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An industrial approach to evaluation of pyrolysis and combustion hazards.

In addition to the usual toxicology studies necessary for the safe manufacture and use of polymers at room temperature, special studies are needed for polymers which will be used at elevated temperatures. This paper discusses various areas to be investigated and principles for deciding on test materials, tests, and test conditions, polytetrafluoroethylene (PTFE) and fluorinated polyethylene-propylene (PFEP) pyrolysis studies being used as an illustrative case history. Some limitations of animal testing also are mentioned. A toxicological spectrum relating toxicological determinants to PTFE temperature is developed.

Animals↗

Pyrogallol red-molybdate: a reversible, metal chelate stain for detection of proteins immobilized on membrane supports.

Certain metal complexes selectively interact with proteins immobilized on solid-phase membrane supports to form brightly colored products. The metal chelates form protein-dye complexes in the presence of metal ions at acidic pH but are eluted from the proteins by immersing membranes in a solution of basic pH that contains other chelating agents. The reversible nature of the protein staining procedure allows for subsequent biochemical analyses, such as immunoblotting, N-terminal and internal protein sequencing. Among the metal complexes evaluated to date, the triazine dye-ferrous complexes (ferene S, ferrozine) and the ferrocyanide-ferric complexes provide the most sensitive detection of proteins immobilized on membranes. While the pyrogallol red-molybdate complex is commonly used in solution-based total protein assays, its utility as a reversible stain for proteins immobilized on membranes has not been reported. Pyrogallol red-molybdate complexes readily stain proteins on nitrocellulose and polyvinyl difluoride membranes with similar sensitivity as ferrozine-ferrous complexes. Analysis of charge-fractionated carrier ampholytes and synthetic polymers of different L-amino acids indicate that binding is prominently via protonated alpha and epsilon-amino side chains. Carbamylation of amino groups in bovine serum albumin substantially diminishes pyrogallol red-molybdate binding to the protein. The stain is reversible, resistant to chemical interference, and compatible with immunoblotting.

Chelating Agents↗

Comparison of pressurized solvent and reflux extraction methods for the determination of perfluorooctanoic acid in polytetrafluoroethylene polymers using LC-MS-MS.

Both pressurized solvent extraction (PSE) and reflux extraction in various solvents were used to select the most efficient system for the determination of the quantity of perfluorooctanoic acid (PFOA) present in polytetrafluoroethylene polymers. After evaporating the solvent, PFOA was determined using liquid chromatography tandem mass spectrometry. Ethanol, water and methanol gave comparable results and were shown to be good solvents for this extraction. Acetonitrile was a reasonable solvent using the reflux extraction method, but not with PSE. Chloroform resulted in poor recovery for both extraction methods. PSE proved to be the more efficient extraction method.

Caprylates↗

Surface characterisation of bags for total parenteral nutrition by tensiometry and atomic force microscopy.

Bags made of poly-ethylene and poly-vinylchloride and of the copolymer ethylene-vinylacetate were used as containers of perfusion solutions for total parenteral nutrition. The bags were characterised by tensiometry (free energy and its polar and dispersed components) and atomic force microscopy (AFM) before and after various periods of storage of solutions for total parenteral nutrition containing L-aminoacids, electrolytes or glucose. In most of the cases, after storage of these solutions, tensiometric characterisation and atomic force microscopy analysis of the internal surface of bags showed deep modifications which highlight the adsorption of the solutes. The changes of surface characteristics were found to depend on the time of contact, the wettability of the polymer and the compounds present into the solutions, while their concentration has a negligible effect. Generally, the aminoacid solutions produced a higher increase in the polar component even after short storage times. Poly-ethylene and the copolymer ethylene-vinylacetate showed a greater inertia if compared with the poly-vinylchloride bags.

Equipment and Supplies, Hospital↗

Solid-state 19F NMR investigation of poly(vinylidene fluoride) with high-power proton decoupling.

