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.     

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.     

Cytocompatibility and antibacterial activity of a PHBV membrane with surface-immobilized water-soluble chitosan and chondroitin-6-sulfate

A water-soluble chitosan (WSC)/chondroitin-6-sulfate (ChS) polyelectrolyte complex (PEC) is covalently immobilized onto the surface of poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid) (PHBV) membranes via ozone-induced oxidation and poly(acrylic acid) (PAA) graft polymerization. To characterize the modified membranes, X-ray photoelectron spectroscopy (XPS) and water contact angle measurements are performed. It is shown that by coupling WSC as a spacer, the amount of ChS immobilized can be significantly increased. The water contact angle decreases with the amount of PAA, WSC, and ChS immobilized, which indicates the improving hydrophilicity. After WSC- and PEC-immobilization modification, the PHBV membranes possess antibacterial activity against S. aureus, E. coli, P. aeruginosa, and Methicilin resistant Staphylococus aureus (MRSA). According to the L929 fibroblast cell growth inhibition index, the as-prepared PHBV membranes are non-cytotoxic. In addition, the in-vitro evaluation of L929 fibroblast attachment, proliferation, and viability of PEC-immobilized PHBV membranes are ascertained to be superior to those of immobilized WSC or ChS alone. The overall results demonstrate that WSC/ChS PEC immobilization can not only improve the hydrophilicity and cytocompatibility of the PHBV membrane, but also endows antibacterial activity. [GRAPH: SEE TEXT] The bacterial survival ratio of as-prepared PHBV membranes (n=3).     

Adsorption of Lead Ion Using Polymer-Modified Wheat Straw Carboxymethylcellulose

The wheat straw carboxymethylcellulose (WSC), a typical natural polymer, was modified by functional poly(acrylic acid) (PAA) with in situ polymerization, which afforded natural and synthetic polymer composite (WSC/PAA). The polymer (WSC/PAA) was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, and thermogravimetric analysis techniques. WSC/PAA was used as polymer adsorbent for removing Pb(II) ions in wastewater. The removal rate of 99.8% was obtained when the experimental conditions were chosen as follows: initial Pb(II) ion concentration; 600 mg/L, WSC/PAA concentration; 0.1 g/100 mL, pH; 5.0, contact time; 60 minutes at 20°C. Adsorption dynamics were consistent with pseudo-second-order kinetic model and the isotherm model can meet the Langmuir isotherm.     

Polyelectrolyte layer-by-layer self-assembly enhanced by electric field and their multilayer membranes for separating isopropanol–water mixtures

An electric field enhanced method is developed for fabricating layer-by-layer (LbL) self-assembly polyelectrolyte multilayer membranes. Three kinds of electric field enhanced polyelectrolyte multilayer membranes (EPEMs), poly(diallyl dimethylammonium chloride)/poly(styrenesulfonate sodium salt) (PDDA/PSS), poly(diallyldimethylammonium chloride)/poly(acrylic acid sodium salt) (PDDA/PAA) and polyethylenimine/poly(acrylic acid sodium salt) (PEI/PAA), were self-assembled on a reverse osmosis membrane (ROM). The pervaporation performances of EPEMs for separating isopropanol–water mixtures (90/10, w/w) are all superior to those of corresponding normal self-assembled polyelectrolytes membranes (PEMs), and the selectivity increases with PDDA/PSS, PDDA/PAA and PEI/PAA in order. For (PEI/PAA)₄PEI EPEM, the separation factor is 1075 and permeation flux is 4.05 kg m⁻² h⁻¹ at 70 °C. This novel method speeds up the LbL process, which makes it promising for the practical application of the LbL multilayer membrane.     

Formation of high-capacity protein-adsorbing membranes through simple adsorption of poly(acrylic acid)-containing films at low pH

