The addition of only ∼1.7 wt% (∼0.06 M) ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate to aqueous solutions of six popular cationic dyes resulted in the precipitation of almost all of the dye from the solution.
The recent development of the chemical speciation of trace metals in seawater is described. The speciation studies reveal that metal ion complexation is one of the most important processes in seawater; especially, most bioactive trace metals, such as Fe(III) and Cu, exist as complexes with ligands in dissolved organic matter. The organic ligands in seawater are characterized with metal ions selected by the HSAB concept. A strong organic ligand, which originates from marine microorganisms, is classified as a hard base including carboxylates. The free organic ligand concentrations in seawater are buffered by complexation with excess amounts of Ca and Mg in seawater. The chemical equilibrium model suggested that the concentrations of bioactive free metal ions are at an optimal level to activities of marine microorganisms. For chemical speciation, it is important to have a better understanding of the ecological roles of trace metals in seawater.
A cationic surfactant ion-selective field-effect transistor (cationic surfactant-ISFET) has been developed based on the tetraphenylborate derivative known as sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. The cationic surfactant-ISFET shows an almost Nernstian response to tetradecyldimethylbenzylammonium chloride (Zephiramine) over a concentration range between 1.0 × 10-6 M and 1.0 × 10-3 M, with a slope of 58.5 ± 1.7 mV/decade. The cationic surfactant-ISFET can be used over a range of pH values, between pH 3 and 9. The cationic surfactant-ISFET shows excellent selectivity for Zephiramine over small inorganic cations, but shows similar selectivity for other cationic surfactants, such as hexadecyltrimethylammonium and stearyltrimethylammonium ions. A microfluidic polymer chip was integrated with the cationic surfactant-ISFET, and this was fabricated using polystyrene plates and stainless wires as a template for the channel. Cationic surfactant-ISFETs used in a batch system and microchips integrated with cationic surfactant-ISFETs showed very similar performance in terms of low detection limits, slope sensitivity and the stability of the potential response. The microfluidic polymer chip was then applied to the determination of cationic surfactants in dental rinses.
DNA was immobilized on glassy carbon electrodes to fabricate DNA-modified electrodes. The direct electron transfer of horse heart cytochrome c on DNA-modified glassy carbon electrode was achieved. A pair of well-defined redox peaks of cytochrome c appeared at Epc = -0.017 V and Epa = 0.009 V (vs. Ag/AgCl) in 10 mM phosphate buffer solution (pH 7.0) at a scan rate of 50 mV/s. The electron transfer coefficient (α) and the standard rate constant of the surface reaction (Ks) of cytochrome c on DNA-modified electrodes could be estimated to be 0.87 and 34.52 s-1, respectively. The DNA-modified glassy carbon electrode could be applied to detect cytochrome c by means of differential pulse voltammetry (DPV). The cathodic peak current was proportional to the quantity of cytochrome c in the range of 4.0 × 10-6 M to 1.2 × 10-5 M. The correlation coefficient is 0.996, and with the detection limit was 1.0 × 10-6 M (three times the ratio of signal to noise, S/N = 3).
The preparation of a lead-selective electrode based on 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis-(diphenylphosphinoylmethoxy)calixarene (1) as an ionophore is reported. The plasticized PVC membrane containing 30% PVC, 57% ortho-nitrophenyloctylether (NPOE), 4% sodium tetraphenylborate (NaTPB) and 9% ionophore 1 was directly coated on a graphite electrode. It exhibits a nearly Nernstian slope of 28.0 ± 0.2 mV decade-1 over a concentration range of 1 × 10-5 - 1 × 10-2 mol dm-3 with a detection limit of 1.4 × 10-6 mol dm-3. The response time of the electrode was found to be ca. 17 s. The potential of the sensor was independent of the pH variation in the range 3.5 - 5.0. The selectivity of the electrode performance towards lead ions over Th4+, La3+, Sm3+, Dy3+, Y3+, Ca2+, Sr2+, Cd2+, Mn2+, Zn2+, Ni2+, Co2+, NH4+ Ag+, Li+, Na+ and K+ ions was investigated. The prepared electrode was used successfully as an indicator electrode for a potentiometric titration of a lead solution using a standard solution of EDTA. The applicability of the sensor for Pb2+ measurements in various synthetic water samples spiked with lead nitrate was also checked.
