Organocatalytic Enantioselective Synthesis of Inherently Chiral Calix[4]arenes.

Inherently chiral calix[4]arenes are an excellent structural scaffold for enantioselective synthesis, chiral recognition, sensing, and circularly polarized luminescence. However, their catalytic enantioselective synthesis remains challenging. Herein, we report an efficient synthesis of inherently chiral calix[4]arene derivatives via cascade enantioselective cyclization and oxidation reactions. The three-component reaction features a broad substrate scope (33 examples), high efficiency (up to 90 % yield), and excellent enantioselectivity (>95 % ee on average). The potential applications of calix[4]arene derivatives are highlighted by their synthetic transformation and a detailed investigation of their photophysical and chiroptical properties.

Light-Responsive Supramolecular Liquid-Crystalline Metallacycle for Orthogonal Multimode Photopatterning.

The development of multimode photopatterning systems based on supramolecular coordination complexes (SCCs) is considerably attractive in supramolecular chemistry and materials science, because SCCs can serve as promising platforms for the incorporation of multiple functional building blocks. Herein, we report a light-responsive liquid-crystalline metallacycle that is constructed by coordination-driven self-assembly. By exploiting its fascinating liquid crystal features, bright emission properties, and facile photocyclization capability, a unique system with spatially-controlled fluorescence-resonance energy transfer (FRET) is built through the introduction of a photochromic spiropyran derivative, which led to the realization of the first example of a liquid-crystalline metallacycle for orthogonal photopatterning in three-modes, namely holography, fluorescence, and photochromism.

Dynamic Covalent Bond Cross-Linked Luminescent Silicone Elastomer with Self-Healing and Recyclable Properties.

Two aldehyde-modified tetraphenylene derivatives with different functionality are synthesized and exhibit different fluorescence properties. By incorporating tetraphenylene derivatives into polydimethylsiloxane (PDMS) networks, two elastomers are prepared through dynamic covalent cross-linking. The elastomers show excellent fluorescence properties, mechanical properties, thermal stability as well as self-healing and recycle properties. At the same time, the mechanical properties of the elastomers are influenced by the functionality of the tetraphenylene derivatives and the molecular weight of the PDMS. The self-healing process takes place quickly and the recycling process can be carried out by solution processing and hot pressing. It shows the similar tensile properties between the pristine and healed samples.

Self-assembly of an alkynylpyrene derivative for multi-responsive fluorescence behavior and photoswitching performance.

Highly emissive fluorophores based on polyaromatic hydrocarbons with tunable emission properties and aggregated structures play a very important role in relevant functional studies. In this study, a novel alkynylpyrene derivative 1 was synthesized, which exhibits unimolecular to excimer emission in methanol with an increasing concentration accompanied by the formation of nanovesicles via the π-π stacking, hydrogen bond and hydrophobic interaction. The self-assembly behavior as well as emission properties of 1 in aprotic polar solvents (ACN, acetone, DMF and DMSO) can also be adjusted by the volume fraction of the poor solvent H2O, which can induce 1 self-assembly to excimer state and could be applied in information transfer. Moreover, upon visible light irradiation, photoswitchable performance of nanovesicles of 1 was observed in which the emission markedly changes from yellow to blue; this is attributed to the cycloaddition reaction of alkynyl groups and singlet oxygen, which can be generated without the addition of external photosensitizers. The multi-responsive and fluorescence behavior of the alkynylpyrene derivative show that the self-assembly can be used to expand the development of this type of fluorophores, and the novel photoinduced tunability of the fluorescence emission provides an effective strategy to obtain high-performance transmitting and sensing materials.

Facile Construction of Structurally Defined Porous Membranes from Supramolecular Hexakistriphenylamine Metallacycles through Electropolymerization.

The construction of well-controlled porous materials is very challenging. Herein, we report the successful preparation of structurally defined porous membranes based on hexakistriphenylamine metallacycles through electropolymerization. The newly designed porous materials were characterized by the typical cyclic voltammograms, XPS, SEM, and TEM investigations. Further investigations revealed that the metallacycle-based polymer films displayed a good size-selective molecular-sieving behavior.

Host-Guest Interaction-Mediated Construction of Hydrogels and Nanovesicles for Drug Delivery.

Hand-in-hand or head-to-head: A novel naphthalimide derivative is successfully designed and synthesized, which can self-assemble to produce hydrogels. When injecting this compound into CB[8] solution, the nanovesicles are obtained with a narrow size distribution. The cytotoxicity assay confirms that doxorubicin-loaded nanocarriers show therapeutic effects to cancer cells.

