Micromachined severinghaus-type carbon dioxide electrode

The Severinghaus-type pCO(2) electrode was miniaturized and batch-fabricated using semiconductor and micromachining techniques. Anodically grown iridium oxide film (AIROF) was employed as the pH sensing element to detect a local pH change caused by the infusion of CO(2). The AIROF showed a super-Nernstian response with a slope of approximately -80 mV/pH at 25 °C. A novel thin-film Ag/AgCl structure was also used. It features a hydrophobic membrane which covers the entire silver layer and the AgCl layer grown from the periphery of the silver pattern. The open-circuit potential of the Ag/AgCl element drifted to the negative side at -0.1 to -0.2 mV h(-1). A microcavity in which the electrolyte solution was filled was anisotropically etched in a silicon substrate, and a silicone rubber gas-permeable membrane was formed on the sensitive area. The miniature pCO(2) electrode showed a distinct response to the variation in concentration of dissolved CO(2). The inherent characteristics of the Severinghaus electrode were confirmed in terms of its response and calibration curve. The selectivity of the electrode was satisfactory in view of its application to clinical analysis.     

A lipophilic sol-gel matrix for the development of a carbonate-selective electrode

Organic-inorganic hybrid sol-gel matrixes were used as hosts for trifluoroacetyl-p-decylbenzene (TFADB), a traditional ionophore for carbonate. The sol-gel precursor was prepared by the reaction of (3-isocyanopropyl)triethoxysilane with ethylene glycol. Hexadecyltrimethoxysilane (HDTMOS) was employed as a co-precursor. An appropriate amount of tridodecylmethylammonium chloride (TDMAC) and 2-nitrophenyloctyl ether (NPOE) were used as membrane components. On mixing with an acidic catalyst, the sol-state precursors slowly gelled, yielding a membrane in which the active components, TFADB and TDMAC, were encapsulated. Infrared, (1)H, and (29)Si MAS NMR spectrometers were employed to monitor the sol-gel process and the degree of polymerization. The performances of the sol-gel membrane-based electrodes were compared to those of TFADB-based poly(vinyl chloride) (PVC) membrane electrodes. Membranes with a molar ratio of TFADB:TDMAC (1:0.14) showed extended lifetime and stable baseline potential. The response slope toward carbonate was approximately 27 mV/decade between 10(-)(5) and 10(-)(3.5) M at 18 degrees C. Interestingly, selectivity toward carbonate over salicylate and other lipophilic anions was improved, clearly deviating from the Hofmeister selectivity pattern. Responses toward small inorganic anions including chloride and sulfate were negligible. The selectivity coefficients measured by the matched potential method in 0.1 M tris-sulfuric acid buffer, pH 8.75, were log = -0.3, log = -4.2, and log = -2.5.     

Itraconazole formation using supercritical carbon dioxide

A new method of preparing Itraconazole (C₃₅H₃₈Cl₂N₈O₄), a synthetic triazole antifungal agent, was developed using supercritical carbon dioxide (SC CO₂) while eliminating the use of toxic solvents. Dissolution amounts of the product were measured in gastric fluid and compared to those of conventional drug formulations. Different operating conditions (five levels of treatment temperature ranging between 110-140°C, four levels of treatment pressure ranging between 30-400 atm, and four different treatment times ranging from 10-60 minutes) were tested in order to produce a desired Itraconazole product, which does not degrade during the product formation and has the highest extent of dissolution in gastric fluid after one hour. Itraconazole dissolution of 100% at one-hour was achieved for the drug produced at the optimum treatment condition: 135°C, 300 atm, and 30 minutes. Extent of dissolution obtained from this solvent and detergent-free process is 10% higher than that of the conventional method involving toxic organic solvents. Itraconazole produced using SC CO₂ should provide minimal side effects in human body.     

