Polyelectrolyte Surface Research Articles

Improved hemocompatibility of silk fibroin fabric using layer‐by‐layer polyelectrolyte deposition and heparin immobilization

ABSTRACTSilk fibroin has long been used as implantable surgical sutures and it has acceptable mechanical properties and patency rates in animal models and in clinical end‐uses. However, fibroin has been shown to be hemolytic and can cause damage to red blood cells. So to be used as an implantable vascular prosthesis its hemocompatibility needs to be improved. This study has taken two sequential steps to address this problem. First, to create a positively charged layer on the fibroin fibers' surface, a 1.5 and 2.5 bilayers polyelectrolyte surface deposition layer‐by‐layer technique was used with the positive counterion poly(allylamine hydrochloride) and the negative counterion poly(acrylic acid). Second, negatively charged low molecular weight heparin was then immobilized on these positively charged self‐assembled surfaces. The presence of the heparin was confirmed with Alcian Blue staining and a toluidine blue assay, and the increased roughness and hydrophilicity of the modified surfaces were characterized by scanning electron microscopy, contact angle measurements, and atomic force microscopy. In addition, a negligible hemolytic effect, reduced protein adsorption, and a higher concentration of free hemoglobin measured by a kinetic clotting time test were found to be enhanced with the use of 2.5 bilayers compared to the 1.5 bilayers self‐assembly technique. Given the success of these preliminary results, it is anticipated that this novel approach of surface modification and heparin immobilization will demonstrate long‐term patency during future animal trials of small caliber silk fibroin vascular grafts. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40772.

Growth Factor Release from Polyelectrolyte-Coated Titanium for Implant Applications

Polyelectrolyte multilayer coatings based on poly(methacrylic acid) and poly-l-histidine were formed on anodized titanium surfaces with adsorbed bone morphogenetic protein 2 (BMP-2) or basic fibroblast growth factor (FGFb). These coatings are proposed for use on titanium implanted devices. Coatings were capable of sustained release of growth factor over 25 days, with BMP-2 and FGFb exhibiting approximately identical release profiles. Cell culture on growth factor-eluting surfaces was more effective for preosteoblasts on BMP-2-eluting surfaces than for fibroblasts on FGFb-eluting surfaces. Cell counts at all time points on BMP-2-eluting surfaces were significantly higher than for those on anodized titanium or polyelectrolyte surfaces that did not contain BMP-2. Alkaline phosphatase levels were significantly higher after 21 days on BMP-2-eluting surfaces, indicating increased bone growth.

Patterned Friction and Cell Attachment on Schizophobic Polyelectrolyte Surfaces

A series of copolyelectrolytes with randomly positioned fluorinated (hydrophobic) and zwitterionic (hydrophilic) repeat units was synthesized and used to assemble multilayers. Regular layer-by-layer growth was observed for polymers with a charge density as low as 6%. The hydrophobicity of these "schizophobic" surfaces increased with increasing fluorine content. Polymer-on-polymer stamping was used to create patterned areas of low and high friction, probed by lateral force microscopy using a modified hydrophobic tip. "Contractile" A7r5 smooth muscle cells adhered to the fluorinated surfaces, but the introduction of zwitterion functionality induced a motile, less firmly attached morphology consistent with the "synthetic" motile phenotype of this cell line. In contrast with cells well adhered (on fluorinated) or completely nonadhering (on zwitterionic) films, incorporation of closely spaced repeat units with strongly contrasting hydrophobicity appears to generate intermediate cell adhesion behavior.

