Synthesis and Antibacterial Study of Sulfobetaine/Quaternary Ammonium-Modified Star-Shaped Poly[2-(dimethylamino)ethyl methacrylate]-Based Copolymers with an Inorganic Core.

Cationic polymethacrylates are interesting candidates for bacterial disinfectants since they can be made in large-scale by various well-established polymerization techniques such as atom transfer radical polymerization (ATRP). However, they are usually toxic or ineffective in serum and various strategies to improve their biocompatibility or nonfouling property have often resulted in compromised bactericidal activity. Also, star-shaped polymers are less explored than linear polymers for application as antibacterial compounds. In this paper, star polymers with poly[2-(dimethylamino)ethyl methacrylate] (PDMA) as the arms and polyhedral oligomeric silsesquioxane (POSS) as the core (POSS-g-PDMA) were successfully synthesized by ATRP. The minimum inhibition concentrations (MICs) of the synthesized POSS-g-PDMA are in the range of 10-20 µg/mL. POSS-g-PDMA was further modified by various hydrophilization strategies in attempting to reduce hemolysis. With quaternization of POSS-g-PDMA, the antibacterial activities of the obtained quaternary polymers are almost unchanged and the copolymers become relatively nonhemolytic. We also copolymerized sulfobetaine (SB) with POSS-g-PDMA to obtain random and block PDMA-co-PSB arm structures, where the PDMA and poly(sulfobetaine) were the cationic and zwitterionic blocks, respectively. The random cationic-zwitterionic POSS-g-(PDMA-r-PSB) copolymers showed poor antibacterial activity, while the block POSS-g-(PDMA-b-PSB) copolymers retained the antibacterial and hemolytic activity of the pristine POSS-g-PDMA. Further, the block copolymers of POSS-g-(PDMA-b-PSB) showed enhanced antifouling property and serum stability as seen by their nanoparticle size stability in the presence of serum and reduced red blood cell aggregation; the POSS-g-(PDMA-b-PSB) also somewhat retained its MIC in blood unlike the quaternized or random zwitterionic copolymers. The antibacterial kinetics study showed that Escherichia coli can be killed within 30 min by both random and block copolymers of POSS-g-(PDMA-co-PSB). Finally, our POSS star polymers showed low toxicity to zebrafish embryo and could be potentially used in aquaculture antibacterial applications.

Using Diphenylphosphoryl Azide (DPPA) for the Facile Synthesis of Biodegradable Antiseptic Random Copolypeptides.

A facile method has been developed for the large-scale synthesis of random copolypeptides composed of multiple (i.e., cationic, hydrophobic, and hydrophilic) amino acids and their relative ratios have been optimized for broad-spectrum antibacterial effect. The copolypeptides obtained have measured compositions close to the design ratios in spite of the differing reactivities of the different amino acids. An optimized random copolypeptide of lysine, leucine, and serine (denoted as KLS-3) mimicking the composition of LL-37 host defense peptide gives broad spectrum antibacterial activity against clinically relevant Gram-negative and Gram-positive bacteria such as methicillin-resistant Staphylococcus aureus (MRSA) and Pseudomonas aeruginosa (PAO1) with minimum inhibitory concentrations (MICs) of 32-64 µg mL-1 , as well as good MICs against multidrug resistant Gram-negative bacteria of Escherichia coli EC 958 (64 µg mL-1 ) and Klebseilla pneumoniae PTR3 (128 µg mL-1 ). This method can be applied to the facile large-scale copolymerization of multiple amino acids, including unnatural amino acids, to make effective antibacterial copolypeptides.

Modulating Antimicrobial Activity and Mammalian Cell Biocompatibility with Glucosamine-Functionalized Star Polymers.

