A target value for iminoctadine triacetate residues in tap water was set at 6 µg/l in Japan. We have developed a highly selective and sensitive analytical method for iminoctadine triacetate by solid phase extraction LC/ESI/MS using hydrophilic interaction chromatography. The recovery rates at concentration of 0.06, 0.6, and 6 µg/l in distilled water, tap water, and raw water were 77.1 - 96.7%, and CV were 3.7 - 13.2%. The quantitation limit of the present method was 0.04 µg/l, and it was able to measure even one-hundredth of the target value of iminoctadine triacetate quantitatively.
Monolithic silica columns and their use in high peak-capacity HPLC separations are reviewed. Monolithic silica columns can potentially provide higher overall performance than particle-packed columns based on the variable external porosity and variable through-pore size/skeleton size ratios. The high permeability of monolithic silica columns resulting from the high porosity is shown to be advantageous to generate large numbers of theoretical plates with long capillary columns. High permeability together with the high stability of the network structures of silica allows their use in high-speed separations required for a second-dimension column in two dimensional HPLC. Disadvantages of monolithic silica columns are also described.
Solid-phase extraction (SPE) is an effective tool for the preconcentration of trace elements and their separation from various sample constituents. Octadecyl and other alkyl-bonded silica gels are most widely used for these purposes. The fundamentals of the SPE of inorganic ions are reviewed and compared with those of related techniques (liquid-liquid extraction and reversed-phase liquid chromatography). The extraction of ions in the form of chelate compounds, inorganic salts solvated by neutral reagents, and ion-pair compounds is considered. Numerous applications of SPE to the separation and preconcentration of different elements and their species, including on-line combinations with instrumental determination techniques, are described and tabulated.
The molecular interaction force of the intermonolayer hydrogen bonding between phenylurea groups on a probe tip and carboxyl groups in self-assembled monolayers was measured directly by means of atomic force microscopy in ethanol. Gold-coated AFM probe tips were modified chemically with 2-(N′-phenylureido)ethanethiol possessing a terminal urea moiety, which is a well-known powerful functionality for forming stable hydrogen bondings with neutral and anionic species. Adhesion force measurements were carried out on gold substrates coated with a COOH-terminated SAM composed of 6-mercaptohexanoic acid in ethanol using the phenylurea-functionalized probe tip. The adhesion force observed was decreased in the presence of H2PO4- in the measurement bath, indicating that the intermonolayer hydrogen bonding between the phenylurea moieties and carboxyl groups attached covalently to the probe tip and substrate, respectively, is suppressed by the anion added to the measurement solution. The specific hydrogen-bonding force was measured on binary mixed SAMs prepared by mixing 6-mercaptohexanoic acid with 1-hexanethiol. The individual hydrogen-bonding force between the phenylurea-modified tip and the binary mixed SAMs with various fractions of MHA was evaluated by repetitive force measurements and their statistical analyses by an autocorrelation method. We discuss the effect of diluting the COOH-terminated component in the mixed SAM on the adhesion force and the single force between the phenylurea and carboxyl groups in terms of competition between intermonolayer and intramonolayer hydrogen bonding.
We developed a fabrication method and a liquid filling method for a nano chemical reactor that used Y-shaped nanochannels specially designed for mixing and reacting. In order to reduce the pressure loss and to utilize the characteristics of the nanochannel, inlet microchannels were fabricated just beside the nanochannels. We investigated an initial liquid filling method into the nanochannels that ensured there were no air bubbles that could cause a flow stack due to the capillary pressure. In our method, the micro- and nanochannels were filled with carbon dioxide and any remaining air during the initial liquid introduction was dissolved utilizing the high solubility of carbon dioxide. We propose that chemical reactions in nanospaces can be realized by utilizing these fabrication and liquid introduction techniques.
