Copper Speciation for Natural Water by On-site Sample Treatment/Solid-phase Extraction/Inductively Coupled Plasma Mass Spectrometry.

Herein, we determined the contents of Cu(I), Cu(II), and hydrophobic Cu in natural water using on-site sample treatment, solid-phase extraction (SPE), and inductively coupled plasma mass spectrometry (ICP-MS) analysis. To prevent Cu species changes in the sampling, filtering and preconditioning steps were performed in a closed system using plastic syringes and a disposable membrane filter. Bathocuproin disulfonate (BCS) and ethylenediaminetetraacetic acid (EDTA) were selected as a Cu(I)-selective complexing agent and a Cu(II) masking agent, respectively, whereas ascorbic acid (AA) was used to reduce Cu(II) to Cu(I). Pre-conditioned samples were passed through a hydrophobic SPE column, and the retained Cu species were eluted with ethanol. Subsequently, the eluate was concentrated, and the residue was re-dissolved in 2 M HNO3 and subjected to ICP-MS analysis. No artificial changes of Cu(I) and Cu(II) species were observed at any time, with the analytical detection limit of total Cu and the blank value equaling 0.0008 and 0.0025 µg kg-1, respectively. The developed method was applied to real estuarine, riverine, and seawater samples collected in Tokushima prefecture, Japan.

Determination of the Acid-Base Dissociation Constant of Acid-Degradable Hexamethylenetetramine by Capillary Zone Electrophoresis.

The acid-base equilibrium of hexamethylenetetramine (hexamine) was analyzed with its effective electrophoretic mobility by capillary zone electrophoresis. Although hexamine is degradable in a weakly acidic aqueous solution, and the degraded products of ammonia and formaldehyde can be formed, the effective electrophoretic mobility of hexamine was measured in the pH range between 2.8 and 6.9. An acid-base dissociation equilibrium of the protonated hexamine was analyzed based on the mobility change, and an acid dissociation constant of pKa = 4.93 ± 0.01 (mean ± standard error, ionic strength: 0.020 mol dm-3) was determined. The monoprotic acid-base equilibrium of hexamine was confirmed through comparisons of its electrophoretic mobility with the N-ethylquinolinium ion and with the monocationic N-ethyl derivative of hexamine, as well as a slope analysis of the dissociation equilibrium.

Determination of Acid Dissociation Constant of Pravastatin under Degraded Conditions by Capillary Zone Electrophoresis.

The acid dissociation constant of pravastatin was determined under degraded conditions. Pravastatin was degraded in an acidic solution (pH = 2.0) for 5 h, and the degradation solution was subjected to the measurement of the effective electrophoretic mobility by capillary zone electrophoresis. Although the amount of pravastatin decreased by the acid degradation, its acid dissociation constant was successfully determined with the residual pravastatin through its effective electrophoretic mobility. The determined acid dissociation constant value agreed well with the one obtained with freshly prepared solution and with some reported values.

Determination of trace elements in Ethiopian, Vietnamese, and Japanese women using high-resolution IC-PMS.

OBJECTIVES: Humans and other living organisms require small quantities of trace elements throughout life. Both insufficient and excessive intakes of trace elements can have negative consequences. However, there is little information on serum level of trace elements in different populations. This study examines serum levels of trace elements in Ethiopian, Japanese, and Vietnamese women. METHODS: Random samples of healthy women who were referred for routine hospital laboratory examinations in the cities of Hanoi, Sapporo, and Gondar were invited to participate in the study. Serum levels of magnesium, zinc, copper, iron, selenium, and calcium were determined using an inductively coupled plasma mass spectrometer. Furthermore, body mass index of each study participant was determined. RESULTS: The mean ± SD serum concentrations of zinc (µg/dL), copper (µg/dL), iron (µg/dL), selenium (µg/dL) and calcium (mg/dL), respectively, were 76.51 ± 39.16, 152.20 ± 55.37, 385.68 ± 217.95, 9.15 ± 4.21, and 14.18 ± 3.91 in Ethiopian women; 111.49 ± 52.92, 105.86 ± 26.02, 155.09 ± 94.83, 14.11 ± 3.41, and 11.66 ± 2.51 in Vietnamese women; and 60.69 ± 9.76, 107 ± 156, 268 ± 128, 8.33 ± 3.65, and 11.18 ± 0.68 in Japanese participants. Ethiopian women had significantly higher level of serum calcium than Vietnamese and Japanese women (both P < 0.05). Although the mean calcium concentration in Vietnamese women was higher than in women from Japan, the difference was not statistically significant (P > 0.05). Furthermore, compared with Japanese women, Ethiopian women had significantly high iron and copper concentrations (P < 0.05). Serum selenium and zinc levels were higher in Vietnamese than Ethiopian women. CONCLUSION: The study revealed a remarkable difference in serum concentrations of trace elements in women from different countries, implying differences in trace elements in the food or soil.

