Hemocompatibility of poly(vinylidene fluoride) membrane grafted with network-like and brush-like antifouling layer controlled via plasma-induced surface PEGylation

In this work, the hemocompatibility of PEGylated poly(vinylidene fluoride) (PVDF) microporous membranes with varying grafting coverage and structures via plasma-induced surface PEGylation was studied. Network-like and brush-like PEGylated layers on PVDF membrane surfaces were achieved by low-pressure and atmospheric plasma treatment. The chemical composition, physical morphology, grafting structure, surface hydrophilicity, and hydration capability of prepared membranes were determined to illustrate the correlations between grafting qualities and hemocompatibility of PEGylated PVDF membranes in contact with human blood. Plasma protein adsorption onto different PEGylated PVDF membranes from single-protein solutions and the complex medium of 100% human plasma were measured by enzyme-linked immunosorbent assay (ELISA) with monoclonal antibodies. Hemocompatibility of the PEGylated membranes was evaluated by the antifouling property of platelet adhesion observed by scanning electron microscopy (SEM) and the anticoagulant activity of the blood coagulant determined by testing plasma-clotting time. The control of grafting structures of PEGylated layers highly regulates the PVDF membrane to resist the adsorption of plasma proteins, the adhesion of platelets, and the coagulation of human plasma. It was found that PVDF membranes grafted with brush-like PEGylated layers presented higher hydration capability with binding water molecules than with network-like PEGylated layers to improve the hemocompatible character of plasma protein and blood platelet resistance in human blood. This work suggests that the hemocompatible nature of grafted PEGylated polymers by controlling grafting structures gives them great potential in the molecular design of antithrombogenic membranes for use in human blood.     

Various approaches to modify biomaterial surfaces for improving hemocompatibility

In this paper, the mechanism of thrombus formation on the surface of polymeric materials and the various approaches of modifying biomaterial surfaces to improve their hemocompatibility are reviewed. Moreover, the blood compatibility of the cellulose membrane grafted with O-butyrylchitosan (OBCS) by using a radiation grafting technique was studied. Surface analysis of grafted cellulose membrane was verified by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and electron spectroscopy for chemical analysis (ESCA), which confirmed that OBCS was successfully grafted onto the cellulose membrane surfaces. Blood compatibility of the grafted cellulose membranes was evaluated by platelet rich plasma (PRP) contacting experiments and protein adsorption experiments using blank cellulose membranes as the control. The blood compatibility of OBCS grafted cellulose membranes is better than that of blank cellulose membranes. These results suggest that the photocrosslinkable chitosan developed here has the potential of serving in blood-contacting applications in medical use.     

Understanding and tuning of polymer surfaces for dialysis applications

Tailoring membrane properties for biomedical applications, e.g., hemodialysis, have been a challenge which material scientists have been addressing for last few decades. The fundamental challenge lies in identifying and controlling the parameters which are responsible for yielding cytocompatibility and hemocompatibility to the material. The present article is an attempt to understand the physical parameters which are responsible for the biological manifestations of a polymer membrane. Two types of dialysis membranes, viz., high performance membrane and high cutoff, have been synthesized. Membrane surfaces were modified via dry and wet annealing, and conditions of annealing were optimized. Subsequently, physical and surface properties of the membranes after annealing were investigated. In‐depth investigation of biological and blood response has been undertaken on the basis of fundamental parameters like polarizability and surface rigidity. Cell adhesion, proliferation, protein adsorption, hemolysis, platelet adhesion, thrombus formation, and complement activation tests were performed on the membranes. It was observed that dry heating increases surface smoothness but in the process develops cracks on membrane surface as well as increases work of adhesion for blood contact. On the other hand, wet heating of membrane surface not only improves biological performance but it is also easy to retrofit with existing spinning technologies for spinning dialysis membranes. In‐house spinning technology was used to synthesize hemodialysis membranes which were annealed at the optimized conditions, and their surfaces were compared with commercial fibers to ascertain the rationale of annealing as a facile method to lend desired surface properties to membranes. Copyright © 2016 John Wiley & Sons, Ltd.     