This paper gives two empirical correlations of formation Gibbs energies of gaseous clusters ΔGfn as function of number of solvent molecules attached to the ion, n, and one correlation connecting the ΔGfn for each individual cluster with the total ΔGohydr value. The experimental ratios of ΔGf2/ΔGf1 and ΔGf3/ΔGf1 for both alkali metal and halide ions are on average equal to 0.75 and 0.5, respectively. ΔGfn values for n ≥ 4 are correlated with n as ΔGfn = [a/(n - 1)] ΔGf1 + b ΔGf1. For all available data on cluster energies and each individual cluster, the ΔGfn's are straight-line functions of ΔGohydr. This well corresponds to another empirical rule stating that the Gibbs energies of transfer of ions between two solvents are often as well straight-line functions of ΔGohydr [J. Rais and T. Okada, J. Phys. Chem. A, 2000, 104, 7314]. Tentative models of the found behavior are proposed. A full data set of the gaseous cluster energies of formation based on inclusion of new, usually not used entries from the literature is provided.
A new method for the qualitative analysis of adenosine nucleotides (AMP, ADP, and ATP) and synthetic oligonucleotides has been proposed, utilizing a pH- and temperature-responsive polymer of N-isopropylacrylamide (NIPAAm), butyl methacrylate (BMA) and N,N-dimethylaminopropylacrylamide (DMAPAAm) as the stationary phase of HPLC. In the chromatographic system using the copolymer with ionizable groups of modified packing materials, we investigated how to separate adenosine nucleotides and oligonucleotides by temperature. The properties of the surface of the copolymer-grafted stationary phase altered from hydrophilic to hydrophobic and from charged to non-charged due to changes in the temperature and in the pH, respectively. In addition, it is possible to exhibit and hide ion-exchange groups on the polymer chain surface by temperature changes. These phenomena result from changes in the charge and hydrophobicity of the pH- and temperature-responsive polymer on the stationary surface with the controlling temperature. A pH- and temperature-responsive chromatography would be greatly useful for biopolymer and nucleotide separation and purification.
Various cationic rhenium(I) and ruthenium(II) mono- and multinuclear complexes were successfully separated by size-exclusion chromatography (SEC), using a 50:50 (v/v) mixture of methanol and acetonitrile with CH3CO2NH4 as an eluent. The logarithms of the molecular weights were accurately linear in the distribution coefficients: for linear-shaped rhenium(I) multinuclear complexes, log MW = -2.86KSEC + 5.24 (r = -0.990 and n = 15); for ring-shaped rhenium(I) multinuclear complexes, log MW = -2.94KSEC + 5.40 (r = -0.999; n = 5); for bimetallic complexes including ruthenium(II), log MW = -0.40KSEC + 3.37 (r = -0.959; n = 6). This separation method is applicable to the preparative-scale separation of cationic multinuclear complexes from a mixture.
This study developed a methodology to analyze trace rare earth elements (REEs) in geological materials by capillary electrophoresis (CE). Changed from dilute HNO3 into a water medium by heating, REE ions are detectable at ∼2 ng mL-1. In the presence of coexisting elements from geological samples, REE separations were carried out. After sample fusion with Na2O2 and interference separation with ammonium pyrrolidinedithiocarbamate chelate, REE analytes were coprecipitated with Mg(OH)2 at pH 8.5, and then prepared into a water medium for CE determination. Using the standard addition method, this protocol was validated by analyses with better than 5% precision. This method was applied to geological materials; the REE results are in consistence with their certified values. With electrokinetic injection, internal standard (IS) selected among lanthanides is a prerequisite of high-quality REE data. An approach was proposed to derive the IS content for further correcting its contribution from unknown samples.
A large-volume sample injection (> 5 µL) with an extremely high theoretical plate number (N > 107) was achieved when the sweeping-MEKC mode and a coupled-capillary (100 - 50 µm i.d.) were simultaneously used in a capillary electrophoresis (CE) separation. A low-cost and compact violet-LED (∼2 mW) was used as the fluorescence excitation source. As a result, the theoretical plate numbers of the detected peaks (two model compounds: naphthalene-2,3-dicarboxaldehyde derivatized-dopamine and -norepinephrine) were 1.0 × 107 and 7.4 × 106, respectively. The limits of detection (at S/N = 3) of these were determined to be 2.8 × 10-10 M (92 ppt) and 2.3 × 10-10 M (83 ppt), respectively.