The use of high-power proton decoupling has enabled highly-resolved spectra of fluorine polymers to be recorded, as is exemplified herein for semicrystalline poly(vinylidene fluoride) (PVDF). By means of high MAS speeds (up to 17 kHz), the spinning sidebands are removed from the whole of the relevant chemical shift range. For spectra of the crystalline regions of the polymer, the high-power decoupling is necessary, though its effect is not large. Various relaxation techniques have been used to examine the semicrystallinity and the polymorphism of PVDF, with special pulse sequences used to discriminate between the various domains. Different chemical shifts have been observed for the signals of the amorphous and crystalline phases. Those of the more immobile parts cover a substantial range.

Chemical Phenomena↗

Solid-phase sequence analysis of proteins electroblotted or spotted onto polyvinylidene difluoride membranes.

Electroblotted proteins noncovalently bound to polyvinylidene difluoride (PVDF) membranes are typically sequenced using adsorptive sequencer protocols (gas-phase or pulsed-liquid) that do not require a covalent linkage between protein and surface. We have developed simple chemical protocols where proteins are first electroblotted onto unmodified PVDF membranes, visualized with common protein stains, and then immobilized for solid-phase sequence analysis. Adsorbed, stained proteins are first treated with phenylisothiocyanate (PITC) to modify alpha and epsilon amines. The protein is then overlayed with a solution of 1,4-phenylene di-isothiocyanate (DITC), followed by a few microliters of a basic solution containing a poly(alkylamine). As the polymer dries onto the surface both polymer and remaining protein amino groups are crosslinked by DITC. The protein is thus immobilized to the membrane surface by entrapment in a thin polymer coating. The coating is transparent to the degradation chemistry, and extensive enough to remain immobilized even in the absence of any covalent link between polymer and surface. Partial modification with PITC allows for identification of N-terminal and internal lysine residues during sequencing. The process was tested with a variety of poly(alkylamines), linear and branched, with molecular weights ranging from 600 to over 100,000. Proteins bound in this manner were successfully sequenced using covalent (solid-phase) sequencer protocols with cycle times as short as 26 min.

Absorption↗

Electrocoating carbon fiber microelectrodes with Nafion improves selectivity for electroactive neurotransmitters.

A method which improves carbon fiber microelectrode selectivity for cationic amines by electrocoating the fiber with a thin film of the ionic polymer, Nafion, is described. The selectivity and response speed of these electrodes for the detection of electroactive cationic and anionic species found in brain extracellular fluid was evaluated using differential pulse voltammetry and chronoamperometry and compared to uncoated fibers. Carbon fiber microelectrodes electrocoated with Nafion are highly sensitive to cationic amines such as dopamine and serotonin and have minimal sensitivity to anions such as ascorbic acid and uric acid at physiological concentrations.

Carbon↗

Biosensing nitrite using the system nitrite redutase/Nafion/methyl viologen--a voltammetric study.

This work describes the construction and voltammetric characterization of a nitrite biosensor based on a cytochrome c-type nitrite reductase (ccNiR) and the Nafion ionomeric matrix loaded with methyl viologen as redox mediator. Despite the potential electrostatic repulsions between the anionic substrate and the Nafion sulfonate groups, the resulting bioelectrode exhibited electrocatalytic activity toward nitrite. This phenomenon must be due to the nonuniformity of the enzyme/Nafion membrane, which allows the direct interaction between the substrate and numerous enzyme molecules. Nevertheless, the anionic nature of Nafion exerted a certain diffusion barrier to nitrite, as revealed by the unusually elevated limits of the linear dynamic range and k(m)(app). The irregularity of the composite membrane also contributed to slow down the rate of charge transfer throughout the Nafion polymer. The level of viologens incorporated within the Nafion membrane had a strong influence in the analytical parameters: as much mediator was present, lower was the sensitivity and wider was the linear range. For an optimized ratio enzyme/mediator the sensitivity was 445+/-8 mA M(-1)cm(-2), within the linear range 75-800 microM; the lowest detected nitrite concentration was 60 microM. The operational stability of the biosensor and the influence of some possible interferences were evaluated.

Biosensing Techniques↗

Thermolysis of fluoropolymers as a potential source of halogenated organic acids in the environment.