Preparation and characterization of PVDF‐based blend membranes as polymer electrolyte membranes in fuel cells: Study of factor affecting the proton conductivity behavior

There is a huge demand especially for polyvinylidene fluoride (PVDF) and its copolymers to provide high performance solid polymer electrolytes for use as an electrolyte in energy supply systems. In this regard, the blending approach was used to prepare PVDF‐based proton exchange membranes and focused on the study of factor affecting the ir proton conductivity behavior. Thus, a series of copolymers consisting of poly (methyl methacrylate) (PMMA), polyacrylonitrile (PAN), and poly(2‐acrylamido‐2‐methyl‐l‐propanesulfonic acid) (PAMPS) as sulfonated segments were synthesized and blended with PVDF matrix in order to create proton transport sites in PVDF matrix. It was found that addition of PMMA‐co‐PAMPS and PAN‐co‐PAMPS copolymers resulted in a significant increase in porosity, which favored the water uptake and proton transport at ambient temperature. Furthermore, crystallinity degree of the PVDF‐based blend membranes was increased by addition of the related copolymers, which is mainly attributed to formation of hydrogen bonding interaction between PVDF matrix and the synthesized copolymers, and led to a slight decrease in proton conductivity behavior of blend membranes. From impedance data, the proton conductivity of the PVDF/PMMA‐co‐PAMPS and PVDF/PAN‐co‐PAMPS blend membranes increases to 10 and 8.4 mS cm⁻¹ by adding only 50% of the related copolymer (at 25°C), respectively. Also, the blend membranes containing 30% sulfonated copolymers showed a power density as high as 34.30 and 30.10 mW cm⁻² at peak current density of 140 and 79.45 mA cm⁻² for the PVDF/PMMA‐co‐PAMPS and PVDF/PAN‐co‐PAMPS blend membranes, respectively. A reduction in the tensile strength was observed by the addition of amphiphilic copolymer, whereas the elongation at break of all blend membranes was raised.     

Effect of conjugated linoleic acid grafting on the hemocompatibility of polyacrylonitrile membrane

Polyacrylonitrile (PAN) membrane was hydrolyzed with NaOH_(aq) and grafted with conjugated linoleic acid (CLA) via esterification with 1,3‐propanediol. The resulting CLA grafted PAN membranes were characterized using Fourier transform infrared spectrometry (FT‐IR) and X‐ray photoelectronic spectroscopy (XPS). The effects of CLA grafting on the blood coagulation, platelet aggregation, and oxidative stress were evaluated using human blood. The complete blood count (CBC) and coagulation time (CT) was evaluated in vitro for hemocompatibility. After CLA grafting, the proliferation of human umbilical vein endothelial cells (HUVECs) on the membranes were improved. In addition, the production of reactive oxygen species (ROS) was measured by the chemiluminescence (CL) method to evaluate the oxidative stress. The results showed that the CLA‐grafted PAN membrane could keep the CBC values more stable than unmodified PAN membrane. The CLA‐grafted PAN membranes also showed longer CT. CLA‐grafted PAN membrane could keep the CL counts of hydrogen peroxide and superoxide values more stable than unmodified PAN membrane. These results suggest that a CLA‐grafted PAN membrane could offer protection for patients against oxidative stress and would be helpful for reducing the dosage of anticoagulant during hemodialysis. Copyright © 2006 John Wiley & Sons, Ltd.     