2,5-Dimercapto-1,3,4-thiadiazol (DMTD) can bind on the surface of a gold electrode through the strong gold-sulfur interaction. The fabrication and electrochemical characteristics of the DMTD self-assembled monolayer (SAM)-modified gold electrode were investigated. The DMTD SAM electrode exhibited a significantly increased sensitivity. Cu(II) was accumulated in phosphate buffer (pH 4.6) at a potential of -0.6 V (vs. Ag/AgCl) for 40 s and then determined by anodic stripping voltammetry (ASV) in copper-free phosphate buffer (pH 5.0). The effects of various parameters, such as the pH values of the preconcentration solution and measurement solution, the accumulation potential, and the accumulation time, were investigated. Under the optimum conditions, a linear calibration graph was obtained in the concentration range of 8.0 × 10-6 to 8.0 × 10-5 mol l-1 with a correlation coefficient of 0.9978. The relative standard deviations for eight successive determinations were 4.3 and 2.9% for 1.0 × 10-5 and 2.0 × 10-5 mol l-1 Cu(II), respectively. The detection limit (three times signal to noise) was 4.0 × 10-7 mol l-1. The proposed voltammetric method was utilized successfully to detect the concentration of Cu(II) ions in tap water samples.
In this study, a simple and sensitive method for the determination of arsenic in water samples was developed. The method is based on the formation of micro particles of Ethyl Violet and molybdoarsenate, which gives an apparently homogeneous blue color to the solution. The absorption of the excess dye gradually decreases due to its conversion to a colorless carbinol species under strongly acidic conditions. Consequently, the sufficiently low reagent blank enables the spectrophotometric determination of arsenic with the detection limit of 4 µg l-1. The coefficient of variation for the spectrophotometry at 50 µg l-1 was 3.5% (n = 5). Furthermore, it is possible to detect concentrations as low as 10 µg l-1 of arsenic visually. Our method will be useful as a simple, rapid, and cost-effective field test of arsenic, requiring no complex apparatus or skilled laboratory support.
A new method is proposed to determine the calibration factor (CF) of methyl and ethyl peroxy radicals in a chemical amplifier. The radical source comes from the reactions of excess methane and ethane, respectively, with known concentrations of OH radicals generated by the photolysis of water vapor at 184.9 nm in air in a flow tube. This yields a mixed radical source with equal amounts of HO2 and RO2 (R = CH3, C2H5). The CF for RO2 can be derived from the CF for HO2 and an average CF for the mixed radicals. The reliability of the method was evaluated by comparing the CF ratios of RO2 to HO2 obtained from both the experiments and theoretical calculations.
A flow-injection method is reported for the determination of thyroxine based on its enhancement effect on the tris(2,2′-bipyridyl)ruthenium(III) chemiluminescence reaction in the presence of NADH using immobilized alcohol dehydrogenase purified from baker yeast. The limit of detection (3 σ blank) was 5.0 × 10-8 M with a sample throughput of 80 h-1. The calibration graph was linear over the range 0.5 - 10 × 10-7 M (r2 = 0.9988) with the relative standard deviation in the range 1.4 - 3.5% (n = 4). The effect of common excipients used in pharmaceutical preparations, some organic compounds and metal ions was studied. The method was applied to pharmaceutical thyroxine tablets, and the obtained results were not significantly different from the amount quoted.
