Self-decontaminating properties of fluorinated copolymers integrated with ciprofloxacin for synergistically inhibiting the growth of <i>Escherichia coli</i>

<div><p>In this paper, copolymers composed of antibacterial monomer containing ciprofloxacin, methyl methacrylate (MMA), and 2-perfluorooctylethyl methacrylate (FMA) were prepared, and the surface properties and antibacterial performance of the copolymers and blends-mixed PMMA were investigated. Surface characterization using dynamic contact angle measurement and X-ray photoelectron spectroscopy showed that anti-adhesive fluorinated moieties and antimicrobial moieties were highly concomitant on the material surface. All the copolymers and blends films exhibited excellent antibacterial properties. It was found that the fluorinated antibacterial copolymers showed significantly enhanced antibacterial efficiency toward <i>Escherichia coli</i> bacterium, and even markedly prevented the formation of biofilm for long term. The PMMA films blended with fluorinated antibacterial polymer also show similar results. In contrast, the common copolymer without fluorinated units cannot effectively resist bacterial adhesion, proliferation, and prevent biofilm formation. The desirable antibacterial polymer prohibiting the biofilm formation performance of copolymer with special push-me/pull-you structure which weaken the interaction among polymer chains resulted in the more easy segregation of ciprofloxacin on surface in real environment by the help of synergistic effect of fluorinated units, potentially enabling the design of new self-decontaminating biomaterials for control biofouling.</p></div

Effect of Surface Compositional Heterogeneities and Microphase Segregation of Fluorinated Amphiphilic Copolymers on Antifouling Performance

In this paper, a series of fluorinated amphiphilic copolymers composed of 2-perfluorooctylethyl methacrylate (FMA) and 2-hydroxyethyl methacrylate (HEMA) monomers were prepared, and their surface properties and antifouling performance were investigated. Bovine serum albumin (BSA) and human plasma fibrinogen (HFg) were used as model proteins to study protein adsorption onto the fluorinated amphiphilic surfaces. All the fluorinated amphiphilic surfaces exhibit excellent resistant performance of protein adsorption measured by X-ray photoelectron spectroscopy (XPS). The surface compositional heterogeneities on the molecular scale play an important role in the antifouling properties. It was found that the copolymers exhibited better antifouling properties than the corresponding homopolymers did, when the percentage of hydrophilic hydroxyl groups is from 4% to 7% and the percentage of hydrophobic fluorinated moieties is from 4% to 14% on the surface. In addition, the protein molecular size scale and the pattern of microphase segregation domains on the surface strongly affect the protein adsorption behaviors. These results demonstrate the desirable protein-resistant performance from the fluorinated amphiphilic copolymers and provide deeper insight of the effect of surface compositional heterogeneity and microphase segregation on the protein adsorption behaviors

Metalloporphyrin-based porous polymers prepared via click chemistry for size-selective adsorption of protein

<p>Zinc porphyrin-based porous polymers (PPs-Zn) with different pore sizes were prepared by controlling the reaction condition of click chemistry, and the protein adsorption in PPs-Zn and the catalytic activity of immobilized enzyme were investigated. PPs-Zn-1 with 18 nm and PPS-Zn-2 with 90 nm of pore size were characterized by FTIR, NMR and nitrogen absorption experiments. The amount of adsorbed protein in PPs-Zn-1 was more than that in PPs-Zn-2 for small size proteins, such as lysozyme, lipase and bovine serum albumin (BSA). And for large size proteins including myosin and human fibrinogen (HFg), the amount of adsorbed protein in PPs-Zn-1 was less than that in PPs-Zn-2. The result indicates that the protein adsorption is size-selective in PPs-Zn. Both the protein size and the pore size have a significant effect on the amount of adsorbed protein in the PPs-Zn. Lipase and lysozyme immobilized in PPs-Zn exhibited excellent reuse stability.</p

Surface Structure of Spin-Coated Fluorinated Polymers Films Dominated by Corresponding Film-Formation Solution/Air Interface Structure

In this paper, the relationship between the surface structures of spin-coated fluorinated polymer films and their corresponding film-formation solution/air interface structures was investigated. Film-forming poly­(<i>n</i>-alkyl methacrylate) end-capped with 2-perfluorooctylethyl methacrylate (FMA; PFMA_<i>y</i>-ec-PnAMA_<i>x</i>-ec-PFMA_<i>y</i>) was synthesized via a controlled/living atom-transfer radical polymerization (ATRP) technique. The structures both at solution interface and on the spin-coated film surface for these polymers were studied by X-ray photoelectron spectroscopy (XPS), sum frequency spectroscopy (SFG), and surface tension measurements. The results showed that, with increasing polymerization degree of PnAMA, the fluorinated moieties in PFMA_<i>y</i>-ec-PnAMA_<i>x</i>-ec-PFMA_<i>y</i> adsorbed at the solution/air interface were gradually completely replaced by PnAMA segments, resulting in an increase in corresponding solution surface tension until it was equal to that of poly­(<i>n</i>-alkyl methacrylate) solution. Additionally, it was observed for the first time that the surface F/C ratios of spin-coated films decreased linearly with increasing surface tension of the corresponding film-formation polymer solution. Overall, the results indicate that the ultimate surface composition of spin-coated films of these fluorinated methacrylates was mainly dominated by their corresponding film-formation solution/air interfacial structure. This work provides a fundamental understanding of the formation of film surface structures from fluorinated polymer solution to the resulting solid film