Determination of total calcium in plasma by flow injection analysis with tris(2,2 '-bipyridyl)ruthenium(II) electrochemiluminescent detection

We described here a new method for the determination of total calcium in plasma. The method is based on the precipitation of calcium with excess oxalate and the measurement of residual oxalate by flow injection analysis with Ru(bpy)(3)(2+) electrochemiluminescent detection. It has the advantages of extremely stable reagent, user-friendly instrument, high selectivity, good analytical recovery, wide dynamic range, and nice correlation with atomic absorption spectroscopy. The calibration plot for calcium is linear over a concentration range from 0.5 mmol L-1 to 4.8 mmol L-1, which is wider than those obtained by most other methods. The analytical recoveries for plasma calcium are 98.4-101.2% with coefficients of variation (CVs) of 1.96-2.52%. The within-day CVs range from 0.76% to 0.95%, and between-day CVs were from 1.12% to 1.46%. The time for each injection is one minute. Because the proposed method can be readily carried out on increasingly popular instruments for Ru(bpy)(3)(2+) ECL immunoassays and DNA probe assays, Ru(bpy)32+ ECL method is suitable for routine clinical analysis of calcium.

Rapid automated in-situ monitoring of total dissolved iron and total dissolved manganese in underground water by reverse-flow injection with chemiluminescence detection during the process of water treatment

Measurement of iron and manganese is very important in evaluating the quality of natural waters. We have constructed an automated Fe(II), total dissolved iron(TDI), Mn(II), and total dissolved manganese(TDM) analysis system for the quality control of underground drinking water by reverse flow injection analysis and chemiluminescence detection(rFIA-CL), The method is based on the measurement of the metal-catalyzed light emission from luminol oxidation by potassium periodate. The typical signal is a narrow peak, in which the height is proportional to light emitted and hence to the concentration of metal ions. The detection limits were 3 x 10(-6) mu g ml(-1) for Fe(II) and the linear range extents up to 1.0 x 10(-4) and 5 x 10(-6) mu g ml(-1) for Mn(II) cover a linear range to 1.0 x 10(-4) mu g ml(-1). This method was used for automated in-situ monitoring of total dissolved iron and total dissolved in underground water during water treatment. (C) 1997 Elsevier Science B.V.

ON HALL AND KIERS TOPOLOGICAL STATE AND TOTAL TOPOLOGICAL INDEX

The topological state and the total topological index, tau, have been tested systematically. Counterexamples are provided proving that the topological state method cannot determine classes of symmetrically equivalent atoms in a molecule fully correct. The

EASTMAN-AQ/NIII MODIFIED ELECTRODE CHARACTERIZATION AND APPLICATION IN FLOW-INJECTION DETERMINATION OF CARBOHYDRATES AND AMINO-ACIDS

A novel Eastman-AQ/Ni(II) chemically modified electrode (CME) produced by "double coating step" deposition of a poly(ester sulphonic acid) polymer film and Ni2+-containing crystalline species onto glassy carbon instead of a metallic nickel electrode exhibited stable electrocatalytic oxidation of numerous alpha-hydrogen compounds including carbohydrates, amines and amino acids. In cyclic voltammetry, the electrocatalysis appeared with an irreversible anodic wave at +0.55 V (vs. Ag/AgCl). The CME was adapted for constant-potential amperometric detection of these compounds in flow injection analysis. Using the CME, the linear response concentration range was between 1.0 x 10(-5) and 5.0 x 10(-2) mol/l and the detection limit was 5.0 x 10(-6) mol/l for glucose. The stability of the CME was adequate for routine quantitative application.

