Bio-inspired immobilization of low-fouling phospholipid polymers via a simple dipping process: a comparative study of phenol, catechol and gallol as tethering groups
Abstract:Low-fouling phospholipid polymer was conjugated with bio-inspired tethering groups. Immobilization efficiencies of these polymers onto various surfaces were investigated.
“…[1][2][3] Whereas early publications focused upon method development and data interpretation, the field has shifted toward application. Now, there are many reports of the technique being used as a powerful tool to understand a variety of phenomena including fouling, [4][5][6] swelling, [7][8][9][10][11] sorption, 12,13 and ion exchange. 14,15 The ability to sensitively monitor mass changes (e.g., 17.7 ng/[cm 2 ÁHz] for a 5 MHz crystal) over small time scales (>100 pts per sec) allows for unprecedented access to mass transport phenomena on a molecular scale.…”
Quartz crystal microbalance with dissipation (QCM-D) monitoring is a powerful tool used to sensitively examine the real-time responses of polymer films to external responses. For example, the technique is commonly used to monitor film growth, material adsorption, thin film swelling, and ion exchange. With its rapidly expanding use, this review is intended to introduce new users to the basic principles of QCM-D, along with practical challenges and remedies specific to polymer thin films. For both new and experienced users, specific case studies are highlighted including layer-by-layer assembly, electrochemical QCM-D, swelling, sensing, and biological application. Last, the review recommends future directions for research and areas of growth.
“…[1][2][3] Whereas early publications focused upon method development and data interpretation, the field has shifted toward application. Now, there are many reports of the technique being used as a powerful tool to understand a variety of phenomena including fouling, [4][5][6] swelling, [7][8][9][10][11] sorption, 12,13 and ion exchange. 14,15 The ability to sensitively monitor mass changes (e.g., 17.7 ng/[cm 2 ÁHz] for a 5 MHz crystal) over small time scales (>100 pts per sec) allows for unprecedented access to mass transport phenomena on a molecular scale.…”
Quartz crystal microbalance with dissipation (QCM-D) monitoring is a powerful tool used to sensitively examine the real-time responses of polymer films to external responses. For example, the technique is commonly used to monitor film growth, material adsorption, thin film swelling, and ion exchange. With its rapidly expanding use, this review is intended to introduce new users to the basic principles of QCM-D, along with practical challenges and remedies specific to polymer thin films. For both new and experienced users, specific case studies are highlighted including layer-by-layer assembly, electrochemical QCM-D, swelling, sensing, and biological application. Last, the review recommends future directions for research and areas of growth.
“…Similarly, P1HS, P2HS, and P3HS-based copolymers were synthesized (Supplementary Figs. 6 – 8 ) as reference compounds 17 , 22 , 23 (see SI for synthetic details). Fig.…”
Robust underwater adhesion is challenging because a hydration layer impedes the interaction between substrates and adhesives. Phenolic adhesives inspired by marine creatures such as mussels were extensively studied, but these adhesives have not reached the adhesion strength and substrate diversity of Man-made dry adhesives. Here, we report a class of ultrastrong underwater adhesives with molecular phenolic designs extending beyond what nature has produced. These non-canonical phenolic polymers show versatile adhesion on various materials, with adhesion strengths exceeding 10 MPa on metal. Incorporating even just a small amount (<10%) of non-canonical phenolic groups into a polymer is sufficient for dramatically enhancing underwater adhesion, suggesting that this new class of phenolic materials will be incorporated into various industrial polymer systems in the future.
“…The abovementioned results demonstrated that the catechol groups provided much stronger adhesion between the conjugated backbone and the surface of silica microspheres than phenol groups did. The property owned by catechol-functionalized polymers should not only be related to the contents of hydroxyl groups but also associated with the unique chemical structure of catechol groups which provides the multidentate interactions. , With such interactions, the relatively strong and stable adhesion can be realized with a simple operation, such as the immersion-separation process.…”
Incorporating conjugated polymers with functionalities to provide good adhesion to solid substrates is favorable to prepare fluorescent solid materials for various applications. Inspired by the wide range and robust adhesion property of mussel, a series of conjugated polymers with the poly[p-(phenylene ethynylene)-alt-(thienylene ethynylene)] backbone and pendant catechol groups via Sonogashira coupling polymerization were designed and synthesized. The contents of catechol groups were precisely tuned through copolymerization, followed by selective deprotection. For comparison, similar polymers with pendant phenol groups were also synthesized. The conjugated polymers were demonstrated to have expected chemical structures via systematic characterizations. All the polymers had good solubility in common organic solvents and displayed strong fluorescence in solution. To evaluate the adhesion performance of different polymers, fluorescent silica microspheres were selected as the substrate for loading the abovementioned polymers via immersing the silica microspheres into solutions of conjugated polymers. To find out the loading amount, a calibration curve for each polymer was set up based on the linear relationship between the fluorescence intensities of the suspension of microspheres and the polymer concentrations. The loading amounts of catecholfunctionalized polymers were significantly higher than those of phenol-functionalized polymers; the highest loading amount is over 14-fold of the amount of the control polymer without any catechol/phenol functionality. By combining the abovementioned results with the preliminary mechanism investigation based on the solvent washing, it was concluded that catechol functionality and its content in the polymers greatly affected the adhesion performance. The multidentate interaction provided by catechol groups may enable the conjugated polymers to be widely used for fluorescence coating and staining of a variety of substrates.
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