Flow velocity profiles of micro counter-current flow of aqueous and butylacetate phases in a microchannel having a width of 100 µm were measured by micro particle image velocimetry. In order to analyze the hydrodynamic characteristics of the counter-current flow, we derived a simple analytical model for the velocity profile. When flow rates of the aqueous and organic phases were 0.2 and 0.1 µl/min, the model agreed well with the experimental results. Predictions about the velocity profile will contribute to estimation of the extraction efficiency in the co-current and counter-current extraction process.
In this study, a rapid colorimetric method for arsenic detection was developed. Different reagents containing magnesium turnings in combination with a series of acids were tested for arsine generation. The arsine was then allowed to react with auric chloride on Whatman filter paper No. 3, which in turn changed color. The detection time and detection limit were measured for each acid. Oxalic acid was found to be the most appropriate acid among all the acids used for detection in this study. It took 10 min to detect 10 ppb arsenic concentration and only 1 min to detect concentrations higher than 50 ppb. This method thus reduced the detection time for arsenic and has the potential to develop better field kit.
Application of generalized two-dimensional (2D) correlation in various analytical fields is explored. 2D correlation is a powerful and versatile technique applicable to spectroscopy, chromatography, and other measurements. Construction of 2D spectra is relatively straightforward, requiring only a series of systematically varying analytical signals, like spectra or chromatograms, induced by an external perturbation applied to the system of interest. Perturbation can take many different forms, like change in temperature, pressure or concentration, chemical reactions, electrical or mechanical stimuli, and so on. A set of analytical signals collected under a perturbation are then converted to 2D correlation spectra, which provide rich and useful information about the presence of coordinated or independent changes among signals, as well as relative directions and sequential order of signal intensity variations. The signal resolution is also enhanced by spreading overlapped bands along the second dimension. Illustrative examples of 2D correlation are given for spectroscopic and chromatographic applications.
Glassy test strips partially coated with PVC-film including O-donor macrocyclic receptors (L), tetrabromophenolphthalein ethyl ester (TBPE-), and a plasticizer sensed Pb2+ in aqueous solutions by a unique color change. Yellow films successively changed color to green, dark-blue and purple with increases of the Pb2+ concentration. In contrast with the ordinary “optode”, a characteristic absorption band at 525 nm was newly appeared independently of the protonation and deprotonation of HTBPE (yellow to blue). The unique color change occurred only when asymmetric receptors with respect to the basal plane were coupled with Pb2+. This optical-structural correlation is likely to be induced by the H aggregate of two sets of TBPE- in the 1:2 ion-pair, [Pb-L]2+·(TBPE-)2. The color change, based on metachromasy, was exclusive for Pb2+ among common metal cations (Ca2+, Al3+, Cd2+, Zn2+, Fe3+, Co2+, Hg2+) and anions (Cl-, SO42-, PO43-, S2O32-).
A sensitive, selective and rapid high-performance liquid chromatographic (HPLC) method with chemiluminescence (CL) detection was developed and validated for the analysis of positron emission tomography (PET) radiopharmaceuticals. This method is based on the CL reaction of PET compounds with tris(2,2′-bipyridyl)ruthenium(II) [Ru(bpy)32+] and acidic potassium permanganate [KMnO4]. After optimization of the reaction conditions, 12 of the 14 PET compounds investigated could be successfully detected and showed good performance in terms of sensitivity, linearity and reproducibility. In particular, for compounds with a tertiary amine functional group, the limits of detection were ppb levels for a 20 µL injection volume. Finally, this method was used to determine PET compounds for calculating of specific radioactivity in pharmaceutical samples.
Attomole quantities of catechins were determined by a capillary liquid chromatography system with electrochemical detection (CLC-ECD) and the system is applied to the determination of catechins in human plasma. The eight catechins: catechin (C), epicatechin (EC), gallocatechin (GC), epigallocatechin (EGC), catechin gallate (Cg), epicatechin gallate (ECg), gallocatechin gallate (GCg), and epigallocatechin gallate (EGCg), were separated within 10 min using a capillary column (0.2 mm i.d.) and a mobile phase of phosphoric acid (85%)-methanol-water (0.5:27.5:72.5, v/v/v), and were detected at +0.85 V vs. Ag/AgCl. Peak heights were found to be linearly related to the amount of catechins injected, from 200 amol to 500 fmol (r > 0.998). The detection limits of the catechins were 61 amol for EGC, 75 amol for EC, 54 amol for GC, 61 amol for C, 67 amol for GCg, 75 amol for EGCg, 75 amol for ECg and 89 amol for Cg (S/N = 3). Because the present method is highly sensitive and allows facile pretreatment for plasma sample, the time courses of concentrations of catechins (GCg, EC, EGCg, ECg, and Cg) and their conjugates in human plasma obtained from a 10 µl plasma sample after ingestion of green tea could be determined.