Improving hydrophilicity and protein resistance of poly(vinylidene fluoride) membranes by blending with amphiphilic hyperbranched-star polymer

To endow hydrophobic poly(vinylidene fluoride) (PVDF) membranes with reliable hydrophilicity and protein resistance, an amphiphilic hyperbranched-star polymer (HPE-g-MPEG) with about 12 hydrophilic arms in each molecule was synthesized by grafting methoxy poly(ethylene glycol) (MPEG) to the hyperbranched polyester (HPE) molecule using terephthaloyl chloride (TPC) as the coupling agent and blended with PVDF to fabricate porous membranes via phase inversion process. The chemical composition changes of the membrane surface were confirmed by X-ray photoelectron spectroscopy (XPS), and the membrane morphologies were measured by scanning electron microscopy (SEM). Water contact angle, static protein adsorption, and filtration experiments were used to evaluate the hydrophilicity and anti-fouling properties of the membranes. It was found that MPEG segments of HPE-g-MPEG enriched at the membrane surface substantially, while the water contact angle decreased as low as 49 degrees for the membrane with a HPE-g-MPEG/PVDF ratio of 3/10. More importantly, the water contact angle of the blend membrane changed little after being leached continuously in water at 60 degrees C for 30 days, indicating a quite stable presence of HPE-g-MPEG in the blend membranes. Furthermore, the blend membranes showed lower static protein adsorption, higher water and protein solution fluxes, and better water flux recovery after cleaning than the pure PVDF membrane.     

In-vitro hemocompatibility evaluation of a thermoplastic polyurethane membrane with surface-immobilized water-soluble chitosan and heparin

The surface of a thermoplastic polyurethane (TPU) membrane was treated with low temperature plasma (LTP) and was then grafted with poly(acrylic acid) (PAA), followed by the grafting of water-soluble chitosan (WSC) and heparin (HEP). The surface was characterized with static contact-angle and X-ray photoelectron spectroscopy (XPS). The results showed that the surface densities of peroxides and PAA reached a maximum when treated with LTP for 90 s. A higher pH of the reacting solution led to higher graft densities of WSC and HEP. After WSC and HEP grafting, the hydrophilicity of the TPU membrane was increased. The adsorption of proteins on HEP-grafted TPU membranes was effectively curtailed. In addition, HEP grafting also reduced platelet adhesion, elevated thrombin inactivation, and prolonged the blood coagulation time. According to the L929 fibroblast cell growth inhibition index, the HEP-grafted TPU membranes exhibited non-cytotoxicity. Overall results demonstrated that the HEP immobilization could not only improve the hydrophilicity but also the hemocompatibility of the TPU membrane, while maintaining the ascendant biocompatibility.     

Biofouling resistance of ultrafiltration membranes controlled by surface self-assembled coating with PEGylated copolymers

Block and random PEGylated copolymers of poly(ethylene glycol) methacrylate (PEGMA) and polystyrene (PS) were synthesized with a controlled polydispersity using an atom transfer radical polymerization method and varying molar mass ratios of PS/PEGMA. Two types of PEGylated copolymers were self-assembly coated onto the surface of poly(vinylidene fluoride) (PVDF) ultrafiltration membranes for enhancing biofouling resistance. It was found that the adsorption capacities of random copolymers on PVDF membranes were all higher than those of block copolymers. However, the specific and overall protein resistance of bovine serum albumin (BSA) on PVDF membranes coated with block copolymers was much higher than that with random copolymers. The increase in styrene content in copolymer increased the amount of polymer coating on the membrane, and the increase in PEGMA content enhanced the protein resistance of membranes. The optimum PS/PEGMA ratio was found to be close to 2 for the best resistance of protein adsorption and bacterial adhesion on the PEGylated diblock copolymer-coated membranes. The PVDF membrane coated with such a copolymer owned excellent biofouling resistance to BSA, humic acid, negatively surface charged bacteria E. coli, and positively surface charged bacteria S. maltophilia.     

直接甲醇燃料电池新型聚合物膜的研究

通过溶液共混方法 ,制备了聚偏氟乙烯与聚苯乙烯磺酸 (PVDF_PSSA)、聚偏氟乙烯与Nafion(PVDF_Nafion)两种共混膜 .研究了膜组成对膜电导率和甲醇透过率的影响 .与Nafion 1 1 7膜相比 ,PVDF_Nafion共混膜在Nafion含量为 2 5wt%时 ,电导率σ下降 2个数量级 ,而甲醇透过率P却降低 3个数量级 .若以 (σ/P)为综合指标 ,则PVDF_Nafion共混膜和PVDF_PSSA共混膜的综合性能分别比Nafion 1 1 7膜高约 4 0倍、1 6倍     

