Fabrication of protein-resistant blend based on PVDF-HFP and amphiphilic brush copolymer made from PMMA and PEGMA

doi:10.1016/j.apsusc.2012.09.046

Applied Surface Science

Volume 263, 15 December 2012, Pages 291-296

https://doi.org/10.1016/j.apsusc.2012.09.046 Get rights and content

Abstract

Polymeric blends provide a facile route to obtaining materials with various synergistic properties arising from the individual components. Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), a hydrophobic polymer, is finding new applications in polymer electrolytes, membranes, and heat-resistant structural materials owing to its high thermal stability, mechanical strength, and weatherability. In this report, blends of PVDF-HFP and polymer brush were prepared with enhanced water uptake and protein resistance, which are important requirements for membranes used in food and biological applications. Polymer brush is composed of poly(methyl methacrylate) main chains, which are miscible with PVDF-HFP, and hydrophilic poly(ethylene glycol) (PEG) brush chains. Incorporation of PEG chains through the polymer brush structure not only enhanced water uptake and protein adsorption resistance but also produced a well-distributed morphology of the blending components through the matrix as evidenced by observation of the morphology after selective extraction of polymer brush from the matrix.

Highlights

► The miscibility of PVDF-HFP with amphiphilic brush copolymer poly(MMA-co-PEGMA) were evaluated by DSC. ► The surface hydrophilicity of PVDF-HFP was improved by blending with polymer brush. ► Protein adsorption resistance was enhanced by both of PMMA and PEG of polymer brush.

Introduction

Amphiphilic polymer brush has attracted a great deal of interest due to its potential antifouling applications in biomedical devices, sensors, and membranes [1], [2]. Poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) copolymer, which are hydrophobic, have been widely utilized as a matrix for membrane and polymer electrolytes owing to their thermal stability, mechanical strength, and weatherability [3], [4], [5], [6]. In spite of the various advantages of PVDF and PVDF-HFP as membrane materials, their use in the food treatment, bioseparation, and biomedical applications are often hindered by significant protein fouling because of low surface energy and hydrophobicity [7], [8]. Previous work on polymeric membrane substrates suggests that incorporation of a hydrophilic polymer improves antifouling performance. To obtain this goal, various approaches including blending, surface coating, and chemical surface grafting have been proposed for the incorporation of hydrophilic moieties [6], [9], [10], [11]. Among the various approaches, blending of polymers provides the most facile and effective method when the condition of good miscibility between the components is satisfied. In addition, the blending process distributes the hydrophilic material not only on the surface but also through the bulk matrix. Thus, amphiphilic polymer brush composed of miscible hydrophobic matrix and hydrophilic brush offers one of the most appealing structures for improving the antifouling characteristics of hydrophobic polymer matrix. As poly(ethylene glycol) (PEG) is known to be nontoxic, non-immunogenic, and non-antigenic as well as hydrophilic [12], [13], PEG brushes are expected to effectively resist nonspecific protein adsorption [9].

In this study, we demonstrate the fabrication and protein adsorption resistance of a blend based on PVDF-HFP and amphiphilic brush polymer, which is composed of hydrophilic brushes and hydrophobic main chains and is compatible with PVDF-HFP. We also investigated the effect of polymer brush on the blend morphology by comparing blends made from PVDF-HFP/poly(methyl methacrylate-co-poly(ethylene glycol) methacrylate) (PVDF-HFP/poly(MMA-co-PEGMA) or PVDF-HFP/polymer brush) and PVDF-HFP/poly(methyl methacrylate) (PVDF-HFP/PMMA).

Section snippets

Materials

PVDF-HFP (Kynar Flex^® 2801, Arkema, M_w 822,500), PMMA (IF 870, LG MMA, M_w = 86,000) were used as received. PEGMA (M_n 526) and methyl methacrylate (MMA) were purchased from Aldrich and Junsei, respectively. α,α′-Azobis(isobutyronitrile) (AIBN, Junsei), and tetrahydrofuran (THF, Junsei) were used as an initiator and reaction media, respectively. N,N-dimethylformamide (DMF) from Junsei was used as a solvent to prepare films and membrane. Bovine serum albumin (BSA, ICN Biomedicals Inc.) was used as a

Synthesis and characterization of polymer brush

Polymer brush was synthesized by free radical polymerization using MMA and PEGMA. The structure and composition of the polymer brush were investigated using ¹H NMR. From the spectrum shown in Fig. 1, the peaks resulting from the methoxy hydrogen( single bond OCH₃) of the methyl methacrylate unit and the methylene hydrogens(OCH₂) of the pendant PEG chain in the PEGMA monomer appeared 3.594 ppm and 3.640 ppm, respectively, confirming the successful synthesis of the polymer brush. Peaks at 4.109 and 0.845–1.839

Conclusions

PVDF-HFP properties, such as water uptake and resistance to protein adsorption, can be altered by blending these materials with polymer brush. We anticipate that this blending approach using miscible hydrophobic polymer/amphiphilic polymer brush will widen the potential applications of hydrophobic polymers, especially in the biomedical and food industries.

