Abstract  A new amperometric biosensor, based on deposition of glucose oxidase (GOD) onto crystalline gold (Au) nanoparticle modified multiwalled carbon nanotube (MWNT) electrode, is presented. MWNTs have been synthesized by catalytic chemical vapor decomposition of acetylene over rare-earth-based AB2 (DyNi2) alloy hydride catalyst. Purified MWNTs have been decorated with nanocrystalline Au metal clusters using a simple chemical reduction method. The characterization of metal-decorated CNTs has been done using X-ray diffraction analysis, scanning electron microscopy, transmission electron microscopy (TEM), high-resolution TEM, and energy-dispersive X-ray analysis. Amperometric biosensor fabricated by depositing GOD over Nafion-solubilized Au-MWNT electrode retains its biocatalytic activity and offers fast and sensitive glucose quantification. The performance of the biosensor has been studied using cyclic voltammetry, amperometry, and hydrodynamic voltammetry, and the results have been discussed. The fabricated glucose biosensor exhibits a linear response up to 22 mM glucose and a detection limit of 20 microM.

Abstract  Abstract: Nanofibrous glucose electrodes were fabricated by the immobilization of glucose oxidase (GOx) into an electrospun composite membrane consisting of polymethylmethacrylate (PMMA) dispersed with multiwall carbon nanotubes (MWCNTs) wrapped by a cationic polymer (poly(diallyldimethylammonium chloride) (PDDA)) and this nanofibrous electrode (NFE) is abbreviated as PMMA–MWCNT(PDDA)/GOx–NFE. The NFE was characterized for morphology and electroactivity by using electron microscopy and cyclic voltammetry, respectively. Field emission transmission electron microscopy (FETEM) image reveals the dispersion of MWCNT(PDDA) within the matrix of PMMA. Cyclic voltammetry informs that NFE is suitable for performing surface-confined electrochemical reactions. PMMA–MWCNT(PDDA)/GOx–NFE exhibits excellent electrocatalytic activity towards hydrogen peroxide (H2O2) with a pronounced oxidation current at +100mV. Glucose is amperometrically detected at +100mV (vs. Ag/AgCl) in 0.1M phosphate buffer solution (PBS, pH 7). The linear response for glucose detection is in the range of 20μM to 15mM with a detection limit of 1μM and a shorter response time of ∼4s. The superior performance of PMMA–MWCNT(PDDA)/GOx–NFE is due to the wrapping of PDDA over MWCNTs that binds GOx through electrostatic interactions. As a result, an effective electron mediation is achieved. A layer of nafion is made over PMMA–MWCNT(PDDA)/GOx–NFE that significantly suppressed the electrochemical interference from ascorbic acid or uric acid. In all, PMMA–MWCNT(PDDA)/GOx–nafion–NFE has exhibited excellent properties for the sensitive determination of glucose like high selectivity, good reproducibility, remarkable stability and without interference from other co-existing electroactive species. [Copyright 2008 Elsevier] Copyright of Biosensors & Bioelectronics is the property of Elsevier Science Publishing Company, Inc. and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts)

Abstract  The two members of peroxide-based explosives, triacetone triperoxide (TATP) and hexamethylene triperoxide diamine (HMTD), can be manufactured from readily accessible reagents, and are difficult to detect by conventional analytical methods. TATP and HMTD were securely synthesized, taken up with acetone, hydrolyzed with 4 M HCl to hydrogen peroxide, the acidic solution containing H(2)O(2) was neutralized, and assayed by the copper(II)-neocuproine spectrophotometric method. The chromophore of the reaction was the Cu(I)-neocuproine chelate responsible for light absorption at 454 nm. The molar absorptivity (epsilon) of the method for TATP and HMTD was 3.45 x 10(4) and 4.68 x 10(4) L mol(-1) cm(-1), respectively. The TATP recovery from a synthetically contaminated loamy clay soil was 91-99%. The colorimetric method was also applied to a Cu(ii)-neocuproine-impregnated polymeric Nafion membrane sensor developed for the first time in this work for peroxide explosive assay. The absorbance-concentration response was perfectly linear, and the limit of detection (LOD) of the procedure for both TATP and HMTD was approximately 0.2 mg L(-1). Neither common soil ions (Ca(2+), K(+), Cl(-), SO(4)(2-), Mg(2+) and NO(3)(-)) at 100-fold amounts nor military-purpose nitro-explosives of TNT, RDX, and PETN at 10-fold amounts interfered with the proposed assay. Active oxygen constituents of laundry detergents (perborates and percarbonates), which normally interfered with the assay, could easily be separated from the analytes by solubility differences. The method was statistically validated against standard reference methods of TiOSO(4) colorimetry and GC-MS.