Analysis of ion-association equilibrium of precipitable dipicrylaminate ion in aqueous solution by capillary zone electrophoresis.

The ion-association equilibrium of the dipicrylaminate ion (DPA(-)) was investigated in an aqueous solution with alkali metal ions and with its 18-crown-6 ether complexes as pairing cations by capillary zone electrophoresis (CZE). Although DPA(-) is precipitable with the pairing cations of K(+) and Cs(+) in a homogenous aqueous solution, a low concentration of DPA(-) below its solubility suppressed the formation of the precipitates, and DPA(-) was detected as a usual CZE signal. Changes in the electrophoretic mobility of DPA(-) was analyzed for its ion-association equilibrium. The ion association constants determined were almost comparable among alkali metal ions, while the ion association constants were meaningfully large with a hydrophobic 18-crown-6 ether complex of K(+). The CZE separation was also proved to be useful for the equilibrium analysis under precipitating conditions. It was suggested that the precipitable property of DPA(-) with K(+) and Cs(+) could not be attributed to the ion-association process in an aqueous solution, but to the condensation process concerning the intermolecular CH···O bond in the precipitate crystals, as reported.

Micellar electrokinetic chromatography of graphene and chemically modified graphenes with dodecylbenzenesulfonate.

Graphene and chemically modified graphenes were resolved by micellar electrokinetic chromatography (MEKC) using sodium dodecylbenzenesulfonate (SDBS) as a micelle matrix. Graphene was successfully dispersed in a micellar solution, and a consecutive and broad signal was obtained by the MEKC with a 20 mmol dm⁻³ aqueous SDBS solution for Graphene Nanoplatelets. Chemically oxidized graphene was less retained to the micelle than the Graphene Nanoplatelets by the proposed MEKC, and they were resolved with each other.

Fabrication and characterization of a thermostable quinoprotein aldose sugar dehydrogenase immobilized electrode.

We fabricated a thermostable quinoprotein aldose sugar dehydrogenase (tPQQ-ASD derived from a hyperthermophilic archaeon Pyrobaculum aerophilum) immobilized electrode. The electrode was prepared by immobilizing agarose gel mixed with the enzyme and carbon nanofiber (CNF) on a carbon paste (CP) electrode containing p-benzoquinone (BQ) as an electron mediator. The electrocatalytic response was clearly observed by the addition of D-glucose at the electrode. The electrode properties such as pH, temperature dependency and substrate selectivity basically followed the enzyme properties. The current response against D-glucose increased with measurement temperatures up to 70°C, and response perturbation caused by dissolved oxygen level was not observed at the electrode. As for the results of long-term stability evaluation, the current response was stable for 30 days when the electrode was stored in HEPES buffer solution (pH 7.0) at 4°C.

Micronutrient levels and nutritional status of school children living in Northwest Ethiopia.

BACKGROUND: Several micronutrients are essential for adequate growth of children. However, little information is available on multiple micronutrient status of school children in Ethiopia. The present study was designed to evaluate the relationship between multiple micronutrient levels and nutritional status among school children. METHOD: In this cross-sectional study, anthropometric data, blood and stool samples were collected from 100 children at Meseret Elementary School in Gondar town, Northwest Ethiopia. Serum concentration of magnesium, calcium, iron, copper, zinc, selenium and molybdenum were measured by inductively coupled plasma mass spectrometer. Anthropometric indices of weight-for-age, height-for-age and BMI-for-age were used to estimate the children's nutritional status. Stool samples were examined by standard microscopic methods for intestinal parasites. RESULTS: The prevalence of stunting, underweight, wasting and intestinal parasitoses among school children was 23%, 21%, 11% and 18%, respectively. The mean serum levels of magnesium, calcium, iron, copper, zinc, selenium and molybdenum were 2.42±0.32 (mg/dl), 15.31±2.14 (mg/dl), 328.19±148.91 (µg/dl), 191.30±50.17 (µg/dl), 86.40±42.40 (µg/dl), 6.32±2.59 (µg/dl), and 0.23±0.15 (µg/dl), respectively. Selenium deficiency, zinc deficiency and magnesium deficiency occurred in 62%, 47%, and 2% of the school children, respectively. Height-for-age showed significant positive correlation with the levels of copper and molybdenum (p = 0.01) and with the levels of magnesium (p = 0.05). CONCLUSION: Deficiencies of selenium and zinc were high among the school children although the deficiencies were not significantly related with their nutritional status. The prevalence of both malnutrition and intestinal parasitism was not negligible. These calls for the need to undertake multicentre studies in various parts of the country to substantiate the data obtained in the present study so that appropriate and beneficial strategies for micronutrient supplementation and interventions on nutritional deficiencies can be planned.