Acknowledgment

This research was supported by the Converging Research Program through the Korean Ministry of Education, Science, and Technology (2012K001262) and Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology, Korea (2012-0007619).

References (30)

C.M. Magin et al.
Non-toxic antifouling strategies
Mater. Today
(2010)
L. Shi et al.
Fabrication of poly(vinylidene fluoride-co-hexafluropropylene) (PVDF-HFP) asymmetric microporous hollow fiber membranes
J. Membr. Sci.
(2007)
W.-H. Seol et al.
Enhancement of the mechanical properties of PVdF membranes by non-solvent aided morphology control
J. Power Sources
(2007)
Y. Tang et al.
Effect of spinning conditions on the structure and performance of hydrophobic PVDF hollow fiber membranes for membrane distillation
Desalination
(2012)
F. Liu et al.
Preparation of hydrophilic and fouling resistant poly(vinylidene fluoride) hollow fiber membranes
J. Membr. Sci.
(2009)
A. Rahimpour et al.
Preparation and characterization of modified nano-porous PVDF membrane with high antifouling property using UV photo-grafting
Appl. Surf. Sci.
(2009)
P. Wang et al.
Plasma-induced immobilization of poly(ethylene glycol) onto poly(vinylidene fluoride) microporous membrane
J. Membr. Sci.
(2002)
K.-S. Chung et al.
Inorganic adsorbent containing polymeric membrane reservoir for the recovery of lithium from seawater
J. Membr. Sci.
(2008)
J.-Y. Choi et al.
Fabrication of pore size controllable polymeric composite membrane using phase change material
Desalination
(2012)
K.Y. Cho et al.
Protein release microparticles based on the blend of poly(d,l-lactic-co-glycolic acid) and oligo-ethylene glycol grafted poly(l-lactide)
J. Control. Release
(2001)

J.-H. Cao et al.

Structure and ionic conductivity of porous polymer electrolytes based on PVDF-HFP copolymer membranes

J. Membr. Sci.

(2006)

C. Yao et al.

Antibacterial activities of surface modified electrospun poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) fibrous membranes

Appl. Surf. Sci.

(2009)

W. Ma et al.

Effect of PMMA on crystallization behavior and hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate) blend prepared in semi-dilute solutions

Appl. Surf. Sci.

(2007)

Q. Wang et al.

Effects of solvent compositions on physicochemical properties and anti-fouling ability of PVDF microfiltration membranes for wastewater treatment

Desalination

(2012)

H. Susanto et al.

Influence of ultrafiltration membrane characteristics on adsorptive fouling with dextrans

J. Membr. Sci.

(2005)

Cited by (10)