(3-Aminopropyl)-4-methylpiperazine End-capped Poly(1,4-butanediol diacrylate-co-4-amino-1-butanol)-based Multilayer Films for Gene Delivery

Biodegradable polyelectrolyte surfaces for gene delivery were created through electrospinning of biodegradable polycations combined with iterative solution-based multilayer coating. Poly(β-amino ester) (PBAE) poly(1,4-butanediol diacrylate-co-4-amino-1-butanol) end-capped with 1-(3-aminopropyl)-4-methylpiperazine was utilized because of its ability to electrostatically interact with anionic molecules like DNA, its biodegradability, and its low cytotoxicity. A new DNA release system was developed for sustained release of DNA over 24 h, accompanied by high exogenous gene expression in primary human glioblastoma (GB) cells. Electrospinning a different PBAE, poly(1,4-butanediol diacrylate-co-4,4'-trimethylenedipiperidine), and its combination with polyelectrolyte 1-(3-aminopropyl)-4-methylpiperazine end-capped poly(1,4-butanediol diacrylate-co-4-amino-1-butanol)-based multilayers are promising for DNA release and intracellular delivery from a surface.

Adsorption Kinetics of DPPG Liposome Layers: A Quantitative Analysis of Surface Roughness

Roughness of a positively charged poly(allylamine hydrochloride) (PAH) polyelectrolyte surface was shown to strongly influence the adsorption of 1.2-dipalmitoyl-sn-3-glycero-[phosphorrac-(1-glycerol)] (DPPG) liposomes on it. The adsorption kinetic curves of DPPG liposomes onto a low-roughness PAH layer reveal an adsorbed amount of 5 mg/m², pointing to liposome rupture, whereas a high-roughness surface leads to adsorbed amounts of 51 mg/m², signifying adsorption of intact liposomes. The adsorption kinetic parameters calculated from adsorption kinetic curves allow us to conclude that the adsorption process is due to electrostatic interactions and also depends on processes such as diffusion and reorganization of lipids on the surface. Analysis of the roughness kinetics enabled us to calculate a growth exponent of 0.19 ± 0.07 and a roughness exponent of around 0.84, revealing that DPPG liposomes adsorbed onto rough surfaces follow the Villain self-affine model. By relating self-affine surfaces with hydrophobicity, the liposome integrity was explained by the reduction in the number of water molecules on the PAH surface, contributing to counterion anchorage near PAH ionic groups, reducing the liposome/PAH layer electrostatic forces and, consequently, avoiding liposome rupture.

Effect of polyelectrolytes and polyelectrolyte mixtures on the electrokinetic potential of dispersed particles. 2. Electrokinetic potential of silica particles in electrolyte, polyelectrolyte and polyelectrolyte mixtures solutions

The effect pH, ionic strength (KCl concentration), weakly and medium charged anionic and cationic polyelectrolytes (PEs) as well as their binary mixtures on the electrokinetic potential of silica particles as a function of the polyelectrolyte/mixture dose, its composition, charge density (CD) of the PE, and way of adding the polymers to the suspension has been studied. It has been shown that addition of increasing amount of anionic PEs increases the absolute value of the negative zeta-potential of particles at pH > pH isoelectric point (IEP = 2.5); this increase is stronger the charge density of the polyelectrolyte is higher. Adsorption of cationic polyelectrolytes at these pH values gives a significant decrease in the negative ζ-potential and overcharging the particles; changes in the ζ-potential are more pronounced for PE samples with higher CD. In mixtures of cationic and anionic PE at pH > pHIEP, the ζ-potential of particles is determined by the adsorbed amount of the anionic polymer independently of the CD of PEs, the mixture composition and the sequence of addition of the mixture components. Unexpectedly, the ζ-potential of silica at pH = 2.1, i.e. < pHIEP, turned out to be positive in the presence of both anionic PE and cationic + anionic PE mixtures. This is explained by formation (and adsorption onto positively charged silica surface) of pseudo-cationic PEs from anionic ones due to transfer of protons from the solution to the amino-group of the anionic polymer. Considerations about the role of coulombic and non-coulombic forces in the mechanism of PE adsorption are presented.

