Antifouling and antimicrobial cobaltocenium-containing metallopolymer double-network hydrogels.

Compared with single-network hydrogels, double-network hydrogels offer higher mechanical strength and toughness. Integrating useful functions into double-network hydrogels can expand the portfolios of the hydrogels. We report the preparation of double-network metallopolymer hydrogels with remarkable hydration, antifouling, and antimicrobial properties. These cationic hydrogels are composed of a first network of cationic cobaltocenium polyelectrolytes and a second network of polyacrylamide, all prepared via radical polymerization. Antibiotics were further installed into the hydrogels via ion-complexation with metal cations. These hydrogels exhibited significantly enhanced hydration, compared with polyacrylamide-based hydrogels, while featuring robust mechanical strength. Cationic metallopolymer hydrogels exhibited strong antifouling against oppositely charged proteins. These antibiotic-loaded hydrogels demonstrated a synergistic effect on the inhibition of bacterial growth and antifouling of bacteria, as a result of the unique ion complexation of cobaltocenium cations.

Polymerization-Induced Self-Assembly of Metallo-Polyelectrolyte Block Copolymers.

Cobaltocenium-containing polyelectrolyte block copolymer nanoparticles were prepared via polymerization-induced self-assembly (PISA) using aqueous dispersion RAFT polymerization. The cationic steric stabilizer was a macromolecular chain-transfer agent (macro-CTA) based on poly (2-cobaltocenium amidoethyl methacrylate chloride) (PCoAEMACl), and the core-forming block was poly(2-hydroxypropyl methacrylate) (PHPMA). Stable cationic spherical nanoparticles were formed in aqueous solution with low dispersity without adding any salts. The chain extension of macro-CTA with HPMA was efficient and fast. The effects of block copolymer compositions, solid content, charge density, and addition of salts were studied. It was found that the degree of polymerization of both the stabilizer PCoAEMACl and the core-forming PHPMA had a strong influence on the size of nanoparticles.

Gold Nanoparticles with Antibiotic-Metallopolymers toward Broad-Spectrum Antibacterial Effects.

Bacterial infection has evolved into one of the most dangerous global health crises. Designing potent antimicrobial agents that can combat drug-resistant bacteria is essential for treating bacterial infections. In this paper, a strategy to graft metallopolymer-antibiotic bioconjugates on gold nanoparticles is developed as an antibacterial agent to fight against different bacterial strains. Thus, these nanoparticle conjugates combine various components in one system to display enhanced bactericidal efficacy, in which small sized nanoparticles provide high surface area for bacteria to contact, cationic metallopolymers interact with the negatively charged bacterial membranes, and the ß-lactam antibiotics' sterilzation capabilities are improved via evading intracellular enzymolysis by ß-lactamase. This nanoparticle-based antibiotic-metallopolymer system exhibits an excellent broad-spectrum antibacterial effect, particularly for Gram-negative bacteria, due to the synergistic effect of multicomponents on the interaction with bacteria.

Metallo-polyelectrolytes as a class of ionic macromolecules for functional materials.

The fields of soft polymers and macromolecular sciences have enjoyed a unique combination of metals and organic frameworks in the name of metallopolymers or organometallic polymers. When metallopolymers carry charged groups, they form a class of metal-containing polyelectrolytes or metallo-polyelectrolytes. This review identifies the unique properties and functions of metallo-polyelectrolytes compared with conventional organo-polyelectrolytes, in the hope of shedding light on the formation of functional materials with intriguing applications and potential benefits. It concludes with a critical perspective on the challenges and hurdles for metallo-polyelectrolytes, especially experimental quantitative analysis and theoretical modeling of ionic binding.

Recyclable magnetic nanoparticles grafted with antimicrobial metallopolymer-antibiotic bioconjugates.

Over-prescription and improper use of antibiotics has led to the emergence of bacterial resistance, posing a major threat to public health. There has been significant interest in the development of alternative therapies and agents to combat antibiotic resistance. We report the preparation of recyclable magnetic iron oxide nanoparticles grafted with charged cobaltocenium-containing metallopolymers by surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization. ß-Lactam antibiotics were then conjugated with metallopolymers to enhance their vitality against both Gram-positive and Gram-negative bacteria. The enhanced antibacterial activity was a result of synergy of antimicrobial segments that facilitate the inhibition of hydrolysis of antibiotics and local enhancement of antibiotic concentration on a nanoparticle surface. These magnetic nanoparticles can be recycled numerous times without losing the initial antimicrobial potency. Studies suggested negligible toxicity of metallopolymer-grafted nanoparticles to red blood cells and minimal tendency to induce resistance in bacteria.

