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Direct grafting of tetraaniline via perfluorophenylazide photochemistry to create antifouling, low bio-adhesion surfaces.

ABSTRACT: Conjugated polyaniline has shown anticorrosive, hydrophilic, antibacterial, pH-responsive, and pseudocapacitive properties making it of interest in many fields. However, in situ grafting of polyaniline without harsh chemical treatments is challenging. In this study, we report a simple, fast, and non-destructive surface modification method for grafting tetraaniline (TANI), the smallest conjugated repeat unit of polyaniline, onto several materials via perfluorophenylazide photochemistry. The new materials are characterized by nuclear magnetic resonance (NMR) and electrospray ionization (ESI) mass spectroscopy. TANI is shown to be covalently bonded to important carbon materials including graphite, carbon nanotubes (CNTs), and reduced graphene oxide (rGO), as confirmed by transmission electron microscopy (TEM). Furthermore, large area modifications on polyethylene terephthalate (PET) films through dip-coating or spray-coating demonstrate the potential applicability in biomedical applications where high transparency, patternability, and low bio-adhesion are needed. Another important application is preventing biofouling in membranes for water purification. Here we report the first oligoaniline grafted water filtration membranes by modifying commercially available polyethersulfone (PES) ultrafiltration (UF) membranes. The modified membranes are hydrophilic as demonstrated by captive bubble experiments and exhibit extraordinarily low bovine serum albumin (BSA) and Escherichia coli adhesions. Superior membrane performance in terms of flux, BSA rejection and flux recovery after biofouling are demonstrated using a cross-flow system and dead-end cells, showing excellent fouling resistance produced by the in situ modification.

SUBMITTER: Lin CW

PROVIDER: S-EPMC6487792 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature

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Direct grafting of tetraaniline via perfluorophenylazide photochemistry to create antifouling, low bio-adhesion surfaces.

Lin Cheng-Wei CW Aguilar Stephanie S Rao Ethan E Mak Wai H WH Huang Xinwei X He Na N Chen Dayong D Jun Dukwoo D Curson Paige A PA McVerry Brian T BT Hoek Eric M V EMV Huang Shu-Chuan SC Kaner Richard B RB

Chemical science 20190313 16

Conjugated polyaniline has shown anticorrosive, hydrophilic, antibacterial, pH-responsive, and pseudocapacitive properties making it of interest in many fields. However, in situ grafting of polyaniline without harsh chemical treatments is challenging. In this study, we report a simple, fast, and non-destructive surface modification method for grafting tetraaniline (TANI), the smallest conjugated repeat unit of polyaniline, onto several materials via perfluorophenylazide photochemis ...[more]

PMID: 31057772

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Project description:Antifouling properties of materials play crucial roles in many important applications such as biomedical implants, marine antifouling coatings, biosensing, and membranes for separation. Poly(ethylene glycol) (or PEG) containing polymers and zwitterionic polymers have been shown to be excellent antifouling materials. It is believed that their outstanding antifouling activity comes from their strong surface hydration. On the other hand, it is difficult to develop underwater glues, although adhesives with strong adhesion in a dry environment are widely available. This is related to dehydration, which is important for adhesion for many cases while water is the enemy of adhesion. In this research, we applied sum frequency generation (SFG) vibrational spectroscopy to investigate buried interfaces between mussel adhesive plaques and a variety of materials including antifouling polymers and control samples, supplemented by studies on marine animal (mussel) behavior and adhesion measurements. It was found that PEG containing polymers and zwitterionic polymers have very strong surface hydration in an aqueous environment, which is the key for their excellent antifouling performance. Because of the strong surface hydration, mussels do not settle on these surfaces even after binding to the surfaces with rubber bands. For control samples, SFG results indicate that their surface hydration is much weaker, and therefore mussels can generate adhesives to displace water to cause dehydration at the interface. Because of the dehydration, mussels can foul on the surfaces of these control materials. Our experiments also showed that if mussels were forced to deposit adhesives onto the PEG containing polymers and zwitterionic polymers, interfacial dehydration did not occur. However, even with the strong interfacial hydration, strong adhesion between mussel adhesives and antifouling polymer surfaces was detected, showing that under certain circumstances, interfacial water could enhance the interfacial bio-adhesion.

Project description:The aim of this work was to study the initial events of Escherichia coli adhesion to polydimethylsiloxane, which is critical for the development of antifouling surfaces. A parallel plate flow cell was used to perform the initial adhesion experiments under controlled hydrodynamic conditions (shear rates ranging between 8 and 100/s), mimicking biomedical scenarios. Initial adhesion studies capture more accurately the cell-surface interactions as in later stages, incoming cells may interact with the surface but also with already adhered cells. Adhesion rates were calculated and results shown that after some time (between 5 and 9 min), these rates decreased (by 55% on average), from the initial values for all tested conditions. The common explanation for this decrease is the occurrence of hydrodynamic blocking, where the area behind each adhered cell is screened from incoming cells. This was investigated using a pair correlation map from which two-dimensional histograms showing the density probability function were constructed. The results highlighted a lower density probability (below 4.0 × 10-4) of the presence of cells around a given cell under different shear rates irrespectively of the radial direction. A shadowing area behind the already adhered cells was not observed, indicating that hydrodynamic blocking was not occurring and therefore it could not be the cause for the decreases in cell adhesion rates. Afterward, cell transport rates from the bulk solution to the surface were estimated using the Smoluchowski-Levich approximation and values in the range of 80-170 cells/cm2.s were obtained. The drag forces that adhered cells have to withstand were also estimated and values in the range of 3-50 × 10-14 N were determined. Although mass transport increases with the flow rate, drag forces also increase and the relative importance of these factors may change in different conditions. This work demonstrates that adjustment of operational parameters in initial adhesion experiments may be required to avoid hydrodynamic blocking, in order to obtain reliable data about cell-surface interactions that can be used in the development of more efficient antifouling surfaces.

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Direct grafting of tetraaniline via perfluorophenylazide photochemistry to create antifouling, low bio-adhesion surfaces.

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Direct grafting of tetraaniline <i>via</i> perfluorophenylazide photochemistry to create antifouling, low bio-adhesion surfaces.

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