A microfluidic solid phase extraction (SPE) array for sample enrichment was prepared by a simple method, a hot embossing technique. Five fused-silica capillaries (250 µm i.d., 380 µm o.d.) were partly embedded parallel in a polymethyl methacrylate (PMMA) microchip to serve as the extraction channels. Within each of the channels, a 2-mm-long monolithic porous polymer was prepared by in-situ photoinitiated polymerization. This then acted as the frit for packing of the extraction materials (octadecylsilica beads, ODS). By defining the light-exposure window on the channels, one can easily control the length and location of the polymer frits and the ODS beads can be packed at the desired location. With this method, solid phase extraction channels for microfluidic use can be easily prepared without complex fabrication of microstructures. Several SPE channels can be conveniently made in one microchip since the frits can be prepared in different channels through one polymerization; packing of the different channels can also be performed simultaneously. With the use of dilute ephedrine solutions, the sample loading capacity, linearity, and reproducibility were characterized. Coupled with the fast capillary electrophoresis separation, this microchip SPE array was applied for the detection of ephedrines in human urine.
Two new chelating materials (Si-DDE-o-HB, and Si-DDS-o-HB) were synthesized by modifying the activated silica gel phase with Schiff bases of 4,4′-diaminodiphenylether (DDE)/4,4′-diaminodiphenylsulfone (DDS) and o-hydroxybenzaldehyde (o-HB). The synthesized materials were characterized by FTIR and BET surface area measurement techniques. The extraction of metal ions such as Zn2+, Mn2+ and Cr3+ by the chelating material Si-DDE-o-HB was found to be higher than that by Si-DDS-o-HB. The order of metal sorption was found to be Zn2+ > Mn2+ > Cr3+. The correlation coefficients for Freundlich and Langmuir adsorption isotherms were compared for the sorption of Zn2+ onto the chelating material. The loading and elution of the metal ion solution was examined at optimum pH 7.5 and 0.5 cm3 min-1 flow rate of the solution using a column technique. The preconcentration factor for the elution of Zn2+ using dilute HNO3 was found to be 66.2 with a breakthrough volume of 15 cm3. The data obtained for the preconcentration of Zn2+ by the column technique suggested that the material Si-DDE-o-HB can find industrial applications.
Some raw materials that have different places of production for the plant sources of the drugs Astragalus membranaceus and ginseng have been studied, based on their near-infrared reflectance spectra. The experimentally recorded spectra represent heavily ill-posed and highly correlative data sets. Three related methods, i.e. the Fisher linear discriminant analysis (FLDA), the ridge-type linear discriminant analysis (RLDA) and a newly proposed penalized ridge-type linear discriminant analysis (PRLDA), have been investigated. FLDA over-fits for the training objects of the two data sets to a high extent and is unstable for the predictive objects of the two data sets. RLDA shows obvious improvement in terms of over-fitting and unstability, but the stability for the predictive objects of the two data sets is too sensitive to their ridge-type penalized weights, tending to produce erroneous discrimination results. The proposed PRLDA can circumvent the two aforementioned problems with a large domain of penalized weights for correct discriminant analysis of the two data sets studied. The combination of the PRLDA method and near infrared reflectance spectroscopy can be adapted for the discrimination of the production places of plant sources of these drugs.
Multilayered thin films containing poly(allylamine) (PAA) and brilliant yellow (BY) were prepared on a quartz slide by a layer-by-layer (LBL) deposition technique. The UV-visible spectra of the PAA/BY films were sufficiently changed depending upon the pH value of the solution in which the film was immersed. The response of the PAA/BY films was very fast (within a second) upon pH change from 9.0 to 5.0, while the response time was ca. 100 s upon pH change from 5.0 to 9.0.
The precipitation titration of sodium chloride with electrogenerated silver ion was studied. The production of a precipitate of silver chloride had a significant effect on the titration results because the precipitate involved unreacted chloride or unreacted silver ion. The accuracy of the method was investigated by changing the introduction time of a sodium chloride solution to the coulometric cell during the process of electrolysis, and examining the dependency on the sample size. The accuracy of the measurement of the precipitation titration is discussed.