Processing of microcellular preceramics using carbon dioxide

An innovative processing route for developing microcellular ceramics has been developed. This newly designed technology relies on the implementation of the principle of inducing a thermodynamic instability in the production process for microcellular preceramic polymers that are further transformed into microcellular ceramics using pyrolysis. In this work, we have particularly focused on studying the feasibility of fabricating microcellular ceramics and the processing parameter-cell density relationships in the processing of microcellular preceramic polymers. The presented results indicate that the proposed novel processing method is suitable for the manufacture of porous ceramics with high uniformity of the cell size, shape, and volume.     

直接电解法制备二氧化锰正极的研究

首次通过电解方法直接制得二氧化锰-碳电极.通过恒电流放电、XRD 衍射、差热-热重实验以及环境扫描电镜等现代实验方法研究了合成条件与放电性能的关系.结果表明,在二氧化锰-碳电极上经过420℃处理的二氧化锰具有四方结构(空间群 P42/mnm).以0.1C的电流倍率放电时放电容量达到219mAh/g.不必涂敷粘结剂,二氧化锰就可以与石墨集电极牢固的结合在一起,直接作为正极使用.     

Testing carbon sequestration site monitor instruments using a controlled carbon dioxide release facility

Two laser-based instruments for carbon sequestration site monitoring have been developed and tested at a controlled carbon dioxide (CO(2)) release facility. The first instrument uses a temperature tunable distributed feedback (DFB) diode laser capable of accessing the 2.0027-2.0042 microm spectral region that contains three CO(2) absorption lines and is used for aboveground atmospheric CO(2) concentration measurements. The second instrument also uses a temperature tunable DFB diode laser capable of accessing the 2.0032-2.0055 mum spectral region that contains five CO(2) absorption lines for underground CO(2) soil gas concentration measurements. The performance of these instruments for carbon sequestration site monitoring was studied using a newly developed controlled CO(2) release facility. A 0.3 ton CO(2)/day injection experiment was performed from 3-10 August 2007. The aboveground differential absorption instrument measured an average atmospheric CO(2) concentration of 618 parts per million (ppm) over the CO(2) injection site compared with an average background atmospheric CO(2) concentration of 448 ppm demonstrating this instrument's capability for carbon sequestration site monitoring. The underground differential absorption instrument measured a CO(2) soil gas concentration of 100,000 ppm during the CO(2) injection, a factor of 25 greater than the measured background CO(2) soil gas concentration of 4000 ppm demonstrating this instrument's capability for carbon sequestration site monitoring.     

Optical sensing scheme for carbon dioxide using a solvatochromic probe

The novel sensing scheme, unlike previous ones that are based on the use of pH indicator probes, is making use of solvatochromic probe Nile Red (NR). Dissolved in a matrix of ethyl cellulose, it can report the polarity of its microenvironment that is modulated by an additive (a hydrophobic amidine) that is capable of reversibly binding carbon dioxide. The spectra of NR undergo a strong solvatochromic shift both in color (from brick-red to magenta) and in fluorescence (from orange to red) if the respective sensor layer is exposed to gaseous CO(2) (gCO(2)) or dissolved CO(2) (dCO(2)). Both visual and instrumental readouts are possible. The sensor layer responds to gCO(2) in the range from 0 to 100% and to dCO(2) in the range from 0 to 1 M solutions of bicarbonate (equivalent to a CO(2) partial pressure of up to 255 hPa). The detection limits are around 0.23% for gCO(2) and 1.53 hPa for dCO(2). The response time is in the order of 10 min in the forward direction and 3 min in the reverse direction for gCO(2) but up to 25 min in the case of dCO(2). The optical response also was quantified using a digital camera by extracting the spectral information using the blue and green color channels (in reflectometry) and the green and red channels (in fluorescence), respectively, and by generating pseudocolor pictures.     

