This paper presents an integrated microfluidic system that performs cleanup for polycyclic aromatic hydrocarbons (PAHs) from diesel exhaust particles on silica gel beads in a microchip. A column chromatography phase was constructed by filling the silica gel beads into a microchannel that had a dam structure 25 µm high. The height of the dam structure was determined according to the rate of the wet etching. This work on the cleanup of PAHs from diesel exhaust particles showed that the microchip-based system has the same performance as the conventional method on the solid phase extraction column and has some advantages, such as less reagent consumption and shorter pretreatment time, over the conventional method.
A carbodiimide derivative having a dithiolane part at its terminus was designed and synthesized for use to construct carbodiimide-coated self-assembly monolayers (SAMs) on a gold surface with 6-mercaptohexanol (6MH). When treated with poly(dT), poly(dA), or poly(dA)poly(dT), only poly(dT) was immobilized on the surface of the SAMs through a specific reaction of the free imino moiety of thymine (T) with the carbodiimide moiety. The carbodiimide-covered SAM treated with probe DNA was tested in hybridization with sample DNA. Its hybridization efficiency was estimated by ferrocenylnaphthalene diimide (FND), described previously and the result revealed that the carbodiimide-covered SAM electrode can immobilize a DNA probe through the thymine moiety not involved in base pairing. The resulting electrode was capable of hybridizing with the target DNA, as proven by an increased current response of FND.
A nanodiamond with a mean particle size of 4 nm, which was prepared by the detonation of a nanodiamond, has been characterized and used as a collector for tungstate in water samples. An aqueous solution of nanodiamond was found to be stable over the pH range from 3 to 10. Coagulation of the nanodiamond could be brought about by adding an electrolyte solution. The adsorption characteristics of nanodiamond have been elucidated to be attributable to amino groups on its surface by the elemental-analysis data and the zeta potential measured in weak acid media. The unique adsorption properties of the nanodiamond for oxoacid anions were applied to a selective preconcentration method for tungstate in water samples. An appropriate amount of nanodiamond was added to a sample solution at pH 5 and a calcium chloride solution was added to aggregate nanodiamond. The sample solution was then allowed to stand for 2 h and centrifuged. The nanodiamond was transferred onto a membrane filter, washed with a diluted calcium chloride solution and treated in advance of an ICP-AES measurement by either of the following procedures: (a) redispersion of the nanodiamond into dilute nitric acid with an ultrasonic washer and (b) ashing of the membrane filter and the coagulated nanodiamond at 700°C, followed by a treatment of the ash with hydrochloric and tartaric acids. The average recovery of tungstate from 100-ml artificial river-water was found to be 99% at the 0.25 ppm level with an RSD of 2.2% (n = 3). The concentration factor at present is 10.
The objective of this work is to track the amount of metal complexes distributed in the extraction cell, collection vial, and tubing used in supercritical fluid extraction (SFE) systems after progressive removal of metal ions in supercritical carbon dioxide (SC-CO2). Sodium diethyldithiocarbamate (NaDDC) and dibutylammonium dibutyldithiocarbamate (DBDC) ligands were used to form complexes with Cd, Cu, Pb, and Zn and CO2/5% methanol as a supercritical fluid. The mass balance of metal complexes were obtained before and after extraction, and metals in different locations in the system were flushed out using an organic solvent and nitric acid (HNO3). These results infer that the stability constant (β) of the metal-ligand complex has a strong correlation with SFE. Because of the composition of the stainless-steel cell, Fe, Cr, and Ni or other trace elements in the cell might interfere with the mass balance of metal complexes in SFE due to an exchange mechanism taking place between the cell and the sample.
Using 1-octanol/octane mixed solvents, the extraction of aluminum(III), gallium(III) and indium(III) with 8-quinolinol was carried out at 25°C. The formation constants of the respective metal(III) 8-quinolinolates in the aqueous phase and their partition constants between the mixed solvents and water were determined based on an analysis of the extraction equilibria. The relationship between the partition constants of 8-quinolinol and its complexes was analyzed by the regular solution theory. The molar volumes of aluminum(III), gallium(III) and indium(III) 8-quinolinolates, calculated from the present results, suggest that the electrostriction effect functions in complex forming. It has been found that octane/1-octanol mixed solvents were available not only for the extraction of metal ions, but also for determining the formation constants of these metal 8-quinolinolates in the aqueous phase and their partition constants.