Preparation of PVDF porous membranes by using PVDF-g-PVP powder as an additive and their antifouling property

The hydrophilic PVDF-g-PVP powder was used as additive to prepare a series of PVDF/PVDF-g-PVP blend porous membranes via an immersion precipitation phase inversion process. FTIR-ATR measurements confirmed that the hydrophilic PVP preferentially segregated to the interface between membrane and coagulant. SEM images showed that there was no big change in the membrane cross-section with the amount of PVDF-g-PVP increased. However, the membrane surface roughness increased with the amount of PVDF-g-PVP increased according to AFM data. The mean pore size of membranes reached max when the amount of PVDF-g-PVP was 10 wt%. The water contact angle and filtration experiments revealed that the surface enrichment of PVP endowed the membranes with significantly enhanced surface hydrophilicity and protein-adsorption resistance. The flux recovery of the porous membranes was increased from 37.50% to 77.23% with the amount of PVDF-g-PVP increased from 0 to 50 wt%, also indicating that the antifouling property of the porous membranes was improved.     

Preparation and characterization of controlled heparin release waterborne polyurethane coating systems

In this study, to improve hemocompatibility of biomedical materials, a waterborne polyurethane (WPU)/heparin release coating system (WPU/heparin) is fabricated via simply blending biodegradable WPU emulsions with heparin aqueous solutions. The surface compositions and hydrophilicity of these WPU/heparin blend coatings are characterized by attenuated total reflectance infrared spectroscopy (ATR-FTIR) and water contact angle measurements. These WPU/heparin blend coatings show effectively controlled release of heparin, as determined by the toluidine blue method. Furthermore, the biocompatibility and anticoagulant activity of these blend coatings are evaluated based on the protein adsorption, platelet adhesion, activated partial thromboplastin time (APTT), thrombin time (TT), hemolysis, and cytotoxicity. The results indicate that better hemocompatibility and cytocompatilibity are obtained due to blending heparin into this waterborne polyurethane. Thus, the WPU/heparin blend coating system is expected to be valuable for various biomedical applications.     

Surface modification of poly(tetramethylene adipate-co-terephthalate) membrane via layer-by-layer assembly of chitosan and dextran sulfate polyelectrolyte multiplayer

The improvement of hydrophilicity and hemocompatibility of poly(tetramethylene adipate-co-terephthalate) (PTAT) membrane was developed via polyelectrolyte multilayers (PEMs) immobilization. The polysaccharide PEMs included chitosan (CS, as a positive-charged and antibacterial agent) and dextran sulfate (DS, as a negative-charged and anti-adhesive agent) were successfully prepared using the aminolyzed PTAT membrane in a layer-by-layer (LBL) self-assembly manner. The obtained results showed that the contact angle of as-modified PTAT membranes reached to the steady value after four bilayers of coating, hence suggesting that the full coverage was achieved. It could be found that the PTAT–PEMs membranes with DS as the outmost layer could resist the platelet adhesion and human plasma fibrinogen (HPF) adsorption, thereby prolonging effectively the blood coagulation times. According to L929 fibroblast cell growth inhibition index, the as-prepared PTAT membranes exhibited non-cytotoxic. Overall results demonstrated that such an easy, valid and shape-independent processing should be potential for surface modification of PTAT membrane in the application of hemodialysis devices.     

两亲性梳状聚醚硅氧烷对相转化法聚偏氟乙烯多孔膜的共混改性作用研究

以聚醚链段为侧链的两亲性梳状聚醚硅氧烷(ACPS)为改性剂,研究了相转化法制备聚偏氟乙烯(PVDF)多孔膜的改性效果与机理.采用SEM、XPS、接触角、水通量等考察了ACPS对膜结构与性能的影响.研究发现,ACPS在相转化成膜过程中不流失,随着制膜液中ACPS含量的增加,相分离速度降低,膜中微孔由指状结构向蜂窝状结构发展,膜强度提高,亲水性显著提高.提出了ACPS在膜表面的富集现象和在膜中的稳定性机理和模型.结果表明,两亲性梳状聚醚硅氧烷在原理上是一类适合于相转化法制备聚合物微孔膜表面亲水化改性的有效物质.     

