A Facile Method for Construction of Antifouling Surfaces by Self-Assembled Polymeric Monolayers of PEG-Silane Copolymers Formed in Aqueous Medium

2006 ◽  
Vol 6 (11) ◽  
pp. 3507-3511
Author(s):  
Sangjin Park ◽  
Young Shik Chi ◽  
Insung S. Choi ◽  
Jiehyun Seong ◽  
Sangyong Jon

Self-assembled polymeric monolayers (PMs) on Si/SiO2 wafers were prepared in water from a series of random copolymers of poly(ethylene glycol) methyl ether methacrylate (PEGMA) and 3-(trimethoxysilyl)propyl methacrylate (TMSMA), denoted as poly(TMSMA-r-PEGMA). Four polymers of poly(TMSMA-r-PEGMA) were synthesized by free radical polymerization with a systematic variation of co-monomer feed ratios. Regardless of PEG grafting density in the copolymers, all PMs formed approximately 1 nm-thick film as measured by ellipsometry. However, the PMs with a higher grafting density of PEG resulted in more hydrophilic surfaces in terms of water contact angle. The protein resistance of the PMs was evaluated using bovine serum albumin (BSA) as a model protein. Analyses by ellipsometry, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) showed that the PMs of the copolymers markedly reduced the nonspecific adsorption of proteins compared to the unmodified Si/SiO2 wafers. The study also revealed that the PMs prepared from the copolymers with a higher PEG grafting density were more effective in resisting the nonspecific protein adsorption.

2017 ◽  
Vol 95 (5) ◽  
pp. 605-611 ◽  
Author(s):  
Lei Wang ◽  
Shaoqing Wen ◽  
Zhanxiong Li

A series of novel amphiphilic ABA-type poly(tridecafluorooctylacrylate)-poly(ethylene glycol)-poly(tridecafluorooctylacrylate) (henceforth referred to as p-TDFA-PEG-p-TDFA) triblock oligomers were successfully synthesized via atom transfer radical polymerization (ATRP) using well-defined Br-PEG-Br as macroinitiator and copper as catalyst. The block oligomers were characterized by Fourier transform infrared (FTIR) spectroscopy and 1H and 19F nuclear magnetic resonances (NMR). Gel permeation chromatography (GPC) showed that the block oligomers have been obtained with narrow molecular weight distributions of 1.22–1.33. X-ray photoelectron spectroscopy (XPS) was carried out to confirm the attachment of p-TDFA-PEG-p-TDFA onto the silicon substrate, together with the chemical compositions of p-TDFA-PEG-p-TDFA. The wetabilities of the oligomer films were measured by water contact angles (CAs). Water CAs of p-TDFA-PEG-p-TDFA film were measured and their morphologies were tested by atomic force microscopy (AFM). The result showed that the CAs of the oligomer films, which possess fluoroalkyl groups assembled on the outer surface, increase after heating due to the migration of fluoroalkyl groups and the resulted microphase separation of the p-TDFA-PEG-p-TDFA.


2021 ◽  
Vol ahead-of-print (ahead-of-print) ◽  
Author(s):  
María V. Puc-Oxté ◽  
Máximo A. Pech-Canul

Purpose This paper aims to prepare highly hydrophobic films on aluminum AA3003 using myristic acid (MA) and evaluate its corrosion protection efficiency in a low-chloride solution. Design/methodology/approach The aluminum surface was initially treated with boiling water to develop a porous nanostructure, and then surface modification was carried out in ethanolic solutions with different concentrations of MA. The surface morphology, wetting behavior and film composition were first characterized, and then, the corrosion behavior was evaluated with electrochemical techniques. Findings The best hydrophobicity and corrosion resistance were obtained with 50 mM of MA. For such concentration, a water contact angle of 140° and protective efficiency of 96% were achieved. A multilayer structure was revealed by scanning electron microscope and X-ray photoelectron spectroscopy. Originality/value The results of this work shed light on the anticorrosion performance of fatty acid self-assembled multilayers on the surface of Al–Mn alloys.


2017 ◽  
Vol 13 ◽  
pp. 648-658 ◽  
Author(s):  
Loïc Pantaine ◽  
Vincent Humblot ◽  
Vincent Coeffard ◽  
Anne Vallée

Aniline-terminated self-assembled monolayers (SAMs) on gold surfaces have successfully reacted with ArSO2NHOSO2Ar (Ar = 4-MeC6H4 or 4-FC6H4) resulting in monolayers with sulfamide moieties and different end groups. Moreover, the sulfamide groups on the SAMs can be hydrolyzed showing the partial regeneration of the aniline surface. SAMs were characterized by water contact angle (WCA) measurements, Fourier-transform infrared reflection absorption spectroscopy (IRRAS) and X-ray photoelectron spectroscopy (XPS).