Differences in Caco-2 cell attachment, migration on collagen and fibronectin coated polyelectrolyte surfaces

Metastasis mechanisms depend on cell metabolism changes, migration and adhesion to different tissues. To understand their choice of interaction site, the tumoral cell adhesion to model surfaces was studied. The response of Caco-2 tumoral cells cultured on polyelectrolyte film-functionalized surfaces with or without adhesion proteins (fibronectin or collagen IV) was analyzed. Using the layer-by- layer method, multilayer films were prepared with cationic poly(allylamine hydrochloride) and anionic poly(sodium 4-styrenesulfonate) polyelectrolytes. Film surface wettability was evaluated. The electrochemical impedance spectroscopy analyses were carried out to control the elaborated surfaces on which Caco-2 tumoral cells were cultured. The cell velocity was studied by video-microscopy and a cell colorimetric assay (WST-1) was used to quantify cell viability. The film surface parameters as well as the protein nature and localization in the film were found to modulate cell response. Results demonstrated that the cancer cell motility and proliferation were higher when cultured onto pure collagen located above the polyelectrolyte film and that the reverse surprisingly was observed when proteins were inserted into the polyelectrolyte film. Data also showed that cell motility was correlated with a high charge transfer resistance (Rct) and a low surface free energy (SFE) polar component (electron donor character). This relationship was valid only for pure external proteins. Thus, fibronectin exhibited a low Rct and a high SFE polar component, which decreased cell motility and proliferation.

Self-crosslinking borate anions for the production of tough UV-cured polyelectrolyte surfaces

The first anion with four polymerizable groups has been synthesized and used to produce durable, crosslinked polyelectrolyte (PE) coatings in a single step. Sodium tetrakis(4-vinylphenyl)borate (NaBSty4) was produced by the reaction of BCl3 and the Grignard of 4-bromostyrene. The full series of borates NaBPhxSty4−x, x = 1−3, were also synthesized analogously by reaction of the styryl-Grignard and PhBCl2, Ph2BCl, or Ph3B. Anion exchange of the borates with tributyl 4-vinylbenzylphosphonium chloride gave a family of organic salts developed for applications in photopolymerized coatings. The percent UV cure of the polymer films was determined by infrared spectroscopy and this relative level of curing was corroborated by differential scanning calorimetry analysis. The degree of crosslinking imparted to the polymer films by the different monomers has resulted in varied mechanical properties, which were probed by diamond tip scratch tests and nanoindentation. These clearly demonstrated that as the number of polymerizable groups increased, the film hardness increased correspondingly. The final hardness of the films exceeds those of other related systems and identifies styryl borates as viable crosslinking additives in UV curable technologies, especially in the production of durable PE films. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

Temperature-Induced Ultradense PEG Polyelectrolyte Surface Grafting Provides Effective Long-Term Bioresistance against Mammalian Cells, Serum, and Whole Blood

We report a facile method of generating ultradense poly(l-lysine)-graft-poly(ethylene glycol) (PLL-g-PEG) surface by using high temperature alone, which in turn provides dramatic improvement in resisting nonspecific bioadsorption. X-ray photoelectron spectroscopy (XPS) revealed that the surface graft density increased ~4 times higher on the surface prepared at 80 °C compared to 20 °C. The studies from small-angle X-ray scattering (SAXS) and the effect of varying ionic strength during/post assemblies at 20 and 80 °C indicated that the "cloud point grafting effect" is not the cause for obtaining high density grafting. Stringent long-term bioresistance tests have been conducted and the temperature-induced PLL-g-PEG surfaces have achieved (1) zero mammalian cell adsorption/migration for up to 36 days and (2) extremely close-to-zero protein adsorptions have been observed even after 36 days in 10% serum media and 24 h in whole blood within the ultrasensitive detection limit of time-of-flight secondary ion mass spectrometry (ToF-SIMS).

