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Electrochemical behavior of [ReI(DMPE)3]+, where DMPE = 1,2-bis(dimethylphosphino)ethane, at perfluorosulfonated ionomer-modified electrodes.

The perfluorosulfonated ionomer Nafion shows potential utility as a polymer film to enhance the electrochemical detection of [ReI(DMPE)3]+, where DMPE = 1,2-bis-(dimethylphosphino)ethane. [ReI(DMPE)3]+, a nonradioactive radiopharmaceutical analog for heart imaging, partitions strongly into Nafion films on glassy carbon. Well-defined, chemically reversible cyclic voltammograms are obtained for the [ReI(DMPE)3]+/[ReII(DMPE)3]2+ couple with Eo' shifted positively by 60 mV relative to its value on bare glassy carbon. [ReI(DMPE)3]+ partitions into Nafion more strongly than the oxidized form, [ReII-(DMPE)3]2+. The detection limit for [ReI(DMPE)3]+ by cyclic voltammetry was improved by 2-3 orders of magnitude by the Nafion film. Differential pulse voltammetry for oxidation of [ReI(DMPE)3]+ at the Nafion-modified electrode has a detection limit of 2.5 x 10(-9) M compared to 1.0 x 10(-7) M at the bare electrode. A preconcentration factor of 1 x 10(6) for partitioning of [ReI(DMPE)3]+ from 0.05 M NaCl into Nafion on a glassy carbon electrode was measured.

Electrochemistry↗

Water makes it hydrophobic: contraphilic wetting for polyurethanes with soft blocks having semifluorinated and 5,5-dimethylhydantoin side chains.

A series of polyurethanes with novel copolymer soft blocks display a new surface phenomenon, contraphilic wetting, in which the dry surface is hydrophilic and the wetted surface is hydrophobic. A precursor polymer was prepared with copolymer soft blocks containing semifluorinated (trifluoroethoxy, 3FOx, or pentafluoropropoxy, 5FOx) and bromomethyl functional pendant groups with 2:1, 1:1, and 1:2 semifluorinated/bromomethyl ratios. The hard block consists of isophorone diisocyanate (IPDI) and 1,4-butanediol (BD). 5,5-Dimethylhydantoin was introduced by the substitution of Br via reaction-on-polymer. The composition, structure, and percent of 5,5-dimethylhydantoin substitution for both the precursor and the 5,5-dimethylhydantoin-substituted polyurethanes were analyzed by 1H NMR. The difference between the advancing contact angle on the wetted surface and that on the dry surface (deltaC) is highest (38 degrees ) for the polyurethane with the highest ratio of semifluorinated/hydantoin soft block side chains. A model is proposed according to which contraphilic wetting is driven enthalpically by hydrogen bonding. For the dry surface, hydrogen bonding of 5,5-dimethylhydantoin amide carbonyl groups to methylene hydrogens of semifluorinated groups disrupts the normal surface concentration of semifluorinated groups, whereas the geometric arrangement of hydantoin N-H results in availability for hydrogen bonding with water. Upon exposure to water, amide groups switch from hydrogen bonding to -CH2CF2CF3 to stronger hydrogen bonding with water. As a result, semifluorinated groups are "released", and the surface becomes hydrophobic. Drying the coating (50 degrees C) reversibly restores hydrophilic character. Coatings stored at ambient temperature and humidity have deltaC values intermediate between dry and wet states.

Fluorocarbon Polymers↗

Stabilisation of deoxyribonuclease in hydrofluoroalkanes using miscible vinyl polymers.

A mix of biocompatible macromolecules (poly(vinyl alcohol) (PVA) and poly(vinyl pyrrolidone) (PVP)) has been shown previously to enhance the physical stability of non-aqueous pharmaceutical suspensions. The aim of this work was to assess the feasibility of employing such a combination to facilitate the formulation of deoxyribonuclease I (DNase I) in a metered dose inhaler (MDI) using hydrofluoroalkane (HFA) propellants. DNase I was combined with the selected excipients and formed into an inhalable microparticle by spray-drying. When spray-dried alone DNase I lost almost 40% of its original biological activity, but stabilising DNase I with trehalose and PVA (DTPVA) retained 85% biological activity and trehalose, PVA and PVP (DTPVAPVP) retained 100%. Suspending the DTPVAPVP microparticles within a HFA pMDI for 24 weeks led to no further reduction in the biological activity of DNase I and the formulation delivered almost 60% of the dose expelled to the second stage of a twin-stage impinger. The solubility of PVP in HFA propellants suggests that the enhanced physical stability observed with PVA and PVP may partially be as a result of steric stabilisation. However, the large zeta potential associated with the suspensions suggested that charge stabilisation may also influence the pMDI physical stability.