The modification of carbon powder with manganese dioxide using a wet impregnation procedure with electrochemical characterisation of the modified powder is described. The process involves saturation of the carbon powder with manganese(II) nitrate followed by thermal treatment at ca. 773 K leading to formation of manganese(IV) oxide on the surface of the carbon powder. The construction of composite electrodes based on manganese dioxide modified carbon powder and epoxy resin is also described, including optimisation of the percentage of the modified carbon powder. Composite electrodes showed attractive performances for electroanalytical applications, proving to be suitable for the electrochemical detection of hydrogen peroxide, ascorbic acid and nitrite ions with limits of detection comparable to the detection limits achieved by other analytical techniques. The results obtained for detection of these analytes, together with composite electrodes flexible design and low cost offers potential application of composite electrodes in biosensors.
A new salicylate-selective PVC membrane electrode based on a new Schiff base tetranuclear copper complex of O-vannlin-methionine (Cu(II)4-TVM) as a neutral carrier is described. This electrode displays a preferential potentiometric response to salicylate and an anti-Hofmeister selectivity sequence in the following order: Sal- > ClO4- > SCN- > I- > NO2- > NO3- > Br- > Cl- > SO32- > SO42- > H2PO4-. The electrode exhibits near-Nernstian potential linear range of 1.5 × 10-6 - 1.0 × 10-1 M with a detection limit of 8.0 × 10-7 M and a slope of -56.3 mV/decade in pH 3.0 - 8.0 of phosphorate buffer solution at 20°C. Thanks to the tetranuclear copper(II) in the carrier, the electrode has the advantages of simplicity, fast response, fair stability and reproducibility and low detection limit. The response mechanism to the electrodes is discussed by the a.c. impedance technique and the UV spectroscopy technique. The electrode can be applied to analyses of medicine and the results obtained are in fair agreement with the results given by a standard method.
We report here a novel strategy for the high-sensitive detection of target biomolecules with very low concentrations on a quartz crystal microbalance (QCM) device using gold nanoparticles as signal enhancement probes. By employing a streptavidin-biotin interaction as a model system, we could prepare biotin-conjugated gold nanoparticles maintaining good dispersion and long-term stability by controlling the biotin density on the surface of gold nanoparticles that have been investigated by UV-vis spectra and AFM images. These results showed that 10 µM N-(6-[biotinamido]hexyl)-3′-(2′-pyridyldithio)propionamide (biotin-HPDP) was the critical concentration to prevent the nonspecific aggregation of gold nanoparticles in this system. For sensing streptavidin target molecules by QCM, biotinylated BSA was absorbed on the Au surface of the QCM electrode and subsequent coupling of the target streptavidin to the biotin in the sensing interface followed. Amplification of the sensing process was performed by the interaction of the target streptavidin on the sensing surface with gold nanoparticles modified with 10 µM biotin-HPDP. The biotinylated gold nanoparticles were used as signal amplification probes to improve the detection limit, which was 50 ng/ml, of the streptavidin detection system without signal enhancement, and the calibration curve determined for the net frequency changes showed good linearity over a wide range from 1 ng/ml to 10 µg/ml for the quantitative streptavidin target molecule analysis. In addition, the measured dissipation changes suggested that the layer of biotin-BSA adsorbed on the Au electrode and the streptavidin layer assembled on the biotin-BSA surface were highly compact and rigid. On the other hand, the structure formed by the biotinylated gold nanoparticles on the streptavidin layer was flexible and dissipative, being elongated outward from the sensing surface.
Capillary electrophoresis (CE) coupling with a tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)32+) electrochemiluminescence (ECL) detection technique was developed for the analysis of two β-blockers, atenolol (AT) and metoprolol (ME). The parameters that influence the separation and detection, including the buffer pH and concentration, the separation voltage, the detection potential and Ru(bpy)32+ concentration, were optimized in detail. The calibration curve was linear over a concentration range of two or three orders of magnitude for the two β-blockers. The detection limits for AT and ME were 0.075 and 0.005 µM (S/N = 3). The relative standard deviations (n = 8) of the ECL intensity and the migration time were 2.65 and 0.22% for AT, 2.82 and 0.34% for ME, respectively. The proposed method was applied to determine AT and ME in spiked urine samples; satisfactory results were obtained.