Following the introduction of hydrochlorofluorocarbon (HCFCs) and hydrofluorocarbon (HFCs) gases as replacements for the ozone-destroying chlorofluorocarbons (CFCs), it has been discovered that HCFCs/HFCs can degrade in the atmosphere to produce trifluoroacetic acid, a compound with no known loss mechanisms in the environment, and higher concentrations in natural waters have been shown to be mildly phytotoxic. Present environmental levels of trifluooracetic acid are not accounted by HCFC/HFC degradation alone. Here we report that thermolysis of fluorinated polymers, such as the commercial polymers Teflon and Kel-F, can also produce trifluoroacetate and the similar compound chlorodifluoroacetate. This can occur either directly, or indirectly via products that are known to degrade to these haloacetates in the atmosphere. The environmental significance of these findings is confirmed by modelling, which indicates that the thermolysis of fluoropolymers in industrial and consumer high-temperature applications (ovens, non-stick cooking utensils and combustion engines) is likely to be a significant source of trifluoroacetate in urban rain water ( approximately 25 ng l-1, as estimated for Toronto). Thermolysis also leads to longer chain polyfluoro- and/or polychlorofluoro- (C3-C14) carboxylic acids which may be equally persistent. Some of these products have recently been linked with possible adverse health and environmental impacts and are being phased out of the US market. Furthermore, we detected CFCs and fluorocarbons-groups that can destroy ozone and act as greenhouse gases, respectively-among the other thermal degradation products, suggesting that continued use of fluoropolymers may also exacerbate stratospheric ozone-depletion and global warming.

Acids↗

In vivo nitric oxide sensor using non-conducting polymer-modified carbon fiber.

Nitric oxide (NO) is emerging as a very important and ubiquitous gaseous messenger in the body. The response characteristics of NO sensors made of non-conducting polymer modified carbon fiber electrodes are investigated to determine their selectivity, sensitivity, and stability for in vivo use. A composite polymer, comprising Nafion, m-phenylenediamine, and resorcinol, showed the best selectivity and stability to amperometric NO detection. The non-conducting, self-limiting polymer film protects the electrode from interference and fouling by other biochemicals. Although the relative sensitivity to NO of the modified sensor is lower than that of the unmodified carbon fiber electrodes (less than 6%), the composite polymer electrode showed high selectivity against ascorbic acid (> 2000:1), nitrite (> 600:1), and dopamine (> 200:1). The stability of the NO sensor was maintained for at least 1 week. The NO sensitivity after in vivo experiments (n = 8) is 88.1 +/- 5.6% of initial sensitivity data obtained before in vivo experiments. Preliminary in vivo experiments done with this electrode are shown to capture elevated NO levels in brain following an ischemic injury.

Animals↗

Enhanced photocatalytic activity of nafion-coated TiO2.

Photocatalytic degradation (PCD) of aqueous paraquat was accelerated by the addition of either phosphate or sulfate salt. Attachment of these anions to the TiO2 surface possibly results in increased adsorption of the cationic paraquat species and in turn its photocatalysis rate. The same effect was obtained more consistently using the Nafion (an anionic polymer)-coated TiO2. Enhanced PCD of paraquat and some amine compounds was noted. However the anionic and neutral compounds were not affected significantly. Nafion proved to be stable against photocatalysis. It has been suggested that the degradation rate is larger for the cationic compounds with higher pK(B). For a phenol-paraquat-TiO2 system, paraquat degradation did not begin till near-complete phenol removal. Using the Nafion-coated TiO2, both phenol and paraquat degradations started simultaneously. Nevertheless, complete paraquat removal still took longer than phenol.

Catalysis↗

Potentiometric saccharide detection based on the pK(a) changes of poly(aniline boronic acid).

A novel approach for the potentiometric detection of saccharides using poly(aniline boronic acid) is presented. A model is described in which the electrochemical potential is sensitive to the change in the pK(a) of the conducting polymer as a result of boronic acid-diol complexation. In this system, boronic acid complexation is the mode of transduction and it is manifested as changes in the electrochemical potential of the polymer with remarkable selectivity. Characteristics of both transient and steady-state response associated with the complexation are discussed. The presence of Nafion and fluoride during the electrochemical polymerization of 3-aminophenylboronic acid are shown to impact the sensitivity and the stability of the electrode response. The sensor sensitivity is improved significantly by increasing the concentration of sodium fluoride during the polymerization. Finally, the nature of the selectivity of the boronic acid-diol reaction under these conditions is explored by using molecular orbital calculations.