Multielemental elution behavior of metal ions adsorbed on iminodiacetic acid chelating resin by using hydrogen peroxide as an eluent.

In the present work, we investigated the multielemental elution behavior of metal ions absorbed on iminodiacetic acid (IDA) chelating resin by using hydrogen peroxide (H(2)O(2)) as an eluent. As a result, V(V), Mo(VI), W(VI), Nb(V) and Ta(V) were efficiently eluted by H(2)O(2). In contrast, other metal ions were rarely recovered. The oxidation states of V(V), Mo(VI), and W(VI) were not changed through the H(2)O(2) eluting process, checked by X-ray photoelectron analysis. In addition, the UV-vis adsorption spectra and IR spectra of V(V), Mo(VI) and W(VI) in the H(2)O(2) eluent suggested the formation of metal-peroxo complexes through H(2)O(2) elution. The desorption of these metal ions from IDA functional groups is explained in term of destabilization along with the coordination of peroxo-ligands to the V(V)-, Mo(VI)- and W(VI)-IDA complexes, and a decrease in the adsorption capacity by electrostatic repulsion between dissociated carboxylic groups of IDA and the oxoanions in the neutral pH shown in 30 wt% H(2)O(2). When this method was applied to the selective separation of V(V), Mo(VI) and W(VI) from other metals in an acid soluble fraction of fly-ash, 83.4 ± 2.5% of V(V), 88.1 ± 3.3% of Mo(VI), and 69.3 ± 5.4% of W(VI) were recovered in a 30 wt% H(2)O(2) eluent.

Highly selective needle-type glucose sensors prepared by the immobilization of glucose oxidase on γ-polyglutamic acid film.

Fine needle-type glucose sensors with an outer diameter of less that 0.2 mm were fabricated using a low-cost biodegradable γ-polyglutamic acid (PGA) not only as a glucose oxidase (GOx) immobilizing material, but also as a permselective inner membrane. PGA film was prepared on a cellulose acetate-coated Pt-Ir wire electrode, and GOx was covalently immobilized on its surface using water-soluble carbodiimide. The obtained electrode was practically not affected by the existence of electroactive compounds, and provided long-term stability for approximately one month. It also functioned in horse serum with a good linear relationship between the current and glucose concentrations within the range of 2.8 to 22.4 mM.

[Study of the removal of Pb2+ from aqueous solution by poly-gamma-glutamic acid coated magnetic nanoparticles].

In this study, a novel low cost magnetic adsorbent material prepared by poly-gamma-glutamic acid (gamma-PGA) coating Fe3o4 magnetic particles, which was called coated magnetic namoparticles (PG-M) was developed for the removal of Pb2+ from water by Dr. Yasuzawa. The particle size of PG-M was about 120-320 nm, and there was no significant difference in Fe3O4 and PG-M particle size, Fe3O4 was only as the support of PG-M core and did not directly involve in the reaction. The shape of PG-M was irregular cubic structure. The experiments were applied to quantify adsorptive time, pH, competitive ion and organics on the removal effect of Pb2+. The results showed that PG-M was effective in removal of Pb2+; the equilibrium amount of adsorptive was as high as 93.3 mg/g and the optimized condition of pH value for metal ions removal was 7.0, while contact time was about 45 min. The removal efficiency of Pb2+ was not significantly influenced by Na+ while was reduced with the increasing concentration of Ca2+. The removal of Pb2+ was enhanced with the presence of organic matter (humic acid, HA) when the concentration of HA was below 5 mg/L, and decreased when the concentration of HA exceeded 5 mg/L. Langmuir isotherms fitted the experimental data better compared to Freundlich isotherms. Pseudo second order model well described the sorption kinetics of Pb2+. The used PG-M can be desorbed by 0.1 mol/L HCl and became reusable. PG-M is nontoxic and eco-friendly, which have a good prospect in water treatment.

Catalytic properties and crystal structure of quinoprotein aldose sugar dehydrogenase from hyperthermophilic archaeon Pyrobaculum aerophilum.