Layer-by-layer polyelectrolyte adsorption is a simple, convenient method for introducing ion-exchange sites in porous membranes. This study demonstrates that adsorption of poly(acrylic acid) (PAA)-containing films at pH 3 rather than pH 5 increases the protein-binding capacity of such polyelectrolyte-modified membranes 3-6-fold. The low adsorption pH generates a high density of -COOH groups that function as either ion-exchange sites or points for covalent immobilization of metal-ion complexes that selectively bind tagged proteins. When functionalized with nitrilotriacetate (NTA)-Ni(2+) complexes, membranes containing PAA/polyethylenimine (PEI)/PAA films bind 93 mg of histidine(6)-tagged (His-tagged) ubiquitin per cm(3) of membrane. Additionally these membranes isolate His-tagged COP9 signalosome complex subunit 8 from cell extracts and show >90% recovery of His-tagged ubiquitin. Although modification with polyelectrolyte films occurs by simply passing polyelectrolyte solutions through the membrane for as little as 5 min, with low-pH deposition the protein binding capacities of such membranes are as high as for membranes modified with polymer brushes and 2-3-fold higher than for commercially available immobilized metal affinity chromatography (IMAC) resins. Moreover, the buffer permeabilities of polyelectrolyte-modified membranes that bind His-tagged protein are ~30% of the corresponding permeabilities of unmodified membranes, so protein capture can occur rapidly with low-pressure drops. Even at a solution linear velocity of 570 cm/h, membranes modified with PAA/PEI/PAA exhibit a lysozyme dynamic binding capacity (capacity at 10% breakthrough) of ~40 mg/cm(3). Preliminary studies suggest that these membranes are stable under depyrogenation conditions (1 M NaOH).     

Stabilization of gamma alumina slurry for chemical-mechanical polishing of copper

Stabilization of gamma-alumina suspension for chemical-mechanical polishing (CMP) of copper was investigated. Citric acid and poly(acrylic acid) (PAA) (M(w)=5000) were used as dispersant. The stability of suspension was evaluated from the changes in viscosity, particle size and zeta potential. It appears that metastable gamma-alumina mainly due to its high specific surface area and to the presence of aluminol groups on its surface is progressively transformed to bayerite (beta-Al(OH)(3)) by hydration procedure. Citric acid molecules were adsorbed onto gamma-alumina surface effectively and exhibited the excellent hydration inhibition effect. Although citrate-alumina surface complexes give barrier to the flocculation, the repulsion potential is based mainly on the electrostatic repulsion, thereby steric hindrance caused by the adsorption of these small molecules is very weak. The electrosteric repulsion, which provides more effective dispersion stability than electrostatic repulsion force, can be expected by using polyelectrolyte such as PAA; however, adsorbed layers of PAA onto solid/liquid interface are loosely formed. Therefore, a large amount of PAA was required to inhibit the surface hydration of gamma-alumina suspension, thereby the excess addition of PAA decreased the electrosteric repulsion and re-bridging of the dispersant between particles caused an increase in suspension viscosity. Therefore, synergistic effect can be expected in mixed dispersant system of citric acid and PAA, since small citric acid molecules are adsorbed faster than PAA, inhibiting the progress of surface hydration, and then adsorbed PAA layers exhibit the effective electrosteric repulsion interaction between particles with a small amount compared with PAA alone. It was revealed that the gamma-alumina slurry dispersed by mixed dispersant exhibited the improved removal rate of Cu layer by CMP polishing test.     

Facile tailoring of film morphology and release properties using layer-by-layer assembly of thermoresponsive materials

Layer-by-layer self-assembly was used to prepare thermoresponsive thin films of poly(N-isopropylacrylamide) (PNIPAAm) and poly(acrylic acid) (PAA) based on hydrogen bonding. The temperature of PNIPAAm adsorption was shown to significantly affect both the mass proportion of PNIPAAm in the film and the film surface morphology. When the adsorption was conducted at temperatures close to the lower critical solubility temperature of PNIPAAm, the amount of PNIPAAm in the film increased significantly (from 51 to 59%), and the total film mass increased by 30-40%. The films prepared at 30 degrees C also exhibited a lower surface roughness (1-2 nm) compared with 5-8 nm when prepared at 10 or 21 degrees C. The resulting multilayer films ([PAA/PNIPAAm]10) were capable of being reversibly loaded and unloaded with dye (Rhodamine B) by exposure to solutions at elevated temperatures. The rate of loading and release was shown to depend on both the solution temperature and film preparation temperature, leading to tunable loading/release properties.     

