The role of secondary structures of peptide polymers on antimicrobial efficacy and antibiotic potentiation.

The rise of antibiotic resistance, biofilm formation, and dormant bacterial populations poses serious global health threats. Synthetic antimicrobial peptide (AMP) mimics offer promising alternatives, though the impact of secondary structures in polymeric AMP mimics on antimicrobial efficacy is underexplored. This study investigates chirality-controlled α-peptide polymers (D-PP and DL-PP), synthesized via ring-opening polymerization of allylglycine -carboxy anhydrides and post-polymerization modification through thiol-ene click chemistry.

One-Pot Self-Assembly of Sequence-Controlled Mesoporous Heterostructures via Structure-Directing Agents.

Multimaterial heterostructures have led to characteristics surpassing the individual components. Nature controls the architecture and placement of multiple materials through biomineralization of nanoparticles (NPs); however, synthetic heterostructure formation remains limited and generally departs from the elegance of self-assembly. Here, a class of block polymer structure-directing agents (SDAs) are developed containing repeat units capable of persistent (covalent) NP interactions that enable the direct fabrication of nanoscale porous heterostructures, where a single material is localized at the pore surface as a continuous layer.

Intrinsic antimicrobial resistance: Molecular biomaterials to combat microbial biofilms and bacterial persisters.

The escalating rise in antimicrobial resistance (AMR) coupled with a declining arsenal of new antibiotics is imposing serious threats to global public health. A pervasive aspect of many acquired AMR infections is that the pathogenic microorganisms exist as biofilms, which are equipped with superior survival strategies. In addition, persistent and recalcitrant infections are seeded with bacterial persister cells at infection sites.

Theoretical Examination of the Hydroxide Transport in Cobaltocenium-Containing Polyelectrolytes.

Polymers incorporating cobaltocenium groups have received attention as promising components of anion-exchange membranes (AEMs), exhibiting a good balance of chemical stability and high ionic conductivity. In this work, we analyze the hydroxide diffusion in the presence of cobaltocenium cations in an aqueous environment based on the molecular dynamics of model systems confined in one dimension to mimic the AEM channels. In order to describe the proton hopping mechanism, the forces are obtained from the electronic structure computed at the density-functional tight-binding level.

Facial amphiphilic naphthoic acid-derived antimicrobial polymers against multi-drug resistant gram-negative bacteria and biofilms.

Inspired by the facial amphiphilic nature and antimicrobial efficacy of many antimicrobial peptides, this work reported facial amphiphilic bicyclic naphthoic acid derivatives with different ratios of charges to rings that were installed onto side chains of poly(glycidyl methacrylate). Six quaternary ammonium-charged (QAC) polymers were prepared to investigate the structure-activity relationship. These QAC polymers displayed potent antibacterial activity against various multi-drug resistant (MDR) gram-negative pathogens such as Escherichia coli, Pseudomonas aeruginosa, Klebsiella pneumoniae, and Acinetobacter baumannii.

Membrane-Active Metallopolymers: Repurposing and Rehabilitating Antibiotics to Gram-Negative Superbugs.

Among multiple approaches to combating antimicrobial resistance, a combination therapy of existing antibiotics with bacterial membrane-perturbing agents is promising. A viable platform of metallopolymers as adjuvants in combination with traditional antibiotics is reported in this work to combat both planktonic and stationary cells of Gram-negative superbugs and their biofilms. Antibacterial efficacy, toxicity, antibiofilm activity, bacterial resistance propensity, and mechanisms of action of metallopolymer-antibiotic combinations are investigated.

Facially Amphiphilic Bile Acid-Functionalized Antimicrobials: Combating Pathogenic Bacteria, Fungi, and Their Biofilms.

We report facially amphiphilic bile acid-based antimicrobials with a broad spectrum of activity against both bacterial and fungal pathogens and negligible detrimental effects on mammalian cells. Two lead compounds eliminated dormant subpopulations of various bacterial species, unlike conventional antibiotics. The lead compounds were also effective in eradicating biofilms of methicillin-resistant (MRSA), , and .

