Photoswitchable Enantioselective and Helix-Sense Controlled Living Polymerization.

A pair of enantiomeric photoswitchable Pd catalysts, alkyne-Pd /L and alkyne-Pd /L , were prepared via the coordination of alkyne-Pd and azobenzene-modified phosphine ligands L and L . Owing to the cis-trans photoisomerization of the azobenzene moiety, alkyne-Pd /L and alkyne-Pd /L exhibited different polymerization activities, helix-sense selectivities, and enantioselectivities during the polymerization of isocyanide monomers under irradiation of different wavelength lights. Furthermore, the achiral isocyanide monomer A-1 could be polymerized efficiently using alkyne-Pd /L under dark condition in a living/controlled manner.

Precise Synthesis of Optically Active and Thermo-degradable Poly(trifluoromethyl methylene) with Circularly Polarized Luminescence.

Developing high performance and environment-friendly fluoropolymers is greatly desired. In this work, we found that 2-diazo-1,1,1-trifluoroethane can be polymerized by air-stable alkyne-palladium(II) catalysts following a living polymerization mechanism, affording a fluoropolymer, poly(trifluoromethyl methylene) in high yield with controlled molar mass and low dispersity. This polymer bears trifluoromethyl on every main chain atom and thus has good resistance to chemical corrosion, high hydrophobicity, and excellent dielectric constant with low dielectric loss.

Nickel(II)-catalyzed living polymerization of diazoacetates toward polycarbene homopolymer and polythiophene-block-polycarbene copolymers.

Diazoacetate polymerization has attracted considerable research attention because it is an effective approach for fabricating carbon-carbon (C-C) main chain polymers. However, diazoacetate polymerization based on inexpensive catalysts has been a long-standing challenge. Herein, we report a Ni(II) catalyst that can promote the living polymerization of various diazoacetates, yielding well-defined C-C main chain polymers, polycarbenes, with a predictable molecular weight (M) and low dispersity (M/M).

Helicity- and Molecular-Weight-Driven Self-Sorting and Assembly of Helical Polymers towards Two-Dimensional Smectic Architectures and Selectively Adhesive Gels.

Self-sorting plays a crucial role in living systems such as the selective assembly of DNA and specific folding of proteins. However, the self-sorting of artificial helical polymers such as biomacromolecules has rarely been achieved. In this work, single-handed helical poly(phenyl isocyanide)s bearing pyrene (Py) and naphthalene (Np) probes were prepared, which exhibited interesting self-sorting properties driven by both helicity and molecular weight (M ) in solution, solid state, gel, and on the gel surface as well.

Controlled Synthesis of Shell Cross-Linked Helical Poly(phenylborate isocyanide) Nanoparticles with HO/Redox Dual Responsiveness and Their Application in Antitumor Drug Delivery.

To mimic the helical structure and function of biopolymers, shell cross-linked nanoparticle (P4) composed of left-handed helical poly(phenylborate isocyanide) in core and hydrophilic polyisocyanide in shell was prepared. The phenylborate in the core and the disulfide bonds in the cross-linkage render the nanoparticle with excellent dual stimuli-responsiveness to glutathione (GSH) and HO. Nevertheless, it has good stability in normal physiological conditions.

Synthesis of Redox-Responsive Core Cross-Linked Micelles Carrying Optically Active Helical Poly(phenyl isocyanide) Arms and Their Applications in Drug Delivery.

In this manuscript, we designed and synthesized three core cross-linked micelles (-, -, and -) with redox-responsive disulfide bonds in the core and carrying optically active helical polyisocyanide arms. Their arms were different in the helicity of the main chain and the chirality of the side groups. These micelles showed excellent redox-responsiveness to reducing agent.