Structure and pH‐sensitive properties of poly (vinylidene fluoride) membrane changed by blending poly (acrylic acid) microgels

pH‐sensitive poly (vinylidene fluoride) (PVDF)/poly (acrylic acid) (PAA) microgels membranes are prepared by phase inversion of the N, N‐dimethylformamide solution containing PAA microgels and PVDF in aqueous solution. The composition and structure of the blend membrane are investigated by Fourier transform infrared spectra, X‐ray photoelectron spectroscopy measurements, thermo gravimetric analysis, field‐emission scanning electron microscope and atomic force microscope. The results indicate the surface and cross section of the blend membranes have a porous structure with PAA microgels immobilized inside the pore and on the membrane surface. The blend PVDF membranes exhibit pH‐sensitive water flux, with the most drastic change in permeability observed between pH 3.7 and 6.3. The blend membranes are fouled by bovine serum albumin, and their antifouling property is enhanced by increasing PAA microgels, mainly derived from the improved hydrophilic property. Copyright © 2013 John Wiley & Sons, Ltd.     

Alkaline Zn-air and Al-air cells based on novel solid PVA/PAA polymer electrolyte membranes

High ionic conducting solid polymer electrolyte membranes (SPEM) had been successfully prepared from poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA). The solution casting method yielded highly hydrophilic membranes with uniform structure that were suitable for electrochemical applications. The room temperature ionic conductivity of the alkaline PVA/PAA polymer electrolyte membranes was in the range of 0.142–0.301 S cm⁻¹ depending on the composition. The cyclic voltammetry analysis was carried out using Zn|SPEM|Zn and Al|SPEM|Al cells. The analysis results revealed the excellent electrochemical stability of these newly developed alkaline solid PVA/PAA polymer electrolyte membranes. Metal-air fuel cells were also prepared from the alkaline solid PVA/PAA polymer electrolyte membranes. The electrochemical cell performance was evaluated based on Zn-air and Al-air cells at C/10 and C/5 discharge rates. The experimental results exhibited high percent of utilization for metal powders at room temperature. It was up to 90% for Zn-air cell when assembled with PVA:PAA = 10:7.5 polymer electrolyte membrane and discharged at C/10 rate. The power density could be as high as 50 mW cm⁻² at room temperature. However, the cell percent utilization was reduced to 73% with the same composition electrolyte membrane when C/5 discharge rate was tested.     

氧化石墨烯/聚电解质层层自组装制备单价离子选择性膜

采用层层自组装法在改性聚丙烯腈(PAN)膜表面交替沉积聚乙烯亚胺(PEI)和聚丙烯酸-氧化石墨烯(PAA-GO)混合液,制得了单价离子选择性复合膜。X射线衍射(XRD)测试结果表明成功合成了氧化石墨烯(GO)并在复合膜中均匀分散。扫描电镜(SEM)观察结果证实了多层聚电解质PEI/PAA-GO成功地组装在基膜上,并用紫外-可见(UV-Vis)光谱进一步证实了组装过程的均匀性和连续性。接触角和性能测试表明加入GO后,复合膜的亲水性和单价阳离子的选择性明显增大。这种高通量、高选择性的防污复合膜在分离和水的软化方面有很好的应用前景。     

Stimuli-responsive polyelectrolyte block copolymer brushes synthesized from the Si wafer via atom-transfer radical polymerization

Surface-tethered oppositely charged weak polyelectrolyte block copolymer brushes composed of poly(2-vinyl pyridine) (P2VP) and poly(acrylic acid) (PAA) were grown from the Si wafer by atom-transfer radical polymerization. The P2VP-b-PAA brushes were prepared through hydrolysis of the second PtBA block to the corresponding acrylic acid. The P2VP-b-PAA brushes with different PAA block length were obtained. The P2VP-b-PAA brushes revealed a unique reversible wetting behavior with pH. The difference between the solubility parameters for P2VP and PAA, the changes of surface chemical composition and surface roughness, and the reversible wetting behavior illustrated that the surface rearrangement occurred during treatment of the P2VP-b-PAA brushes by aqueous solution with different pH value. The reversible properties of the P2VP-b-PAA brushes can be used to regulate the adsorption of the sulfonated PS nanoparticles.     