Algorithms↗

Transducer system for the noninvasive recording of arterial pressure contours.

A transducer system is described that permits noninvasive recordings of the pressure-vs-time arterial profile at any palpable site on the body. A thin (30 microns) piezoelectric polymer film of polyvinylidene fluoride serves as the active element and as the mechanical coupler to the skin. The system has high frequency response and a low frequency cut-off of 0.16 Hz. The active element and its support provides a good mechanical impedance match with the skin. The transducer housing resembles a thick wrist watch and is strapped in place. The complete system is designed to record as many as four simultaneous profiles on a subject. Comparisons of the noninvasive transducer records with records taken with an indwelling catheter indicate congruence of the two signals and the first and second derivatives of the two signals, both when the transducer is applied directly to the skin and when a layer of fat is interposed between the skin and the transducer. The system provides a simple atraumatic means of periodically screening and/or monitoring cardiovascular changes in large populations of subjects and would provide a means of tracking changes induced by therapeutic programs.

Arteriosclerosis↗

Simultaneous determination of the monoamine neurotransmitters and glucose in rat brain by microdialysis sampling coupled with liquid chromatography-dual electrochemical detector.

A new type of chemically modified electrode based ring-disk electrode as the dual electrochemical detector (DECD) for high-performance liquid chromatography (HPLC) to simultaneously determine the monoamine neurotransmitters and glucose is described. The ring electrode was modified with an ion-exchange polymer-overoxidized polypyrrole (OPPy) and the disk electrode was modified with nano Au colloid and glucose oxidase (GOD). The electrochemical behaviors of dopamine (DA) and ascorbic acid (AA) at the OPPy chemically modified electrode (CME) were investigated by differential pulse voltammetry (DPV). It was found that the CME could permeate dopamine cations and repelled the ascorbate anions, which could be used to determine the monoamine neurotransmitters and avoid the interference of AA. The electrochemical behavior of glucose at the Nafion/GOD-Au colloid/GC CME was investigated by amperometry and flow injection analysis (FIA). It was found that the sensitivity of the CME increased apparently in determination of glucose. In order to obtain better separation and current responses of the analytes in HPLC-DECD, several operational parameters have been investigated. Under the optimum conditions, the method showed good stability and reproducibility. The application of this method coupled with microdialysis sampling for in vivo simultaneous determination of monoamine neurotransmitters and glucose in rat brain was satisfactory.

Animals↗

[Os(bpy)2(PVP)10Cl]Cl polymer and Nafion dual-film modified graphite electrode for the amperometric determination of trace amounts of norepinephrine.

A chemically modified graphite electrode was prepared by using a dual film of [Os(bpy)2(PVP)10Cl]Cl polymer and Nafion. The modified electrode showed excellent electrocatalytical activity for the oxidation of norepinephrine (NE) and an ability to eliminate efficiently the interference of ascorbic acid and other anions. The catalytic peak currents obtained from the cyclic voltammograms increased linearly with increasing concentration of NE. A log-log plot of catalytic current versus NE concentration showed a dual-linear relationship in the ranges 1.8 x 10(-8)-4.4 x 10(-6) M and 4.4 x 10(-6)-2.9 x 10(-4) M with correlation coefficients of 0.990 and 0.999, respectively. The detection limit was about 18 nM (3 delta). At a potential of +500 mV the chronoamperometric response showed a linear relationship between the steady state current and NE concentration in the range 1.3-130 microM. With a further increase in NE concentration a Michaelis-Menten-shaped response was observed. The apparent Michaelis-Menten constant and the maximum current were 1.7 mM and 86 microA, respectively. The modified electrode showed excellent reproducibility, sensitivity and stability for the determination of NE at trace levels.

Electrochemistry↗

Improved drug delivery properties of PVDF membranes functionalized with beta-cyclodextrin--application to guided tissue regeneration in periodontology.