Determination of cyanide in wastewaters using modified glassy carbon electrode with immobilized silver hexacyanoferrate nanoparticles on multiwall carbon nanotube

The sensitive determination of cyanide in wastewaters using modified GC electrode with silver hexacyanoferrate nanoparticles (SHFNPs) immobilized on multiwall carbon nanotube (MWCNT) was reported. The immobilization of SHFNPs on MWCNT was confirmed by transmission electron microscopy (TEM). The TEM image showed that the SHFNPs retained the spherical morphology after immobilized on MWCNT. The size of SHFNPs was examined around 27 nm. The GC/MWCNT-SHFNPs was used for the determination of cyanide in borax buffer (BB) solution (pH 8.0). Using square wave voltammetry, the current response of cyanide increases linearly while increasing its concentration from 40.0 nM to 150.0 μM and a detection limit was found to be 8.3 nM (S/N=3). The present modified electrode was also successfully used for the determination of 5.0 μM cyanide in the presence of common contaminants at levels presenting in industrial wastewaters. The practical application of the present modified electrode was demonstrated by measuring the concentration of cyanide in industrial wastewater samples. Moreover, the studied sensor exhibited high sensitivity, good reproducibility and long-term stability.     

Chromatography using a water stationary phase and a carbon dioxide mobile phase

A novel chromatographic separation method is introduced which employs water (saturated with CO(2)) as a stationary phase and CO(2) (saturated with water) as a mobile phase. Since water and CO(2) have little miscibility, conditions can be attained that create a stationary phase of water lining the inside of an uncoated stainless steel capillary. Because altering temperature and pressure can change both the density of the mobile phase and the polarity of the stationary phase, these experimental parameters offer good flexibility for optimizing separations and allow for different gradient programmed separation options. Further, since this method is free of organic stationary and mobile phase components, it is environmentally compatible and allows the use of universal flame ionization detection. This system offers very good sample capacity, peak symmetry, and retention time reproducibility (～1% RSD run-to-run, ～4% RSD day-to-day). Analytes such as alcohols, carboxylic acids, phenols, and tocopherols are employed to investigate this relatively inexpensive and robust method. As an application, the system is used to quantify ethanol in alcoholic beverages and biofuel and to analyze caffeine levels in drinks. In all cases, quantitative results are obtained with quick throughput times and often little need for sample preparation.     

V-type nerve agent detection using a carbon nanotube-based amperometric enzyme electrode

An enzyme electrode for the detection of V-type nerve agents, VX (O-ethyl-S-2-diisopropylaminoethyl methylphosphonothioate) and R-VX (O-isobutyl-S-2-diethylaminoethyl methylphosphonothioate), is proposed. The principle of the new biosensor is based on the enzyme-catalyzed hydrolysis of the nerve agents and amperometric detection of the thiol-containing hydrolysis products at carbon nanotube-modified screen-printed electrodes. Demeton-S was used as a nerve agent mimic. 2-(Diethylamino)ethanethiol (DEAET) and 2-(dimethylamino)ethanethiol (DMAET), the thiol-containing hydrolysis product and hydrolysis product mimic of R-VX and VX, respectively, were monitored by exploiting the electrocatalytic activity of carbon nanotubes (CNT). As low as 2 microM DMAET and 0.8 microM DEAET were detected selectively at a low applied potential of 0.5 V vs Ag/AgCl at a CNT-modified mediator-free amperometric electrode. Further, the large surface area and the hydrophobicity of CNT was used to immobilize organophosphorus hydrolase mutant with improved catalytic activity for the hydrolysis of the P-S bond of phosphothiolester neurotoxins including VX and R-VX nerve gases to develop a novel, mediator-free, membrane-free biosensor for V-type nerve agents. The applicability of the biosensor was demonstrated for direct, rapid, and selective detection of V-type nerve agents' mimic demeton-S. The selectivity of the sensor against interferences and application to spiked lake water samples was demonstrated.     

Determination of sulfur dioxide in wine using a quartz crystal microbalance

A new method for the analysis of both total and bound SO(2) in wine is proposed, based on a quartz crystal microbalance (QCM), and it is compared with the widely used Ripper method. The proposed method is faster than the Ripper's, and the instrumentation is either home-made or widely available. When both methods are applied to the same sample, the results obtained using the QCM method are bracketed in an interval less than one-tenth the size of that obtained using the Ripper method. Although the SO(2) concentrations found using the QCM method correlate well with the ones obtained with the Ripper method, the results are systematically higher, which can be explained as due to the absence of interferences known to affect the Ripper method.     