Polymers ◽  
2020 ◽  
Vol 12 (10) ◽  
pp. 2181
Author(s):  
Sumita Swar ◽  
Veronika Máková ◽  
Ivan Stibor

Different forms of unmodified and modified Poly(ethylene glycols) (PEGs) are widely used as antifouling and antibacterial agents for biomedical industries and Nylon 6 is one of the polymers used for biomedical textiles. Our recent study focused on an efficient approach to PEG immobilization on a reduced Nylon 6 surface via N,N′–disuccinimidyl carbonate (DSC) conjugation. The conversion of amide functional groups to secondary amines on the Nylon 6 polymer surface was achieved by the reducing agent borane-tetrahydrofuran (BH3–THF) complex, before binding the PEG. Various techniques, including water contact angle and free surface energy measurements, atomic force microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and Fourier-transform infrared spectroscopy, were used to confirm the desired surface immobilization. Our findings indicated that PEG may be efficiently tethered to the Nylon 6 surface via DSC, having an enormous future potential for antifouling biomedical materials. The bacterial adhesion performances against S. aureus and P. aeruginosa were examined. In vitro cytocompatibility was successfully tested on pure, reduced, and PEG immobilized samples.


2012 ◽  
Vol 1403 ◽  
Author(s):  
Wei Gao ◽  
Yakai Feng ◽  
Jian Lu ◽  
Jintang Guo

ABSTRACTPhosphorylcholine glyceraldehyde (PCGA) was used as a phosphorylcholine (PC) group containing compound to graft onto the surface of polycarbonateurethane (PCU) film using 1,6-hexanediamine (HDA) or α,ω-diamino-poly(ethylene glycol) (APEG, Mn = 200) as a spacer, in order to introduce biomimetic structure onto the polymer surface. X-ray photoelectron spectroscopy (XPS) analysis shows that PCGA has been covalently linked to the PCU surface. Water contact angle test suggests that the surface hydrophilicity has been improved after PCGA is grafted onto the surface of PCU film. Scanning electron microscope (SEM) observation of the modified PCU films after contacting with plasma-rich plasma demonstrates that platelets rarely adhere but a large number of platelets adhere to the original PCU surface. The hemocompatibility of the PC modified PCU film has been improved obviously after grafting with PCGA with PEG spacer.


2012 ◽  
Vol 1403 ◽  
Author(s):  
Dazhi Yang ◽  
Yakai Feng ◽  
Marc Behl ◽  
Andreas Lendlein ◽  
Haiyang Zhao ◽  
...  

ABSTRACTPolyurethanes (PU) have been widely used as biomaterial in recent years, while thrombus may still occur when contacting with blood especially for extended period of time. Poly(ethylene glycol) (PEG) and phosphorylcholine (PC)-based polymers are commonly employed for surface modification to create protein repellent surfaces. PC-based polymers have been investigated as biomimetic materials because PC is the major component in the outer layer of cell membranes. In this study, the biomimetic copolymer brush of PEG-b-poly(2-methacryloyloxyethyl phosphorylcholine) on PU surfaces was synthesized via atom transfer radical polymerization (ATRP) with a surface initiator. The flexible PEG chain was 200 g·mol-1, while the poly(2-methacryloyloxyethyl phosphorylcholine) (poly(MPC)) chain length was controlled by the ratio of monomer to sacrificial initiator in solution. The topology of the modified surfaces was characterized by the phase image of atomic force microscopy (AFM) to study the synergy effect between PEG chains and poly(MPC) chains. The unmodified and modified surfaces were characterized by Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), water contact angle and platelet adhesion. The results demonstrated that efficient grafting of PEG-b-poly(MPC) brushes on the surfaces was achieved. The PU surfaces modified with PEG and phosphorylcholine zwitterionic brushes showed effective resistance to platelet adhesion and high hemocompatibility in vitro. These PEG and PC-grafted PU materials might be potentially applied in blood-contacting materials or devices due to their good mechanical and hemocompatible properties.