The purpose of this study was to develop a membrane for guided tissue regeneration applicable in periodontology that could release antimicrobial agent during the healing period. Our strategy consisted to graft beta-cyclodextrin (beta-CD), a molecule that is known to form inclusion complexes with a large variety of drugs, onto PVDF membranes. Grafting occurred by using citric acid that provoked a crosslinking reaction of beta-CD, and the resulting polymer was imprisoned into the porous structure of the PVDF membrane. The reaction produced a weight increase of the membrane, the range of which depended on the temperature and on the time of curing applied in the process. The biological behavior of the membranes evaluated by proliferation and vitality tests showed good proliferation and improved activity of L132 epithelial cells on the raw and on the grafted membranes. Doxycyclin (DOX) and chlorhexidine (CHX) were used as antimicrobial agents. Their inclusion into the beta-CD cavity in aqueous solutions was confirmed by NMR spectroscopy. After the impregnation of the membranes with DOX and CHX, their release was studied in vitro in batch type experiments and measured by UV spectrophotometry. Low amounts of DOX and CHX were delivered from the raw membranes within the first few hours of tests. Grafted membranes, however, delivered DOX and CHX in larger quantities within 24 h and 10 days respectively.

Anti-Infective Agents↗

Highly selective and sensitive determination of dopamine using a Nafion/carbon nanotubes coated poly(3-methylthiophene) modified electrode.

A poly(3-methylthiophene) modified glassy carbon electrode coated with Nafion/single-walled carbon nanotubes film was fabricated and used for highly selective and sensitive determination of dopamine. The hybrid film surface of the modified electrode was characterized by scanning electrochemical microscopy (SECM) and the results indicated that the carbon nanotubes were dispersed uniformly on the conductive polymer. The experimental results suggest that the hybrid film modified electrode combining the advantages of poly(3-methylthiophene), carbon nanotubes with Nafion exhibits dramatic electrocatalytic effect on the oxidation of dopamine (DA) and results in a marked enhancement of the current response. In 0.1M phosphate buffer solution (PBS) of pH 7.0, the differential pulse voltammetric (DPV) peak heights are linear with DA concentration in three intervals, viz. 0.020-0.10 microM, 0.10-1.0 microM and 1.0-6.0 microM, with correlation coefficients of 0.9993, 0.9996 and 0.9993, respectively. The detection limit of 5.0 nM DA could be estimated (S/N=3). Moreover, the interferences of ascorbic acid (AA) and uric acid (UC) are effectively diminished. This hybrid film modified electrode can be applied to the determination of DA contents in dopamine hydrochloride injection and human serum. These attractive features provide a potential application for either in vitro measurement of DA in the presence of excess AA and UA or as detectors in flow injection analysis (FIA) and high performance liquid chromatography (HPLC).

Biosensing Techniques↗

Amperometric and impedimetric characterization of a glutamate biosensor based on Nafion and a methyl viologen modified glassy carbon electrode.

An electrochemical biosensor based on a glassy carbon (GC) electrode chemically modified with the perfluorinated cation-exchange polymer Nafion and methyl viologen (MV) is described. The enzyme was immobilized by cross-linking with glutaraldehyde in the presence of bovine serum albumin (BSA), methyl viologen and Nafion. Operating variables such as the enzyme/BSA ratio, cross-linking time in glutaraldehyde vapor, methyl viologen and Nafion percentages were investigated with regard to their influence on the biosensor sensitivity by using glucose oxidase as the enzyme model due to its high stability and low cost. The glutamate biosensor was elaborated by using optimized parameters and its electrochemical properties were investigated by cyclic voltammetry, amperometry and by electrochemical impedance spectroscopy. The glutamate biosensor shows a detection limit of 20 microM and a linear range extended to 0.75 mM. Its selectivity was tested with 15 different amino acids, each with a concentration of 20 microM, 25 microM acetaminophen, 20 microM uric acid and 200 microM ascorbic acid. No amperometric response was observed for the interfering species. This good selectivity allows glutamate detection in biological media without previous separation of the analyte.

Biosensing Techniques↗

Transport of organic solutes through amorphous teflon AF films.