Evaluation of 28 marine algae from the Qingdao coast for antioxidative capacity and determination of antioxidant efficiency and total phenolic content of fractions and subfractions derived from Symphyocladia latiuscula (Rhodomelaceae)

The extracts obtained from 28 species of marine algae were evaluated for their antioxidant activity (AA) versus the positive controls butylated hydroxytoluene (BHT), gallic acid (GA), and ascorbic acid (AscA). Most of the tested samples displayed antioxidant activity to various degrees. Among them, the extract of Symphyocladia latiuscula exhibited the strongest AA, which was comparable to BHT, GA, and AscA in radical scavenging activity, as shown in the DPPH (alpha,alpha-diphenyl-beta-picrylhydrazyl) assay, and higher than those of the positive controls in beta-carotene-linoleate assay system. In addition, the ethyl acetate-soluble fraction isolated from the crude extract of S. latiuscula exhibited the highest antioxidant activity in both assay systems. This fraction was further fractionated into seven subfractions (F1-F7) by vacuum liquid chromatography (VLC). F1 and F4 were found to be the most effective subfractions in scavenging DPPH radical assay and in the beta-carotene-linoleate assay, respectively. The total phenolic content (TPC) and reducing power (RP) for all of the extracts, fractions, and subfractions (F1-F7) were also determined. The TPC of the 28 extracts ranged from 0.10 to 8.00 gallic acid equivalents (mg/g seaweed dry weight) while the RP ranged from 0.07 to 11.60 ascorbic acid equivalents (mg center dot g(-1) seaweed dry weight). Highly positive relationships between AA and TPC as well as between AA and RP were found for the extracts and fractions, while for the subfractions F1-F7 only weak or no such relations were found. The results obtained from this study indicate that further analysis is needed of those marine algal species that contain the most antioxidant activity in order to identify the active principles.

Dynamic changes of total bacteria and Vibrio in an integrated seaweed-abalone culture system

Polyculture of seaweeds alongside fed animal aquaculture is an environmentally friendly means of avoiding eutrophication problem both in land-based and sea-based monoculture systems. Many aspects of such polyculture systems have been described, but little attention has been given to the impact of live seaweeds on the microbiological properties of the water that connects the algae and animals. In this investigation, the Pacific red alga Gracilaria textorii was cultured in a recirculated dual tank system (150 L) with the juvenile abalone Haliotis discus hannai. Dynamic changes of total bacteria (TB) and total Vibrio (TV) in the water of polyculture and monoculture systems were evaluated. Results revealed that (1) level of TB in the polyculture was constantly higher than in the monoculture over a 6.5-day period. While levels of TV in the polyculture was detected to be constantly lower than in the monoculture, (2) integration of G. textorii in the abalone culture changed the Vibrio compositions in the water as judged by the changes of bacteria colony types; (3) application of artificial diet led to dramatic increase of the levels in TB and TV in both systems at 12 h after application in the 24-h test and resulted in selective propagation of Vibrio in the water in the monoculture system; (4) polyculture of G. textorii with juvenile abalone in combination with feeding with live algal diet helped to maintain low levels of TV and the balance of the Vibrio composition; (5) living biomass of G. textorii was effective in preventing propagation of two purified Vibrio strains (V alginolaticus and V logei) in the water. These results provide a general basis of the dynamic changes of levels in TB and TV in a seaweed-abalone polyculture system with or without artificial diet in tanks. (c) 2005 Elsevier B.V All rights reserved.

Determination of Total Arsenic and Arsenic Metabolites in Human Liver Hepatocytes

The effects of direct sampling and three digestion methods were investigated on the determination of arsenic in Chang liver hepatocytes after ultrasonic disintegration were investigated. The results showed that the efficiency of microwave digestion and obturator digestion was better than cold digestion and direct sampling. The day precision (present as RSD) of microwave digestion and obturator digestion were 2.1% and 1.2% the inter-day precision were 1.2% and 2.0%, respectively. The spike recovery for the total As in the sample is 95.7% - 108.1%. The As detection limits with these four sample treatment methods (including direct sampling) were 0.74 - 0.93 mu g/L. In addition, arsenic speciation in Chang liver hepatocytes was also analyzed using the hyphenated technique of high performance liquid chromatography coupled with inductively coupled plasma-mass spectrometry. The experimental results indicated that dimethylarsinic acid (DMA) and an intermediate metabolite of DMA were found lit Chang liver hepatocytes besides inorganic arsenic (As(III) and As(V)).