Recently, multiwalled carbon nanotubes (MWCNTs) have been at the center of attention because of their applications in many fields. Efforts to investigate the possibility of MWCNTs as SPE absorbents for the enrichment of environmental pollutants yielded positive results. The goal of the present work was to compare the enrichment power of MWCNTs with that of regular adsorbents, such as C18 silica for SPE of five sulfonylurea herbicides. The results indicated that multiwalled carbon nanotubes were very suitable for the preconcentration of sulfonylurea herbicides in complex water samples, yielding better recoveries. C18 gave a lightly lower enrichment performance, and could not enrich nicosulfuron in complex samples. All of these experimental results indicated that multiwalled carbon nanotubes could be used as a valuable alternative adsorbent for the SPE of sulfonylurea herbicides in many real water samples.
A very simple, ultra-sensitive and fairly selective direct spectrophotmetric method is presented for the rapid determination of lead(II) at ultra-trace level using 1,5-diphenylthiocarbazone (dithizone) in micellar media. The presence of the micellar system avoids the previous steps of solvent extraction and reduces the cost and toxicity while enhancing the sensitivity, selectivity and the molar absorptivity. The molar absorptivities of the lead-dithizone complex formed in the presence of the cationic cetyltrimethylammonium bromide (CTAB) surfactants are almost ten times the value observed in the standard method, resulting in an increase in the sensitivity of the method. The reaction is instantaneous and the absorbance remains stable for over 24 h. The average molar absorption coefficient was found to be 3.99 × 105 L mol-1 cm-1 and Sandell's sensitivity was 30 ng cm-2 of Pb. Linear calibration graphs were obtained for 0.06 - 60 mg L-1 of Pb(II); the stoichiometric composition of the chelate is 1:2 (Pb:dithizone). The interference from over 50 cations, anions and complexing agents has been studied at 1 mg L-1 of Pb(II). The method was successfully used in the determination of lead in several standard reference materials (alloys and steels), environmental water samples (potable and polluted), biological samples (human blood and urine), soil samples and solutions containing both lead(II) and lead(IV) and complex synthetic mixtures. The method has high precision and accuracy (σ = ±0.01 for 0.5 mg L-1).
A standardization algorithm, called WPTS, which is based on a wavelet packet transform (WPT) and entropy criteria, is proposed to transfer spectra between two near-infrared spectrometers. First, the spectra of the standardization samples measured on both spectrometers are collected and the difference mean spectrum is calculated; then, a wavelet packet transform is performed and a best WPT-tree is generated, of which a node is selected to establish a transfer matrix. Once the transfer matrix has been built, spectra measured on one spectrometer can be successfully transferred to another spectrometer as if they have been measured directly on the latter. By comparison, the proposed WPTS can reach a transfer performance comparable to WTS1, which is the best existing method, and better than WTS2 and classical PDS by a simpler technique of variable selection and lower computational cost of calibration transfer.
The multielement determination of PM10 (airborne particulate matter smaller than 10 µm) samples, which was collected by a high volume air sampler at the urban site of Nagoya City, was carried out by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The present analytical method was validated by analyzing urban particulate matter standard reference material of NIST SRM 1648. The analytical data for ca. 30 elements in PM10 samples collected during a period from 8 September to 9 October, 2003, were obtained in the concentration range from sub-µg g-1 to several-10 mg g-1, but the data for 18 elements among ca. 30 elements were available for the characterization of PM10 samples in ambient air, because of problems caused by the filter blanks. Then, the trends concerning the distributions of diverse elements in PM10 samples were analyzed based on the enrichment factors and size distribution factors. The lithophile and siderophile elements were distributed more than 50% in coarse particle fraction (>2.1 µm), which was derived mainly from natural sources, such as soils and crustal minerals. On the other hand, chalcophile elements were distributed more than 50% in fine particle fraction (<2.1 µm), which was derived mostly from anthropogenic emission sources. The large enrichment of chalcophile elements in PM10 samples as well as their mining influence factors (MIFs) suggested their wide use in industrial productions.
