Forgot your password?
New user?
New Window Opens on the Secret Life of Microbes: Scientists Develop First Microbial Profiles of Ecosystems
CAS announces the release of SciFinder Scholar for Mac OS X
Press Releases
Press Releases
| Check out our New Publishers' Select for Free Articles |
Analytical and Bioanalytical Chemistry (v.369, #5)
Selectivity and specificity in analytical chemistry. General considerations and attempt of a definition and quantification by Klaus Danzer (pp. 397-402).
Selectivity and specificity are performance characteristics of analytical methods which are frequently used in analytical literature. In general, the terms are applied verbally and a quantification of selectivity and specificity is given rarely. Excepted are methods like chromatography and ISE sensoring which use individual quantities such as selectivity coefficients, indices and other parameters to characterize analytical procedures and systems. Here a proposal is given to characterize selectivity and specificity quantitatively by relative values in a range of 0 to 1 expressing so a certain degree of selectivity and specificity. By examples it will be shown that the derived quantities characterize analytical methods and problems in a plausible way.
On the effect of catalyst status in the quantitative determination of platinum in Pt-Sn/MgO materials by S. Recchia; Damiano Monticelli; Andrea Pozzi; Laura Rampazzi; Carlo Dossi (pp. 403-406).
The development of an analytical method for the determination of platinum in MgO based Pt/Sn catalysts is described. Electrothermal atomic absorption spectroscopy (ETAAS) was chosen because of its high sensitivity and robustness against spectral interferences. All the sources of chemical interferences were statistically analyzed and corrections were adopted for the presence of magnesium oxide support. The effectiveness of different mineralization procedures was critically evaluated as a function of the chemical of the solid catalyst. Microwave digestion allowed recovery of metal of 100% for all the catalysts analyzed and exhibited significant better precision values than other digestion methods, which could nevertheless be utilized under proper conditions in selected cases.
Analysis of sintered products of iron ore fines by flame atomic absorption spectrometry using a matrix modifier by P. Chattopadhyay; P. Datta; A. K. Jouhari (pp. 407-411).
A very precise and accurate method for chemical analysis of sintered products (from iron ore fines in “pot grate furnace”) is discussed. A matrix modifier/ buffer (a mixture of KCl, tartaric acid, HCl and H2SO4) is used to prevent interference of iron in the determination of calcium and magnesium by flame atomic absorption spectrometry. Also, an EDTA titration method is recommended for calcium and magnesium after separating iron in the form of mixed oxides by ammonia-ammonium chloride buffer. Statistical data for a series of experiments are presented and precision values are found to be comparable with those of conventional methods used for complex metallurgical products. For the majority of cases, the agreement between the two methods is extremely good. A slight deviation has been noted in a few samples which may be overcome by a more thorough sampling prior to analysis.
A comparison of phosphated and sulfated β-cyclodextrins as chiral selectors for capillary electrophoresis by E. G. Yanes; S. R. Gratz; R. M. C. Sutton; A. M. Stalcup (pp. 412-417).
The enantioseparation capabilities of three different functionalized β-cyclodextrins, two sulfated β-cyclodextrins with 4 and 15 nominal degrees of substitution and a phosphated β-cyclodextrin with 8 degrees of substitution, were compared. While anodic detection was used with both sulfated cyclodextrins, the phosphated cyclodextrin required cathodic detection suggesting either lower ionization of the phosphated cyclodextrin or generally lower affinity of the analytes for the phosphated cyclodextrin. The effects of several experimental parameters were evaluated with respect to enantioseparation. The degrees of substitution of the cyclodextrin, pH of the background electrolyte as well as the concentration of the functionalized β-cyclodextrin, each had a significant influence on the successful enantiomeric separation of the chiral drugs investigated.
Continuous preconcentration system for nitrate ions using anionic reverse osmosis tubes coupled to an ion chromatograph by Hisanori Kenmotsu; J.-M. Lin; Katsumi Uchiyama; Toshiyuki Hobo (pp. 418-421).