Lateral Distribution of Charged Species along a Polyelectrolyte Probed with a Fluorescence Blob Model

The distribution of metal counterions binding onto the oppositely charged surface of a model polyelectrolyte, namely, DNA, was characterized by conducting fluorescence quenching experiments. In these experiments, DNA was used as a molecular ruler to measure the average distance (d(blob)) over which electron transfer takes place between DNA-intercalated ethidium bromide (DNA-EB) and the electrostatically bound divalent metal cations Ni(2+) and Cu(2+). Analysis of the fluorescence decays of DNA-EB quenched by Cu(2+) and Ni(2+) with the fluorescence blob model showed that d(blob) was equal to the Debye length (κ(-1)). This surprisingly simple result considering the overall complexity of the system under study led to the straightforward proposal that counterions bind to a polyelectrolyte by distributing themselves randomly into an array of self-defined subdomains of dimension κ(-1). In turn, this insight can be utilized to rationalize the complex behavior of polyelectrolytes in aqueous solution.

The effect of polyelectrolyte multilayer coated titanium alloy surfaces on implant anchorage in rats

Advances have been achieved in the design and biomechanical performance of orthopedic implants in the last decades. These include anatomically shaped and angle-stable implants for fracture fixation or improved biomaterials (e.g. ultra-high-molecular-weight polyethylene) in total joint arthroplasty. Future modifications need to address the biological function of implant surfaces. Functionalized surfaces can promote or reduce osseointegration, avoid implant-related infections or reduce osteoporotic bone loss. To this end, polyelectrolyte multilayer structures have been developed as functional coatings and intensively tested in vitro previously. Nevertheless, only a few studies address the effect of polyelectrolyte multilayer coatings of biomaterials in vivo. The aim of the present work is to evaluate the effect of polyelectrolyte coatings of titanium alloy implants on implant anchorage in an animal model. We test the hypotheses that (1) polyelectrolyte multilayers have an effect on osseointegration in vivo; (2) multilayers of chitosan/hyaluronic acid decrease osteoblast proliferation compared to native titanium alloy, and hence reduce osseointegration; (3) multilayers of chitosan/gelatine increase osteoblast proliferation compared to native titanium alloy, hence enhance osseointegration. Polyelectrolyte multilayers on titanium alloy implants were fabricated by a layer-by-layer self-assembly process. Titanium alloy (Ti) implants were alternately dipped into gelatine (Gel), hyaluronic acid (HA) and chitosan (Chi) solutions, thus assembling a Chi/Gel and a Chi/HA coating with a terminating layer of Gel or HA, respectively. A rat tibial model with bilateral placement of titanium alloy implants was employed to analyze the bones’ response to polyelectrolyte surfaces in vivo. 48 rats were randomly assigned to three groups of implants: (1) native titanium alloy (control), (2) Chi/Gel and (3) Chi/HA coating. Mechanical fixation, peri-implant bone area and bone contact were evaluated by pull-out tests and histology at 3 and 8weeks. Shear strength at 8weeks was statistically significantly increased (p<0.05) in both Chi/Gel and Chi/HA groups compared to the titanium alloy control. No statistically significant difference (p>0.05) in bone contact or bone area was found between all groups. No decrease of osseointegration of Chi/HA-coated implants compared to non-coated implants was found. The results of polyelectrolyte coatings in a rat model showed that the Chi/Gel and Chi/HA coatings have a positive effect on mechanical implant anchorage in normal bone.

Preliminary characterization of N-trimethylchitosan as a nanocarrier for malarie vaccine

With the current snags from the use of Artemisinin - combination therapies (ACTs) in malaria treatment in addition to fear of cross- resistance to unrelated drugs, raising the immunocompetence of individuals in malaria endemic areas by vaccination is the best approach to malaria - free world. Water - soluble cationic derivative, N, N, N- trimethylchitosan (TMC) was synthesized from chitosan. Nanoparticles of the TMC were prepared in various media [milliQ water, Na2CO3 (pH 10.92), Na2HPO4 (PBS, pH 9.01 and alhydrogel® ] which were characterized as adjuvants for possible vaccine delivery. The nanoparticles were characterized for particle size, surface charge and morphology using microscopy (Phase contrast microscope and Confocal laser scanning microscope), and Malvern zetasizer Nano - ZS. Time - resolved particle size analysis was performed after one month storage of the TMC nanoparticles at 4°C. The result of the study showed that PBS was the best medium that produced cationic, monodispersed and stable TMC nanoparticles of < nm forming a compatibly homogeneous system even upon storage. Details of the polyelectrolyte - doped nanoparticles in PBS showed clear coatings due to Sodium poly (styrene sulfonate) [PSS, MW ~70 kDa] at the periphery of the particles and a fluorescent core with some tiny central hollow cavities implying that the nanoparticles can either entrap the vaccine candidate into the hollow cavities or adsorb them unto the surface of the peripheral polyelectrolyte coatings. This preliminary study established that TMC has the desired qualities for the intending antigen delivery. Further research regarding the biological activity of this TMC is indicated.