聚偏氟乙烯-Nafion共混膜的制备及阻醇质子导电性能研究

直接甲醇燃料电池 (Ｄｉｒｅｃｔｍｅｔｈａｎｏｌｆｕｅｌｃｅｌｌ,ＭＤＦＣ)以高效、清洁和燃料储运方便等优点成为一类极具发展潜力的新型动力源 .但目前ＤＭＦＣ中普通使用的全氟磺酸膜 (如ＮａｆｉｏｎＴＭ 系列膜 )阻醇性能太差 ,导致大量甲醇从阳极穿过膜直接透到阴极 ,造成燃料的浪费和电池整体性能的下降 .据文献报道 ,即使甲醇浓度低到 1ｍｏｌ Ｌ ,也有近40 %的醇透过膜 .缺乏高性能的阻醇质子导电聚合物电解质膜是制约ＤＭＦＣ发展的瓶颈之一 .已有一些研究人员致力于新型膜材料的开发 ,如有人研制了聚苯并咪唑膜[1] 及各种掺杂…     

Effect of conjugated linoleic acid immobilization on the hemocompatibility of cellulose acetate membrane

Conjugated linoleic acid (CLA) was covalently immobilized onto cellulose acetate (CA) membranes. The effects of CLA immobilization on the blood coagulation, platelet aggregation, and oxidative stress were evaluated using human blood. The resulting CLA grafting CA membranes were characterized with X-ray photoelectronic spectroscopy (XPS). The complete blood count (CBC) and coagulation time (CT) was evaluated in vitro for the hemocompatibility. Human serum albumin (HSA) and human plasma fibrinogen (HPF) was evaluated for the protein affinity. The production of reactive oxygen species (ROS) was measured by chemiluminescence (CL) method to evaluate the oxidative stress. The results showed that the CLA-immobilizing CA membrane could keep the CBC values more stable than unmodified CA membrane. The CLA-immobilized CA membranes also showed longer CT and less adsorption of plasma proteins. CLA-immobilized CA membrane could keep the CL counts of hydrogen peroxide and superoxide values more stable than unmodified CA membrane. These results suggest that a CLA-immobilized CA membrane could offer protection for patients against oxidative stress and would be helpful for reducing the dosage of anticoagulant during hemodialysis.     

Improving Hemocompatibility of Membranes for Extracorporeal Membrane Oxygenators by Grafting Nonthrombogenic Polymer Brushes

Nonthrombogenic modifications of membranes for extracorporeal membrane oxygenators (ECMOs) are of key interest. The absence of hemocompatibility of these membranes and the need of anticoagulation of patients result in severe and potentially life‐threatening complications during ECMO treatment. To address the lack of hemocompatibility of the membrane, surface modifications are developed, which act as barriers to protein adsorption on the membrane and, in this way, prevent activation of the coagulation cascade. The modifications are based on nonionic and zwitterionic polymer brushes grafted directly from poly(4‐methyl‐1‐pentene) (TPX) membranes via single electron transfer‐living radical polymerization. Notably, this work introduces the first example of well‐controlled surface‐initiated radical polymerization of zwitterionic brushes. The antifouling layers markedly increase the recalcification time (a proxy of initiation of coagulation) compared to bare TPX membranes. Furthermore, platelet and leukocyte adhesion is drastically decreased, rendering the ECMO membranes hemocompatible.     