Fluorous media have great potential for selective extraction (e.g., as applied to organic synthesis). Fluorous polymer films would have significant advantages in fluorous separations. Stable films of Teflon AF 2400 were cast from solution. Films appear defect-free (SEM; AFM). Rigid aromatic solutes are transported (from chloroform solution to chloroform receiving phase) in a size-dependent manner (log permeability is proportional to -0.0067 times critical volume). Benzene's permeability is about 2 orders of magnitude higher than in comparable gas-phase experiments. The films show selectivity for fluorinated solutes in comparison to the hydrogen-containing control. Transport rates are dependent on the solvent making up the source and receiving phases. The effect of solvent is, interestingly, not due to changes in partition ratio, but rather it is due to changes in the solute diffusion coefficient in the film. Solvents plasticize the films. A less volatile compound, -COOH-terminated poly(hexafluoropropylene oxide) (4), plasticizes the films (T(g) = -40 degrees C). Permeabilities are decreased in comparison to 4-free films apparently because of decreased diffusivity of solutes. The slope of dependence of log permeability on critical volume is not changed, however.

Benzene↗

Polyethylene glycol significantly enhances the transfer of membrane immunoblotting.

Poly(ethylene glycol)n is a group of water-soluble, hydrophobic, optically transparent and biomacromolecule-nondenaturing polymers. These properties have caused it be widely used for various purposes in the biological sciences. In this study, the effects of poly(ethylene glycol)n on protein preservation, electrotransferring, and immunoblotting from sodium dodecyl sulfate (SDS)-polyacrylamide gel onto polyvinylidene difluoride (PVDF) membrane have been systematically evaluated. After SDS-polyacrylamide gel electrophoresis, 30% poly(ethylene glycol)n may be applied to reversibly fix proteins within the gel more completely, differing from irreversible fixation produced by solutions such as trichloroacetic acid-sulfosalicylic acid or acetic acid-methanol systems. The intragel proteins, fixed by poly(ethylene glycol)n, can be electroblotted directly onto PVDF membranes in the presence of 30% poly(ethylene glycol)n. We have shown that treatment with poly(ethylene glycol)n may reduce background, raise signal-to-noise ratio, sharpen protein bands, and increase resolution, resulting in enhancement of the immunoblotting transfer. It is possible to visualize a few picograms of a single protein band, increasing the sensitivity of the method by 10- to 100-fold, as compared with standard immunoblotting techniques.

Animals↗

Electrically charged polymeric substrates enhance nerve fibre outgrowth in vitro.

The physical, chemical and electrical properties of synthetic guidance devices are known to influence nerve regeneration in vivo. In the present study, neurons were cultured directly on electrically charged polymer growth substrates to determine if local electrical charges enhance nerve fibre outgrowth in vitro. Piezoelectric polymers such as polyvinylidene fluoride (PVDF) generate transient surface charges under minute mechanical strain. Mouse neuroblastoma (Nb2a) cells were cultured directly on electrically poled (i.e. piezoelectric) and unpoled (i.e. nonpiezoelectric) PVDF substrates in serum-free and serum-containing media. Nerve fibre outgrowth was analysed 24, 48, 72 and 96 h after plating. Piezoelectric PVDF substrates generated 2-3 mV at 1200 Hz when placed on standard incubator shelves and unpoled PVDF substrates showed no output. Nb2a cells grown on piezoelectric substrates exhibited significantly greater levels of process outgrowth and neurite lengths at all time periods for both media conditions. Detailed surface characterization of PVDF substrates using electron spectroscopy for chemical analysis (ESCA) and a comprehensive wettability profile revealed that poled and unpoled PVDF was chemically indistinguishable and showed similar surface wettabilities and adhesive properties. Therefore, we conclude that enhanced process outgrowth was induced by the film's piezoelectric output, making poled PVDF a unique biomaterial for which cell/polymer interactions are mediated predominantly through bulk electrical properties rather than surface properties.

Animals↗

Carbon nanotubes-polymer-redox mediator hybrid thin film for electrocatalytic sensing.