The development of novel reagents and antibiotics for combating multidrug resistance bacteria has received significant attention in recent years. In this study, new antimicrobial star polymers (14-26 nm in diameter) that consist of mixtures of polylysine and glycopolymer arms were developed and were shown to possess antimicrobial efficacy toward Gram positive bacteria including methicillin-resistant Staphylococcus aureus (MRSA) and vancomycin-resistant Enterococcus (VRE) (with MIC values as low as 16 µg mL(-1)) while being non-hemolytic (HC50 > 10,000 µg mL(-1)) and exhibit excellent mammalian cell biocompatibility. Structure function analysis indicated that the antimicrobial activity and mammalian cell biocompatibility of the star nanoparticles could be optimized by modifying the molar ratio of polylysine to glycopolymers arms. The technology described herein thus represents an innovative approach that could be used to fight deadly infectious diseases.

BiOClBr-coated fabrics with enhanced antimicrobial properties under ambient light.

This study demonstrates the fabrication of ambient light enabled antimicrobial functional fabrics by coating flower-like bismuth oxyhalide i.e. BiOCl0.875Br0.125, with the use of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) as binders for improved coating robustness and durability. The uniformity of the microparticles was ensured with simultaneous probe sonication during the stages of crystal nucleation and growth. The polymeric binders not only strongly anchor the particle on the fabric, but also serve as an ultra-thin protective layer on the BiOClBr that mitigates bismuth leaching. The efficacy of inhibiting bacteria was investigated over the BiOClBr-coated fabrics i.e. cotton and polyester, and the results showed that the coated fabrics could effectively inhibit both Gram-positive and Gram-negative bacteria, i.e. S. aureus and E. coli. In comparison with fabrics coated with other photocatalytic materials including bismuth oxide (Bi2O3) and zinc oxide (ZnO), an exceptionally better antimicrobial efficacy was observed for BiOClBr-coated fabrics. The BiOClBr-coated cotton showed ∼5.0 and ∼6.8 times higher disinfection efficacy towards E. coli compared to that of ZnO and Bi2O3-coated cotton with the same particle weight percentage, respectively. Further elucidation of the probable mechanism by BiOClBr-coated fabrics is related to the excess amount of reactive oxygen species (ROS). Overall, BiOClBr has been shown to be a promising material to fabricate cost-effective antimicrobial functional surfaces for both environmental and biomedical applications e.g. protective laboratory and factory clothing.

High-Performance Capacitive Deionization Disinfection of Water with Graphene Oxide-graft-Quaternized Chitosan Nanohybrid Electrode Coating.

Water disinfection materials should ideally be broad-spectrum-active, nonleachable, and noncontaminating to the liquid needing sterilization. Herein, we demonstrate a high-performance capacitive deionization disinfection (CDID) electrode made by coating an activated carbon (AC) electrode with cationic nanohybrids of graphene oxide-graft-quaternized chitosan (GO-QC). Our GO-QC/AC CDID electrode can achieve at least 99.9999% killing (i.e., 6 log reduction) of Escherichia coli in water flowing continuously through the CDID cell. Without the GO-QC coating, the AC electrode alone cannot kill the bacteria and adsorbs a much smaller fraction (<82.8 ± 1.8%) of E. coli from the same biocontaminated water. Our CDID process consists of alternating cycles of water disinfection followed by electrode regeneration, each a few minutes duration, so that this water disinfection process can be continuous and it only needs a small electrode voltage (2 V). With a typical brackish water biocontamination (with 10(4) CFU mL(-1) bacteria), the GO-QC/AC electrodes can kill 99.99% of the E. coli in water for 5 h. The disinfecting GO-QC is securely attached on the AC electrode surface, so that it is noncontaminating to water, unlike many other chemicals used today. The GO-QC nanohybrids have excellent intrinsic antimicrobial properties in suspension form. Further, the GO component contributes toward the needed surface conductivity of the CDID electrode. This CDID process offers an economical method toward ultrafast, contaminant-free, and continuous killing of bacteria in biocontaminated water. The proposed strategy introduces a green in situ disinfectant approach for water purification.