Regulation of the microstructure of polyvinylidene fluoride membrane via incorporation of nano-ZIF-7 for improving hydrophobicity and antiwetting performance

The design and fabrication of a membrane with super hydrophobicity and antiwetting property is of great importance for improving membrane performance in distillation, desalination, gas absorption, and separation. In this work, polyvinylidene fluoride (PVDF) membranes were modified by Zeolitic Imidazolate Framework-7 (ZIF-7) nanocrystals to improve the hydrophobic property and antiwetting performance. ZIF-7/PVDF hybrid membranes were prepared via the nonsolvent-induced phase separation (NIPS) method. Different concentrations of ZIF-7 nanocrystals (0, 0.5, 1, 2, 3, and 5 wt%) were introduced into the PVDF dope solution, and the physical structure of the resulting membranes were systematically characterized. Due to the hydrophobic nature of ZIF-7 nanocrystals, the solvent–nonsolvent exchange rate had been regulated effectively during phase inversion. The morphology of top and bottom surfaces, together with the inner structures of the hybrid membrane, has been changed obviously, showing a more twisted finger-like macrovoid layer and a thicker sponge-like layer compared to pristine PVDF membrane. Furthermore, the hydrophobicity and antiwetting properties of these hybrid membranes improved obviously when the incorporated concentration of ZIF-7 was higher than 1 wt%. The M(2) membrane, which possessed the highest surface roughness and water contact angles, showed the best antiwetting property and recovered gas permeance ratio (>95%) after being immersed in aqueous solution for 10 hr.     

Cell outer membrane mimetic modification of a cross-linked chitosan surface to improve its hemocompatibility

A novel strategy has been developed to improve the hemocompatibility of chitosan surface by cell outer membrane mimetic structure able to reduce protein adsorption and cell adhesion. Phosphorylcholine dichloride was synthesized and grafted onto a glutaraldehyde-cross-linked chitosan (CS-GA) film surface to prepare phosphorylcholine-coated CS-GA film (CS-GA-PC) through a heterogeneous reaction process. The spectroscopic and contact angle characterization show that a cell outer membrane mimetic structure was formed on the cross-linked chitosan surface, and the significantly improved hemocompatibility of the modified surface was shown by a suppression of 94% on platelet adhesion, a suppression of 60–70% for bovine plasma fibrinogen and bovine serum albumin adsorptions. These results demonstrated that this cell outer membrane mimetic surface modification with phosphorylcholine dichloride is a promising strategy to improve the hemocompatibility of chitosan.     

Improved protein-adsorption resistance of polyethersulfone membranes via surface segregation of ultrahigh molecular weight poly(styrene-alt-maleic anhydride)

A styrene-maleic anhydride (SMA) alternating copolymer with ultrahigh molecular weight (M_w > 10⁶) synthesized in super critical carbon dioxide (SC CO₂) medium was used as hydrophilic polymeric additive in the preparation of polyethersulfone (PES) membranes. The PES/SMA blend membranes were prepared by immersion precipitation process. X-ray photoelectronic spectroscopy (XPS) measurements confirmed that the hydrolyzed SMA preferentially segregated to membrane–coagulant interface during membrane formation. For the PES/SMA blend membranes, no big change was observed in the cross-sectional structure and the mechanical properties were well maintained after SMA addition except that a thicker top layer was formed. The surface morphology analysis by atomic force microscopy (AFM) showed that the membrane surface roughness increased with the added SMA amount. The results of water contact angle, water absorbance measurements and static protein adsorption experiments revealed that the surface enrichment of SMA endowed PES/SMA blend membranes with significantly improved surface hydrophilicity and protein-adsorption resistance.     

Morphology and properties of hollow-fiber membrane made by PAN mixing with small amount of PVDF

In this paper, the morphological structure and properties such as, miscibility, tensile strength, flux and retention ratio of hollow-fiber membranes manufactured by PAN mixing with small amounts of PVDF have been studied. The hollow fiber was made from a spinning solution composed of polymer (PAN : PVDF=10 : 0, 9 : 1, 7 : 3), additive (PVP, PEG-600) and solvent (DMAC) when immersed in water. The spinnability of blend polymer and the influences of blending on spinning technology have been observed; the morphology of membranes were examined by SEM. The blend membranes possess much higher flux than PAN membrane and fairly good retention ratio especially for the membrane made by PAN : PVDF=9 : 1.