Aniline Compounds↗

A method for the quantification of low concentration sulfamethazine residues in milk based on molecularly imprinted clean-up and surface preconcentration at a Nafion-modified glassy carbon electrode.

An electrochemical method for the determination of sulfamethazine at a low concentration level (25 microgl(-1)) in milk is reported. The method involves sample clean-up and selective preconcentration of sulfamethazine with a molecularly imprinted polymer (MIP), and a further electrode surface preconcentration of the analyte at a Nafion-coated glassy carbon electrode (GCE). Square wave (SW) oxidative voltammetry of accumulated sulfamethazine was employed for its quantification. Sulfamethazine electrode preconcentration was carried out in 0.1 moll(-1) Britton-Robinson buffer of pH 1.5, and by applying 5 min of accumulation at open circuit. A linear calibration graph was obtained for sulfamethazine at the Nafion-modified GCE over the 1.0x10(-8) to 1.0x10(-6)moll(-1) concentration range, with a detection limit of 6.8x10(-9)moll(-1) (1.9 microgl(-1)). This detection limit is remarkably better than those reported previously in the literature using electroanalytical techniques. Although the detection limit achieved was sufficient to allow the direct determination of sulfamethazine at the concentration level required in milk, a sample clean-up was shown to be necessary to obtain analytically useful SW voltammograms. This was accomplished by processing the deproteinized milk through a cartridge containing a molecularly imprinted polymer for sulfamethazine, also allowing a selective preconcentration of the analyte. Elution of the analyte from the MIP cartridges was carried out with 2 ml of a (9:1) MeOH:acetic acid mixture. Determination of sulfamethazine in milk samples was accomplished by interpolation into a calibration graph constructed with sulfamethazine standard solutions which were subjected to the same procedure than the deproteinized milk samples. Results obtained for five samples, spiked at the 25 microgl(-1) level, showed a mean recovery of (100+/-3)%.

Animals↗

Quantitation of choline in the extracellular fluid of brain tissue with amperometric microsensors.

Amperometric microsensors for the detection of choline in the extracellular fluid of brain tissue have been prepared by immobilizing horseradish peroxidase and choline oxidase onto carbon fiber microcylinder electrodes with a cross-linkable redox polymer. The microcylinders have diameters of 7 or 10 microns and lengths of 200-400 microns. To detect choline, the microsensors are operated at an applied potential of -0.1 V vs SCE. At this potential, ascorbate and other easily oxidizable interferant molecules present in brain tissue are not detected by the electrode. Ascorbate, however, can interfere with the response to choline by acting as a reducing agent in the enzyme-containing polymer film. So, a Nafion overlayer is required in order to reliably detect choline in the presence of physiologically relevant concentrations of ascorbate (approximately 200 microM). The Nafion-coated microsensors have a detection limit of approximately 5 microM choline and give a linear response beyond 100 microM when calibrated in vitro at 37 degrees C. Exposure of the microsensors to brain tissue for several hours causes less than a 10% loss in redox polymer surface coverage and less than a 25% loss in sensitivity to choline. To assess the ability of the microsensors to monitor choline levels in brain tissue, small volumes of a choline solution were injected into brain tissue at a site about 1 mm away from a microsensor. The current arising at the microsensor was converted to choline concentration by calibrating the sensor following the in vivo experiment. The resultant choline concentrations were in excellent agreement with those predicted by appropriate diffusion equations.

Animals↗

Excess proton solvation and delocalization in a hydrophilic pocket of the proton conducting polymer membrane nafion.