Abstract  In this paper, a simple one-step electrodeposition method is described to fabricate chitosan-Prussian blue-multiwall carbon nanotubes-hollow PtCo nanochains (CS-PB-MWNTs-H-PtCo) film onto the gold electrode surface, then glucose oxidase (GOD) and Nafion were modified onto the film subsequently to fabricate a glucose biosensor. The morphologies and electrochemistry of the composite were investigated by using Fourier transform infrared (FTIR) spectrometry, scanning electron microscopy (SEM) and electrochemical techniques including cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), respectively. The performances of the biosensor have been investigated by chronoamperometry method under the optimized conditions. This biosensor showed a linear response to glucose range from 1.5 μM to 1.12 mM with a detection limit of 0.47 μM (S/N=3), a high sensitivity of 23.4 μA mM(-1) cm(-2), and a fast response time. The apparent Michaelis-Menten constant (K(M)(app)) was 1.89 mM. In addition, the biosensor also exhibited strong anti-interference ability, excellent stability and good reproducibility.

Abstract  A highly ordered mesoporous Nafion membrane with a remarkable water retention ability was synthesized via a micelle templating method with self-assembled Pluronic F108 surfactants and its capability to operate under completely dry gas streams is demonstrated.

Abstract  Electrochemically active composite film that contains multiwalled carbon nanotubes (MWCNTs), Nafion (NF), and poly(malachite green) (PMG) has been synthesized on glassy carbon electrode (GCE), gold, and indium tin oxide (ITO) electrodes by potentiodynamic method. The presence of MWCNTs in the composite film (MWCNT-NF-PMG) enhances the surface coverage concentration (Γ) of PMG by fivefold. Similarly, an electrochemical quartz crystal microbalance study revealed enhancement in the deposition of PMG at MWCNT-NF film when compared with bare and only NF modified electrodes. The surface morphology of the composite film was studied using atomic force microscopy, which revealed that the PMG incorporated on MWCNT-NF film. The composite film exhibited enhanced electrocatalytic activity toward the mixture of biochemical compounds catechol and quinol. The electrocatalytic responses of analytes at MWCNT-NF-PMG composite film were measured using both cyclic voltammetry (CV) and differential pulse voltammetry (DPV). From electrocatalysis studies, well-separated voltammetric peaks were obtained at the composite film for catechol and quinol with a peak separation of 147mV. The sensitivity values of the composite film toward catechol and quinol by the DPV technique were 0.4 and 3.2mAmM(-1)cm(-2), respectively, which are higher than the values obtained by the CV technique. Similarly, the above-mentioned values are better than the previously reported electroanalytical values for the same analytes.

Abstract  A novel disposable amperometric biosensor strip for determination of blood alcohol concentration (BAC) with small volume of sample has been constructed using screen-printed electrodes (SPE), nanocomposite film and alcohol dehydrogenase (ADH). Firstly, the GNPs-MWCNT-Nafion nanocomposite film modified on a working electrode was made of Nafion-117, multi-wall carbon nanotubes (MWCNT) and gold nanoparticles (GNPs). After that Meldola's blue (MB) acted as an electron transfer mediator and the mixed solution of ADH, nicotinamide adenine dinucleotide (NAD(+)) were modified in order on the nanocomposite film. At last, a hydrophilic membrane which had an eyehole in center was placed at the outermost of the working area to make a reaction tank of 5 μL, then the hydrophilic membrane/ADH-NAD(+)/GNPs-MWCNT-MB-Nafion/SPE was prepared. The detection of BAC can be accomplished with 5 μL of blood sample obtained precisely by siphonage. Optimum conditions of the biosensor were experimentally determined by varying several important parameters: working potential, solution pH value, environmental temperature and interferences. Experimental results indicated that the biosensor possessed a good accuracy and stability, the linear response range was 2.0 × 10(-4) to 25 × 10(-3)mol/L and the detection limit of the biosensor was 5.0 × 10(-5)mol/L (S/N=3). In the measurement of blood samples, the proposed biosensor had excellent detection performance for measuring BAC and showed a good correlation with gas chromatography. The prepared biosensor strip can be valid for the analysis of BAC.

