Quantitative Determination of Microcystins in Rat Plasma by LC-ESI Tandem MS

A rapid and sensitive method was developed and validated for the determination of MCYST (microcystin)-RR, -LR, and [Dha(7)] MCYST-LR in rat plasma by liquid chromatography-tandem mass spectrometry. The analytes were extracted from rat plasma by protein precipitation, followed by solid-phase extraction. Liquid chromatography with electrospray ionization mass spectrometry, operating in selected reaction monitoring (SRM) mode, was used to quantify MCYST-RR, -LR, and [Dha(7)] MCYST-LR in rat plasma. The recoveries for each analyte in rat plasma ranged from 70.8 to 88.7%. The calibration curve was linear within the range from 0.005 to 1.25 mu g mL(-1). The limit of detection were 1.4, 1.0, 0.6 ng mL(-1) for MCYST-RR, -LR, and [Dha(7)] MCYST-LR. The overall precision was determined on three different days. The values for within- and between-day precision in rat plasma were within 15%. This method was applied to the identification and quantification of microcystins in rat plasma with acute exposure of microcystins via intravenous injection.

Detection of the hepatotoxic microcystins in 36 kinds of cyanobacteria Spirulina food products in China

Gel filtration chromatography, ultra-filtration, and solid-phase extraction silica gel clean-up were evaluated for their ability to remove microcystins selectively from extracts of cyanobacteria Spirulina samples after using the reversed-phase octadecylsilyl ODS cartridge for subsequent analysis by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The reversed-phase ODS cartridge/silica gel combination were effective and the optimal wash and elution conditions were: H2O (wash), 20% methanol in water (wash), and 90% methanol in water (elution) for the reversed-phase ODS cartridge, followed by 80% methanol in water elution in the silica gel cartridge. The presence of microcystins in 36 kinds of cyanobacteria Spirulina health food samples obtained from various retail outlets in China were detected by LC-MS/MS, and 34 samples (94%) contained microcystins ranging from 2 to 163 ng g(-1) (mean=1427 ng g(-1)), which were significantly lower than microcystins present in blue green alga products previously reported. MC-RR-which contains two molecules of arginine (R)-(in 94.4% samples) was the predominant microcystin, followed by MC-LR-where L is leucine-(30.6%) and MC-YR-where Y is tyrose-(27.8%). The possible potential health risks from chronic exposure to microcystins from contaminated cyanobacteria Spirulina health food should not be ignored, even if the toxin concentrations were low. The method presented herein is proposed to detect microcystins present in commercial cyanobacteria Spirulina samples.

Simultaneous determination of microcystin-LR and its glutathione conjugate in fish tissues by liquid chromatography-tandem mass spectrometry

A sensitive and selective liquid chromatography-tandem mass spectrometry method was developed and validated for the simultaneous quantitative determination of microcystin-LR (MC-LR) and its glutathione conjugate (MC-LR-GSH) in fish tissues. The analytes were extracted from fish liver and kidney using 0.01 M EDTA-Na-2-5% acetic acid, followed by a solid-phase extraction (SPE) on Oasis HLB and silica cartridges. High-performance liquid chromatography (HPLC) with electrospray ionization mass spectrometry, operating in selected reaction monitoring (SRM) mode, was used to quantify MC-LR and its glutathione conjugate in fish liver and kidney. Recoveries of analytes were assessed at three concentrations (0.2, 1.0, and 5 mu g g(-1) dry weight [DW]) and ranged from 91 to 103% for MC-LR, and from 65.0 to 75.7% for MC-LR-GSH. The assay was linear within the range from 0.02 to 5.0 mu g g(-1) DW, with a limit of quantification (LOQ) of 0.02 mu g g(-1) DW. The limit of detection (LOD) of the method was 0.007 mu g g(-1) DW in both fish liver and kidney. The overall precision was determined on three different days. The values for within- and between-day precision in liver and kidney were within 15%. This method was applied to the identification and quantification of MC-LR and its glutathione conjugate in liver and kidney of fish with acute exposure of MC-LR. (c) 2007 Elsevier B.V. All rights reserved.