Preparation of rapidly curable hydrogels from gelatin and poly (carboxylic acid) and their adhesion to skin

Papidly curable hydrogels were prepared through chemical crosslinking of gelatin with poly(carboxylic acid)s including poly (L-glutamic acid) (PLGA), hyaluronic acid (HA), and poly (acrylic acid) (PAA) by use of water-soluble carbodiimide (WSC). The effects of the nature of added poly (carboxylic acid)s on gelation of mixed gelatinpoly (carboxylic acid) aqueous solutions and adhesion of the resulting hydrogels to the mouse skin were evaluated. The addition of poly (carboxylic acid) s reduced the gelation time of gelatin aqueous solutions except for HA. Mixed gelatin-PLGA solutions were cured more rapidly than other mixed solutions and the gelation time was shortened with the increasing PLGA molecular weight. The resulting gelatin-PLGA hydrogels exhibited stronger adhesion to the mouse skin than gelatin-HA and gelatin-PAA hydrogels. The bonding strength increased with the increase in PLGA molecular weight up to 83,000 and thereafter decreased. The longer gelation time and lower adhesion of the gelatin-PAA hydrogels than the gelatin-PLGA hydrogels seem to be due to poorer compatibility of gelatin with PAA than with PLGA. The mixed gelatin-PLGA solution underwent phase separation when the concentration and molecular weight of PLGA became higher than a threshold. The insignificant or suppressive effect of HA addition might be ascribed to the HA-WSC reaction which was the least effective in hydrogel formation.     

Blood compatibility of surface-engineered poly(ethylene terephthalate) via o-carboxymethylchitosan

Poly(ethylene terephthalate) (PET) films were treated by argon plasma following by graft copolymerization with acrylic acid (AAc). The obtained PET-surface grafted PAA (PET-g-PAA) was coupled with chitosan (CS) and o-carboxymethylchitosan (OCMCS) molecules, respectively. Their surface physicochemical properties were characterized by X-ray photoelectron spectroscopy (XPS), water contact angle and streaming potential measurements. The PET-g-PAA surface containing carboxylic acid, CS immobilized PET surface containing amino and OCMCS immobilized PET surface containing both carboxylic acid and amino groups, make the PET surface exhibited a hydrophilic character. The blood compatibility was evaluated by platelet contacting experiments and protein adsorption experiments in vitro. The results demonstrate that the PET surface coupling OCMCS shows much less platelet adhesive and fibrinogen adsorption compared to the other surface modified PET films. The anticoagulation of PET-OCMCS is ascribed to the suitable balance of hydrophobicity/hydrophilicity, surface zeta potential and the low adsorption of protein.     

Adsorption of poly(acrylic acid) onto the surface of titanium dioxide and the colloidal stability of aqueous suspension

The adsorption of poly(acrylic acid) (PAA) in aqueous suspension onto the surface of TiO(2) nanoparticles was investigated. FTIR spectroscopic data provided evidence in support of hydrogen bonding and chemical interaction in the case of the PAA-TiO(2) system. Adsorption isotherms demonstrated that part of the PAA initially added to the suspension was adsorbed onto the TiO(2) surface, after which there was a gradual attainment of an adsorption plateau. The adsorption density of PAA was found to increase with an increase of PAA molecular weight, while it decreased with an increase of pH. The thickness of the PAA adsorption layer was calculated based on measurements of suspension viscosities in the absence and presence of PAA. It was shown that the thickness of the adsorption layer increased with the increase of pH, PAA molecular weight, and its concentration. The surface charge density, the diffuse charge density, and the zeta potential of TiO(2) varied distinctly after PAA adsorption. The shift of pH(iep) toward a lower pH value was observed in the presence of PAA. PAA was found to stabilize the suspension of TiO(2) nanoparticles through electrosteric repulsion. The influence of factors such as PAA molecular weight and its concentration on the colloidal stability of the aqueous suspension was also investigated.     

Fabrication of polyelectrolyte multilayer films comprising nanoblended layers

Polyelectrolyte multilayer thin films were prepared via the alternate deposition of poly(allylamine hydrochloride) (PAH) and a blend of poly(acrylic acid) (PAA) and poly(styrenesulfonate) (PSS). When the pH of the blend solution was 3.5, the presence of PAA in this solution significantly increased the total film thickness. With only 10 wt % PAA in the blend adsorption solution, a large increase in film thickness was observed (92 nm cf. 18 nm). It was also demonstrated that the total amount of PSS adsorbed was enhanced by the presence of PAA in the blend solution, showing that the blend solution composition influenced that of the multilayer films. Thin films prepared with nanoblended layers also showed improved pH stability, because they exhibited reduced film rearrangement upon exposure to acidic conditions (pH = 2.5).     

