PM10 samples were collected at an urban site of Nagoya City during September, 2003, to August, 2004, and annual variations of the concentrations of the elements in PM10 samples were examined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The annual concentration variations of ca. 30 elements in ambient air were in the range from sub-ng m-3 to several µg m-3. From an evaluation by the enrichment factors of the elements, elements such as Al, Ca, Fe, Mg, Ti, Mn, Ba, Sr, Ce, La, Nd, Co, Cs, and Pr, in PM10 samples were found to have originated mostly from natural sources, while the elements such as S, Zn, Pb, Cu, Ni, Sb, Sn, Cd, Bi, W, Tl, and In originated from anthropogenic emission sources. Furthermore, in seasonal variations of the elemental concentrations of PM10 samples in ambient air, the elements originated mostly from natural sources provided significantly high concentrations in spring during the “Kosa” period (the dust season from March to May). On the other hand, the elements mainly from anthropogenic emission sources provided relatively higher concentrations in autumn and winter, which may be explained by the fact that the urban atmospheric structure is stabilized by the temperature-inversion layer formed over the city in those seasons. In addition, all of the elements provided significantly low concentrations in the summer, due to the dilution effect of the oceanic winds as well as due to the convection of air mass up to the high levels.
A flow-injection procedure combining electrolytic sample decomposition and inductively coupled plasma atomic emission spectrometry (ICP-AES) is proposed in order to rapidly determine the content of silicon in high-silicon electrical steel. This system is characterized by sample decomposition through electrolysis directly coupled to ICP-AES. A steel sample is dissolved by electrolysis using a 6 mol L-1 HCl solution as an electrolyte with a flow rate of 5 mL min-1; the electrolyte containing a dissolved sample is subsequently introduced into ICP-AES via a nebulizer. The effects of the electrolysis current and the temperature on the decomposition of the sample were studied. Samples were electrolyzed under the condition of a 1.5 A constant current, at room temperature (25°C) to avoid the hydrolysis of silicon to precipitate. Comparing the analytical results of steel samples obtained by this analytical system with those obtained by the gravimetric method, determined values agreed well quantitatively. The RSD of silicon at approximately 3% was 0.3% (n = 6).
This paper reports the determination of ulifloxacin (UFX) by terbium-sensitized fluorescence using a second-order scattering method. UFX and Tb(III) ion form a fluorescence complex in aqueous solution, and its maximum excitation and emission wavelengths are located at 273 and 545 nm, respectively. In optimum conditions, the relative intensity at 545 nm has a linear relationship to the concentration of UFX in the range of 2.0 × 10-8 - 1.0 × 10-5 mol L-1 and the detection limit is 3.9 × 10-9 mol L-1. The proposed method was applied to the determination of UFX in spiked human serum and urine satisfactorily. The luminescence property of UFX is also discussed by comparing with norfloxacin (NFLX) and ofloxacin (OFLX).
This paper proposes a new and effective approach for the quantitative analysis of sulpiride, a significant antipsychotic drug, in human urine samples by the incorporation of excitation-emission matrix (EEM) fluorescence and second-order calibration methodologies based on the alternating fitting residue (AFR) and self-weighted alternating trilinear decomposition (SWATLD) algorithms. With the application of a second-order advantage, the proposed strategy could be utilized for a direct concentration determination of sulpiride with a simple pretreatment step, even in the presence of serious natural fluorescent interferences. The average recoveries of sulpiride in complex urine samples by using AFR and SWATLD with an estimated component number of three were 101.2 ± 2.1 and 94.4 ± 0.7%, respectively. Moreover, the accuracy of the two algorithms was also evaluated through elliptical joint confidence region (EJCR) tests as well as the figures of merit, such as sensitivity (SEN), selectivity (SEL) and limit of detection (LOD). The experimental results demonstrated that both algorithms, as promising quantitative alternatives, have been satisfactorily applied to the determination of sulpiride in human urine, but the performance of AFR was slightly better than that of SWATLD.
A sensitive flow-injection (FI) procedure with spectrophotometric detection in a micellar medium is proposed for the determination of novalgin. The method is based on the instantaneous formation of a red-orange product (λmax = 510 nm) after the reaction between novalgin and p-dimethylaminocinnamaldehyde (p-DAC) in a dilute acid medium. The sensitivity of this reaction was increased by a factor of 5.6 in the presence of sodium dodecyl sulfate (SDS). Experimental design methodologies were used to optimize the chemical and FI variables. The calibration curve was linear in the range of 1.45 × 10-6 to 2.90 × 10-5 mol L-1 with an excellent correlation coefficient (r = 0.9999). The detection limit was 1.31 × 10-7 mol L-1 (n = 20, RSD = 2.0%). No interferences were observed from the common excipients. The results obtained by the proposed method were favorably compared with those given by the iodometric reference method at 95% confidence level.