In this paper, a novel method for the determination of chloroform in drinking water has been described. It is based on liquid-phase microextraction (LPME) and gas chromatography-mass spectrometry (GC-MS). Extraction conditions such as solvent selection, organic solvent dropsize, stirring rate, content of NaCl and extraction time were found to have significant influence on extraction efficiency. The optimized conditions were 1.5 µl xylene, 20 min extraction time at 400 rpm stirring rate without NaCl addition. The linear range was 1.0 - 100 µg l-1 for chloroform. The limit of detection (LOD) was 1.0 µg l-1; and relative standard deviation (RSD) at the 30 µg l-1 level was 2.9%. Tap water samples from a laboratory were successfully analyzed using the proposed method. The relative recovery of spiked water samples was 104%.
Gold nanoparticle modified indium tin oxide (ITO) film coated glass electrodes were prepared for the first time through direct electrochemical deposition from 0.5 M H2SO4 containing 0.1 mM HAuCl4. The resulting electrode surfaces were characterized with AFM. Cyclic voltammetry and linear sweep voltammetry (LSV) of arsenic(III) on the modified electrodes were performed. After optimization, a LOD of 5 ± 0.2 ppb was obtained with 60 s deposition at -0.6 V (vs. SCE) in 1 M HNO3 using LSV.
A rapid differential pulse adsorptive stripping voltammetric method has been developed for the ultra-trace determination of chromium using 2,2′-bipyridine. The base electrolyte used is 0.1 M NH4Cl (pH 6.0). The peak current was found to increase substantially with the addition of nitrite ions. A well-defined peak was observed at -1.3 V. Parameters, like concentration of the ligand, concentration of nitrite ion, accumulation potential, accumulation time, rest period, drop size, scan rate, pulse amplitude etc. have been optimized. Under the optimum conditions, the 3 σ detection limit was found to be 0.02 ppb (3.8 × 10-10 M). The method is highly selective and sensitive, and has been applied to the determination of Cr(VI) in spiked water, effluents and ore samples.
A sensitive method for the determination of chitosan (CTS) by cathodic stripping voltammetry is presented. The method exploits a pair of oxidation-reduction peaks of CTS at -0.62 V (vs. SCE) and -0.54 V (vs. SCE), and an enhancement of the peak current of CTS observed in a 0.05 mol l-1 potassium hydrogenphthalate buffer solution (pH 2.5). The peak current is linear with the concentration of CTS from 5.0 × 10-7 to 1.5 × 10-5 g ml-1, and the detection limit is 1.0 × 10-7 g ml-1. We studied the characteristics and the mechanism of the electrode reaction, which proved that this process was diffusion controlled. This method was applied to determine the content of CTS in real samples with satisfactory results.
A new PVC membrane mercury(II) ion electrode based on N,N-dimethylformamide-salicylacylhydrazone (DMFAS) as an ionophore is described, which shows excellent potentiometric response characteristics and displays a linear log[Hg2+] versus EMF response over a wide concentration range between 6.2 × 10-7 and 8.0 × 10-2 M with a Nerstian slope of 29.6 mV per decade and a detection limit of 5.0 × 10-7 M. The response time for the electrode is less than 30 s and the electrode can be used for more than 2 months with less than a 2 mV observed divergence in a potentials. The proposed electrode exhibits very good selectivity for mercury(II) ions over many cations in a wide pH range (pH 1 - 4). The electrode was also applied to the determination of a mercury(II) ion in vegetables and in Azolla filiculoides.
