Particles accumulated in a coupled acoustic-gravity field, in which the base-material of a particle determines the equilibrium aggregation positions, are eluted from a separation channel by an orthogonal laminar flow. Elution times are controllable by changing the intensity and frequency of the ultrasonic waves.
The surface of a gold (Au) disk electrode was modified with a self-assembled monolayer consisting of phenylboronic acid moiety to fabricate a voltammetric sensor sensitive to sugars. The modified Au electrode exhibited a voltammetric response to sugars in the presence of Fe(CN)63- ion in the sample solution at neutral pH. The peak current of the cyclic voltammograms decreased depending on the type and concentration of sugars. The dynamic range of the electrode is 3 - 100 mM for glucose and mannose and 1 - 30 mM for fructose. The sugar sensor can be used repeatedly after rinsing in 10 mM acetate buffer (pH 4.5).
Due to recent significant enhancement of computer performance as well as computational techniques, molecular modeling and molecular simulations using computational chemistry can be achieved at the level of practical applications. Even in solvent extraction, the application of computational chemistry to simulations of extraction processes and the molecular design of high-performance extracting agents have gradually been increasing during the last decade. With combining the quantitative structure-property relationship between the molecule properties calculated by the computational chemistry methods and the thermodynamic properties obtained from experiments, researchers can precisely predict the next-generation of extracting agents and novel extraction processes. In this review, the concept of computational chemistry, such as molecular mechanics, molecular orbitals and molecular dynamics calculations, frequently used in the filed of solvent extraction, are outlined. Our systematic research on the solvent-extraction process utilizing MM, MO and MD calculations is also presented.
The development during the last 15 years and the state-of-the-art in the analysis of bulk steroid hormone drugs and hormone-like structures and pharmaceutical formulations made thereof are summarized. Other steroids (sterols, bile acids, cardiac glycosides, vitamins D) as well as biological-clinical aspects and pharmacokinetic and metabolic studies are excluded from this review. The state-of-the-art is summarized based on comparisons of monographs in the latest editions of the European Pharmacopoeia, United States Pharmacopoeia and the Japanese Pharmacopoeia. This is followed by sections dealing with new developments in the methodology for the fields of spectroscopic and spectrophotometric, chromatographic, electrophoretic and hyphenated techniques as well electroanalytical methods. The review is terminated by two problem-oriented sections: examples on impurity and degradation profiling as well as enantiomeric analysis.
Polystyrol microchannel-microheater chips were fabricated on the basis of imprinting and photolithography techniques. The solution (i.e., methanol) temperature in the vicinity of the microheater (width = 100 or 200 µm and length = 100 µm) integrated in the channel (width = 100 µm and depth = 20 µm) was evaluated on the basis of the temperature-dependent fluorescence lifetime of Rhodamine B as a function of a flow rate and the voltage applied to the heater. The study demonstrated that the fabricated chip acted certainly as a microheater. The chip was then applied to the thermal reaction between benzaldehyde and malononitrile in methanol. Under optimum conditions, benzilidenemalononitrile as the product of the reaction was obtained in a 96% yield with the reaction time of 84 s.
We developed a method for the evaluation of the partition coefficients (Koc) of hexachlorobenzene (HCB) and 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin (HpCDD) into humic substances (HSs) by using solid-phase microextraction (SPME). In the aqueous solution containing HCB or HpCDD and HS, the unbound species of HCB or HpCDD were accumulated on the SPME fiber. Subsequently, HCB or HpCDD on the SPME fiber was directly analyzed by GC-ECD. When the concentration of organic carbon in HS ([OC]) was plotted against the ratio of [HCB] or [HpCDD] in the absence of HS to that in the presence of HS, linear relationships were observed. The slope of the line corresponded to the Koc value. The log Koc values for HCB and HpCDD evaluated were in the ranges of 3.9 - 4.9 and 5.9 - 7.2, respectively. These values were the same order as those in the literature, which were evaluated by other methods (e.g., solubility enhancement, solid-phase extraction and dialysis). The relative standard deviations of the log Koc values evaluated in this study were within 5%.
A microwave-assisted extraction (MAE) technique for the determination of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in marine sediment samples has been investigated. The analytes were extracted under different treatment conditions, such as temperature, time and extraction solvent. They were quantified by an isotopedilution method, and the observed concentrations and recovery yields obtained under different conditions were compared. The results of a comparison between this MAE and other extraction techniques, such as pressurized fluid extraction, saponification, sonication, and Soxhlet extraction, are also given in this report. The techniques gave comparable results with the values obtained by other extraction techniques and the certified values in the samples. However, the observed concentration values of mono- and dichlorinated biphenyls varied depending on the extraction temperature.