Boron (B) is an essential micronutrient for vascular plants. The function of B has been demonstrated to cross-link monomeric rhamnogalacturonan II (mRG-II) to form dimeric RG-II-borate (dRG-II-B), and thus to stabilize plant cell walls. The dRG-II-B to total RG-II ratio in the cell walls of pumpkin hydroponically grown under various low-B conditions was analyzed to evaluate its applicability to the diagnosis of plant B deficiency. The dRG-II-B ratio in cell walls ranged between ∼0.9 in B-sufficient tissues and ∼0.15 in severe B-deficient tissues, reflecting the B nutritional status of tissues. This result indicates that the degree of B shortage in plant tissues is very likely to be diagnosed by the dRG-II-B ratio in cell walls.
We developed a capillary zone electrophoresis method with indirect UV detection for determination of ammonium cations and alkali and alkaline earth metal cations in jellyfish. As the background electrolyte, a mixture of N-methylbenzylamine, citrate, and 18-crown-6 was used for the complete separation of all analyte cations. The limits of detection were 0.13 - 0.34 mg l-1 at a signal-to-noise ratio of three. The values of the relative standard deviation of peak area were 3.2 - 4.9%. The proposed method successfully determined the above analyte cations in jellyfish for approximately 4 min.
A flow-injection dual biosensor system with microdialysis sampling is proposed for the simultaneous determination of D-lactic and L-lactic acids. The dialysate from the microdialysis tube is delivered to a sample loop of the six-way autoinjector and then automatically injected into the flow-injection line with a dual enzyme electrode arranged in perpendicular to the flow direction. The dual enzyme electrode is constructed by hybridizing a poly(1,2-diaminobenzene) film into two sensing parts which respond selectively to D-lactic and L-lactic acids, respectively, without any cross-reactivity. The proposed flow-injection analysis method can be successfully applied to the simultaneous determination of D,L-lactic acids in alcoholic beverages.
A flow-injection system with an enzyme reactor was proposed for the measurement of fructosyl amino acids and fructosyl peptides in protease-digested blood samples. A fructosyl-amino acid oxidase (FAOX-TE) and two fructosyl-peptide oxidases (FPOX-CE and FPOX-CET) were covalently immobilized onto an inert support. They were used as the enzyme reactor in a FIA system with a hydrogen peroxide electrode. In particular, the FPOX-CET reactor possessed high selectivity for the detection of fructosyl valine (FV) and fructosyl valyl histidine (FVH) and an excellent operational stability. The proposed FIA system with the FPOX-CET reactor responded linearly to the concentration of FV over the dynamic range of 7.8 × 10-6 to 5.8 × 10-4 M. The present method could be successfully applied to the assay of FV and FVH in the protease-digested blood samples.
A novel, rapid and sensitive analytical method is described for determination of ofloxacin and levofloxacin by enhanced chemiluminescence (CL) with flow-injection sampling. The method is based on the CL reaction of the Ce(IV)-Na2S2O4-ofloxacin/levofloxacin-H2SO4 system. The enhanced CL mechanism was developed and the optimum conditions for CL emission were investigated. The CL intensity was correlated linearly (r = 0.9988) with the concentration of ofloxacin (or levofloxacin) in the range of 1.0 × 10-8 - 1.0 × 10-7 g ml-1 and 1.0 × 10-7 - 6.0 × 10-6 g ml-1. The detection limit (S/N = 3) is 7 × 10-9 g ml-1. The relative standard derivation (RSD, n = 11) is 2.0% for ofloxacin at 4 × 10-7 g ml-1 and for levofloxacin at 6 × 10-7 g ml-1. This method has been successfully applied for the determination of ofloxacin and levofloxacin in pharmaceutical preparations and biological fluids with satisfactory results.