Robust and Reversible Vapoluminescent Organometallic Copper Polymers.

Emissive organometallic polymers are an important class of functional materials characterized by the combined photoluminescent features of organometallic molecules and the properties of traditional polymers. In this work, the emissive organometallic complex, [CuBr(PPh3 )2 (4-methylpyridine)], is successfully, mechanically ground into a random copolymer built on 4-(diphenylphosphino)styrene (DPVP) and n-butyl acrylate (BA) monomers. The resultant hybrid materials successfully inherit the emissive centers, and are significantly reinforced by the copper complexes as chemical crosslinkers in the polymeric continuum. These organometallic polymers are also proved to have excellent vapoluminescent properties, exhibiting unique responses to many organic solvent vapors, reflecting their rapid loss and recovery of photoluminescence. Mechanically robust and flexible films prepared with these organometallic Cu(I)-polymers are tested as recoverable sensors for hazardous volatile chemical compounds (VOCs) such as toluene, acetone, chloroform, and dichloromethane, and the low limits of detection (LOD) can reach as low as 1 × 10-3 -8 × 10-3 mg L-1 (0.2-3.3 ppmV, parts per million-volume) for various VOCs. This work sheds lights on the design and fabrication of organometallic polymers for advanced applications.

Photochromic Inorganic/Organic Thermoplastic Elastomers.

Photochromic materials are an important class of "smart materials" and are broadly utilized in technological devices. However, most photochromic materials reported so far are composed of inorganic compounds that are challenging to process and suffer from poor mechanical performance, severely limiting their applications in various markets. In this paper, inorganic photochromic tungsten trioxide (WO3 ) nanocrystals are conveniently grafted with polymers to hurdle the deficiency in processability and mechanical properties. This new type of photochromic material can be thermally processed into desired geometries like disks and dog-bone specimens. Fully reversible photochromic response under UV light is also achieved for WO3 -graft polymers, exhibiting tunable response rate, outperforming the pristine WO3 nanocrystals. Notably, the resulted graft polymers show extraordinary mechanical performance with excellent ductility (≈800% breaking strain) and relatively high breaking strength (≈2 MPa). These discoveries elucidate an effective pathway to design smart inorganic/organic hybrid thermoplastic elastomers endowed with outstanding photochromic and mechanical properties as well as exceptional processability.

Metal-containing and related polymers for biomedical applications.

A survey of the most recent progress in the biomedical applications of metal-containing polymers is given. Due to the unique optical, electrochemical, and magnetic properties, at least 30 different metal elements, most of them transition metals, are introduced into polymeric frameworks for interactions with biology-relevant substrates via various means. Inspired by the advance of metal-containing small molecular drugs and promoted by the great progress in polymer chemistry, metal-containing polymers have gained momentum during recent decades. According to their different applications, this review summarizes the following biomedical applications: (1) metal-containing polymers as drug delivery vehicles; (2) metal-containing polymeric drugs and biocides, including antimicrobial and antiviral agents, anticancer drugs, photodynamic therapy agents, radiotherapy agents and biocides; (3) metal-containing polymers as biosensors, and (4) metal-containing polymers in bioimaging.

Antimicrobial metallopolymers and their bioconjugates with conventional antibiotics against multidrug-resistant bacteria.

Bacteria are now becoming more resistant to most conventional antibiotics. Methicillin-resistant Staphylococcus aureus (MRSA), a complex of multidrug-resistant Gram-positive bacterial strains, has proven especially problematic in both hospital and community settings by deactivating conventional ß-lactam antibiotics, including penicillins, cephalosporins, and carbapenems, through various mechanisms, resulting in increased mortality rates and hospitalization costs. Here we introduce a class of charged metallopolymers that exhibit synergistic effects against MRSA by efficiently inhibiting activity of ß-lactamase and effectively lysing bacterial cells. Various conventional ß-lactam antibiotics, including penicillin-G, amoxicillin, ampicillin, and cefazolin, are protected from ß-lactamase hydrolysis via the formation of unique ion-pairs between their carboxylate anions and cationic cobaltocenium moieties. These discoveries could provide a new pathway for designing macromolecular scaffolds to regenerate vitality of conventional antibiotics to kill multidrug-resistant bacteria and superbugs.

Ring-opening metathesis polymerization of 18-e Cobalt(I)-containing norbornene and application as heterogeneous macromolecular catalyst in atom transfer radical polymerization.

In the last decades, metallopolymers have received great attention due to their various applications in the fields of materials and chemistry. In this article, a neutral 18-electron exo-substituted η(4) -cyclopentadiene CpCo(I) unit-containing polymer is prepared in a controlled/"living" fashion by combining facile click chemistry and ring-opening meta-thesis polymerization (ROMP). This Co(I)-containing polymer is further used as a heterogeneous macromolecular catalyst for atom transfer radical polymerization (ATRP) of methyl methacrylate and styrene.

Cobaltocenium-containing block copolymers: ring-opening metathesis polymerization, self-assembly and precursors for template synthesis of inorganic nanoparticles.

Side-chain cobaltocenium-containing block copolymers are prepared by ring-opening metathesis polymerization (ROMP). These block copolymers include one cobaltocenium-containing block, with the second block being either a nonmetal-containing segment or a cobaltocenium-containing segment with different counterions. These block copolymers are self-assembled into spherical core/shell micelles in solutions. A template strategy is used to prepare cobalt (II or III)-containing nanoparticles by treating the self-assembled micelles via UV/ozonolysis and pyrolysis. Characterization by X-ray photon spectroscopy and X-ray diffraction indicates that these nanoparticles consist of different oxidants of cobalt, depending on the chemical compositions of block copolymers.

Anion-Responsive Metallopolymer Hydrogels for Healthcare Applications.

Metallopolymers combine a processable, versatile organic polymeric skeleton with functional metals, providing multiple functions and methodologies in materials science. Taking advantage of cationic cobaltocenium as the key building block, organogels could be simply switched to hydrogels via a highly efficient ion exchange. With the unique ionic complexion ability, cobaltocenium moieties provide a robust soft substrate for recycling antibiotics from water. The essential polyelectrolyte nature offers the metallopolymer hydrogels to kill multidrug resistant bacteria. The multifunctional characteristics of these hydrogels highlight the potential for metallopolymers in the field of healthcare and environmental treatment.