Synthesis of graphene-multiwalled carbon nanotubes hybrid nanostructure by strengthened electrostatic interaction and its lithium ion battery application

We report a novel way of synthesizing graphene-carbon nanotube hybrid nanostructure as an anode for lithium (Li) ion batteries. For this, graphene was prepared by the solar exfoliation of graphite oxide, while multiwalled carbon nanotubes (MWNTs) were prepared by the chemical vapor deposition method. The graphene–MWNT hybrid nanostructure was synthesized by first modifying graphene surface using a cationic polyelectrolyte and MWNT surface with acid functionalization. The hybrid structure was obtained by homogeneous mixing of chemically modified graphene and MWNT constituents. This hybrid nanostructure exhibits higher specific capacity and cyclic stability. The strengthened electrostatic interaction between the positively charged surface of graphene sheets and the negatively charged surface of MWNTs prevents the restacking of graphene sheets that provides a highly accessible area and short diffusion path length for Li-ions. The higher electrical conductivity of MWNTs promotes an easier movement of the electrons within the electrode. The present synthesis scheme recommends a new pathway for large-scale production of novel hybrid carbon nanomaterials for energy storage applications and underlines the importance of preparation routes followed for synthesizing nanomaterials.

Complexation of stimuli-responsive star-like amphiphilic block polyelectrolyte micelles with lysozyme

The complexation between the stimuli-responsive star-like polyelectrolyte micelles formed by the self-assembly of polystyrene-b-poly(sodium(sulfamate-carboxylate)isoprene) (PS-SCPI) amphiphilic diblock copolymer in water and hen egg white lysozyme (HEWL) was investigated by means of dynamic, static and electrophoretic light scattering. Due to the pH-dependent charge density of the SCPI polyelectrolyte block and surface charge distribution of HEWL, the complexation process was studied at both pH 7 and pH 3 (high and low charge density of the SCPI block, or low and high net positive charge of HEWL, respectively) and at low ionic strength conditions. The solution behavior, structure and effective charge of the formed complexes proved to be dependent on the ratio of the two components and the pH of the solution. Moreover, it was found that the degree of charge neutralization caused by complexation determines the conformation and solubility of the complexes. Increasing the ionic strength of the solution led to vast aggregation of the preformed complexes and even precipitation in some cases. The structural investigation of the complexed protein by fluorescence, circular dichroism and infrared spectroscopic measurements revealed no signs of denaturation upon complexation.

Soft functionalization of graphene for enhanced tri-iodide reduction in dye sensitized solar cells

Anchoring functional moieties on the surface of graphene is an important step in the processing of graphene for numerous applications. In this article, the effects of two different functionalization methods on graphene viz. the conventional method involving ultrasonication in acids and a novel polyelectrolyte based method are systematically investigated. While the conventional acid treatment method makes graphene highly hydrophilic, it also causes severe damage to the graphene sheets and leads to disordered restacking. In contrast, the soft functionalization method based on polyelectrolytes preserves the morphology to a significant extent. Moreover, the presence of charges on the surface of polyelectrolyte modified graphene causes mutual repulsion between the sheets, thereby assisting in the fabrication of optically transparent films. The presence of charges also affects the electrochemical behaviour towards tri-iodide reduction, which is investigated via electrochemical impedance spectroscopy. New equivalent circuits are proposed to interpret the observed response.