A single, rapid flow-through optosensor spectrofluorometric system is proposed for the determination of diphenhydramine in different pharmaceutical preparations. This sensor was developed in conjunction with a monochannel flow-injection analysis system with fluorometric solid-phase transduction. Diphenhydramine was directly injected into a carrier stream of ethanol/water, 50% (v:v), and transitorily retained on a sorption gel Sephadex G-15 placed in the detection area into the cell. The determination was carried out without any derivatization reaction by directly measuring the intrinsic fluorescence of the analyte and using the peak height as an analytical signal. The chemical and instrumental variables were optimized, and the influence of some foreign substances that can be found in typical pharmaceutical samples containing diphenhydramine was also investigated. Diphenhydramine could be determined in the concentration ranges of 0.5 - 8 µg ml-1 and 0.1 - 1.2 µg ml-1 with detection limits of 0.088 and 0.019 µg ml-1 at sampling rates of 30 and 19 h-1 for 200 and 800 µl of the sample volume, respectively.
[5,10,15,20-Tetrakis(4-N,N-dimethylaminobenzene)porphyrinato]Mn(III) acetate (MnTDPAc) was applied as an ionophore for an iodide-selective PVC membrane electrode. The influences of the membrane composition, pH of the test solution and foreign ions on the electrode performance were investigated. The sensor exhibited not only excellent selectivity to iodide ion compared to Cl- and lipophilic anions such as ClO4- and salicylate, but also a Nernstian response with a slope of -59.4 ± 1.2 mV per decade for iodide ions over a wide concentration range from 1.0 × 10-2 to 7.5 × 10-6 M at 25°C. The potentiometric response was independent of the pH of the solution in the pH range of 2 - 8. The electrode could be used for at least 2 months without any considerable divergence in the potential. Good selectivity for iodide ion, a very short response time, simple preparation and relatively long-term stability were the silent characteristics of this electrode. It was successfully used as an indicator electrode in the potentiometric titration of iodide ions, and also in the determination of iodide from seawater samples and drug formulations.
A PVC membrane incorporating p-tert-butyl calixcrown with imine units as an ionophore was prepared and used in an ion-selective electrode for the determination of mercury(II) ions. An electrode based on this ionophore showed a good potentiometric response for mercury(II) ions over a wide concentration range of 5.0 × 10-5 - 1.0 × 10-1 M with a near-Nernstian slope of 27.3 mV per decade. The detection limit of the electrode was 2.24 × 10-5 M and the electrode worked well in the pH range of 1.3 - 4.0. The electrode showed a short response time of less than 20 s. The electrode also showed better selectivity for mercury(II) ions over many of the alkali (Na+, -1.69; K+, -1.54), alkaline-earth (Ca2+, 3.30; Ba2+, -3.32), and heavy metal ions (Co2+, -3.67; Ni2+, -3.43; Pb2+, -3.31; Fe3+, -1.82). Ag+ ion was found to be the strongest interfering ion. Also, sharp end points were obtained when the sensor was used as an indicator electrode for the potentiometric titration of mercury(II) ions with iodide and dichromate ions.
A novel membrane coated platinum-wire electrode (MCPWE) based on N,N′-bis(2-thienylmethylene)-1,2-diaminobenzene (BTMD) for highly selective determination of Ag+ ion has been developed. The influences of membrane composition and pH on the potentiometric responses of electrode were investigated. The potentiometric responses are independent of the pH of the test solution in the range of 5.0 - 9.0. The electrode shows a linear response for Ag+ ion over the concentration range of 1.0 × 10-6 to 1.0 × 10-1 M with a lower detection limit of 6.0 × 10-7 M. The electrode possesses a Nernstian slope of 59.7 mV decade-1 and a fast response time of ≤ 17 s and can be used for at least 2 months without any observable deviation. The proposed electrode displayed very good selectivity for Ag+ ion with respect to NH4+ and alkali, alkaline earth and some common transition metal ions. The practical utility of the electrode has been demonstrated by its use as the indicator electrode in the potentiometric titration of an AgNO3 solution with a NaI solution and in determination of the silver content of a developed radiological film.