The optimization of high performance liquid chromatographic method for analysis of trace microcystins in natural water bodies

The ratio of methanol., water and trifluoroacetic acid ( TFA) was regulated to change the polarity and the pH of the rinse solution and the eluent, so as to improve the high performance liquid chromatography HPLC) detection method for trace microcystines (MCs) in natural water bodies. The results showed that 40 % similar to 45 % methanol-water solution containing 0. 1 % TFA could get good effects on the rinse of impurity, and 70% methanol-water solution containing 0. 1% TFA could elute all the MCs in solid phase extraction ( SPE) cartridge ( C-18), In this way. it is suggested that, in analysis of environmental samples with high concentration of impurity, impurity should be washed with 40% similar to 45% methanol-water solution containing 0. 1% TFA, and MCs should be eluted with 70% similar to 100% methanol-water solution containing 0. 1% TFA.

Mobilization potential of heavy metals: A comparison between river and lake sediments

Toxic metals introduced into aquatic environments by human activities accumulation in sediments. A common notion is that the association of metals with acid volatile sulfides (AVS) affords a mechanism for partitioning metals from water to solid phase, thereby reducing biological availability. However, variation in environmental conditions can mobilize the sediment-bound metal and result in adverse environmental impacts. The AVS levels and the effect of AVS on the fate of Cu, Cd, Zn, Ni in sediments in the the Changjiang River, a suboxic river with sandy bottom sediment and the Donghu Lake, a anoxic lake with muddy sediment in China, were compared through aeration, static adsorption and release experiments in laboratory. Sips isotherm equation, kinetic equation and grade ion exchange theory were used to describe the heavy metal adsorb and release process. The results showed that AVS level in the lake sediment are higher than that of the river. Heavy metals in the overlying water can transfer to sediments incessantly as long as the sediment remains undisturbed. The metal release process is mainly related to AVS oxidation in lake sediment while also related to Org-C and Fe-Mn oxyhydroxide oxidation in river sediment. The effect of sulfides on Zn and Ni is high, followed by Cd, and Cu is easy bound to Org-C. AVS plays a major role in controlling metals activity in lake sediment and its presence increase the adsorption capacity both of the lake and river sediments.

Nonylphenol, bisphenol-A and DDTs in Lake Donghu, China

A preliminary survey was carried out in April 2003 to estimate the levels of nonylphenol (NP), bisphenol-A (BPA) and residual DDTs in Lake Donghu. After then, the sediments of some areas of the lake were moved out for clearing the lake by the local government. Therefore, the variance of NP and BPA after the clearance of sediment in the surface water was determined from December 2003 to May 2004. Sediments, surface water and fish were collected from four sub-lake areas and the analytes were qualified by GC/MS in SIM mode after concentration onto an Oasis solid phase extraction cartridge. NP and BPA values ranged between 5.46-119.10 and 0.9913.42 mg/kg dw, respectively, in sediments, 75.2-179.6 and 15.1-62.5 mu g/L in surface water. Meanwhile, the bioaccumulation factors (BCFs) of NP and BPA were calculated in fish livers. Plasma vitellogenin (VTG), a sensitive biomarker showing oestrogenicity was detected in the captured male Wuchang bream (Megalobrama amblycephala Yih) and common carp (Cyprinus carpio). After sediment clearance, the concentrations of NP and BPA decreased to 0.65-25.04 and 0.04-21.32 mu g/L. The results indicate the presence of high-dose xenoestrogenic NP and BPA, probably major contributors which associate with VTG induction in Lake Donghu male fish.

Persistent organic pollutants in water and surface sediments of Taihu Lake, China and risk assessment

Organic pollutants, especially persistent organic pollutants were examined in the water and surface sediments of Taihu Lake, China. Both 12 water and 12 sediment samples were collected over the lake. C-18 solid-phase extraction technique was applied to extract organic pollutants in collected water samples. Soxhlet extraction procedure was used to extract organic pollutants in sediment samples. The analysis was performed by GC-MS controlled by a Hewlett Packard chemstation. Two hundred and seventy-three kinds of organic chemicals in water were examined, 200 more than that detected in 1985; 188 kinds of chemicals in sediments were detected as well. Among them 21 kinds of chemicals belong to priority pollutants as well as 17 kinds to be the endocrine disruptors. The concentrations of the pollutants were more than 2 times higher than that in 1985. The possible source and relation to anthropogenic activity were discussed. (C) 2002 Elsevier Science Ltd. All rights reserved.