Thermostated micro planar chromatography was applied for systematic separation studies of C60 and C70 fullerenes using n-alkanes as mobile phases on TLC and HPTLC plates coated with polyamide, silica gel, aluminum oxide as well as two types of octadecylsilica (C18) sorbents. Retention data were collected at constant temperature at 20°C (±0.05°C) using an unsaturated chamber mode with an eluent, such as n-pentane, n-hexane and n-heptane. The separation results under both saturated and unsaturated chamber modes for selected mobile/stationary phases were also examined, and several parameters, including separation factor (α) and resolution (RS), were compared with data obtained with high-performance liquid chromatography conditions. Interestingly, C60/C70 fullerenes separation performed on HPTLC plates with a developing distance of 45 mm was better for those observed on a 25 cm length analytical HPLC column under similar conditions to that on carbon coverage of the stationary phase, n-hexane as the mobile phase and separation temperature (RS = 1.84 and 1.68 for HPTLC, and HPLC, respectively). Moreover the advantage of the planar chromatographic separation of fullerenes studied is a short elution time of less than 6 min. Furthermore, the reported separation protocol shows a capability for the evaluation of fullerenes quantity in commercial samples.
Temperature and pressure dependences of the 129Xe NMR chemical shift and the signal intensity have been investigated using ZSM-5 as an adsorbent under routine conditions without using any high-pressure or especially high-temperature facilities. The use of a rigorously shielded system and a calibration sample for the signal intensity was found to be valuable to obtain reliable data about the chemical shift and the signal intensity. The 129Xe NMR data obtained between 0.05 and 1.5 atm and from 24 to 80°C were analyzed based on the Dubinin-Radushkevich equation as well as the Langmuir type equation. In both analyses, chemical shift data succeeded only partially in providing the profile of adsorption, such as energetic aspects, surface area, saturated amount of Xe adsorption and specific parameters of 129Xe chemical shift. It was shown that the reliable total analysis was achieved when the chemical shift data were used together with the intensity data. Such an analysis of the chemical shift data, aided by the intensity data, will be useful in performing nano-material analysis on 129Xe NMR without invoking the traditional methodology of gravimetric or volumetric adsorption experiments.
Ga(III), In(III) and Tl(III) ions in the presence of different sulfate salts have been successfully separated using 1-(3,4-dihydroxybenzaldehyde)-2-acetylpyridiniumchloride hydrazone (DAPCH) loaded on Duolite C20 in batch and column modes. The obtained modified resin as well as the metal complexes was characterized by elemental analysis and infrared spectra. The extraction isotherms were determined at different pH values. Ga(III) and In(III) are sorbed from aqueous solution at pH 2.5 - 3.0 while Tl(III) is sorbed at 2.0. The stripping of the adsorbed ions can be carried out using different concentrations of HCl as eluent. The saturation sorption capacities of Ga(III), In(III) and Tl(III) were 0.82, 0.96 and 0.44 mmol g-1, where the preconcentration factors are 150, 150 and 100, respectively. The metal(III):Duolite C20-DAPCH ratio was 1:2 for Tl(III) and 1:1 for In(III) and Ga(III). The loaded resin can be regenerated for at least 50 cycles. The utility of the modified resin was tested in aqueous samples and the results show an RSD value of < 5% reflecting their accuracy and reproducibility.
Poly(dimethylsiloxane) microfluidic channels alternately modified by poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate) were successfully used to separate uric acid and ascorbic acid. Results show that uric acid and ascorbic acid can be well separated and detected simultaneously in modified microchips coupled with in-channel electrochemical detection. Under the optimal conditions, the linear ranges of uric acid and ascorbic acid were both from 25 to 600 µM, with the correlation coefficients of 0.997 and 0.996, respectively. The detection limits were 8 µM for uric acid and 5 µM for ascorbic acid. Factors influencing separation and detection, including buffer solution, detection potential and separation voltage, were investigated and optimized. In addition, the dependences of the current response on sensitivity and reproducibility were studied, and the stability of the device was also evaluated in detail. This method was successfully used to determine uric acid and ascorbic acid in human urine.