An electrochemical method based on a single-wall carbon nanotubes (SWNTs) film-coated glassy carbon electrode (GCE) was described for the determination of tinidazole. In a 0.1 M Britton-Robinson buffer with a pH of 10.0, tinidazole yields a very sensitive and well-defined reduction peak at -0.78 V (vs. SCE) on a SWNTs-modified GCE. Compared with that on a bare GCE, the reduction peak of tinidazole increases significantly on the modified GCE. Thus, all of the experimental parameters were optimized and a sensitive voltammetric method is proposed for tinidazole determination. It is found that the reduction peak current is proportional to the concentration of tinidazole over the range from 5 × 10-8 to 4 × 10-5 M, and that the detection limit is 1 × 10-8 M at 3 min open-circuit accumulation. This new analysis method was demonstrated with tinidazole drugs.
A Nafion-modified glassy carbon electrode incorporated with tobramycin for the voltammetric stripping determination of Cu2+ has been explored. The electrode was fabricated by tobramycin containing Nafion on the glassy carbon electrode surface. The modified electrode exhibited a significantly increased sensitivity and selectivity for Cu2+ compared with a bare glassy carbon electrode and the Nafion modified electrode. Cu2+ was accumulated in HAc-NaAc buffer (pH 4.6) at a potential of -0.6 V (vs. SCE) for 300 s and then determined by differential pulse anodic stripping voltammetry. The effects of various parameters, such as the mass of Nafion, the concentration of tobramycin, the pH of the medium, the accumulation potential, the accumulation time and the scan rate, were investigated. Under the optimum conditions, a linear calibration graph was obtained in the concentration range of 1.0 × 10-9 to 5.0 × 10-7 mol l-1 with a correlation coefficient of 0.9971. The relative standard deviations for eight successive determinations were 4.3 and 2.9% for 1.0 × 10-8 and 2.0 × 10-7 mol l-1 Cu2+, respectively. The detection limit (three times signal to noise) was 5.0 × 10-10 mol l-1. A study of interfering substances was also performed, and the method was applied to the direct determination of copper in water samples, and also in analytical reagent-grade salts with satisfactory results.
Based on a flow-injection spectrophotometry, an automatic analytical method for determination of ppb-level chloride-ion has been established. By use of this method, a novel FIA method for the determination of SBAER performance has also been developed. In this paper, the effects of concentration, dosage, and flow rate of the regenerant on BEC of SBAER were first investigated dynamically by the FIA method. In addition, the flow rate of the sample water and the temperature of the ion exchange resin were also examined. The optimum conditions were obtained: the volume of the regenerant (sodium hydroxide) was 50 mL (0.15 g resin), and its concentration was 3% (w/v); the volumetric flow rates of the regenerant and the sample water were 0.5 ml/min (4.3 m/h) and 1.5 ml/min (13 m/h), respectively. The exchanging temperature was 25 ± 5°C. The method is characterized by the use of a micro resin-column, shorter testing cycle, easy operation, and high reproducibility. The proposed method is approximately 30 times more efficient than the manual method, and it can be used for the exchange performance comparison of various SBAER.
A simple FI and two different SI systems have been investigated for the determination of paracetamol by employing a simple reagent for a nitrosation reaction. It is based on the on-line nitrosation of paracetamol with sodium nitrite in an acidic medium. The formed nitroso derivative species reacts further with sodium hydroxide to convert it to a more stable compound. The yellow product is continuously monitored at 430 nm. The FI system is very simple and cost effective for fast manual operation (60 injections/h; y = 0.268x + 44.314, r2 = 0.9910 for 400 - 1000 mg/l and y = 0.1687x + 145.72, r2 = 0.9970 for 1000 - 2500 mg/l). The two SI systems with different components and configurations are automated and optimized for the conditions for which no extra dilution is to be required for sample handling: one with a syringe pump and two selection valves (60 samples/h; y = 0.1488x - 4.7297, r2 = 0.9946 for 400 - 1000 mg/l and y = 0.0858x + 63.933, r2 = 0.9849 for 1000 - 2500 mg/l); the other is simpler and more cost-effective, with an autoburette and only one selection valve (15 samples/h; y = 0.0072x + 1.1467, r2 = 0.9977 for 200 - 1000 mg/l and y = 0.0028x + 5.4699, r2 = 0.9879 for 1000 - 2500 mg/l). They have all been applied to assay paracetamol in pharmaceutical preparations. The obtained results agree with those by the US Pharmacopeia method.