Bench-scale experiments were conducted in the laboratory, aiming to remove aluminum from water. They were based on using powdered activated carbon (PAC), which was prepared from olive stones generated as plant wastes and modified with an aqueous oxidizing agent as HNO3 as an effective sorbent and oleic acid (HOL) as a surfactant. The main parameters (namely: initial solution pHs, sorbent, surfactant and aluminum concentrations, shaking time, ionic strength and the presence of foreign ions) that influence the sorptive-flotation process were examined. Good results were obtained under the optimum conditions, according to which nearly 100% of aluminum, at pH 7 and at room temperature (∼25°C), was removed. The procedure was successfully applied to recover aluminum spiked to some natural water samples. Moreover, a sorption and flotation mechanism is suggested.
A micro-miniature array of sensing capsules for optical monitoring of pH, potassium and glucose is described. Optode technology translates the respective ionic levels into variable colors of ionophore/dye/polymeric liquid micro-beads stuffed into individual capsules. Glucose is monitored indirectly, by coupling through glucose oxidase (GOX) immobilized in cellulose acetate phthalate (CAP) based microscopic beads that are stuffed into another microcapsule together with pH sensitive optical microscopic beads. The electrolyte and glucose sensing capsules are embedded in a transparent cellulose acetate bar 300 - 500 µm wide and 2 - 2.5 mm long called the sliver sensor that includes also a white capsule made of micro-beads without dye for optical reference. By adding further capsules custom combinations of analytes can be monitored in biomedical and non-biological contexts. In this work, as an example, design, fabrication and testing of a sliver sensor that could be developed for in vivo use are described.
A selective and sensitive stripping voltammetric method for the determination of trace amounts of copper(II) with cyclopentanone thiosemicarbazone (CPTSC) is presented. The method is based on the adsorptive accumulation of the resulting copper-CPTSC complex on a hanging mercury drop electrode, followed by the stripping voltammetric measurements at the reduction current of the adsorbed complex at -0.37 V vs. Ag/AgCl. The optimal conditions for the stripping analysis of copper include pH 9.3, deposition time of 120 s, and a deposition potential of -0.1 V (vs. Ag/AgCl). The peak current is linearly proportional to the copper concentration over a range 3.14 × 10-9 M to 1.57 × 10-6 M with a limit of detection of 1.57 × 10-9 M. The technique has been applied to the determination of copper in biological samples, like urine and whole blood.
A cobalt(II) tetrakisphenylporphyrin (Co(II)TPP) film modified glassy carbon electrode (Co(II)TPP-GCE) was prepared by just coating Co(II)TPP solution on the surface of the electrode. It can be used for the simultaneous determination of ascorbic acid and uric acid. The anodic peaks of AA and UA can be separated well. Owing to the strongly hydrophobic property of porphyrin, the modified electrode has good stability and long life. The linear range for UA and AA were 2.0 × 10-6 - 1.0 × 10-4 M and 9.0 × 10-6 - 2.0 × 10-3 M with detection limits of 5.0 × 10-7 and 5.0 × 10-6 M, respectively. Furthermore, metalloporphyrins of other kinds were also used to construct modified electrodes. Their performances were inferior compared with that of the Co(II)TPP modified electrode.
The toluidine blue O (TBO) functionalized multiwall carbon nanotubes (MWNTs) nanomaterials (TBO-MWNTs) were prepared by assembling TBO onto the surface of a MWNTs modified glassy carbon (GC) electrode. Also TBO-MWNTs modified GC electrodes exhibiting a strong and stable electrocatalytic response toward β-nicotinamide adenine dinucleotide (NADH) were described. Compared with a bare GC electrode, the TBO-MWNTs modified GC electrodes could decrease the oxidization overpotential of NADH by 730 mV, with a peak current at 0.0 V, since there was a positively synergistic electrocatalytic effect between the MWNTs and TBO toward NADH. Furthermore, the TBO-MWNTs modified GC electrodes had perfect performances, such as a low detection limit (down to 0.5 µM), being very stable (the current diminutions is lower than 6% in a period over 35 min), a fast response (within 3 s), and a wide linear range (from 2.0 µM to 3.5 mM). Such an ability of TBO-MWNTs to promote the NADH electron-transfer reaction suggests great promise for dehydrogenase-based amperometric biosensors.