Charged Metallopolymer-Grafted Silica Nanoparticles for Antimicrobial Applications.

Inappropriate and frequent use of antibiotics has led to the development of antibiotic-resistant bacteria, which cause infectious diseases that are difficult to treat. With the rising threat of antibiotic resistance, the need to develop effective new antimicrobial agents is prominent. We report antimicrobial metallopolymer nanoparticles, which were prepared by surface-initiated reversible addition-fragmentation chain transfer polymerization of a cobaltocenium-containing methacrylate monomer from silica nanoparticles. These particles are capable of forming a complex with ß-lactam antibiotics, such as penicillin, rejuvenating the bactericidal activity of the antibiotic. Disk diffusion assays showed significantly increased antibacterial activities against both Gram-positive and Gram-negative bacteria. The improved efficiencies were attributed to the inhibition of hydrolysis of the ß-lactam antibiotics and enhancement of local antibiotics concentration on a nanoparticle surface. In addition, hemolysis evaluations demonstrated minimal toxicity to red blood cells.

Cationic Metallo-Polyelectrolytes for Robust Alkaline Anion-Exchange Membranes.

Chemically inert, mechanically tough, cationic metallo-polyelectrolytes were conceptualized and designed as durable anion-exchange membranes (AEMs). Ring-opening metathesis polymerization (ROMP) of cobaltocenium-containing cyclooctene with triazole as the only linker group, followed by backbone hydrogenation, led to a new class of AEMs with a polyethylene-like framework and alkaline-stable cobaltocenium cation for ion transport. These AEMs exhibited excellent thermal, chemical and mechanical stability, as well as high ion conductivity.

Binding of Cobaltocenium-containing Polyelectrolytes with Anionic Probes.

Cationic cobaltocenium-containing polyelectrolytes have a unique ability to form ionic complex with various anionic species. We carried out two sets of model study to compare the relative binding strength of a cobaltocenium-containing polyelectrolyte. First, the nature and relative strength of intermolecular interaction between cobaltocenium-containing polyelectrolytes and different anionic probes were investigated by spectroscopic methods. A dye-displacement method was used to monitor absorbance and fluorescence emissions. Second, the binding strength of this cobaltocenium-containing polyelectrolyte was compared with a classical quaternary ammonium polymer. Formation of polyelectrolyte complex between the cobaltocenium-containing polyelectrolyte and a common anionic polyelectrolyte at various concentrations was examined by optical absorption and light scattering.

Trio Act of Boronolectin with Antibiotic-Metal Complexed Macromolecules toward Broad-Spectrum Antimicrobial Efficacy.

Bacterial infections, particularly by Gram-negative pathogens, have become a serious threat to global healthcare due to the diminishing effectiveness of existing antibiotics. We report a nontraditional therapy to combine three components in one macromolecular system, in which boronic acid adheres to peptidoglycan or lipopolysaccharide via boron-polyol based boronolectin chemistry, cationic metal polymer frameworks interact with negatively charged cell membranes, and ß-lactam antibiotics are reinstated with enhanced vitality to attack bacteria via evading the detrimental enzyme-catalyzed hydrolysis. These macromolecular systems exhibited high efficacy in combating pathogenic bacteria, especially Gram-negative strains, due to synergistic effects of multicomponents on interactions with bacterial cells. In vitro and in vivo cytotoxicity and hemolysis evaluation indicated that these multifunctional copolymers did not induce cell death by apoptosis, as well as did not alter the phenotypes of immune cells and did not show observable toxic effect on red blood cells.

Recent Advances in Metal-Containing Polymer Hydrogels.

Metal-containing polymer hydrogels have attracted increasing interest in recent years due to their outstanding properties such as biocompatibility, recoverability, self-healing, and/or redox activity. In this short review, methods for the preparation of metal-containing polymer hydrogels are introduced and an overview of these hydrogels with various functionalities is given. It is hoped that this short update can stimulate innovative ideas to promote the research of metal-containing hydrogels in the communities.

Metallocene-Containing Homopolymers and Heterobimetallic Block Copolymers via Photoinduced RAFT Polymerization.

We report the synthesis of cationic cobaltocenium and neutral ferrocene containing homopolymers mediated by photoinduced reversible addition-fragmentation chain transfer (RAFT) polymerization with a photocatalyst fac-[Ir(ppy)3]. The homopolymers were further used as macromolecular chain transfer agents to synthesize diblock copolymers via chain extension. Controlled/"living" feature of photoinduced RAFT polymerization was confirmed by kinetic studies even without prior deoxygenation. A light switch between ON and OFF provided a spatiotemporal control of polymerization.

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.