A simultaneous extraction of Cr3+ and Cr6+ species in aqueous solution was developed. The extraction behaviors of ammonium pyrrolidinedithiocarbamate (APDC) for both Cr6+ and Cr3+ are carefully discussed in this report. X-ray diffraction and spectroscopic studies indicate that Cr6+ reacts with the ammonium pyrrolidinedithiocarbamate ligand to form two products, Cr(PDC)2(OPDC) and Cr(PDC)3, where OPDC represents an oxygen insertion between Cr and S atoms. A high concentration of APDC in the phthalate buffer under an elevated temperature (50°C) was applied in solvent extraction (SE) to increase the extraction efficiency of Cr3+, so that both Cr3+ and Cr6+ could be extracted by APDC simultaneously. The complex involving the oxygen insertion bonding Cr-O-S is separable from the normal Cr(PDC)3 complex chromatographically, thus allowing the quantification of Cr6+. The major product of Cr6+ has a structure of Cr(PDC)2(OPDC) and the minor product is Cr(PDC)3 with a ratio of Cr(PDC)2(OPDC)/Cr(PDC)3 being 8.5. The extraction conditions for Cr6+ and Cr3+ as well as the chromatographic separation of the complexes using highperformance liquid chromatography (HPLC) are reported. Potential applications for the chemical speciation of chromium by SE/HPLC in environmental aqueous solutions are also discussed.
Two new 4-aminoantipyrene chemically-immobilized silica gel phases: ii (N,N-donor) and iii (N,O-donor), were synthesized and characterized by IR and surface coverage determination. The latter was accomplished by thermal desorption and metal probe methods, giving 0.300 and 0.312 mmol g-1 for ii and 0.220 and 0.250 mmol g-1 for iii. Moreover, potentiometric titration provided a surface coverage of 0.323 mmol g-1 for ii. The metal capacity values in mmol g-1 of ii, iii and the active silica gel phase i for a series of di- and trivalent metal ions were determined at pH 1.0 - 6.7. Phase i showed the lowest values, while ii and iii reflected higher affinity toward most of the metal ions. The highest values were 0.300 for Hg(II)-ii and 0.220 mmol g-1 for Cd(II)-iii. Distribution coefficients (log Kd) were in the range of 3.57 - 4.76 for ii and 2.32 - 3.46 for iii, thus confirming certain selectivity characters of the solid extractors. The application of the phases as solid extractors and preconcentrators for some heavy metal ions is presented. Good percentage extraction and removal of 94 - 98 ± 4 - 6% of the spiked 1.000 µg ml-1 of Hg(II), Cd(II), Pb(II), Cu(II) and Zn(II) and good percentage recovery of 94 - 99 ± 3 - 6% of 50 ng ml-1 of these ions from tap water samples were obtained. Stability constants of H(I) and Cu(II) with ii for the two-phase mixture at 25°C and I = 0.1 (KCl) were determined potentiometrically. The pKa of ii are 5.6 and 8.4, while the log K values for CuHL and CuL (L = ii) are 6.3 and 5.8, respectively, leading to the determination of several analytical data for Cu(II)-ii.
The feasibility of using bis(Δ2-2-imidazolinyl)-5,5′-dioxime (H2L) for the selective extraction of iron(III) from aqueous solutions was investigated by employing an solvent-extraction technique. The extraction of iron(III) from an aqueous nitrate solution in the presence of metal ions, such as cobalt(II), copper(II) and nickel(II), was carried out using H2L in binary and multicomponent mixtures. Iron(III) extraction has been studied as a function of the pH, equilibrium time and extractant concentration. From the extracted complex species in the organic phase, iron(III) was stripped with 2 M HNO3, and later determined using atomic-absorption spectrometry. The extraction was found to significantly depend on the aqueous solution pH. The extraction of iron(III) with H2L increases with the pH value, reaching a maximum in the zone of pH 2.0, remaining constant between 2 and 3.5 and subsequently decreasing. The quantitative extraction of iron(III) with 5 × 10-3 M H2L in toluene is observed at pH 2.0. H2L was found to react with iron(III) to form ligand complex having a composition of 1:2 (Fe:H2L).
A method is described for the determination of volatile compounds in Magnolia bark using microwave-assisted extraction coupled to headspace solid-phase microextraction (MAE-HS-SPME), followed by gas chromatography with mass spectrometry (GC-MS). Parameters affecting the extraction efficiency, such as sampling time and temperature, microwave irradiation power and desorption time, were investigated to achieve the optimal conditions. The result obtained was compared with that of steam distillation; only small differences existed between these two methods. Therefore, the proposed method seems to be a feasible and relatively simple, fast and solvent-free procedure for identification of essential oils in Magnolia bark.