The mathematical model for predicting the precision, limit of detection (LOD) and range of quantitation (ROQ) in a competitive enzyme-linked immunosorbent assay (ELISA) proposed by Hayashi et al. (Anal. Chem., 2004, 76, 1295) was validated. The model describes the relative standard deviation (RSD) of concentration estimates by the RSDs of pipetting volumes of analyte, enzyme-conjugated antigen, antibody and substrate solutions, and the standard deviation (SD) of inherent absorbances between the wells in an ELISA plate. For 6 kinds of direct competitive ELISA kits, the LOD and ROQ predicted by the model agreed well with those obtained by experiments with real samples. It was also confirmed that the model is applicable to the prediction of uncertainty that depends on the pipetting error of the viscous antiserum solution. The model was demonstrated to be useful for estimating the LOD and ROQ of competitive ELISA.
When an aqueous solution of 5,5-dimethyl-1-pyrroline N-oxide (DMPO) was heated at 70°C for 30 min, formation of DMPO-OH was observed by ESR. This DMPO-OH radical formation was suppressed under an argon atmosphere. When water was replaced with ultra-pure water for ICP-MS experiments, DMPO-OH radical formation was also diminished. Under an argon atmosphere in ultra-pure water, the intensity of the DMPO-OH signal decreased to about 1/20 of that observed under aerobic conditions with regular purified water. The addition of hydroxyl radical scavengers such as mannitol did not affect the formation of DMPO-OH, but the signal turned faint in the presence of EDTA. We suggest that DMPO reacted with dissolved oxygen to form DMPO-OH.
A simple and highly sensitive spectrophotometric method for the determination of uric acid (UA) was established based on fading of the o-hydroxyhydroquinonephthalein-palladium(II)-hexadecyltrimethylammonium complex. In the determination of UA, Beer's law is obeyed in the range of 0.01 - 0.20 µg ml-1, with an effective molar absorptivity at 635 nm, the relative standard deviation being 6.5 × 105 dm3 mol-1 cm-1 and 1.5% (n = 5). This method is about 20-times more sensitive than the conventional methods. The method was successfully applied to the assay of UA in human urine.
In our previous study, we proposed molecular recognition of mono- and disaccharides making use of the interaction between their diol groups and p-iodophenylboronic acid in capillary electrophoresis with a chemiluminescence detection system. Here, to extend our knowledge of molecular recognition, we first examined the enhancing effects of four phenylboronic acid compounds other than p-iodophenylboronic acid i.e., 4-biphenylboronic acid, 4-octyloxyphenyl-boronic acid, 3-octyloxyphenylboronic acid, and 4-dodecyloxyphenylboronic acid, for luminol-hydrogen peroxide-horseradish peroxidase reaction in the capillary electrophoresis-chemiluminescence detection system. Only 4-biphenylboronic acid showed an enhancing effect similar to that of p-iodophenylboronic acid; the effect was determined over the range of 0.5 - 10 µM in this system. Second, we estimated the apparent stability constants between the diol groups of saccharides (1-methyl-D-glucoside, D-saccharose, and D-fructose) and the boronic acid moieties of the two enhancers, p-iodophenylboronic acid and 4-biphenylboronic acid. The apparent binding constants obtained here provided insight to confirm the principle of molecular recognition for the saccharides examined here.
An internal solid contact sensor (ISCS) for the determination of methacycline hydrochloride (MC·Cl), Pt/PPy/PVC(MC-PT), is described, based on the use of conducting poly(pyrrole) (PPy) as solid contact material and MC-phosphotungstate (PT) as the ion exchanger and dibutyl phthalate (DBP) as the plasticizer. A direct potentiometric method for the quantitative analysis of MC·Cl is also described. Under the condition of pH 2.7, the linear concentration range, slope (25°C) and detection limit of the sensor are 6.4 × 1.0-6 - 3.0 × 1.0-3 M, 52.4 ± 0.2 mV/decade and 4.4 × 1.0-6 M, respectively. The response time is <5 s. The determinations of MC·Cl in tablets were carried out by direct potentiometry. The average recovery and relative standard deviation are 100.1 and 0.7% (n = 4), respectively.
A direct electrochemical biosensing platform has been fabricated by covalent incorporation of carbon nanotubes (CNT) and gold nanoparticles (GNP) onto the poly(thionine) (PTH) film deposited by electropolymerization. With the synergic effects of the composite nanomaterials together with the excellent mediating redox polymer, the proposed platform could allow for faster electron transfer and higher enzyme immobilization efficiency than the platforms designed by using CNT or GNP alone. Comparison studies indicated that the as-developed H2O2 sensor could show greatly improved performances of amperometric responses.