A continuous preconcentration system for nitrate ions was developed using cation exchange tubing made from Nafion perfluorosulfonic acid membrane. This method is based on ion exclusion effects and reverse osmosis phenomena. The system was evaluated by connecting it to an ion chromatograph. The concentration ratios could be increased by raising the pressures between the two sides of the cation exchange tubing. Twenty-fold concentration of nitrate ion was achieved when the pump pressure was 20 × 105 Pa. The relative standard deviations of the preconcentration ratio at four different pump pressures, 5, 10, 15 and 20 × 105 Pa were 1.2 ∼ 2.8% (n = 5).
Synthesis of glycosylated porphyrins as neutral ionophores for a berberine-sensitive electrode by X.-B. Zhang; C.-C. Guo; S.-H. Chen; G.-L. Shen; R.-Q. Yu (pp. 422-427).
For preparing a berberine-sensitive electrode, 5,10,15,20-tetrakis[2-(2,3,4,6-tetraacetyl-β-D-glucopyranosyl)-1-O-phenyl]porphyrin (T(o-glu)PPH2) was synthesized from the reaction of pyrrole with ortho-acetylglycosylated benzaldehyde by Lindsay’s method. The electrode based on T(o-glu)PPH2 with an optimized membrane composition exhibits Nernstian response to berberine in the concentration range 2.4 × 10–7–5.0 × 10–3 mol L–1, with a pH range from 3.9 to 10.2, and a fast response time of 30 s. The electrode shows fair selectivity towards berberine with respect to common co-existing species. T(o-glu)PPH2 shows better potentiometric response characteristics comparing to chloro[5,10,15,20-tetrakis[2-(2,3,4,6-tetraacetyl-β-D-glucopyranosyl)-1-O-phenyl]-porphinato]-manganese (MnT(o-glu)PPCl) and better selectivity towards berberine than tetraphenylporphyrin (TPPH2). The effect of the composition of the electrode membrane has been studied and the experimental conditions optimized. The contents of berberine in pharmaceutical tablets were determined by direct potentiometry and the results agreed with values obtained by the pharmacopoeia method.
Characterization of single-stranded DNA on chitosan-modified electrode and its application to the sequence-specific DNA detection by Chun Xu; Hong Cai; Qun Xu; Pingang He; Yuzhi Fang (pp. 428-432).
Single-strand DNA could bind with chitosan on a platinum electrode via forming a tight DNA-chitosan complex. The salt concentration of the ssDNA solution had an obvious effect on the surface coverage, the immobilization was remarkably reduced at high salt concentration. The sample ssDNA immobilized on the chitosan-modified electrode can hybridize efficiently with the complementary sequences and be successfully used for the sequence-specific DNA detection. The same results could be obtained using a gold or graphite electrode modified with chitosan. The stability of this electrode has been also discussed.
Voltammetric behavior of L-cysteine in the presence of CPB at a silver electrode by Baizhao Zeng; Faqiong Zhao (pp. 433-437).
The voltammetric behavior of L-cysteine at a silver electrode is described. L-Cysteine can be anodically accumulated at a silver electrode surface as a sparingly soluble silver salt; at more negative potentials, the insoluble compound is stripped cathodically yielding a small current peak at about –1.10 V (vs. SCE). In the presence of cetyl pyridine bromide (CPB), the stripping peak shifts slightly to a more negative potential, and the peak height increases significantly. Thus, the peak becomes more useful for the determination of L-cysteine. In contrast to other surfactants, CPB can improve the accumulation and stripping of L-cysteine obviously. The voltammetric behavior of cysteamine, 3-mercaptopropionic acid and homocysteine is discussed as well.
Continuous determination of chloroquine in plasma by laser-induced photochemical reaction and fluorescence by J. Amador-Hernández; J. M. Fernández-Romero; M. D. Luque de Castro (pp. 438-441).