In order to simultaneously monitor the concentrations of PAHs and POPs in the atmosphere, an activated carbon fiber filter paper (ACFP) was used as the adsorbing material in this study. The pressurized liquid extraction method (PLE method) was used to extract PAHs and POPs collected on the ACFP. Toluene was an effective solvent to extract them from ACFP using the PLE method, but some of PAHs, such as benzo(a)pyrene, benzo(g,h,i)perylene, dibenzo(a,h)anthracene and indeno(1,2,3-cd)pyrene, were hardly extracted. These PAHs were adsorbed on the particulate matter in the atmosphere. In general, these forms of particulate matter could be collected using a quartz fiber paper (QFP); these PAHs were efficiently extracted from the QFP using the PLE method with toluene. In this study, the collecting method of the PAHs was modified by using QFP overlapped in front of the ACFP. Atmospheric monitoring of PAHs and POPs in Niigata area was performed using this method, and most of the target compounds were detected. However, some of the POPs, such as aldrin, endrin, mirex, could not be detected. The POPs, such as hexachlorobenzene, α-hexachlorocyclohexane and chlordanes, and most of the PAHs were detected from all of the samples collected throughout the monitoring period. It was confirmed that these methods were effective to simultaneously monitor the concentrations of the PAHs and POPs in the atmosphere.
A sequential injection analysis (SIA) spectrophotometric procedure for cefadroxil determination has been developed. The SIA instrumentation was modified to achieve the desired function and operations by using the software developed to interface the PC with the conventional SIA system. The method is based on the measurement of a red, water-soluble product formed by the reaction between cefadroxil and 4-aminoantipyrine in the presence of alkaline potassium hexacyanoferrate(III) at 510 nm. Optimum conditions for determining the drug were investigated. Beer's law was obeyed over the concentration ranges of 1 - 10 mg L-1 and 10 - 50 mg L-1 with a detection limit (3 σ) of 0.17 mg L-1 and a limit of quantification (10 σ) of 0.56 mg L-1. The relative standard deviations of 1.98% and 1.93% for 5 mg L-1 and 30 mg L-1 of the drug, respectively (n = 11) are obtained. The proposed method has been applied satisfactorily to the determination of cefadroxil in commercial pharmaceutical formulations with a sampling rate of 100 h-1. Results obtained were in good agreement with those obtained by the official HPLC method at the 95% confidence level.
In order to obtain the depth profile of a thin film, we investigated the emission characteristics of a voltage modulation glow discharge to optimize the modulation parameters (modulation voltage, offset voltage, and modulation frequency). In this study, a phase-sensitive detection method with a lock-in amplifier to the modulation technique led to a higher sensitivity and a larger signal-to-noise ratio in the emission analysis compared to the normal dc amplification method. Upon increasing the maximum voltage, the emission intensity of the Cu atomic line (CuI 239.34 nm) increased linearly at a modulation voltage of 400 V and an offset voltage of 300 V. On the other hand, the emission intensity was gradually reduced when a modulation frequency increased. It is advantageous for surface analysis that the voltage modulation technique gives a lower sputtering rate rather than the conventional dc discharge.
The development of molecular spectroscopy has enabled us to select chlorinated aromatic hydrocarbons very rapidly. In particular, the laser ionization TOFMS (time-of-flight mass spectrometry) method is expected to be useful as an on-line, selective, and sensitive method. In the present work, real-time laser ionization TOFMS measurements were carried out on gaseous chlorinated aromatic hydrocarbons. The laser ionization method used resonance-enhanced two-photon ionization with the direct introduction of gas into the vacuum chamber. This method for analyzing aromatic hydrocarbons was developed using a pulsed supersonic molecular beam method. In the context of developing a highly selective and sensitive method, excitation of monochlorinated benzene at λ = 263.07 nm was found to be effective in the wavelength region from 263 nm to 265 nm. Also the excitation of polychlorinated biphenyls at λ = 266 nm was found to be substantially more effective than at λ = 280, 300 or 320 nm. The achievable sensitivity for real-time (1 min) measurements using the laser ionization TOFMS technique was found to be in the ppbV range.
A new fluorescent reagent, 2-hydroxy-1-naphthaldehydene-8-aminoquinoline (HNAAQ), was synthesized. The fluorescent reaction of this reagent with mercury was also studied. Based on this chelation, a highly sensitive spectrofluorometric method was developed for the determination of trace amounts of mercury in a water-ethanol (5 + 1, v/v) medium at pH 8.0. Under these conditions, the Hg-HNAAQ complex has excitation and emission maxima at 406 and 445 nm, respectively. The linear range of the method is from 0 to 16 µg L-1 and the detection limit is 0.056 µg L-1 of mercury. The interference of other ions was studied. In order to enhance the selectivity in the determination of mercury by the present method, we also applied the separation of mercury by distillation. Thus, the selectivity of the method could be increased remarkably. The procedure can be easily performed, and affords good precision and accuracy. This method has been successfully applied to the determination of mercury in waste water and prawns.