Abstract  A prototype amperometric immunosensor was evaluated based on the adsorption of antibodies onto perpendicularly oriented assemblies of single wall carbon nanotubes called SWNT forests. The forests were self-assembled from oxidatively shortened SWNTs onto Nafion/iron oxide coated pyrolytic graphite electrodes. The nanotube forests were characterized using atomic force microscopy and resonance Raman spectroscopy. Anti-biotin antibody strongly adsorbed to the SWNT forests. In the presence of a soluble mediator, the detection limit for horseradish peroxidase (HRP) labeled biotin was 2.5 pmol ml(-1) (2.5 nM). Unlabelled biotin was detected in a competitive approach with a detection limit of 16 nmol ml(-1) (16 microM) and a relative standard deviation of 12%. The immunosensor showed low non-specific adsorption of biotin-HRP (approx. 0.1%) when blocked with bovine serum albumin. This immunosensing approach using high surface area, patternable, conductive SWNT assemblies may eventually prove useful for nano-biosensing arrays.

Abstract  A novel amperometric sensor and chromatographic detector for determination of parathion has been fabricated from a multi-wall carbon nano-tube (MWCNT)/Nafion film-modified glassy-carbon electrode (GCE). The electrochemical response to parathion at the MWCNT/Nafion film electrode was investigated by cyclic voltammetry and linear sweep voltammetry. The redox current of parathion at the MWCNT/Nafion film electrode was significantly higher than that at the bare GCE, the MWCNT-modified GCE, and the Nafion-modified GCE. The results indicated that the MWCNT/Nafion film had an efficient electrocatalytic effect on the electrochemical response to parathion. The peak current was proportional to the concentration of parathion in the range 5.0x10(-9)-2.0x10(-5) mol L(-1). The detection limit was 1.0x10(-9) mol L(-1) (after 120 s accumulation). In high-performance liquid chromatography with electrochemical detection (HPLC-ED) a stable and sensitive current response was obtained for parathion at the MWCNT/Nafion film electrode. The linear range for parathion was over four orders of magnitude and the detection limit was 6.0x10(-9) mol L(-1). Application of the method for determination of parathion in rice was satisfactory.

Abstract  The direct electrochemistry of myoglobin (Mb) entrapped in the Nafion film on a multi-walled carbon nanotubes (MWCNTs) modified carbon ionic liquid electrode (CILE) had been investigated in this paper. By using a hydrophilic ionic liquid of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF(4)) as the modifier, a high-performance basal electrode was fabricated and further modified by MWCNTs, Mb and Nafion by a step-by-step casting method. Spectroscopic results indicated that the Mb molecule on the surface of MWCNTs/CILE retained its native structure. Cyclic voltammetric results showed that a pair of well-defined quasi-reversible redox peaks appeared in the pH 7.0 phosphate buffer solution (PBS), which was attributed to the direct electron transfer of Mb heme Fe(III)/Fe(II) redox couples with the modified electrode. The Nafion/Mb/MWCNTs/CILE gave excellent electrocatalytic activity towards different substrates including trichloroacetic acid (TCA), hydrogen peroxide (H(2)O(2)) and sodium nitrite (NaNO(2)).

Abstract  Electrical impedance properties of different type of carbon nanotubes based bulk electrodes have been investigated to develop chemical and biosensors. The bulk composite electrodes were fabricated with single-wall and multi-wall carbon nanotubes involving ionic conducting host polymer, Nafion, by using traditional solution-casting techniques. Under the various amounts of buffer solution, resistance and capacitance of the electrodes were measured with LCR meter and their characteristics due to ionic conducting host polymer were investigated by means of electrokinetic analysis. The capacitance values showed drastic change while the resistances only changed within few percent ranges. Electrical impedance measurement provided rapid and simple sensing mechanism to develop chemical sensor and biosensors with bulk nano electrodes.