2018 ◽  
Vol 71 (11) ◽  
pp. 855
Author(s):  
Lei Wang ◽  
Lei Chen ◽  
Zhanxiong Li

In this study, three novel side-chain fluoroalkyl oligoethers with different molecular weights were synthesised via a ring-opening reaction of 2,2,3,3,4,4,5,5,5-nonafluoropentyloxirane. The fluorooligoethers were then silanized and characterised by FT-IR,1H, and 19F NMR spectroscopies. These silanlized fluorooligoethers were used to fabricate hydrophobic coatings on silicon substrates, which were pre-treated with O2 plasma, by the method of liquid phase deposition. The chemical compositions and structures of the film surfaces were analysed by X-ray photoelectron spectroscopy and the results showed that silanized fluorooligoethers formed self-assembled films on the silicon wafer. The surface wettability of the coatings was measured by water contact angles. It is noted that the annealing process can improve the hydrophobicity with the highest water contact angle being 115.2 ± 1° and hexadecane contact angle being 67.2 ± 1°. The surface morphologies and roughness of the self-assembled films were measured by atomic force microscopy (AFM), as a result, the surface was found to be rougher with the increment of the molecular weight of the fluorooligoethers.


Polymers ◽  
2018 ◽  
Vol 10 (10) ◽  
pp. 1125 ◽  
Author(s):  
Lulu Liu ◽  
Yuanyuan Gao ◽  
Juan Zhao ◽  
Litong Yuan ◽  
Chenglin Li ◽  
...  

In the paper, poly(ethylene glycol) (PEG) was grafted on the surface of poly(ester-urethane) (SPEU) film with high grafting density for biomedical purposes. The PEG-surface-grafted SPEU (SPEU-PEG) was prepared by a three-step chemical treatment under mild-reaction conditions. Firstly, the SPEU film surface was treated with 1,6-hexanediisocyanate to introduce -NCO groups on the surface with high density (5.28 × 10−7 mol/cm2) by allophanate reaction; subsequently, the -NCO groups attached to SPEU surface were coupled with one of -NH2 groups of tris(2-aminoethyl)amine via condensation reaction to immobilize -NH2 on the surface; finally, PEG with different molecular weight was grafted on the SPEU surface through Michael addition between terminal C = C bond of monoallyloxy PEG and -NH2 group on the film surface. The chemical structure and modified surface were characterized by FT-IR, 1H NMR, X-ray photoelectron spectroscopy (XPS), and water contact angle. The SPEU-PEGs displaying much lower water contact angles (23.9–21.8°) than SPEU (80.5°) indicated that the hydrophilic PEG chains improved the surface hydrophilicity significantly. The SPEU-PEG films possessed outstanding mechanical properties with strain at break of 866–884% and ultimate stress of 35.5–36.4 MPa, which were slightly lower than those of parent film, verifying that the chemical treatments had minimum deterioration on the mechanical properties of the substrate. The bovine serum albumin adsorption and platelet adhesion tests revealed that SPEU-PEGs had improved resistance to protein adsorption (3.02–2.78 μg/cm2) and possessed good resistance to platelet adhesion (781–697 per mm2), indicating good surface hemocompatibility. In addition, due to the high grafting density, the molecular weight of surface-grafted PEG had marginal effect on the surface hydrophilicity and hemocompatibility.


2019 ◽  
Vol 32 (6) ◽  
pp. 611-619 ◽  
Author(s):  
Xiaoli Liu ◽  
Zhen Ge ◽  
Wenguo Zhang ◽  
Yunjun Luo

Due to their unique physicochemical properties, polysilazanes exhibit excellent performance when combined with some resin matrixes, which had drawn great research attention. In this article, polyurethane (PU) was firstly prepared by polytetrahydrofuran glycol, isophorone diisocyanate, and 1,4-butanediol as main materials. Then, the prepared PU was blended with polysilazane by mixing the two solutions together, which was cured to films via dip-coating method at room temperature. The structure, thermal stability, and surface properties of the composite coatings were investigated by Fourier-transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, and X-ray photoelectron spectroscopy. The results demonstrated that after modification with polysilazane, the heat resistance, hydrophobicity, and mechanical property of the PU coatings were improved. When the content of polysilazane was 6 wt%, the mechanical property of the composite films was optimized, with a maximum tensile strength of 25.7 MPa and elongation at break of 797%. Meanwhile, the water contact angle of the composite film was 107° and the water absorption reached a minimum of 2.1%, which showed improved hydrophobicity and water resistance.


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