Construction and performance of PVDF-HFP-matrix comb-like gel copolymer electrolyte for high-performance quasi-solid-state lithium-metal batteries
2023, Journal of Energy Storage
Rechargeable lithium metal batteries (LMBs) have encountered bottlenecks in energy density, durability, and safety issues. Designing functional polymer electrolytes has been considered as an effective way to develop high-performance of LMBs. In this study, PVDF-HFP-matrix polymeric electrolytes blended with copolymer P(MMA-co-PEGMEMA) (PPxPy) via a simple one-pot free-radical polymerization are successfully designed and prepared. It has been found that the PPxPy electrolytes can construct different comb-like networks via systematically tuning monomer ratios. The tailored PP5P5 gel electrolyte exhibited high ionic conductivity of 0.74 × 10⁻³ S cm⁻¹ at room temperature (RT), an enlarged electrochemical window up to 4.77 V, high lithium-ion transference number t_Li+ of 0.65, and good mechanical property with Yang's modulus up to 131 MPa. Benefited from these good properties, the Li||LiFePO₄ batteries assembled with PP5P5 gel electrolyte achieved an exceptional discharge capacity of 152 mAh g⁻¹ with nearly 100 % Coulombic efficiency after 150 cycles at 1C. Furthermore, the Li|PP5P5|NCM811 cell exhibits excellent reversible specific capacity of 188 mAh g⁻¹ at 0.1C. Consequently, it can be anticipated the as-prepared functional polymer structure to provide a reliable method for the preparation of polymer electrolytes in quasi-solid-state batteries with high-energy-density.
Effect of MWCNTs and P[MMA-IL] on the crystallization and dielectric behavior of PVDF composites
2018, European Polymer Journal
Citation Excerpt :
It is well known that PVDF is usually blended with poly(methyl methacrylate) (PMMA) to improve processability and endow the blend with the desired properties which result from micro phase separation [15–17]. The specific interaction between hydrogen atom of PVDF and oxygen atom of carbonyl groups of PMMA can lead to the completely compatibility in PVDF/PMMA blend [18,19]. PVDF/PMMA blend is a classical blend comprising of crystalline and amorphous phases and exhibit the crystallization-induced micro phase separation.
Multiwall carbon nanotubes (MWCNTs) and MWCNTs modified by copolymer (P[MMA-IL]) with 1-vinyl-3-ethyl imidazole bromine ionic liquids (IL) and methyl methacrylate (MMA) were incorporated into polyvinylidene fluoride (PVDF) by solution mixing. MWCNTs modified by P[MMA-IL] exhibit better dispersion than that these modified by PMMA. Modified MWCNTs can promote the T_c and T_m of PVDF because of the appearance of β crystalline phase. XRD and FTIR-ATR results confirm that PMMA and MWCNTs cannot induce the β phase, but P[MMA-IL] and MWCNTs can promote the content of β phase due to the ion-dipolar interaction between the imidazolium cation of IL and the >CF₂ of PVDF, and the strong induction is brought by the template of MWCNTs. The experimental dielectric data were analyzed within the formalism of complex permittivity and electric modulus. In the frequency spectra of PVDF/P[MMA-IL]/MWCNTs composite, MWS interfacial polarization and electrode polarization result in high value of dielectric permittivity that is related to the large number of the mobile charge carriers. The conductivity relaxation of PVDF/P[MMA-IL]/MWCNTs composite is thermally activated with the hops of charge carriers because P[MMA-IL]/MWCNTs can improve the hops of charge carriers through amorphous and interphase region by ion-dipolar interaction and dipolar ordering reinforced by the template of MWCNTs.
Surface modification of polypropylene nonwoven fabrics via covalent immobilization of nonionic sugar-based surfactants
2014, Applied Surface Science
Citation Excerpt :
A surface with solely hydrophobic or hydrophilic properties is often inadequate in resisting fouling upon the prolonged exposure to complex environments [39]. Based on the above considerations, amphiphilic polymer brushes have been developed to effectively suppress nonspecific protein adsorption [35,40,41]. The adherence of proteins to amphiphilic polymer-functionalized surface via either hydrophobic or hydrophilic interactions becomes energetically unfavorable, thereby weakening the interactions of the organism with the surface.
Amphiphilic N-alkyl-1-amino-1-deoxy-D-glucitol (C_nAG, n = 8, 12) were successfully prepared. Polypropylene nonwoven fabrics (PP_NWF) were grafted with glycidyl methacrylate (GMA) via a technique of UV-induced graft polymerization combined with plasma pre-treatment, and then PP_NWF-g-GMA was used for the covalent immobilization of C_nAG. The surface graft polymerization was confirmed by ATR-FTIR and XPS, respectively. Effect of grafting parameters, e.g., acetone content, monomer concentration and UV irradiation time on the grafting density of GMA was investigated. And the hemocompatibility of the modified PP_NWF was evaluated by protein adsorption and platelet adhesion. It was founded that the C_nAG-modified substrates greatly suppressed protein adsorption and platelet adhesion compared with the native and pGMA-grafted PP_NWF.
Facile Fabrication of Superwetting PVDF Membrane for Highly Efficient Oil/Water Separation
2023, Polymers
Preparation and performance of silica-di-block polymer hybrids for BSA-resistance coatings
2020, Materials
Role of quaternary ammonium compound immobilized metallic graphene oxide in PMMA/PEG membrane for antibacterial, antifouling and selective gas permeability properties
2018, Polymer Bulletin

View all citing articles on Scopus

View full text

Fabrication of protein-resistant blend based on PVDF-HFP and amphiphilic brush copolymer made from PMMA and PEGMA

Abstract

Highlights

Introduction

Section snippets

Materials

Synthesis and characterization of polymer brush

Conclusions

Acknowledgment

Mater. Today

J. Membr. Sci.

J. Power Sources

Desalination

J. Membr. Sci.

Appl. Surf. Sci.

J. Membr. Sci.

J. Membr. Sci.

Desalination

J. Control. Release

J. Membr. Sci.

Appl. Surf. Sci.

Appl. Surf. Sci.

Desalination

J. Membr. Sci.