Solvation properties of the hydrated excess proton are studied in a hydrophilic pocket of Nafion 117 through a series of molecular dynamics simulations. The multistate empirical valence bond (MS-EVB) methodology, which enables the delocalization of the excess proton through the Grotthuss hopping mechanism, was employed for one of the excess protons in the simulation cell. Simulations were performed such that "classical" nondissociable hydronium cations and a single excess proton treated with the MS-EVB methodology were at a concentration ratio of 39:1. Two degrees of hydration of the Nafion polymer electrolyte membrane were simulated, each displaying the same marked difference between the solvation structures of the classical versus MS-EVB treated (Grotthuss shuttling) excess proton species. These differences are attributed to the solvent dynamics needed to transfer the cation between the solvent separated and contact pair positions about the sulfonic acid counterion. The results demonstrate that it is generally impossible to describe the low pH conditions in the hydrophilic domains of Nafion without the explicit treatment of Grotthuss delocalization in the underlying molecular dynamics model for the excess protons.

Fluorocarbon Polymers↗

Light-dependent, covalent immobilization of biomolecules on 'inert' surfaces.

We describe a novel, versatile procedure for the light-dependent immobilization of ligands to 'inert' material surfaces. Covalent immobilization of ligands differing in chemical nature and complexity is accomplished under mild and non-destructive conditions. Topical interaction of ligands with organic or inorganic surfaces is mediated by photoactivable polymers with carbene generating trifluoromethyl-aryl-diazirines which serve as linker molecules. Light activation of aryl-diazirino functions at 350 nm yields highly reactive carbenes, and covalent coupling is achieved by simultaneous carbene insertion into both the ligand and inert surface. Thus, reactive functional groups are not required on either the ligand or the supporting material. These procedures are applicable whenever ligands, from molecules to cells--synthetically or genetically produced, or isolated from biological sources--need to be immobilized for improved performance.

Alkaline Phosphatase↗

Effect of poly(vinylidene fluoride) on solvation of NaSCN in PEO.

The blend-based electrolyte, polyethylene oxide (PEO)-poly(vinylidene fluoride) (PVdF)-NaSCN, was prepared and characterized by FT-IR, X-ray diffraction (XRD) and differential thermal analysis (DTA) measurements at room temperature, and the effect of PVdF content on solvation and ion association was discussed over the content of 5-95%. It is shown that PEO has much stronger ability of solvation to NaSCN than PVdF does, indicating that the polymeric donor number is more important than its dielectric constant in solvating effect of polymer. However, PVdF can keep its semicrystalline nature and form microporous structure in blend-based electrolytes. These characters make PVdF not only enhance the mechanical stability of the electrolyte thin films, but also transform PEO crystalline phase into fully amorphous phase. Although PVdF can effectively disrupt the crystalline complex P(EO)(3)NaSCN, it does not affect the component of triple aggregations. In addition, the effect of PVdF content on ion association is also discussed in PEO-NaSCN electrolytes.

Complex Mixtures↗

Control of surface properties using fluorinated polymer brushes produced by surface-initiated controlled radical polymerization.

Surface-grafted styrene-based homopolymer and diblock copolymer brushes bearing semifluorinated alkyl side groups were synthesized by nitroxide-mediated controlled radical polymerization on planar silicon oxide surfaces. The polymer brushes were characterized by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and time-dependent water contact angle measurements. Angle-resolved XPS studies and water contact angle measurements showed that, in the case of the diblock copolymer brushes, the second block to be added was always exposed at the polymer-air interface regardless of its surface energy. Values of z*/Rg were estimated based on the radius of gyration, Rg, of the grafted homopolymer or block copolymer chains for the grafted brushes and thickness of the brush, z*. The fact that z*/Rg > 1 suggests that all these brushes are stretched. These results support the idea that after grafting the first block onto the surface the nitroxide-end capped polymer chains were able to polymerize the second block in a "living" fashion and the stretched brush so formed was dense enough that the outermost block in all cases completely covers the surface. NEXAFS analysis showed a relationship between the surface orientation of the fluorinated side chains and brush thickness with thicker brushes having more oriented side chains. Time-dependent water contact angle measurements revealed that the orientation of the side chains of the brush improved the surface stability toward reconstruction upon prolonged exposure to water.

Absorption↗