A lab-made chemiluminescence system with a polymer cell for the dropping mode was used to determine ultra-trace metal ions in hydrofluoric acid (HF) and the standard cleaning solution-1 (SC-1) used in semiconductor manufacturing processes. The cell was made of poly(dimethylsiloxane) (PDMS) with dimensions of about 10 mm i.d. and 8 mm in height, was cheap, disposable, chemically inert to alkalis and acids, especially HF, and was optically transparent in the visible region. A dropping method for sample injection was adopted to minimize pulsation and the dramatic pH change of the luminol-H2O2 reagent when adding the sample. The average sample weight of a single drop was 7.17 µg with a remarkable reproducibility of ±0.37% relative standard deviation (RSD). This very small sample volume compared to the reagent volume made it possible to avoid any precipitation being formed when HF was added. For an application, Fe was determined in deionized (d.i.) water, sulfuric acid, SC-1, and a diluted HF (1:200 DHF) solution, which have been commonly used in semiconductor manufacturing processes. The limits of detections for Fe2+ in those solutions were found to be in the range of 42 to 62 pg ml-1. Based on the analytical results, this chemiluminescence system with the PDMS cell was reproducible, resistant to HF, had less sample consumption and waste generation, and was sensitive enough to apply to the semiconductor industry as an on-line monitoring sensor. Although this chemiluminescence system does not have selectivity for each specific metal ion, it can be used as an on-line sensor to monitor the metal contamination level of Fe, Cu, Co, etc., which are major elements of concern in the semiconductor manufacturing process.
The spectrophotometric determination of Cu(II) with an anthraquinone derivative (Alizarin Red S) has been investigated. The experimental conditions, such as the pH of the sample and concentration of ligand, were optimized. This method is simple and sensitive for determination of Cu(II) ion. The interfering effects of diverse ions were investigated. Copper ion was determined by measuring the absorbance of the Cu(II)-ARS complex at 510 nm. Beer's law was obeyed over the concentration range of 0.011 - 0.320 mmol dm-3 and the detection limit (S/N = 3) was 0.038 µg cm-3. The relative standard deviation at 20 µg cm-3 was 1.02% (n = 5). The method was applied for real samples.
A novel flow injection chemiluminescence (CL) method has been developed for the determination of three metal ions, namely Fe2+, Fe3+ and Cr3+, based on the second CL (SCL) signal of the mixture of luminal with KMnO4 in a sodium hydroxide medium by the catalysis of Fe2+, Fe3+ or Cr3+. The possible CL mechanism of the systems, the influencing factors, and the optimum conditions for the reactions were investigated based upon the kinetic curve of the CL reaction, CL spectra, UV-visible spectra and some other experiments. Under the optimum conditions, the SCL intensity was directly proportional to the concentration of these metal ions in solution in the range of 0.10 - 100.00 mg l-1 for Fe2+, 0.50 - 7.50 and 7.50 - 200.00 mg l-1 for Fe3+, 0.01 - 0.25 and 0.25 - 10.00 mg l-1 for Cr3+. The detection limits (3 σ/s) were 9.87 × 10-6 g l-1, 2.71 × 10-6 g l-1 and 5.25 × 10-7 g l-1 for Fe2+, Fe3+ and Cr3+, respectively.