Electrocatalytic sensing of NADH using a hybrid thin film derived from multi-wall carbon nanotubes (CNTs), Nafion (Nf) polymer and electrogenerated redox mediator is described. The redox mediator was electrochemically generated by the oxidation of serotonin on the hybrid thin film modified glassy carbon electrode (GC/Nf-CNT). Controlled potential electrolysis of serotonin at 0.1 V in neutral solution results in the generation of the redox mediator 5,5'-dihydroxy-4,4'-bitryptamine (DHB) on the hybrid thin film. The electrogenerated DHB has redox active quinone-imine structure and was electrochemically characterized by studying the pH dependent redox response. DHB on the hybrid thin film exhibits reversible redox peak at -0.05 V and the formal potential shifts by -55 mV while increasing the solution pH by 1 unit. The quinone-imine structure of DHB efficiently catalyzes the oxidation of NADH with a decrease in the overpotential of about 500 mV compared to the unmodified electrode. The CNTs of the hybrid thin film facilitates the mediated electrocatalytic oxidation of NADH. The hybrid thin film modified electrode exhibits stable amperometric response and it linearly responds to NADH (0.5-400 microM). This hybrid thin film modified electrode could detect NADH as low as 0.1 microM at -0.05 V with a sensitivity of 11.1 nA/microM in physiological pH.

Biosensing Techniques↗

Galactosylated PVDF membrane promotes hepatocyte attachment and functional maintenance.

One of the major challenges in BLAD design is to develop functional substrates suitable for hepatocyte attachment and functional maintenance. In the present study, we designed a poly(vinylidene difluoride) (PVDF) surface coated with galactose-tethered Pluronic polymer. The galactose-derived Pluronic F68 (F68-Gal) was adsorbed on PVDF membrane through hydrophobic-hydrophobic interaction between PVDF and the polypropylene oxide segment in Pluronic. The galactose density on the modified PVDF surface increased with the concentration of the F68-Gal solution, reaching 15.4 nmol galactosyl groups per cm2 when a 1 mg/ml of F68-Gal solution was used. The adsorbed F68-Gal remained relatively stable in culture medium. Rat hepatocytes attachment efficiency on F68-Gal modified PVDF membrane was similar to that on collagen-coated surface. The attached hepatocytes on PVDF/F68-Gal membrane self-assembled into multi-cellular spheroids after 1 day of culture. These attached hepatocytes in spheroids exhibited higher cell functions such as albumin synthesis and P450 1A1 detoxification function compared to unmodified PVDF membrane and collagen-coated surface. These results suggest the potential of this galactose-immobilized PVDF membrane as a suitable substrate for hepatocyte culture.

Albumins↗

Comparison of the fouling release properties of hydrophobic fluorinated and hydrophilic PEGylated block copolymer surfaces: attachment strength of the diatom Navicula and the green alga Ulva.

To understand the role of surface wettability in adhesion of cells, the attachment of two different marine algae was studied on hydrophobic and hydrophilic polymer surfaces. Adhesion of cells of the diatom Navicula and sporelings (young plants) of the green macroalga Ulva to an underwater surface is mainly by interactions between the surface and the adhesive exopolymers, which the cells secrete upon settlement and during subsequent colonization and growth. Two types of block copolymers, one with poly(ethylene glycol) side-chains and the other with liquid crystalline, fluorinated side-chains, were used to prepare the hydrophilic and hydrophobic surfaces, respectively. The formation of a liquid crystalline smectic phase in the latter inhibited molecular reorganization at the surface, which is generally an issue when a highly hydrophobic surface is in contact with water. The adhesion strength was assessed by the fraction of settled cells (Navicula) or biomass (Ulva) that detached from the surface in a water flow channel with a wall shear stress of 53 Pa. The two species exhibited opposite adhesion behavior on the same sets of surfaces. While Navicula cells released more easily from hydrophilic surfaces, Ulva sporelings showed higher removal from hydrophobic surfaces. This highlights the importance of differences in cell-surface interactions in determining the strength of adhesion of cells to substrates.

Biopolymers↗

PVDF as a new polymer for the construction of surgical meshes.