Surface modification of poly(propylene carbonate) by aminolysis and layer-by-layer assembly for enhanced cytocompatibility

Poly(propylene carbonate) (PPC) is a biodegradable polymer with desirable mechanical properties for bone and cartilage repair. However, the poor biocompatibility impedes its applications in tissue engineering. The aim of this study was to evaluate the effect of surface modification of PPC on the improvement of its cytocompatibility. The combination of aminolysis and layer-by-layer (LBL) assembly techniques was used to modify the PPC surface. The results of ATR–FTIR measurement demonstrated that PPC was aminolyzed by polyethylenimine (PEI) at specific reaction conditions and the degree of aminolyzation was quantitatively determined by ninhydrin method. Positively charged PEI and negatively charged gelatin were alternatively deposited on the aminolyzed PPC membranes at pH 7.4, which formed polyelectrolyte multilayers surface with gelatin as the outermost layer. The presence of amino groups on the aminolyzed PPC and gelatin on the multilayers had significant impact on enhancing the hydrophilicity of PPC. Fibroblast and primary human osteoblasts (HOBs) were used to assess the cytocompatibility of PPC. The deposition of PEI and gelatin bilayers on PPC remarkably promoted both fibroblast and HOBs cell attachment, spreading and growth. In particular, the osteogenic gene expression of HOBs cultured on the multilayers modified PPC was substantially increased. The aminolysis followed by LBL assembly is a convenient and cost effective technique for enhancing cell attachment and proliferation. The product has high potential for musculoskeletal tissue engineering applications due to its desirable mechanical strength and tunable cytocompatibility.

Casein Aggregates Built Step-by-Step on Charged Polyelectrolyte Film Surfaces Are Calcium Phosphate-cemented

The possible mechanism of casein aggregation and micelle buildup was studied in a new approach by letting α-casein adsorb from low concentration (0.1 mg·ml(-1)) solutions onto the charged surfaces of polyelectrolyte films. It was found that α-casein could adsorb onto both positively and negatively charged surfaces. However, only when its negative phosphoseryl clusters remained free, i.e. when it adsorbed onto a negative surface, could calcium phosphate (CaP) nanoclusters bind to the casein molecules. Once the CaP clusters were in place, step-by-step building of multilayered casein architectures became possible. The presence of CaP was essential; neither Ca(2+) nor phosphate could alone facilitate casein aggregation. Thus, it seems that CaP is the organizing motive in the casein micelle formation. Atomic force microscopy revealed that even a single adsorbed casein layer was composed of very small (in the range of tens of nanometers) spherical forms. The stiffness of the adsorbed casein layer largely increased in the presence of CaP. On this basis, we can imagine that casein micelles emerge according to the following scheme. The amphipathic casein monomers aggregate into oligomers via hydrophobic interactions even in the absence of CaP. Full scale, CaP-carrying micelles could materialize by interlocking these casein oligomers with CaP nanoclusters. Such a mechanism would not contradict former experimental results and could offer a synthesis between the submicelle and the block copolymer models of casein micelles.

A Universal Approach To Fabricate Ordered Colloidal Crystals Arrays Based on Electrostatic Self-Assembly

We present a novel and simple method to fabricate two-dimensional (2D) poly(styrene sulfate) (PSS, negatively charged) colloidal crystals on a positively charged substrate. Our strategy contains two separate steps: one is the three-dimensional (3D) assembly of PSS particles in ethanol, and the other is electrostatic adsorption in water. First, 3D assembly in ethanol phase eliminates electrostatic attractions between colloids and the substrate. As a result, high-quality colloidal crystals are easily generated, for electrostatic attractions are unfavorable for the movement of colloidal particles during convective self-assembly. Subsequently, top layers of colloidal spheres are washed away in the water phase, whereas well-packed PSS colloids that are in contact with the substrate are tightly linked due to electrostatic interactions, resulting in the formation of ordered arrays of 2D colloidal spheres. Cycling these processes leads to the layer-by-layer assembly of 3D colloidal crystals with controllable layers. In addition, this strategy can be extended to the fabrication of patterned 2D colloidal crystals on patterned polyelectrolyte surfaces, not only on planar substrates but also on nonplanar substrates. This straightforward method may open up new possibilities for practical use of colloidal crystals of excellent quality, various patterns, and controllable fashions.