A flow injection fluorimetric method is proposed for the determination of chloroquine based on the photochemical derivatisation in an alkaline medium of the analyte and fluorescence generation after irradiation with a pulsed Nd:YAG laser operated at 355 nm. Chemical, hydrodynamic and laser variables were studied in order to obtain the best conditions for quantification. A linear range from 25 to 600 μg/L was achieved, with a correlation coefficient of 0.997 (n = 8), an RSD of 4.3% (n = 11) and a detection limit of 8 μg/L (3σ). The sample throughput was 10 h–1. The method was successfully applied to the determination of chloroquine in human plasma. The increase of sensitivity with respect to the method based on monitoring the intrinsic fluorescence of chloroquine itself was 1.7 times.
Validated method for the determination of the novel organo-ruthenium anticancer drug NAMI-A in human biological fluids by Zeeman atomic absorption spectrometry by M. Crul; H. J. G. D. van den Bongard; M. M. Tibben; O. van Tellingen; G. Sava; J. H. M. Schellens; J. H. Beijnen (pp. 442-445).
NAMI-A is a novel ruthenium-containing experimental anticancer agent. We have developed and validated a rapid and sensitive analytical method to determine NAMI-A in human plasma, plasma ultrafiltrate and urine using atomic absorption spectrometry with Zeeman correction. The sample pretreatment procedure is straightforward, involving only dilution with an appropriate hydrochloric acid buffer-solution. Because the response signal of the spectrometer depended on the composition of the sample matrix, in particular on the amount of human plasma in the sample, all unknown samples were diluted to match the matrix composition in which the standard line was prepared (plasma-buffer 1 : 10 v/v). This procedure enabled the measurement of samples of different biological matrices in a single run. The validated range of determination was 1.1–220 μM NAMI-A for plasma and urine, and 0.22–44 μM for plasma ultrafiltrate. The lower limit of detection was 0.85 μM in plasma and urine and 0.17 μM in plasma ultrafiltrate. The lower limit of quantitation was 1.1 and 0.22 μM, respectively. The performance of the method, in terms of precision and accuracy, was according to the generally accepted criteria for validation of analytical methodologies. The applicability of the method was demonstrated in a patient who was treated in a pharmacokinetic phase I trial with intravenous NAMI-A.
Determination of tartaric acid in wines by FIA with tubular tartrate-selective electrodes by M. Goreti F. Sales; Carolina E. L. Amaral; C. M. Delerue Matos (pp. 446-450).
A flow injection analysis (FIA) system comprising a tartrate- (TAT) selective electrode has been developed for determination of tartaric acid in wines. Several electrodes constructed for this purpose had a PVC membrane with a complex of quaternary ammonium and TAT as anion exchanger, a phenol derivative as additive, and a more or less polar mediator solvent. Characterization of the electrodes showed behavior was best for membranes with o-nitrophenyl octyl ether as solvent. On injection of 500 μL into a phosphate buffer carrier (pH = 3.1; ionic strength 10–2 mol/L) flowing at 3 mL/min, the slope was 58.06 ± 0.6 with a lower limit of linear range of 5.0 × 10–4 mol/L TAT and R2 = 0.9989. The interference of several species, e.g. chloride, bromide, iodide, nitrate, gallic acid, tannin, sucrose, glucose, fructose, acetate, and citrate, was evaluated in terms of potentiometric selectivity coefficients. The Hofmeister series was followed for inorganic species and the most interfering organic ion was citrate. When red and white wines were analyzed and the results compared with those from an independent method they were found to be accurate, with relative standard deviations below 5.0%.
Ultrasound-assisted solubilization of trace and minor metals from plant tissue using ethylenediaminetetraacetic acid in alkaline medium by A. V. Filgueiras; I. Lavilla; C. Bendicho (pp. 451-456).