聚丙烯酸在纳米TiO2表面吸附行为的研究

讨论了聚丙烯酸在纳米TiO₂水悬浮体系中的吸附行为.红外光谱分析和吸附实验结果表明,纳米TiO₂通过氢键吸附PAA.PAA吸附量随着浓度的升高而增大直至饱和吸附量,且分子量越大,饱和吸附量越大.pH值增大,则饱和吸附量减小.在相同条件下,表面吸附层的厚度随PAA分子量、浓度和pH值增大而增大.这是由PAA在颗粒表面构型的变化所致.吸附PAA后的纳米TiO₂的表面电荷密度和ζ电位发生变化,pHiep值向低值方向移动.表面吸附自由能的计算结果说明,PAA在纳米TiO₂表面的吸附是自发过程.     

PMOXA/PAA Brushes toward on-Line Preconcentration for BSA in Capillary Electrophoresis

In this work, a binary-mixed-brushes-coated (BBC) capillary with switchable protein adsorption/desorption properties was developed and applied for on-line preconcentration of proteins. Firstly, amine-terminated poly(2-methyl-2-oxazoline) (PMOXA-NH₂) and thiolterminated poly(acrylic acid) (PAA-SH) were synthesized by using cationic ring-opening polymerization (CROP) and reversible addition fragmentation chain transfer (RAFT) polymerization, respectively. Then, the BBC capillary based on poly(2-methyl-2-oxazoline) (PMOXA) and poly(acrylic acid) (PAA) was prepared by sequentially grafting of PMOXA-NH₂ and PAA-SH onto fused-silica capillary inner surface through poly(dopamine) (PDA) as an anchor. The obtained PMOXA/PAA coating formed on the capillary or capillary's raw material was characterized in terms of the thickness, surface chemical composition by using scanning electron microscope (SEM) and X-ray photoelectron spectrum (XPS). The switchable protein adsorption/desorption performance of the BBC capillary was investigated by using fluorescence microscope under di erent solutions with certain pH and ionic strength(I). The results showed that bovine serum albumin (BSA) could be adsorbed on BBC capillary at pH=5.0 (I=10^-5 mol/L), and then the adsorbed BSA could be released at pH=9.0 (I=0.1 mol/L). This switchable protein adsorption/desorption property of coated capillary was then used to preconcentrate proteins on-line for increasing the detection sensitivity of BSA in capillary electrophoresis (CE). With this method, a sensitivity enhancement factor (SEF) more than 5000 for BSA detection was obtained.     

Molecular‐level structures at poly(4‐vinyl pyridine)/acid interfaces probed by nonlinear vibrational spectroscopy

The molecular structures of the interfaces between a solid poly(4‐vinyl pyridine) (P4VP) surface and poly(acrylic acid) (PAA) as well as hydrochloric acid (HCl) solutions were probed using sum frequency generation (SFG) vibrational spectroscopy in situ in real time. Spectroscopic results clearly reveal that the PAA molecules are adsorbed onto the P4VP surface via hydrogen bonding at the P4VP/PAA solution interface while the P4VP surface is protonated at the P4VP/HCl solution interface. Consequently, the water molecules near the interfaces are strongly perturbed by these two interactions, exhibiting different orderings at the two interfaces. This work clearly demonstrates the power of studying the interfacial molecular‐level structures via nonlinear vibrational spectroscopy when molecular adsorption happens at the solid–liquid interface and paves a way for our future study on tracing the adsorption dynamics of polymer chains onto solid surfaces. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 848–852     

Membrane fouling in the ultrafiltration of polyelectrolyte solutions: Polyacrylic acid and bovine serum albumin

Batch ultrafiltration was used to study the reduction in membrane permeability due to fouling by polyelectrolyte solutes. The flexibility of the polymer chain was found to be an important factor in determining the degree of fouling in the ultrafiltration of poly(acrylic acid) (PAA) solutions, as the effects observed were dependent on the pH and the cation concentration. These parameters were found to have a less pronounced effect in the ultrafiltration of bovine serum albumin (BSA) solutions. An observation of the effects of temperature and applied pressure led to the conclusion that membrane fouling by PAA was due to a pore-plugging effect while that caused by BSA was attributed to hydrophobic adsorption.