Abdominal hernia repair is the most frequently performed operation in surgery. Mostly due to lowered recurrence rates mesh repairs in hernia surgery have become an integral component despite increasing mesh-related complications. Current available mesh prosthesis are made of polypropylene (PP). polyethylene-terephtalat or polytetrafluorethylene. though all of them reveal some disadvantages. The introduction of new materials seems to be advisable. Caused by supposed advantageous textile properties and tissue response two mesh modifications made of polyvinylidene fluoride (PVDF) for abdominal hernia repair were developed. In the present study the PVDF meshes were compared to a common heavy weight PP-mesh (Prolene) in regard to functional consequences and morphological tissue response. After implantation in rats as inlay for 3, 14, 21, 42 and 90 days abdominal wall mobility was recorded by three-dimensional photogrammetry. Tensile strength of the suture zone and the mesh itself were determined. Explanted tissue samples have been investigated for their histological reaction in regard to the inflammatory infiltrate. vascularisation, connective and fat tissue ingrowth. Number of granulocytes, macrophages, fibroblasts, lymphocytes and foreign giant body cells have been evaluated to reflect quality of tissue response. The cellular response was grasped by measurement of DNA strand breaks and apoptosis (TUNEL), proliferation (Ki67) and cell stress (HSP70). Analyzing the results confirmed that construction of hernia meshes made of PVDF could be an advantageous alternative to the commonly used materials due to an improved biostability. lowered bending stiffness and a minimum tissue response.

Animals↗

Quantitation of repetitive epitopes in glycosaminoglycans immobilized on hydrophobic membranes treated with cationic detergents.

Glycosaminoglycans (GAGs) are linear carbohydrate polymers containing repetitive sequences of differently sulfated uronic acid and glycosamine residues that are recognized by antibodies raised against proteoglycans. We have developed a method to demonstrate such repetitive sequence motifs in isolated GAG chains immobilized on hydrophobic membranes derivatized with cationic detergents. Six monoclonal antibodies directed against Cs (2B6, 3B3, Cs56, and 1B5), Hs (HepSS), and Ks (5D4) were used to detect native and chondroitinase-generated epitopes in the immobilized GAGs. All antibodies, except 1B5, were able to detect epitopes in both proteoglycans and isolated GAGs. Type of detergent and buffer composition affected the accessibility and the retention of immobilized GAGs. The epitope density, i.e., the number of repetitive epitopes per GAG mass, was estimated as the ratio between antibody (epitope) and Alcian blue (mass) staining measured simultaneously. The epitope profiles, using six antibodies, were different for each sample (CsA, CsC, Ds, Hs, intact cartilage, and human serum). The epitope profile may be used as a structural characteristic of a GAG population. Electrophoretic separation of GAGs based on their glucuronic/ioduronic acid content and O-sulfate/N-sulfate ratio was performed using a diethylene glycol-diaminobutanol agarose gel. The electrophoretic populations were characterized by immunoblotting to detergent-treated membranes.

Alcian Blue↗

Power densities using different cathode catalysts (Pt and CoTMPP) and polymer binders (nafion and PTFE) in single chamber microbial fuel cells.

Cathode catalysts and binders were examined for their effect on power densities in single chamber, air-cathode, microbial fuel cells (MFCs). Chronopotentiometry tests indicated thatthe cathode potential was only slightly reduced (20-40 mV) when Pt loadings were decreased from 2 to 0.1 mg cm(-2), and that Nafion performed better as a Pt binder than poly(tetrafluoroethylene) (PTFE). Replacing the precious-metal Pt catalyst (0.5 mg cm(-2); Nafion binder) with a cobalt material (cobalt tetramethylphenylporphyrin, CoTMPP) produced slightly improved cathode performance above 0.6 mA cm(-2), but reduced performance (<40 mV) at lower current densities. MFC fed batch tests conducted for 35 cycles (31 days) using glucose showed that replacement of the Nafion binder used for the cathode catalyst (0.5 mg of Pt cm(-2)) with PTFE reduced the maximum power densities (from 400 +/- 10 to 480 +/- 20 mW m(-2) to 331 +/- 3 to 360 +/- 10 mW m(-2)). When the Pt loading on cathode was reduced to 0.1 mg cm(-2), the maximum power density of MFC was reduced on average by 19% (379 +/- 5 to 301 +/- 15 mW m(-2); Nafion binder). Power densities with CoTMPP were only 12% (369 +/- 8 mW m(-2)) lower over 25 cycles than those obtained with Pt (0.5 mg cm(-2); Nafion binder). Power densities obtained using with catalysts on the cathodes were approximately 4 times more than those obtained using a plain carbon electrode. These results demonstrate that cathodes used in MFCs can contain very little Pt, and that the Pt can even be replaced with a non-precious metal catalyst such as a CoTMPP with only slightly reduced performance.

Bioelectric Energy Sources↗