Messenger RNA (mRNA) poly(A)+RNA (from mouse kidney) was immobilized on a N-hydroxysuccinimide(NHS)-activated carboxylic acid modified electrode prepared by the treatment of a gold electrode with 3,3′-dithiodipropionic acid, followed by NHS and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC). An electrochemical measurement using this mRNA electrode was carried out in an electrolyte containing ferrocenylnaphthalene diimide (1), and showed an electrochemical signal based on 1 concentrated on immobilized mRNA. After treating this electrode with water containing varied amounts of ribonuclease A (RNase A), the current peak based on 1 decreased with increasing in the amount of RNase A with a linear correlation in the range of 0.2 - 10 pg of RNase A.
Seed-mediated growth of gold nanoparticles on glassy carbon (GC) surfaces was developed. The field emission scanning electron microscopy (FE-SEM) and electrochemical characterization confirmed the effective attachment of gold nanoparticles on GC surface with such a wet-chemical method. The as-prepared gold nanoparticles attached glassy carbon electrode (Au/GCE) presented excellent catalytic ability toward the oxidation of nitrite. Compared with bare GCE and planar gold electrode, the Au/GCE obviously decreased the overpotential of nitrite oxidation and improved the peak current. The catalytic current was found to be linearly proportional to the nitrite concentration in the range of 1 × 10-5 - 5 × 10-3 M, with a detection limit of 2.4 × 10-6 M. The Au/GCE was successfully applied to the electrochemical determination of nitrite in a real wastewater sample, showing excellent stability and anti-interference ability.
The extraction and separation of lanthanides have been investigated using CHON-type extractants, which are composed of only C, H, O, and N atoms. N,N-Dioctyldiglycol amic acid (DODGAA) showed high extraction and separation performances for heavier lanthanides compared with typical CHON-type extractants. On the other hand, N,N,N′,N′-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN) provided an unprecedentedly high selectivity for lighter lanthanides. Furthermore, it was found that the combination of DODGAA and TPEN under suitable conditions enabled the mutual separation of light, middle, and heavy lanthanides.
Chitosan resins modified with amino acids, such as glycine, valine, leucine, and serine, were synthesized for investigating the adsorption behavior of cationic and anionic species, and showed good abilities for the adsorption of trace elements in aquatic media as follows: glycine for lanthanoids at pH 7, leucine for molybdenum at pH 1 - 5, serine for uranium at pH 2 - 7, and amino acids for bismuth at pH 1 - 7. Cationic and anionic species could be adsorbed by a chelating mechanism and an anion-exchange mechanism.
A resin-phase extraction method has been optimized for the trace determination of tin(II) by ETAAS. Tin(II) was extracted on a finely divided anion exchange resin as the complex with ammonium pyrrolidinedithiocarbamate (APDC). The resin was collected on a membrane filter and then dispersed in 1.00 ml of 1 mol l-1 nitric acid containing 100 µg of Pd(II) and 60 µg of Ni(II). The resulting resin suspension was subjected to GFAAS. The proposed method was applied to the determination of tin(II) in hydrochloric acid.
We have applied the maximum entropy method (MEM) to the analysis of quasi-elastic laser scattering (QELS) spectra and have established a technique for determining capillary wave frequencies with a higher time resolution than that of the conventional procedure. Although the QELS method has an advantage in time resolution over mechanical methods, it requires the averaging of at least 20 - 100 power spectra for determining capillary wave frequencies. We find that the MEM analysis markedly improves the S/N ratio of the power spectra, and that averaging the spectra is not necessary for determining the capillary wave frequency, i.e., it can be estimated from one power spectrum. The time resolution of the QELS attains the theoretical limit by using MEM analysis.
We have developed a rapid immunoglobulin G (IgG) and a human serum albumin (HSA) depletion protocol. We depleted both HSA and IgG (> 97%) separately, and in a single procedure. The method is specific and reproducible (RSD < 1.0%), and substantially lowered the detection limit of prostate-specific antigen, a prostate cancer biomarker. The method can be applied to other biomarkers and proteomic studies. Interestingly, the depletion of HSA might not be blankly as beneficial as widely portrayed. Our study suggests the depletion of IgG to be more beneficial than albumin depletion.
Continuous flow analysis using an elemental analyzer interfaced with an isotope ratio mass spectrometer (EA-IRMS) is faster and requires much less material than conventional analytical methods. Although using an EA-IRMS is simple and fast, accurate calibration strongly depends on matching sample and reference peak heights by adjusting the sample weight. This paper describes a new modification for calibration using only the major ion beam intensity (nA) without weighing each sample or increasing the number of reference materials.