Lipoic acid based core cross-linked micelles for multivalent platforms: design, synthesis and application in bio-imaging and drug delivery.

Natural lipoic acid derived small-molecule amphiphiles self-assemble into micelles in water. The presence of numerous disulfides accumulated in the core makes the micelles readily cross-linked to achieve the establishment of core cross-linked micelles (CCMs). Thanks to the inherent biocompatibility, the resulting lipoic acid based CCMs (LA-CCMs) are good multivalent platforms for biomedical applications.

Rapid Access to 2,2'-Bithiazole-Based Copolymers via Sequential Palladium-Catalyzed C-H/C-X and C-H/C-H Coupling Reactions.

A rapid access to 2,2'-bithiazole-based copolymers has been developed on the basis of the sequential palladium-catalyzed CH/CX and CH/CH coupling reactions. To assemble a "copolymer" through homopolymerization, a type of symmetric A-B-A-type building block is designed as the monomer and prepared via the regioselective C5H arylation of thiazole. A PdCl2 /CuCl-cocatalyzed oxidative CH/CH homopolymerization has been established to afford the 2,2'-bithiazole-based copolymers with high Mn (up to 69400). The current protocol features atom- and step-economy and exhibits a potential in the highly efficient construction of conjugated copolymers.

Modular establishment of a diketopyrrolopyrrole-based polymer library via Pd-catalyzed direct C-H (Hetero)arylation: a highly efficient approach to discover low-bandgap polymers.

A concise, highly efficient palladium-catalyzed direct C-H (hetero)arylation is developed to modularly assemble a diketopyrrolopyrrole (DTDPP)-based polymer library to screen low-bandgap and near-infrared (NIR) absorbing materials. The DTDPP-based copolymers P1 and P2 with an alternating donor-acceptor-donor-acceptor (D-A-D-A) sequence and the homopolymer P9 exhibit planarity and excellent π-conjugation, which lead to low bandgaps (down to 1.22 eV) as well as strong and broad NIR absorption bands (up to 1000 nm).

Helical nonracemic tubular coordination polymer gelators from simple achiral molecules.

A novel class of helical nonracemic tubular coordination polymers, which can immobilize a wide range of solvents at very low concentrations, have been synthesized for the first time in the absence of chiral influences and appended groups.

Oxidative Direct Arylation Polymerization Using Oxygen as the Sole Oxidant: Facile, Green Access to Bithiazole-Based Polymers.

The most appealing oxidant, molecular oxygen, is employed for the first time as the sole oxidant in the transition metal-catalyzed oxidative direct arylation polymerization (C-H/C-H-type DArP), which eliminates by-product formation of stoichiometric metal salts except for water . Compared to conventional approaches, other than the avoidance of an end-capping procedure, the current protocol is remarkably advanced in the aspect of eco-friendliness, step- and cost-economy, and, of special significance, the purity of polymer products. As illustrative examples, six 5,5'-bithiazole-based polymers are synthesized using this new method, demonstrating higher number-average molecular weight (Mn up to 33 700) in better yields (up to 93 %) through only one step. The evolution of C-H/C-H-type DArP from heavy metal salts to O2 alone as the oxidant could solve the problem of metal residues in polymers, which is considered harmful to the performance of devices.

Synthesis and biological applications of imidazolium-based polymerized ionic liquid as a gene delivery vector.

The encouraging results of preliminary toxicological studies on imidazolium-based ionic liquids provide good opportunities for the development of ionic liquids in biomedical applications. In this work, the polymerized ionic liquid poly[3-butyl-1-vinylimidazolium L-proline salt] has been synthesized as a gene vector. The interaction of poly[3-butyl-1-vinylimidazolium L-proline salt] with DNA was studied by agarose gel electrophoresis. The cell viability was determined through PI (propidium iodine) staining and flow cytometry, showing marginal toxicity toward the cells examined. The transfection efficiency was evaluated through the in vitro transfection experiment. The results indicated that the imidazolium cation had a high binding ability to DNA, and the condensed DNA in the complexes could be effectively protected against enzymatic degradation. Poly[3-butyl-1-vinylimidazolium L-proline salt] could further transfer the reporter gene into the HeLa cell and successfully mediate the gene expression without the aid of additional agent.

A concept of supported amino acid ionic liquids and their application in metal scavenging and heterogeneous catalysis.

Novel supported task-specific ionic liquids have been developed for the first time via the ionic-pair coupling of imidazolium cation of the modified polystyrene support with L-proline. The materials have shown an efficient metal scavenging ability (e.g., CuI, Pd(OAc)2, Pd0, and IrCl3) without the aid of a nonimmobilized ionic liquid, which relies on the highly synergistic effect of the coordination with the nitrogen atom and the COO- group of the L-proline moiety, electrostatic forces, and steric protection. The resulting metal-soaked supported ionic liquids can be used as efficient heterogeneous catalysts. These materials have been investigated in the CuI-catalyzed N-arylation of nitrogen-containing heterocycles and exhibit much higher catalytic activity and a more extensive structural range of aryl and heteroaryl halides than those exhibited by free L-proline in combination with CuI both in the ionic liquid ([BMIM][BF4]) and in the corresponding homogeneous reaction conditions. The CuI-soaked catalyst 4a-2 can be recycled for nine runs at least without any considerable loss of activity. To the best of our knowledge, our catalytic process is among the most efficient approaches to the N-arylation of imidazoles with aryl halides so far reported. Furthermore, the Pd-soaked material 4a-2 also shows higher catalytic activity in the solvent-free hydrogenation of styrene to ethylbenzene. This new concept is generally applicable and may easily be extended to other supported task-specific ionic liquids.