Abstract  We describe beta- and gamma-cyclodextrins (beta- and gamma-CD)-modified monolithic columns prepared by sol-gel process and chemical modifications. The monolithic silica column was fabricated inside a fused-silica capillary with 100 microm inner diameter by sol-gel process. The monolithic silica matrix was chemically modified chiral selectors of beta- or gamma-CDs with a spacer of 3-glycidoxypropyltrimethoxysilane by on-column reactions. Gamma-CD-modified monolithic column has successfully been applied for the separation of dansyl amino acid enantiomers. Beta-CD-modified monolithic column has been used for the separation of the positional isomers of o-, m-, and p-cresols and the enantioseparation of racemates of benzoin and several dansyl amino acids by capillary electrochromatography, respectively. For the separation of neutral positional isomers, a positive electric field was applied. However, for the separation of negatively charged analytes, a negative electric field was applied at the inlet of column. The separation efficiency of 5.0 x 10(4) theoretical plates/m for dansyl-L-threonine was obtained at electric field strength of -300 V/cm in the mobile phase of 50 mM 2-(N-morpholino)ethanesulfonic acid (MES)-Tris/methanol (70/30) buffer at pH 7.0. L-enantiomers were eluted as the first peak. Scanning electron micrograph showed that monolithic columns have the morphology of continuous skeleton and large through-pores.

Abstract  A new application of capillary electrophoresis (CE) for measuring inorganic anions in hailstones was carried out. Five hailstone specimens were collected from large blocks of ice that fell in January 2000 in some provinces of Spain. Sample handling and preparation procedures were performed with care. CE analysis of anions was carried out using indirect UV detection at 254 nm with a negative power supply (-15 kV) and hydrostatic injection (10 cm for 30 s) at 35 degrees C. Anion separation was completed in less than 4 min. The working electrolyte consisted of 4.7 mM sodium chromate, 4.0 mM OFM-OH (tetradecyltrimethylammonium hydroxide), 10 mM CHES [2-(N-cyclohexylamino)ethanesulfonic acid], and 0.1 mM calcium gluconate (pH 9.1). Good repeatability of migration times after eight injections (<0.7% RSD), adequate linearity responses (r2>0.9) as well as satisfactory detection limits (<0.35 ppm) were achieved. The analytical results provided by CE were compared with those obtained by traditional wet-chemical (WCH) methods. Most of the results obtained by CE were consistent with those of WCH, except for one sample.

Abstract  A new application of capillary electrophoresis for measuring major and trace anions in thermal water and condensed-steam samples is presented. Ten fluid samples were collected from hydrothermal springs and fumaroles located in a volcanic zone of Deception Island, Antarctica. Anion separation was achieved in less than 6 min using indirect UV detection at 254 nm with a negative power supply (-15 kV). The electrolyte consisted of 4.7 mM sodium chromate, 4.0 mM electroosmotic flow modifier (OFM) hydroxide, 10 mM 2-(N-cyclohexylamino)ethanesulfonic acid and 0.1 mM calcium gluconate (pH 9.1). Major anions (Cl-, SO4(2), PO4H2+, and CO3H-) were measured using hydrostatic injection (10 cm for 30 s) at 25 degrees C. Trace amounts of anions (F-, Br-, and NO3-) were better determined by electromigration injection (4 kV, 10 s) at 15 degrees C. Good reproducibility of the migration times (<0.72% RSD), a satisfactory linear response and accuracy as well as acceptable detection limits were successfully obtained.

Abstract  Generation of singlet molecular oxygen ((1)O(2)) by photosensitization with methylene blue (MB) supported in Nafion-Na films has been quantified by integration of the (1)O(2) emission decay at 1270 nm. The quantum yield of (1)O(2) production (Phi(Delta)) in the air-equilibrated solid phase is 0.24 +/- 0.03. Information on the (1)O(2) generation environment has been gained from complementary techniques such as UV-Vis absorption and emission spectroscopy, as well as MB fluorescence and triplet-triplet absorption decay. Results are compared with the (1)O(2) generation by MB in methanol solution (Phi(Delta) = 0.51) and in methanol-swollen Nafion films (Phi(Delta) = 0.49 +/- 0.06). Differences and similarities are discussed in terms of the factors that influence Phi(Delta) in solution and in the solid media. The optical and mechanical features of Nafion, ease of dye loading, compatibility with most solvents, homogeneity, reproducibility and stability of the photosensitizing material makes it a convenient reference for (1)O(2) generation quantum yield measurements in transparent (micro)heterogeneous and homogeneous media.