Spatial and temporal variations in pH and total alkalinity at the beginning of the rainy season in the Changjiang Estuary, China

The results of field observation carried out in May 2003 were used to examine pH and total alkalinity behaviors in the Changjiang Estuary. It was showed that PH and total alkalinity took on clear spatial variations in values with the minima in the low salinity region. Like salinity, transect distributions of PH and total alkalinity (TA) in a downriver direction had a sharp gradient each. These gradients appeared in such a sequence that the TA gradient was earlier than salinity and PH gradients, and the salinity gradient was earlier than the PH gradient. These distribution characteristics seemed to be strongly influenced by the mixing process of freshwater and seawater, for both PH and total alkalinity had significant linear relationships with salinity and temperature. For PH, phytoplankton activities also had a significant impact upon its spatial distribution. During a period of 48 h, PH and total alkalinity changed within wide ranges for every layer of the two anchor stations, namely, Stas 13 and 20, which were located at the mixed water mass and seawater mass, respectively. For both Stas 13 and 20, PH and TA fluctuation of every layer could be very wide during a 4 h period. As a whole, the data of the two anchor stations showed that neither variations in salinity and temperature nor phytoplankton activities were the main factors strongly influencing the total alkalinity temporal variability on a small time scale. The data of Sta. 20 implied that both salinity variation and phytoplankton activities had a significant influence on PH temporal variability, but the same conclusion could not be drawn from the data of Sta. 13.

Variability in radiocarbon ages of biochemical compound classes of high molecular weight dissolved organic matter in estuaries

High molecular weight dissolved organic matter (HMW-DOM, > 1000 Da) represents a major fraction (> 30%) of dissolved organic carbon (DOC) in the ocean and thus plays an important role in the global biogeochemical cycling of carbon and many other elements. Its organic sources and formation mechanisms, however, are still not well understood especially in estuarine and coastal regions where multiple natural and anthropogenic sources contribute to total HMW-DOM. In this paper we report our measurements of natural radiocarbon (C-14) abundances and stable carbon isotope (C-13) compositions of the major biochemical compound classes: amino acids, carbohydrates and lipids separated from eight HMW-DOM samples collected from five US estuaries as part of our on-going study of sources, distribution and transport of chromophoric dissolved organic matter (CDOM) in estuarine and coastal waters. Distinct differences in both C-14 and C-13 values were found among the bulk HMW-DOM samples as well as the individual compound classes. Radiocarbon ages of the major compound classes varied by as much as 27,000 years in a single sample. The calculated average radiocarbon ages of the compound fractions of HMW-DOM indicate that the total lipid fraction is very "old", while the acid-insoluble fraction is slightly younger. Total amino acid and carbohydrate fractions, however, have relatively modern apparent C-14 ages. The significant variability in C-14 ages among the compound classes indicates not only multiple organic carbon sources but also different formation and turnover pathways controlling the cycling of different biochemical components of HMW-DOM in estuarine and coastal waters. (c) 2006 Elsevier Ltd. All rights reserved.

Total synthesis of bis-(2,3-dibromo-4,5-dihydroxyphenyl)-methane as potent PTP1B inhibitor

Protein tyrosine phosphatase 1B (PTP1B) plays an important role as a negative regulator and has been proved to be an effective target for the treatment of type 2 diabetes mellitus. Bis-(2,3-dibromo-4,5-dihydroxyphenyl)-methane 7 was first reported as a natural bromophenol with significant inhibition against PTP1B which was isolated from red algae Rhodomela confervoides. Intrigued by its astonishing activity (IC50 = 2.4 mu mol/L), compound 7 was synthesized with the overall yield of 24% and evaluated for its PTP1B inhibitory activity compared with natural compound. (C) 2008 Li Jun Han. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Comparison of the total amount of eggshell pigments in Dongxiang brown-shelled eggs and Dongxiang blue-shelled eggs