Dithiodibenzoic (DTB) acid and mercaptobenzoic (MB) acid were studied to characterize their abilities as modifier agents for lead(II) sensors. For both sensors, the best results were obtained with modified carbon paste electrodes with 24.1% of ligand. The pH influence on the potentiometric response was studied. The selectivity coefficients for both modified electrodes were tabulated. A potentiometric sensor based on DTB acid exhibited a more sensitive and selective response to lead ions than an MB electrode. The limits of detection for the DTB and MB electrodes were very similar, 5.01 × 10-8 M and 3.98 × 10-8 M, respectively, for lead(II) activity. The DTB sensor was applied to lead(II) ion determination in real samples and as an indicator electrode in potentiometric titrations. Natural and commercial humic acids were titrated using the DTB electrode to estimate the stability constant between these organic compounds and the lead(II) ions with successful results.
Tristimulus colorimetry using a digital still camera (DSC) as a colorimeter has been developed. A photograph of a sample and standard solutions was taken simultaneously with the DSC, and it was transferred to a PC. On the PC, the colors of the sample and of the standard solutions were analyzed and L* (brightness), a* (red-green component), and b* (yellow-blue component) values were determined with laboratory-made software. A dedicated light-box containing white-color LEDs as light source was made of white acrylic to make constant exposure at each photograph. Various settings of the DSC, such as exposure mode, white balance, and so on, that affect analytical figures, were studied with determination of iron with 1,10-phenanthroline. This method was successfully applied to the determinations of iron in a river water sample and of residual chlorine in tap water samples with N,N-diethylphenylenediamine (DPD).
The main objective of the present study is to specify the chemical properties of individual rain droplets. For this purpose, we have combined the collodion replication method and the SR-XRF microprobe technique. The dry residual materials retained in a single rain droplet, which correspond to the former cloud condensation nuclei and the scavenged particles during droplet falling, were successively reconstructed by the multiple elemental maps using SR-XRF microprobe analytical system. Also the SR-XRF microprobe system allows us to quantify the masses of ultra trace elements in residues of individual rain droplet with fg level. The proposed combination method in the present study is found to be helpful to understand the physicochemical properties of individual rain droplets.
Tris(2-methyl-8-quinolinolato)iron(III) was proposed as a sensitive spectrophotometric silanol-detecting probe based on the coordination ability of silanol groups on the surface of octadecylsylanized silica gel (ODS silica gel) for reversed-phase high-performance liquid chromatography. A peak of the iron(III) complex on a chromatogram abruptly collapsed as the silanol content in an ODS column increased, indicating that the iron(III) complex could sense trace amounts of silanol groups. The change of the peak parameters, such as the peak height and the peak area was highly related to the output of some nitrogen-containing compounds used as silanol-detecting probes as a function of the silanol content in an ODS column. The response of the peak height of the iron(III) complex to the silanol content was much more sensitive than the response of the nitrogen-containing probes, and was comparable to that of tris(2-methyl-8-quinolinolato)gallium(III), which had been proposed as a fluorometric silanol-detecting probe based on the coordination ability of the silanol groups.
The binding of lomefloxacin to bovine lactoferrin (BLf) in a dilute aqueous solution was studied using fluorescence spectra. The binding constant (K) and the number of binding sites (n) were obtained by a fluorescence quenching method. The binding distance (r) and energy-transfer efficiency (E) between lomefloxacin and bovine lactoferrin were also obtained according to the mechanism of Foörster-type dipole-dipole nonradiative energy-transfer. The effect of lomefloxacin on the conformation of bovine lactoferrin was also analyzed by synchronous fluorescence spectroscopy. The interaction between lomefloxacin and bovine lactoferrin is strong. Lomefloxacin can affect the conformation of bovine lactoferrin to some degree.