Abstract  We demonstrated the nanocharacterization and nanofabrication of a Nafion thin film using atomic force microscopy (AFM). AFM images showed that the Nafion molecules form nanoclusters in water, in 5% methanol, and in acetic acid. Young's modulus E of a Nafion film was estimated by sequential force curve measurements in water and in 5% methanol on one sample surface. Ewater/E5% methanol was 1.75 +/- 0.40, so the film was much softer in 5% methanol than in water. Even when solvent was replaced from 5% methanol to water, Young's modulus was not recovered soon. We showed the first example of the mechanical properties of a Nafion film on the nanoscale. Furthermore, we succeeded in fabricating 3D nanostructures on a Nafion surface by AFM nanolithography in liquids. Our results showed the new potential of the AFM nanolithography of a polymer film by softening the molecules in liquids.

Abstract  Novel covalently crosslinked membranes based on sulfonated poly(ether ether ketone) and carboxylated polysulfone exhibit much lower methanol crossover and better performance in direct methanol fuel cells at 65 °C in 1 and 2 M methanol solutions compared to Nafion 115 membranes.

Abstract  Proton solvation properties and transport mechanisms have been studied in hydrated Nafion using the self-consistent multistate empirical valence bond (SCI-MS-EVB) method that includes the effects excess proton charge defect delocalization and Grotthuss proton hopping. It was found that sulfonate groups influence excess proton solvation, as well as the proton hydration structure, by stabilizing a more Zundel-like (H(5)O(2)(+)) structure in their first solvation shells. Hydrate proton-related hydrogen bond networks were observed to be more stable than networks with water alone. Diffusion rates, Arrhenius activation energies, and transport pathways were calculated and analyzed to characterize the nature of the proton transport. Diffusion rate analysis suggests that a proton-hopping mechanism dominates the proton transport for the studied water loading levels and that there is a clear degree of anticorrelation with the vehicular transport. The activation energy drops quickly with an increasing water content when the water loading level is smaller than ∼10 H(2)O/SO(3)(-), which is consistent with experimental observations. The sulfonate groups were also found to affect the proton hopping directions. The temperature and water content effects on the proton transport pathways were also investigated.

Abstract  The development of a mass spectrometer-based continuous emission monitor (MS-CEM) for organic emissions from combustion devices is described, and results are presented from evaluations of the device at Louisiana State University. Besides the mass spectrometer, the monitor consisted of a heat-traced line, vacuum pump, particulate filters, and a Nafion dryer to remove water from the sample gas. The MS-CEM was tested by step injection of a mixture of organic compounds into the baghouse inlet of a pilot-scale rotary kiln incinerator, and the stack-gas effluent was monitored. In addition, the mixture of organic compounds was pulse injected into a second sampling line to simulate transient emissions of products of incomplete combustion during operational upsets. Results show that the response time for each organic components was less than 2 min. The accuracy of the monitoring device was affected by the flow rate, the organic mixture preparation measurement, and the evaporation of each component between the time of mixing of the VOCs and the time of injection into the sampling line.

Abstract  A dynamic supported liquid membrane tip extraction (SLMTE) procedure for the effective extraction and preconcentration of glyphosate (GLYP) and its metabolite aminomethylphosphonic acid (AMPA) in water has been investigated. The SLMTE procedure was performed in a semi-automated dynamic mode and demonstrated a greater performance against a static extraction. Several important extraction parameters such as donor phase pH, cationic carrier concentration, type of membrane solvent, type of acceptor stripping phase, agitation and extraction time were comprehensively optimized. A solution of Aliquat-336, a cationic carrier, in dihexyl ether was selected as the supported liquid incorporated into the membrane phase. Quantification of GLYP and AMPA was carried out using capillary electrophoresis with contactless conductivity detection. An electrolyte solution consisting of 12 mM histidine (His), 8 mM 2-(N-morpholino)ethanesulfonic acid (MES), 75 microM cetyltrimethylammonium bromide (CTAB), 3% methanol, pH 6.3, was used as running buffer. Under the optimum extraction conditions, the method showed good linearity in the range of 0.01-200 microg/L (GLYP) and 0.1-400 microg/L (AMPA), acceptable reproducibility (RSD 5-7%, n=5), low limits of detection of 0.005 microg/L for GLYP and 0.06 microg/L for AMPA, and satisfactory relative recoveries (90-94%). Due to the low cost, the SLMTE device was disposed after each run which additionally eliminated the possibility of carry-over between runs. The validated method was tested for the analysis of both analytes in spiked tap water and river water with good success.