Chemical syntheses of bioinspired and biomimetic polymers toward biobased materials.

The rich structures and hierarchical organizations in nature provide many sources of inspiration for advanced material designs. We wish to recapitulate properties such as high mechanical strength, colour-changing ability, autonomous healing and antimicrobial efficacy in next-generation synthetic materials. Common in nature are non-covalent interactions such as hydrogen bonding, ionic interactions and hydrophobic effects, which are all useful motifs in tailor-made materials.

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.

Facial amphiphilicity index correlating chemical structures with antimicrobial efficacy.

Facial amphiphilicity is an extraordinary chemical structure feature of a variety of antimicrobial peptides and polymers. Vast efforts have been dedicated to small molecular, macromolecular and dendrimer-like systems to mimic this highly preferred structure or conformation, including local facial amphiphilicity and global amphiphilicity. This work conceptualizes Facial Amphiphilicity Index (FAI) as a numerical value to quantitatively characterize the measure of chemical compositions and structural features in dictating antimicrobial efficacy.

Stability Analysis of Substituted Cobaltocenium [Bis(cyclopentadienyl)cobalt(III)] Employing Chemistry-Informed Neural Networks.

Cationic cobaltocenium derivatives are promising components of the anion exchange membranes because of their excellent thermal and alkaline stability under the operating conditions of a fuel cell. Here, we present an efficient modeling approach to assessing the chemical stability of substituted cobaltocenium CoCp, based on the computed electronic structure enhanced by machine learning techniques. Within the aqueous environment, the positive charge of the metal cation is balanced by the hydroxide anion through formation of the CoCpOH complexes, whose dissociation is studied within the implicit solvent employing the density functional theory.

Correlation between the Stability of Substituted Cobaltocenium and Molecular Descriptors.

Metallocenium cations, used as a component in an anion exchange membrane of a fuel cell, demonstrate excellent thermal and alkaline stability, which can be improved by the chemical modification of the cyclopentadienyl rings with substituent groups. In this work, the relation between the bond dissociation energy (BDE) of the cobaltocenium (CoCp) derivatives, used as a measure of the cation stability, and chemistry-informed descriptors obtained from the electronic structural calculations is established. The analysis of 12 molecular descriptors for 118 derivatives reveals a nonlinear dependence of the BDE on the electron donating-withdrawing character of the substituent groups coupled to the energy of the frontier molecular orbitals.

Biodegradable polycaprolactone metallopolymer-antibiotic bioconjugates containing phenylboronic acid and cobaltocenium for antimicrobial application.

This paper reports antimicrobial metallopolymers containing biodegradable polycaprolactone as the backbone with boronic acid and cobaltocenium as the side chain. While boronic acid promotes interactions with bacterial cells boronolectin with lipopolysaccharides, cationic cobaltocenium facilitates the unique complexation with anionic β-lactam antibiotics. The synergistic interactions in these metallopolymer-antibiotic bioconjugates were evidenced by re-sensitized efficacy of penicillin-G against four different Gram-negative bacteria (, , and ).

Mechanochemistry of Cationic Cobaltocenium Mechanophore.

Recent research on the mechanochemistry of metallocene mechanophores has shed light on the force-responsiveness of these thermally and chemically stable organometallic compounds. In this work, we report a combination of experimental and computational studies on the mechanochemistry of main-chain cobaltocenium-containing polymers. Ester derivatives of the cationic cobaltocenium, though isoelectronic to neutral ferrocene, are unstable in the nonmechanical control experimental conditions that were accommodated by their ferrocene analogs.

Distal conformational locks on ferrocene mechanophores guide reaction pathways for increased mechanochemical reactivity.

