the gels showed different mechanical properties and thermal stabilities. Mechanism studies showed that π–π stacking interactions between the aromatic Fmoc groups and hydrogen bondings between the amide groups played important roles in the self-assembly process of the different gels. This study strives to shed light on the tuning of chiral gels with various nanostructures via controlled self-assembly, which might have potential use in smart materials.

Controllable self-growth of a hydrogel with multiple membranes

The controllable self-growth of a supramolecular hydrogel of folic acid (FA) was developed based on the conduction of transition metal ions. The growth behavior of the gel could be flexibly controlled by adjusting the ambient environmental factors such as gelator concentration, temperature and external chemical stimuli. The obtained gel was characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic force microscopy (AFM) and rheological measurements. Differential scanning calorimetry (DSC) showed that the gel possessed excellent thermal stability. A mechanism for the fibrous formation of the gel was suggested based on the experimental results of Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (NMR) and UV-Vis spectroscopy. The gel exhibited multiple stimuli-responsive properties to changes in ligand and pH. Furthermore, the gel can be incorporated into multi-layer hydrogels in both artificial and spontaneous ways, showing the advantages of self-growth and flexible control of the gel system. This novel hydrogel and the preparation strategy may provide a new route to rationally design advanced materials for biomedical applications.

Self-recovering β-cyclodextrin gel controlled by good/poor solvent environments

A unique β-cyclodextrin (β-CD) gel with ordered structure was fabricated. The ordered aggregation of β-CD was achieved by controlling the solubility of β-CD in good/poor solvents. Physicochemical properties of the gel were systematically investigated. Mechanical properties were tested by rheological measurements, and the fibrous morphology was observed by confocal laser scanning microscopy. The anisotropic property of gel fibers was detected under polarized optical microscopy. Well-defined tetragonal and channel packed microstructures were formed in gel fibers, which revealed hollow channels of cyclodextrins. By changing physicochemical environments, macroscopic phase transitions were aroused, and self-recovering phenomena occurred when a certain amount of NaCl was added into the gel as a stimulus or the shear rate loop test was performed (thixotropy). By adjusting the concentrations of external stimuli or volume ratios of good/poor solvents, properties of the gel including mechanical strength or thermostability can be easily altered. The ordered empty channels assembled by CDs with the self-recovering properties may shed new light on this traditional host molecule.

Multi-responsive supramolecular organogel with a crystalline-like structure

A multi-responsive cyclodextrin-based organogel with a crystalline-like structure is first reported. An amount of β-cyclodextrin (β-CD) and lithium chloride (LiCl) was added into N,N-dimethylformamide (DMF), and the system obtained could transform instantly from a transparent solution into a gel state by introducing ethylene diamine (EDA), and then the gel could turn into another precipitate-like gel by undergoing a heating-cooling process. Among a series of aliphatic amines, only EDA was found to be able to induce the gel formation. Both the gels possess crystalline-like structures in their morphology with sheet-like layers, in a highly-ordered channel-type packing mode, which were proved by OM, SEM, XRD, and FT-IR measurements. Furthermore, the gel could respond to H(+) and Cu(2+) by transforming into an amorphous precipitate. This research may pave the way for the design of novel smart materials.

Reversible pH-responsive helical nanoribbons formed using camptothecin

The natural antitumor drug camptothecin was found to self-assemble into helical nanoribbons in aqueous solution. The helical nanoribbons showed good reversible pH-responsiveness. The formation and disappearance of the helical nanoribbons can be tuned reversibly through changing the pH value of the solution.