Electrochemical behaviour and voltammetric determination of sulphadiazine using a multi-walled carbon nanotube composite film-glassy carbon electrode

The anodic oxidation of sulphadiazine (SD) was investigated at a glassy carbon electrode modified by multi-walled carbon nanotube (MWCNT–GCE), using cyclic voltammetry and chronoamperometry. The results indicate that MWCNT-modified GCEs show an efficient and selective electrocatalytic activity towards the anodic oxidation of SD among biologically important compounds in buffered solutions at pH?=?7. It was found that oxidation of SD at the surface of MWCNT–GCE occurs at a potential less positive than that of unmodified GCE (about 100?mV). The diffusion coefficient of SD was also estimated using chronoamperometry. The kinetic parameters such as the electron transfer coefficient between SD and modified electrode, α, and the charge transfer rate constant, k_s , for oxidation of SD at the MWCNT–GCE surface were determined according to the Laviron procedure. The dissociation constants of oxidised and reduced acid–base species of SD can be obtained from the E _1/2 versus pH curves. The linear dependence of the peak current on the concentration was observed in the range 10–2000?µmol?L^?1 with a detection limit of 7.1?µmol?L^?1. The method was also applied to determinate the SD in human blood plasma and urine samples.     

Electrochemical impedance-based DNA sensor using a modified single walled carbon nanotube electrode

Carbon nanotubes have become promising functional materials for the development of advanced electrochemical biosensors with novel features which could promote electron-transfer with various redox active biomolecules. This paper presents the detection of Salmonella enterica serovar Typhimurium using chemically modified single walled carbon nanotubes (SWNTs) with single stranded DNA (ssDNA) on a polished glassy carbon electrode. Hybridization with the corresponding complementary ssDNA has shown a shift in the impedance studies due to a higher charge transfer in ssDNA. The developed biosensor has revealed an excellent specificity for the appropriate targeted DNA strand. The methodologies to prepare and functionalize the electrode could be adopted in the development of DNA hybridization biosensor.     

Determination of ultratrace levels of lead (II) in water samples using a modified carbon paste electrode based on a new podand

A new podand of 1,1′-thiobis(naphthalene-2,1-diyl)bis(2-aminobenzoate) (TNBA) was synthesized and used as a suitable carrier for construction of Pb²⁺ modified carbon paste electrode (CPE). The effects of various plasticizers; 2-nitrophenyloctylether (o-NPOE), dioctyl pththalate (DOP), dibutyl phthalate (DBP) and paraffin oil were studied. The best performance was obtained with a matrix composition of CPE with a DOP/graphite powder/TNBA weight percent ratio of 35/60.5/4.5. The sensor exhibits significantly enhanced selectivity toward Pb²⁺ ion over the concentration range 8.0 × 10^? 8 to 1.0 × 10^? 2 mol L^? 1 with a lower detection limit of 5.0 × 10^? 8 mol L^? 1 and a Nernstian slope of 29.0 ± 0.2 mV decade^? 1 of lead activity. It has a fast response time of 8 s with a working pH range from 3.5 to 7. The interaction between TNBA and Pb²⁺ was studied spectrophotometrically and it exhibits that the stoichiometry of the complex is 1:1 in acetonitrile solution. Finally, the electrode was satisfactorily used as an indicator electrode in complexometric titration of Pb²⁺ with EDTA and in direct determination of lead in various water samples.     

Hydrophobization of porous ceramic materials using supercritical carbon dioxide

A process has been proposed for hydrophobizing an inorganic porous material consisting of silica fibers using fluoroalkane dissolution in supercritical carbon dioxide. The process allows one to produce thin, homogeneous polymer coatings both on the surface and in the bulk of the material, ensuring that the material has excellent hydrophobic properties, which significantly improves its performance parameters and extends its potential application field.