A simple and easy method of analysis for diclofenac sodium is reported. A spectrofluorometric method for the microdetermination of diclofenac sodium has been developed through its reaction with cerium(IV) in an acidic solution and measurement of the fluorescence of the Ce(III) ions produced. Under the optimum experimental conditions for the oxidation reaction, 1.0 M H2SO4 with 90 min of heating time (100°C), the range of application is 124.3 - 600 ng mL-1 and the limit of detection is 72.7 ng mL-1. The proposed method was applied to the determination of diclofenac sodium in pharmaceutical tablets. The results of the analysis show a good agreement with those obtained by the official USP 27 HPLC method.
The interaction between carbamazepine (CBZ) and bovine serum albumin (BSA) was studied using fluorescence spectroscopy (FS) and ultraviolet spectroscopy (UV). The experimental results showed that the CBZ could insert into the BSA and quench the inner fluorescence of BSA by forming the CBZ-BSA complex. It was found that both static quenching and non-radiation energy transfer were the main reasons leading to the fluorescence quenching. The apparent binding constants (K) between CBZ and BSA were found to be 1.8 × 104 (27°C) and 2.8 × 104 (37°C) and the binding site values (n) were 0.97 (27°C) and 1.01 (37°C), respectively. According to the Förster theory of non-radiation energy transfer, the binding distances (r) between CBZ and BSA were 3.6 nm and 3.4 nm at 27°C and 37°C, respectively. The process of the binding was a spontaneous molecular interaction in which entropy increased and Gibbs free energy decreased, indicating that the interaction between CBZ and BSA was mainly driven by the hydrophobic force.
The interaction of proflavine with herring sperm DNA has been investigated by cyclic voltammetry and UV-Vis spectroscopy as well as viscosity measurements. Shifts in the peak potentials in cyclic voltammetry, spectral changes in UV absorption titration, an increase in viscosity of DNA and the results of the effect of ionic strength on the binding constant strongly support the intercalation of proflavine into the DNA double helix. The binding constant for the interaction between proflavine and DNA was K = 2.32 (±0.41) × 104 M-1 and the binding site size was 2.07 (±0.1) base pairs, estimated in voltammetric measurements. The value of the binding site size was determined to be closer to that expected for a planar intercalating agent. The standard Gibbs free-energy change is ca. -24.90 kJ/mol at 25°C, indicating the spontaneity of the binding interaction. The binding constant determined by UV absorption measurements was K = 2.20 (±0.48) × 104 M-1, which is very close to the value determined by cyclic voltammetry assuming that the binding equilibrium is static.
A new spectrophotometric method involving flow injection analysis and textile dye aggregation effect is proposed. The method is based on the aggregation effect of Blue Procion HEGN at pH 3, which relocates its maximum absorption wavelength from 620 to 776 nm, avoiding the interference of other blue textile dyes. For this task, a simple and robust flow injection system was designed, which became a very stable analytical method. When the system was applied to Blue Procion determination in effluent of textile industry, precise results were observed (RSD < 2% within 1.0 and 5.0 mg l-1 HEGN). The analytical frequency was 80 measurements per hour; the analytical curve was linear from 1.0 to 5.0 mg l-1 HEGN; the detection limit considering three times the standard deviation of the blank solution (n = 10) was estimated as 0.03 mg l-1 HEGN; and recoveries between 95% and 105% were found. The system consumes 20 mg of sodium citrate and 125 µl of the sample per determination. No baseline drift was observed during extended (5 h) operation periods.
A novel prenylflavonol glycoside, named acetylicariin, has been isolated from the aerial parts of Epimedium koreanum Nakai. The structure has been identified by electrospray ionization multi-stage tandem mass spectrometry (ESI-MSn) and other chemical evidence, which has been elucidated as 8-prenylkaempferol-4′-methoxyl-3-O-α-L-rhamnopyranosyl-7-O-β-D-(2″-O-acetyl)glucopyranoside.