A simplified and fast sample pretreatment method based on ultrasound-assisted solubilization of metals from plant tissue with ethylenediaminetetraacetic acid in alkaline medium is described. Powdered unknown and certified plant samples (particle size < 50 μm) were slurried in the solubilization medium and subjected to high intensity ultrasonication by a probe ultrasonic processor (20 kHz, 100 W). Metal solubilization can be accomplished within 3 min using a 30% vibrational amplitude and 0.1 M EDTA at pH 10, the supernatant obtained upon centrifugation being used for analysis. The method is applied to several food plants with unknown metal contents and certified plant samples such as CRM GBW07605 tea leaves, BCR CRM 61 aquatic moss and BCR CRM 482 lichen, with good trueness and precision. Intensive treatments with concentrated acids involving total matrix decomposition can be avoided. Metal determination (Ca, Cd, Mg, Mn, Pb and Zn) in the alkaline extracts was carried out by flame and electrothermal atomic absorption spectrometry.
Quantification of carbohydrate structures in size fractionated aquatic humic substances by two-dimensional nuclear magnetic resonance by S. Haiber; H. Herzog; P. Burba; B. Gosciniak; J. Lambert (pp. 457-460).
Two-dimensional phase sensitive C,H correlation spectra were successfully applied to the quantification of carbohydrate substructures in aquatic humic substance (HS) fractions obtained by tangential flow multistage ultrafiltration (TFMSTUF) of a selected bog water HS (HO13, German Research Program DFG-ROSIG) as well as a river HS (Suwannee River Fulvic Acid Reference of the International Humic Substances Society, IHSS). It turns out that after size fractionation the HS samples give very well resolved C,H-correlation spectra which offer a great potential for substructure quantification. Details of the combined substructure quantification technique, novel in HS characterization, are presented. The results of the combined procedure point out that carbohydrate moieties predominantly occur in higher molecular mass fractions (> 10 kDa) of isolated HS.
Slurry sampling fluorination assisted electrothermal vaporization-inductively coupled plasma-atomic emission spectrometry for the direct determination of metal impurities in aluminium oxide ceramic powders by Tianyou Peng; Gang Chang; Lei Wang; Zucheng Jiang; Bin Hu (pp. 461-465).
A new analytical procedure for the direct determination of metal impurities (Cr, Cu, Fe and V) in aluminium oxide ceramic powders by slurry sampling fluorination assisted electrothermal vaporization-inductively coupled plasma-atomic emission spectrometry (ETV-ICP-AES) is reported. A polytetrafluoroethylene (PTFE) emulsion was used as a fluorinating reagent to promote the vaporization of impurity elements in aluminium oxide ceramic powders from the graphite tube. A vaporization stage with a long ramp time and a short hold time provided the possibility of temporal analyte-matrix separation. The experimental results indicated that a 10 μL 1% m/v slurry of aluminium oxide could be destroyed and vaporized completely with 600 μg PTFE under the selected conditions. Two aluminium oxide ceramic powder samples were used without any additional pretreatment. Analytical results obtained by using standard addition method with aqueous standard solution were checked by comparison of the results with pneumatic nebulization (PN)-ICP-AES based on the wet-chemical decomposition and analyte-matrix separation. The limits of detection (LODs) between 0.30 μg g–1 (Fe ) and 0.08 μg g–1 (Cu) were achieved, and, the repeatability of measurements was mainly better than 10%.
Simultaneous determination of Fe(II) and Fe(III) in waters by capillary isotachophoresis by Petr Praus; Markéta Blahutová (pp. 466-468).
An ITP method for the simultaneous determination of Fe(II) and Fe(III) in waters, based on separation of their EDTA and fluoride complexes, respectively, was developed. The leading electrolyte used consists of chlorides, La(III) as co-counter ion and is buffered with β-alanine to pH = 3.5. The terminating electrolyte contains caproic acid and L-histidine (pH = 4.5). The method was validated and tested with samples of artificial, ground and treated water with good results, comparable to those obtained by other analytical techniques. Fe(II) and Fe(III) up to 20 mg/L were measured with an RSD = 1.4–1.5% and detection and determination limits of 0.8–0.9 and 3.0–3.5 mg/L, respectively. The ITP method can be recommended for routine utilization in hydroanalytical laboratories.