Based on the knowledge of the heme biosynthetic and metabolic pathway and the structures of biliverdin and protoporphyrin, experiments were carried out to compare the difference between the total quality of eggshell pigments in blue-shelled eggs and brown-shelled eggs from the same population (Dongxiang, China) and to analyze the correlation between the quantity of protoporphyrin and biliverdin in the 2 kinds of eggshells. It was found that there was no significant difference between the total quantity of eggshell pigments in Dongxiang blue-shelled eggs and Dongxiang brown-shelled eggs (P = 0.9006), and a highly significant positive correlation between the quantity of protoporphyrin and biliverdin in blue eggshells (P < 0.01) and a significant positive correlation between the quantity of protoporphyrin and biliverdin in brown eggshells (P < 0.05). These results suggested that eggshell protoporphyrin and eggshell biliverdin probably derived from common precursor material.

LC-DAD-ESI-MS Characterization of Carbohydrates Using a New Labeling Reagent

A novel labeling reagent 1-(2-naphthyl)-3-methyl-5-pyrazolone (NMP) coupling to liquid chromatography with electrospray ionization mass spectrometry for the detection of carbohydrates from the derivatized rape bee pollen samples is reported. Carbohydrates are derivatized to their bis-NMP-labeled derivatives. Derivatives showed an intense protonated molecular ion at m/z [M+H](+) in positive-ion detection mode. The mass-to-charge ratios of characteristic fragment ions at m/z 473.0 could be used for the accurately qualitative analysis of carbohydrates. This characteristic fragment ion is from the cleavage of C2-C3 bond in carbohydrate chain giving the specific fragment ions at m/z [MH-CmH2m+1Om-H2O](+) for pentose, hexose and glyceraldehydes and at m/z [MH-CmH2m-1Om+1-H2O](+) for alduronic acids such as galacturonic acid and glucuronic acid (m = n - 2, n is carbon number of carbohydrate). No interferences for all aliphatic and aromatic aldehydes presented in natural environmental samples were observed due to the highly specific parent mass-to-charge ratio and the characteristic fragment ions. The method, in conjunction with a gradient elution, offered a baseline resolution of carbohydrate derivatives on a reversed-phase Hypersil ODS-2 column. The carbohydrates such as mannose, galacturonic acid, glucuronic acid, rhamnose, glucose, galactose, xylose, arabinose and fucose can successfully be detected.

Analysis of carbohydrates in a tibetan medicine using new labeling reagent, 1-(2-naphthyl)-3-methyl-5-pyrazolone, by HPLC with DAD detection and ESI-MS identification

A new labeling reagent, 1-(2-naphthyl)-3-methyl-5-pyrazolone (NMP), coupling with liquid chromatography (LC) with electrospray ionization mass spectrometry (ESI-MS) for the detection of carbohydrates from a famous Tibetan medicine is reported. Carbohydrates were derivatized to their bis-NMP-labeled derivatives. The method, in conjunction with a gradient elution, offered a baseline resolution of carbohydrate derivatives on a reversed phase Hypersil ODS-2 column. The carbohydrates such as mannose, galacturonic acid, glucuronic acid, rhamnose, glucose, galactose, xylose, arabinose, and fucose could be successfully detected by UV and ESI-MS. Derivatives showed intense protonated molecular ion at m/z [M+H]+ in positive ion mode. The mass to charge ratios of characteristic fragment ions at m/z 473.0 could be used for the accurately qualitative identification of carbohydrates; this characteristic fragment ion was from the cleavage of C2-C3 bond in the carbohydrate chain giving the specific fragment ions at m/z [MH-CmH2m+1Om-H2O](+) for pentose, hexose, and glyceraldehydes, and at m/z [MH-CmH2m-1Om+1-H2O](+) for alduronic acids, such as galacturonic acid and glucuronic acid (m=n-2, n is carbon atom number of carbohydrate). Compared with the traditional 1-phenyl-3-methyl-5-pyrazolone (PMP) reagent, currently synthesized NMP show the advantage of higher sensitivity to carbohydrate compounds with UV and ESI-MS detection.