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 β-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 β-lactamase and effectively lysing bacterial cells. Various conventional β-lactam antibiotics, including penicillin-G, amoxicillin, ampicillin, and cefazolin, are protected from β-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.

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 progess 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 and biocide; 3) metal-containing polymers as biosensors, and 4) metal-containing polymers in bioimaging.

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Inorganic metal-based materials have been widely utilized in catalytic chemistry, life sciences, and engineering. [1] Cobaltrelated materials, including metallic cobalt, [2] cobalt oxide, [3] cobalt alloy, [4] and cobalt phosphide, [5] have been used in magnetic materials, aerospace engineering, and energy storage. With the development of modern nanoelectronic technology and the increasing demand for nanostructured materials, [6] the preparation of nanostructured inorganic cobaltcontaining materials has become a crucial technological challenge. Various methods have been developed to prepare nanoscale inorganic cobalt-containing materials, including electrodeposition, [7] polymeric precursor synthesis, [8] solvothermal/hydrothermal methods, [5b, 9] and sol-gel precipitation. [10] Among them, the utilization of metal-containing polymer precursors to prepare nanostructured cobalt-based materials has been used in particular, for such reasons as controlled molecular weight and architectures offered by well-established controlled/living synthetic methods, various morphologies from polymer self-assembly, [11] and facile manipulation of polymers. [12] As a result, a myriad of metalcontaining polymer precursors in the form of thin films, micelles, or fibers have been designed and utilized for preparation of functional inorganic materials. [8] However, metal-containing polyelectrolytes or charged metallopolymers have been much less studied as precursors to prepare inorganic metal-based materials. [13] Compared with neutral metal-containing polymers, the existence of counterions in charged metallopolymers has several advantages as novel precursors, such as ion-dependent solubility [14] and ioninduced self-assembly. [15] Thus these polyelectrolytes could be universal precursors for access to multifunctional inorganic materials. Unfortunately, it is challenging to perform facile exchange of counterions for charged metallopolymers. Most studies have been limited to specific systems (usually small molecules [16] or super-macromolecules [17] ), thus severely restricting the diversity of charged metallopolymers.Phase transfer has been applied in various organic reactions [18] and utilized in applications such as ionic selfassembly, [19] heterogeneous catalysts, [18,20] and ionic liquids. [21] However, the utilization of phase transfer to tune metalassociated counterions for charged metallopolymers is much less explored. [15, 19b] We have recently demonstrated ion exchange between hexafluorophosphate (PF 6 À ) and tetraphenyl borate (BPh 4 À ) ions in cationic cobaltocenium-containing monomers/polymers, which was clearly a phase transfer-driven reaction. [14b, 22] But this specific reaction was only limited for BPh 4 À anions. It is still challenging to apply a powerful technique to access other types of counterions for cobaltocenium-containing polymers.Herein, we report a facile phase-transfer ion-exchange method to prepare cationic cobaltocenium-containing polyelectrolytes with diverse counterions by the use of tetrabutylam...

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.