A new chromogenic reagent, 5-(2-hydroxy-5-nitrophenylazo)thiorhodanine (HNATR) was synthesized. A highly sensitive, selective and rapid method for the determination µg l-1 level of Au(III) based on the rapid reaction of Au(III) with HNATR and the solid phase extraction of the colored complex with a reversed phase polymer-based C18 cartridge have been developed. The HNATR reacted with Au(III) to form a red complex of a molar ratio 1:2 (Au(III) to HNATR) in the presence of 0.05 - 0.5 mol l-1 of phosphoric acid solution and emulsifier-OP medium. This complex was enriched by the solid phase extraction with a polymer-based C18 cartridge. The enrichment factor of 100 was achieved. The molar absorptivity of the complex is 1.37 × 105 l mol-1 cm-1 at 520 nm in the measured solution. The system obeys Beer's law in the range of 0.01 - 3 µg ml-1. The relative standard deviation for eleven replicates sample of 0.5 µg l-1 level is 2.18%. The detection limit, based on the three times of standard deviation is 0.02 µg l-1 in the original sample. This method was applied to the determination of gold in water and ore with good results.
This study examined the concentration (mg/g) of trans polyunsaturated fatty acid (TPFA) in five soybean oil brands by gas-liquid chromatography. Tricosanoic acid methyl ester was used as the internal standard. All samples analyzed presented trans 18:2 fatty and trans 18:3 acids in detectable amounts. The concentration of TPFA ranged from 5.8 to 30.2 mg/g, with a mean concentration value of 18.4 mg/g. Trans 18:3 fatty acids had the highest TPFA group concentrations, which ranged from 3.9 to 16.3 mg/g. The main isomer of this group presented the 9c, 12c, 15t configuration. For trans 18:2 fatty acids, concentrations ranged from 1.9 to 14.0 mg/g with a mean value of 8.1 mg/g. Alpha-linolenic acid (all cis) concentrations ranged from 30.7 to 60.6 mg/g and their degree of isomerization ranged from 6.0 to 31.5, indicating that the deodorization process varies from one producer to another. From per capita consumption of soybean oil brands in Brazil and their TPFA concentrations, it is possible to conclude that their contribution to the average TPFA intake per person in Brazil is 0.4 g/d.
The cloud-point methodology was successfully employed for the preconcentration of heavy metal cations at trace levels from aqueous samples prior to flame atomic absorption spectrometry (FAAS). Cations were taken into a complex with 8-quinolinol in an aqueous non-ionic surfactant, Triton X-114, medium and concentrated in the surfactant rich phase by bringing the solution to the cloud-point temperature. The preconcentration of only 100 mL of the solution with 1% Triton X-114 and 10-3 M 8-quinolinol at pH 7.0 gave a preconcentration factor higher than 100 for most cations. Under these conditions, the detection limits of the cloud-point extraction-FAAS system were 0.8 - 15 µg/L.
Three saponins were extracted and isolated from starfish by reversed-phase high performance liquid chromatography (HPLC), and analyzed by fast atom bombardment mass spectrometry (FAB-MS). Their molecular weight information could be obtained by the presence of abundant [M+Na]+ ions and weak [M+H]+ ions in FAB-MS spectra. Moreover, high resolution mass measurements of their [M+Na]+ ions were performed at the resolution of 10000 to elucidate the element composition of extracted saponins. The collision-induced dissociation (CID) of sodium-adducted molecules [M+Na]+ yielded diverse product ions via dissociated processes. In the collision-induced dissociation (CID)-MS/MS analysis of [M+Na]+ ion, the sulfate-containing saponins produced characteristic ions such as SO4Na+, [NaHSO4+Na]+, [M+Na—sugar]+ and [M+Na—2sugar]+ ions, whereas the sulfate-free compound showed characteristic ions produced by cleavage of sugar moiety and side chain of aglycone. The fragmentation patterns could provide information on the linkage position of sugar groups in aglycone and sulfate groups.
Silicon is the second-most abundant element on the surface of the earth, and has been considered important for plant growth and development. As for its role in enhanced plant disease resistance, silicon has been reported to reinforce the physical barrier against the penetration and colonization of pathogens. Rice leaves of silicon-treated plants and control plants at the eight- and twelve-leaf growth stages were analyzed by 29Si solid-state nuclear magnetic resonance spectroscopy to characterize the silicon-induced, cell wall fortification of rice leaves, which demonstrated an ability to counter a pathogen attack.