Empirical correlations to estimate agglomerate size and deposition during injection of a polyelectrolyte-modified Fe 0 nanoparticle at high particle concentration in saturated sand

Controlled emplacement of polyelectrolyte-modified nanoscale zerovalent iron (NZVI) particles at high particle concentration (1–10 g/L) is needed for effective in situ subsurface remediation using NZVI. Deep bed filtration theory cannot be used to estimate the transport and deposition of concentrated polyelectrolyte-modified NZVI dispersions (> 0.03 g/L) because particles agglomerate during transport which violates a fundamental assumption of the theory. Here we develop two empirical correlations for estimating the deposition and transport of concentrated polyelectrolyte-modified NZVI dispersions in saturated porous media when NZVI agglomeration in porous media is assumed to reach steady state quickly. The first correlation determines the apparent stable agglomerate size formed during NZVI transport in porous media for a fixed hydrogeochemical condition. The second correlation estimates the attachment efficiency (sticking coefficient) of the stable agglomerates. Both correlations are described using dimensionless numbers derived from parameters affecting deposition and agglomeration in porous media. The exponents for the dimensionless numbers are determined from statistical analysis of breakthrough data for polyelectrolyte-modified NZVI dispersions collected in laboratory scale column experiments for a range of ionic strength (1, 10, and 50 mM Na + and 0.25, 1, and 1.25 mM Ca 2+), approach velocity (0.8 to 55 × 10 −4 m/s), average collector sizes (d 50 = 99 μm, 300 μm, and 880 μm), and polyelectrolyte surface modifier properties. Attachment efficiency depended on approach velocity and was inversely related to collector size, which is contrary to that predicted from classic filtration models. High ionic strength, the presence of divalent cations, lower extended adsorbed polyelectrolyte layer thickness, decreased approach velocity, and a larger collector size promoted NZVI agglomeration and deposition and thus limited its mobility in porous media. These effects are captured quantitatively in the two correlations developed. The application and limitations of using the correlations for preliminary design of in situ NZVI emplacement strategies is discussed.

Functional Fluorinated Modifications on a Polyelectrolyte Coated Polydimethylsiloxane Substrate for Fabricating Antibody Microarrays

Fluorinated compounds exhibit hydrophobic, nonstick, and self-cleaning properties, making them attractive for use as the coating material for biochips. In this study, we copolymerized the fluorinated compound 1H,1H,2H-perfluoro-1-decene (FD) with acrylic acid (AA) and bonded the resulting copolymer with protein G on the surface of polyelectrolyte coated polydimethylsiloxane (PDMS) to form a functional surface that captures antibodies. We demonstrated that the modified PDMS surface remained hydrophobic while becoming resistant to nonspecific protein binding. Thus, aqueous sample solutions formed the droplets (4 μL) on the surface without spreading and drying during the sample printing. Contact angle measurements showed that this functionalized surface was as hydrophobic as the native PDMS with a virtually constant contact angle over seven days of the study under dried condition at 4 °C. Spectroscopic measurements revealed that FD/AA copolymerization formed a homogeneous and highly dense multilayer (50 mg/mm(2)) with a fluorine coverage of 35.4%. Moreover, protein G was shown to covalently bind to AA molecules on the surface at a binding density of 0.24 μg/mm(2). We demonstrated that the fluorinated coating withstood nonspecific binding with extremely low background emission, leading to bioassays that, without the need of blocking agents, exhibited six times more sensitivity than PEG coatings. The fluorinated PDMS antibody microarrays were further applied to accurately determine the absolute concentration of ERα in MCF-7 cells. In conclusion, the unique properties of fluorinated compounds, such as withstanding wetting, nonspecific binding and contamination, make them an excellent coating material for use in sensitive and simple on-chip assays.