Mechanophores can be used to produce strain-dependent covalent chemical responses in polymeric materials, including stress strengthening, stress sensing and network remodelling. In general, it is desirable for mechanophores to be inert in the absence of force but highly reactive under applied tension. Metallocenes possess potentially useful combinations of force-free stability and force-coupled reactivity, but the mechanistic basis of this reactivity remains largely unexplored.

Synthesis of Site-specific Charged Metallopolymers via Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization.

Site-specific cobaltocenium-labeled polymers are synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization using cobaltocenium-labeled chain transfer agents. These chain transfer agents show counterion-dependent solubility. Based on the chemical structure of the chain transfer agents, single cobaltocenium moieties are dictated to be in predetermined locations at either the center or terminals of the polymer chains.

A Highly Elastic and Fatigue-Resistant Natural Protein-Reinforced Hydrogel Electrolyte for Reversible-Compressible Quasi-Solid-State Supercapacitors.

Compressible solid-state supercapacitors are emerging as promising power sources for next-generation flexible electronics with enhanced safety and mechanical integrity. Highly elastic and compressible solid electrolytes are in great demand to achieve reversible compressibility and excellent capacitive stability of these supercapacitor devices. Here, a lithium ion-conducting hydrogel electrolyte by integrating natural protein nanoparticles into polyacrylamide network is reported.

Metallo-Polyelectrolytes: Correlating Macromolecular Architectures with Properties and Applications.

Since the middle of the 20th century, metallopolymers have represented a standalone subfield with a beneficial combination of functionality from inorganic metal centers and processability from the organic polymeric frameworks. Metallo-polyelectrolytes are a new class of soft materials that showcase fundamentally different properties from neutral polymers due to their intrinsically ionic behaviors. This review describes recent trends in metallo-polyelectrolytes and discusses emerging properties and challenges, as well as future directions from a perspective of macromolecular architectures.

ROMPI-CDSA: ring-opening metathesis polymerization-induced crystallization-driven self-assembly of metallo-block copolymers.

Polymerization-induced self-assembly (PISA) and crystallization-driven self-assembly (CDSA) are among the most prevailing methods for block copolymer self-assembly. Taking the merits of scalability of PISA and dimension control of CDSA, we report one-pot synchronous PISA and CDSA ring-opening metathesis polymerization (ROMP) to prepare nano-objects based on a crystalline poly(ruthenocene) motif. We denote this self-assembly methodology as ROMPI-CDSA to enable a simple, yet robust approach for the preparation of functional nanomaterials.

Supramolecular nucleobase-functionalized polymers: synthesis and potential biological applications.

Nucleobase-functionalized covalent polymers are attracting great attention owing to their versatile structures, accessible architectures and robust properties. Although these materials are still inferior compared with DNA-based materials, they have demonstrated tremendous potential for more sophisticated applications in the biomedical field. In this review, we focus on recent advances concerning these materials.

Facial Amphiphilicity-Induced Polymer Nanostructures for Antimicrobial Applications.

New antimicrobial agents are needed to address ever-increasing antimicrobial resistance and a growing epidemic of infections caused by multidrug resistant pathogens. We design nanostructured antimicrobial copolymers containing multicyclic natural products that bear facial amphiphilicity. Bile acid based macromolecular architectures of these nanostructures can interact preferentially with bacterial membranes.

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.

Rational Synthesis of Metallo-Cations Toward Redox- and Alkaline-Stable Metallo-Polyelectrolytes.

Cations are crucial components in emerging functional polyelectrolytes for a myriad of applications. Rapid development in this area necessitates the exploration of new cations with advanced properties. Herein we describe a combination of computational and experimental design of cobaltocene metallo-cations that have distinct electronic and redox properties.

Lignin Biopolymers in the Age of Controlled Polymerization.

Polymers made from natural biomass are gaining interest due to the rising environmental concerns and depletion of petrochemical resources. Lignin isolated from lignocellulosic biomass is the second most abundant natural polymer next to cellulose. The paper pulp process produces industrial lignin as a byproduct that is mostly used for energy and has less significant utility in materials applications.