We identified a gene encoding a soluble quinoprotein glucose dehydrogenase homologue in the hyperthermophilic archaeon Pyrobaculum aerophilum. The gene was overexpressed in Escherichia coli, after which its product was purified and characterized. The enzyme was extremely thermostable, and the activity of the pyrroloquinoline quinone (PQQ)-bound holoenzyme was not lost after incubation at 100 degrees C for 10 min. The crystal structure of the enzyme was determined in both the apoform and as the PQQ-bound holoenzyme. The overall fold of the P. aerophilum enzyme showed significant similarity to that of soluble quinoprotein aldose sugar dehydrogenase (Asd) from E. coli. However, clear topological differences were observed in the two long loops around the PQQ-binding sites of the two enzymes. Structural comparison revealed that the hyperthermostability of the P. aerophilum enzyme is likely attributable to the presence of an extensive aromatic pair network located around a beta-sheet involving N- and C-terminal beta-strands.

Development of a compact system for the determination of lead using a liquid core waveguide and a blue diode as a light source.

A simple and compact system was developed for the on-site analysis of lead in environmental water samples. The system consisted of a custom-made blue diode as a light source, a liquid core waveguide (LCW) as spectrophotometric cell and a compact UV-visible spectrometer. It weighed within 1.5 kg in total. Lead was detected using a spectrophotometric indicator reagent (TPPS: 5,10,15,20-tetraphenyl-21H,23H-porphinetetrasulfonic acid, disulfuric acid, tetrahydrate) after masking interfering ions by coprecipitation with magnesium hydroxide. With an increase in the length of the LCW cell, the detection limit of lead was almost linearly enhanced, and the linear calibration range was shifted to a lower concentration range. The detection limit of lead by using 100 cm of a LCW cell was 2 nmol dm(-3). The observed value (9.6 +/- 0.4 microg dm(-3)) of lead in a river-water reference material (JSAC 0302-3) with this system was in good agreement with the certified value (9.9 +/- 0.2 microg dm(-3)).

Multielemental characterization of airborne particulate matter collected in Bucharest and Tokushima by inductively coupled plasma mass spectrometry and inductively coupled plasma atomic emission spectrometry.

Airborne particulate matter (PM) collected in Bucharest (Romania) and Tokushima (Japan) was comprehensively characterized through multielemental analysis by ICP-MS to the PM samples. Prior to an elemental characterization of the sample, a multielemental determination method composed of acid digestion (HClO(4)/HNO(3)/HF or H(2)O(2)/HNO(3)/HF) and inductively coupled plasma mass spectrometry/inductively coupled plasma atomic emission spectrometry (ICP-MS/ICP-AES) was established to analyze a certified reference material of vehicle exhaust matter (NIES No. 8) for verifying the method. As the results, 39 elements in the certified reference material could be determined. They were a good agreement with the certified and reference values for HClO(4)/HNO(3)/HF acid digestion. Chalcophile elements, such as cadmium, antimony, and lead in Bucharest showed higher enrichment factors than those in Tokushima.

An amperometric D-amino acid biosensor prepared with a thermostable D-proline dehydrogenase and a carbon nanotube-ionic liquid gel.

Carbon nanotube (CNT) gel, which is composed of a mixture of single-wall CNT, an ionic liquid, and a thermostable D-proline dehydrogenase (D-Pro DH) immobilized electrode was utilized for the determination of D-amino acids (DAAs) in food samples. When a critical comparison with CNT, Ketjen Black (KB), and carbon powder (CP) was also carried out, the CNT/D-Pro DH immobilized electrode showed the highest sensitivity and the lowest detection limit of D-proline. In addition, the CNT/D-Pro DH immobilized electrode was applied to detection of DAAs in rice wine and vinegar samples. The concentrations of DAAs in rice wine and vinegar samples were 0.0210 +/- 0.0001 and 0.55 +/- 0.05 mmol L(-1), respectively.

Association of low serum selenium with anemia among adolescent girls living in rural Vietnam.