In the present study the solubility of β-cyclodextrin and 2-hydroxypropyl-β-cyclodextrin at sub-zero and elevated temperatures (-10 and +30°C) for a given composition of methanol/water and acetonitrile/water binary mixtures (Xs = 0.16) was studied. Moreover, the freezing temperature profiles of acetonitrile-based chromatographic mobile phases were measured, and the obtained results were compared with data available in the literature. Furthermore, the effect of the macrocycles concentration on the liquid-phase freezing points was determined. The low solubility of native β-cyclodextrin in a methanol/water mixture at sub-zero temperature as well as the non-linear behavior of acetonitrile/water mixtures that were observed concerning the freezing point profile are discussed from a practical point of view.
p-Nitrocalixarene (CALX-N6, L) formed a 1:1 metal complex, ML, with light rare earth metal ions (M3+), such as La3+, Pr3+ and Nd3+ except Ce3+, but formed a 1:2 (M3+:L) complex, ML2 (the charge of the complex is omitted) with heavy rare earth metal ions, such as Sm3+-Lu3+ including Y3+. The conditional stability constants of these 1:1 and 1:2 complexes, KML and KML2, were measured by a ligand displacement method using absorption spectrophotometry in 4% (v/v) acetone aqueous solution at pH 9.65 ± 0.15 and 25°C.
The drying conditions for primary standards of volumetric analysis have a significant effect on the titration results due to changes in the purity, stability and homogeneity. Amidosulfuric acid, a strong acid used as a reference material for volumetric analysis in Japan, was dried in a vacuum desiccator or heated at different temperatures, and then measured by Karl-Fischer titration, thermogravimetry/mass spectroscopy (TG-MS), ion chromatography and coulometric titration. The optimum drying conditions were at 50°C for 24 h with crushing.
S-Methyl-N-methyl-N′-(4-(N″,N″-dimethylamino)phenyl)isothiourea, a novel isothiourea-based chromoionophore for anions, was synthesized. The reactivity for several anions was estimated by a visual method and UV-vis spectroscopy. By the addition of acetate ion, a blue shift in the absorption spectrum was observed in CHCl3, and the solvent color changed from yellow to colorless. These changes indicated that bound acetate ion interfered with the intramolecular charge transfer from the nitrogen atom of the diethylamino group to the isothiourea moiety. The addition of chloride ion caused a red shift of the chromophore and solvent color remained yellow. By the addition of dihydrogenphosphate ion, the precipitate was formed immediately. These anion-dependent natures of the chromoionophore allowed us to detect acetate and phosphate ions easily.
A method to determine α-, β- and γ-hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA) in water and sediments was presented using solid phase extraction (SPE) and/or solvent extraction. Recoveries from sediments were approximately 100% for all the chemicals, while recoveries of α-, β- and γ-HBCDs from water were dependent on the extraction method. In the case of dichloromethane (CH2Cl2) extraction, recoveries of α-, β- and γ-HBCD from landfill leachates were 77%, 88% and 92%, respectively. Technical difficulties in HBCD measurement are discussed in terms of the physico-chemical properties of HBCD isomers. The method was applied to landfill samples and marine sediment.
The evaluation of a simple and rapid tristimulus colorimetric method for the determination of arsenic in brackish waters and its application to brackish water samples taken from brackish Lake Nakaumi are described. The determinations of arsenic in brackish water samples were made satisfactorily independent of sample salinity. By applying this method to lake water samples, the distributions and behaviors of arsenic in the lake and their controlling factors were clarified, such as seasonal variations of arsenic and the effect of a typhoon.
A continuous flow-type hydrothermal reaction system, in which both temperature and pressure were rapidly and dynamically controlled, was constructed. It is called a real time high temperature and pressure reaction system (RT-HighTP). The RT-HighTP was hyphenated with liquid chromatograph (RT-HighTP-LC) to achieve prompt analysis of the reaction products. The RT-HighTP system produced stable pressure under the supercritical and subcritical phases (%RSD < 3%). The RT-HighTP-LC was able to change the hydrothermal condition rapidly. The hydrothermal products under four conditions were analyzed within 70 min. Further, the hydrothermal products of lignin was easily taken out using the sample collecting loop and analyzed by an external instrument of GC/MS.