Suberoylanilide hydroxamic acid, an inhibitor of histone deacetylase, suppresses vasculogenic mimicry and proliferation of highly aggressive pancreatic cancer PaTu8988 cells.

BACKGROUND: Pancreatic cancer is one of the most aggressive human malignancies with a extremely low 5-year survival rate. Hence, the search for more effective anti-pancreatic cancer agents is urgent. METHODS: PaTu8988 pancreatic cancer cells were treated with different concentrations of suberoylanilide hydroxamic acid (SAHA), cell survival, proliferation, migration and vasculogenic mimicry (VM) were analyzed. Associated signaling changes were also analyzed by RT-PCR and Western blots. RESULTS: Here, we reported that SAHA, a histone deacetylase inhibitor (HDACi), exerted significant inhibitory efficiency against pancreatic cancer cell survival, proliferation, migration and VM. SAHA dose-dependently inhibited PaTu8988 pancreatic cancer cell growth with the IC-50 of 3.4 ± 0. 7 µM. Meanwhile, SAHA suppressed PaTu8988 cell cycle progression through inducing G2/M arrest, which was associated with cyclin-dependent kinase 1 (CDK-1)/cyclin-B1 degradation and p21/p27 upregulation. Further, SAHA induced both apoptotic and non-apoptotic death of PaTu8988 cells. Significantly, SAHA suppressed PaTu8988 cell in vitro migration and cell-dominant tube formation or VM, which was accompanied by semaphorin-4D (Sema-4D) and integrin-ß5 down-regulation. Our evidences showed that Akt activation might be important for Sema-4D expression in PaTu8988 cells, and SAHA-induced Sema-4D down-regulation might be associated with Akt inhibition. CONCLUSIONS: This study is among the first to report the VM formation in cultured human pancreatic cancer cells. And we provided strong evidence to suggest that SAHA executes significant anti-VM efficiency in the progressive pancreatic cancer cells. Thus, SAHA could be further investigated as a promising anti-pancreatic cancer agent.

A supramolecular artificial light-harvesting system based on a luminescent platinum(II) metallacage.

A trigonal luminescent metallacage was constructed by the coordination-driven self-assembly of m-pyridine-modified tetraphenylene ligands with organic Pt(II) acceptors, which exhibited excellent Aggregation-Induced Emission (AIE) properties. An efficient artificial light-harvesting system was successfully constructed by selecting the metallacage as the donor and the hydrophobic fluorescent dye Nile Red (NiR) as the donor molecule in a system of acetone/water (1/9, v/v), The absorption spectra of NiR and the emission spectra of the metallacage showed considerable overlap, achieving energy transfer from the metallacage to NiR.

Design of a large Stokes shift ratiometric fluorescent sensor with hypochlorite detection towards the potential application as invisible security ink.

Hypochlorite (ClO-) as a well-known highly reactive oxygen species (ROS), is widely used as preservative and household disinfectant in daily life. Although many fluorescence imaging sensors for ClO- have been reported, the development of ClO- ratio fluorescence sensors with large Stokes shift is still quite limited. This sensor shows obvious benefits including minimizing environmental intervention and improving signal-to-noise ratio. In the present project, we report an innovative conjugated pyrene-based system, 1-B, as a chlorine fluorescence sensor. The detector exhibits ratio detection performance, large Stokes and emission shifts. Furthermore, the system has desired sensitivity as well as selectivity for ClO-. Based on these excellent properties, the sensor 1-B was successfully used as ink to encrypt patterns and anti-counterfeiting information through inkjet printing technology. Compared with the existing probes, the probe shows some superior characteristics, which provides a promising tool for exploring the role of ClO- response sensor in the field of anti-counterfeiting.

Design and preparation of platinum-acetylide organogelators containing ethynyl-pyrene moieties as the main skeleton.

A series of new platinum-acetylide complexes containing ethynyl-pyrene moieties as the main skeleton were synthesized and characterized. The investigation of the absorption and emission spectra of these complexes revealed that the extension of the molecular size with the introduction of different numbered platinum-acetylide fragments can efficiently tune the absorption and emission bands from the UV to the longer wavelength region. Moreover, the gelation properties of these complexes were investigated by the "stable-to-inversion-of-a-test-tube" method. Most newly designed platinum-acetylide compounds presented a stable gel-formation property in some of the tested solvents. The morphology of the xerogels was investigated by scanning electron microscopy (SEM). Furthermore, the concentration- and temperature-dependent absorption and emission properties of these complexes were investigated, which support the formation of J-type assemblies during the aggregation process. More importantly, it was found that the complexes 4 a-C6, 4 a, and 4 a-C18 with four platinum-acetylide fragments presented potential applications as luminescent organometallic gels.