OBJECTIVE: We investigated the prevalence of anemia and deficiency in trace elements in adolescent girls living in rural Vietnam. METHODS: Two hundred forty-five adolescent girls 11-17 y of age from three schools in rural province of Ha Nam, Vietnam, were assessed. RESULTS: The prevalence of anemia was 20.4%. The incidences of low serum selenium (Se), zinc, and copper in subjects were 15.9%, 26.5%, and 4.1%, respectively. The parameter significantly associated with anemia was the low serum levels of Se and vice versa (odds ratio [OR] 5.36, 95% confidence interval [CI] 2.57-11.18, P < 0.0001). Other risk factors for anemia were a body mass index <17.00 kg/m(2) (OR 2.72, 95% CI 1.37-5.37, P = 0.004) and years of age (OR 1.35, 95% CI 1.14-1.59, P < 0.001). A body mass index <17.00 kg/m(2) (OR 2.65, 95% CI 1.25-5.61, P = 0.011) was also found to be a risk factor for low serum Se. CONCLUSION: The findings of the present study demonstrate that low serum Se is independently associated with anemia in adolescent girls living in rural Vietnam. Interventions are required to gain insight into the potential role of Se on prevention and control of anemia.

Simultaneous determination of trimethyl-and triethyllead in urban dust by species-specific isotope dilution/gas chromatography-inductively coupled plasma mass spectrometry.

Both (206)Pb-labeled trimethyllead (TML) and triethyllead (TEL) were synthesized from (206)Pb-enriched metallic Pb certified reference material (NIST SRM 983) and iodomethane or iodoethane through a one-process reaction in a closed system using centrifuge tubes, respectively. Organolead compounds in an urban dust reference material (BCR CRM 605) were extracted with an acetic acid/methanol (1:1) solution, which was mechanically shaken for 24 h. After adjusting the pH of the extracted solution to pH 5, the extracted organolead compounds were derivatized by tetrabutylammonium tetrabutylborate (TATB) and measured with GC-ICPMS. The analytical results of TML and TEL for BCR CRM 605 were 8.22 +/- 0.04 microg kg(-1) (mean +/- standard deviation, n = 3) and 1.12 +/- 0.06 microg kg(-1), respectively. The analytical results of TML agreed well with the certified value (7.9 +/- 1.2 microg kg(-1)).

Development of a D-amino acids electrochemical sensor based on immobilization of thermostable D-proline dehydrogenase within agar gel membrane.

A novel biosensor for determination of d-amino acids (DAAs) in biological samples by using an electrode based on immobilization of a thermostable d-Proline dehydrogenase (d-Pro DH) within an agar gel membrane was developed. The electrode was simply prepared by spin-coating the agar solution with the d-Pro DH on a glassy carbon (GC) electrode. An electrocatalytic oxidation current of 2,6-dichloroindophenol (DCIP) was observed at -100mV vs. Ag/AgCl with the addition of 5 and 20mmolL(-1)d-proline. The current response and its relative standard deviation were 0.15muA and 7.6% (n=3), respectively, when it was measured in a pH 8.0 phosphate buffer solution containing 10mmolL(-1)d-proline and 0.5mmolL(-1) DCIP at 50 degrees C. The current response of d-proline increased with increase of the temperature of the sample solution up to 70 degrees C. The electrocatalytic response at the d-Pro DH/agar immobilized electrode subsequently maintained for 80 days. Finally, the d-Pro DH/agar immobilized electrode was applied to determination of DAAs in a human urine sample. The determined value of DAAs in the human urine and its R.S.D. were 1.39+/-0.12mmolL(-1) and 8.9% (n=3), respectively.

Micronutrient deficiencies and anemia among preschool children in rural Vietnam.

The prevalence of trace elements deficiencies, vitamin A deficiency, anemia, and their relationships were investigated in a cross sectional study involving 243 children aged from 12 to 72 months in rural Vietnam. Serum levels of copper, zinc, selenium and magnesium were determined by inductively coupled plasma mass spectrometer and that of retinol by high performance liquid chromatography. Hemoglobin concentration in whole blood was measured by the cyanmethemoglobin method. The prevalence of deficiencies in zinc, selenium, magnesium, and copper was 86.9%, 62.3%, 51.9%, and 1.7%, respectively. On the other hand, 55.6% were anemic and 11.3% had vitamin A deficiency. Deficiency in two or more micronutrient was found in 79.4% of the children. Parameters associated significantly with anemia were selenium deficiency (OR 2.80 95% CI 1.63-4.80, p=0.0002) and serum retinol<1.05 micromol/L (OR 1.83, 95% CI 1.10-3.05, p=0.021). Magnesium deficiency (OR 3.09 95% CI 1.36-7.03) was found to be a risk factor for zinc deficiency and vice versa. The results indicate that micronutrient deficiencies are prevalent among preschool children in Vietnam. In addition, the results also demonstrate a strong relationship between selenium deficiency and anemia. Clearly, sustainable strategies are urgently required to overcome the problems in the country.