A method for the determination of phosphorylation sites in phosphoproteins based on column-switching high-performance liquid chromatography (HPLC) has been developed. The HPLC system consisted of a titania precolumn for the selective adsorption of phosphopeptides, an anion-exchange analytical column and a UV detector (215 nm). Rabbit muscle phosphorylase a (RPa) and porcine stomach pepsin (PSP) were tested as model phosphoproteins. After protease digestion, the resulting phosphopeptides were successfully isolated by column-switching HPLC. The phosphopeptide fractions were analyzed by electrospray ionization mass spectrometry with a positive or negative ion mode after purification by reversed-phase HPLC. Pseudo-molecular ion peaks corresponding to Gln-Ile-Ser(p)-Val-Arg (MW 681.7) and Glu-Ala-Thr-Ser(p)-Gln-Glu-Leu (MW 856.8) were detected from the tryptic digest of RPa and chymotryptic digest of PSP, respectively, which agreed with the theoretically expected phosphopeptide fragments.
Carbonyl compounds (aldehydes and ketones) are suspected to be among the chemical compounds responsible for Sick Building Syndrome and Multiple Chemical Sensitivities. A headspace gas chromatography/mass spectrometry (GC/MS) analysis for these compounds was developed using derivatization of the compounds into volatile derivatives with o-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBOA). For GC/MS detection, two ionization modes including electron impact ionization (EI) and negative chemical ionization (NCI) were compared. The NCI mode seemed to be better because of its higher selectivity and sensitivity. This headspace GC/MS (NCI mode) was employed as analysis for aldehydes and ketones in materials (fiber products, adhesives, and printed materials). Formaldehyde was detected in the range of N.D. (not detected) to 39 µg/g; acetaldehyde, N.D. to 4.1 µg/g; propionaldehyde, N.D. to 1.0 µg/g; n-butyraldehyde, N.D. to 0.10 µg/g; and acetone, N.D. to 3.1 µg/g in the samples analyzed.
Techniques to determine the producing country of Welsh onions (Allium fistulosum L.) were developed by using 216 samples from Japan and from Anchu Shandgon, Shanghai and Amoy Fjian in China. Twelve elements (Na, P, K, Ca, Mg, Mn, Fe, Cu, Zn, Sr, Ba, Al, Co, Ni, Rb, Mo, Cd, Cs, La, Ce, Tl and Pb) contained in Welsh onions were determined. In order to determining whether Welsh onions originate in Japan or in China, linear discriminant analysis (LDA) and soft independent modeling of class analogy (SIMCA) were performed, using concentrations of 20 elements excluding Al and Pb in 22 elements. In LDA for two-group discrimination modeled on Welsh onions from Japan and China, 103 samples used for modeling were classified 95% correctly, and 89 other samples were predicted 94% correctly. As the average of predictions by SIMCA modeled on samples selected by 10 times of random selections, 192 samples, including the 103 samples used for modeling, were predicted 96% correctly. In discriminations by combined LDA and SIMCA, all 81 samples produced in Japan were correctly judged to be Japanese ones, and only 8 samples out of 111 samples produced in China were not correctly judged to be Chinese ones.
A specterophotometric method for simultaneous determination of aniline and cyclohexylamine using principal component artificial neural networks is proposed. This method is based on the reactions involving aniline and/or cyclohexylamine, with bis(acetylacetoneethylendiamine)tributylphosphine cobalt(III) perchlorate as a complexing reagent. A nonionic surfactant, Triton X-100, was used for dissolving the complexes and intensifying the signals. The absorption data were based on the spectra registered in the range of 350 - 550 nm. An artificial neural network consisting of three layers of nodes was trained by applying a back-propagation learning rule. Sigmoid transfer functions were used in the hidden and output layers to facilitate nonlinear calibration. The predictive ability of artificial neural networks was examined for the determination of aniline and cyclohexylamine in synthetic mixtures.
Silver ion can perturb the Belousov-Zhabotinskii (B-Z) oscillating chemical reaction. Therefore, the B-Z oscillating system was applied in the determination of silver ion by using a platinum wire as an indicator electrode in the potentiometric method. The amplitude of the potentiometric oscillation increased linearly in proportion to [Ag+] in the range of 9.42 × 10-6 M to 2.54 × 10-4 M, with a correlation coefficient of 0.999 under the optimum conditions. The obtained LOD (2 σ) was 8.85 × 10-6 M and the relative standard deviation (RSD) for five measurements of 1 × 10-4 M silver ion was 5%. The influence of some potentially interference was also investigated.