Characterization of stress induced in SOS and Si/gamma-Al2O3/Si heteroepitaxial thin films by Raman spectroscopy

Raman spectroscopy technique has been performed to investigate the stress induced in as-grown silicon-on-sapphire (SOS), solid-phase-epitaxy (SPE) re-grown SOS, and Si/gamma-Al2O3/Si double-heteroepitaxial thin films. It was demonstrated that the residual stress in SOS film, arising from mismatch and difference of thermal expansion coefficient between silicon and sapphire, was reduced efficiently by SPE process, and that the stress in Si/gamma-Al2O3/Si thin film is much smaller than that of as-grown SOS and SPE upgraded SOS films. The stress decrease for double heteroepitaxial film Si/gamma-Al2O3/Si mainly arises from the smaller lattice mismatching of 2.4% between silicon top layer and the gamma-Al2O3/Si epitaxiial composite substrate, comparing with the large lattice mismatch of 13% for SOS films. It indicated that gamma-Al2O3/Si as a silicon-based epitaxial substrate benefits for reducing the residual stress for further growth of silicon layer, compared with on bulk sapphire substrate. (c) 2005 Elsevier B.V. All rights reserved.

The microstructure and its high-temperature annealing behaviours of a-Si : O : H film

The microstructure and its annealing behaviours of a-Si:O:H film prepared by PECVD are investigated in detail using micro-Raman spectroscopy, X-ray photoelectron spectroscopy and Infrared absorption spectroscopy. The results indicate that the as-deposited a-Si:O:H film is structural inhomogeneous, with Si-riched phases surrounded by O-riched phases. The Si-riched phases are found to be nonhydrogenated amorphous silicon (a-Si) clusters, and the O-riched phases SiOx:H (x approximate to 1. 35) are formed by random bonding of Si, O and H atoms. By high-temperature annealing at 1150 degreesC, the SiOx:H (x approximate to 1.35) matrix is shown to be transformed into SiO2 and SiOx ( x approximate to 0.64), during which all of the hydrogen atoms in the film escape and some of silicon atoms are separated from the SiOx:H ( x approximate to 1.35) matrix; The separated silicon atoms are found to be participated in the nucleation and growth processes of solid-phase crystallization of the a-Si clusters, nano-crystalline silicon (ne-Si) is then formed. The microstructure of the annealed film is thereby described with a multi-shell model, in which the ne-Si clusters are embedded in SiOx (x = 0.64) and SiO2. The former is located at the boundaries of the nc-Si clusters, with a thickness comparable with the scale of nc-Si clusters, and forms the transition oxide layer between the ne-Si and the SiO2 matrix.

The effects of pre-irradiation on the formation of Si1-xCx alloys

Carbon ions were implanted into crystal Si to a concentration of (0.6-1.5)at% at room temperature. Some samples were pre-irradiated with S-29(i)+ ions, while others were not pre-irradiated. Then the two kinds of samples were implanted with C-12(+) ions simultaneously, and Si1-xCx alloys were grown by solid phase epitaxy with high-temperature annealing. The effects of preirradiation on the formation of Si1-xCx alloys were studied. If the dose of implanted C ion was less than that for amorphizing Si crystals, the implanted C atoms would like to combine with defects produced during implantation, and then it was difficult for Si1-xCx alloys to form after annealine, at 950 degreesC. Pre-irradiation was advantageous for Si1-xCx alloy formation. With the increase of C ion dose, the damage produced by C ions increased. Pre-irradiation was unfavorable for Si1-xCx, alloy formation. If the implanted C concentration was higher than that for solid phase epitaxy solution, only part of the implanted C atoms form Si1-xCx alloys and the effects of pre-irradiation could be neglected. As the annealing temperature was increased to 1050 degreesC, Si1-xCx alloys in both pre-irradiated and unpreirradiated samples of low C concentration remained, whereas most part of Si1-xCx alloys in samples with high C concentration vanished.

The formation and characteristics of Si1-xCx alloys in Si crystals by means of implantation of cions with different doses

Carbon ions with concentration of (0.6-1.5)% were implanted into silicon crystals at room temperature and Si1-xCx alloys were grown by solid phase epitaxy with high temperature annealing. The formation and characteristics of Si1-xCx alloys under different implanted carbon doses were studied. If the implanted carbon atom concentration was less than 0.6%, carbon atoms would tend to combine with the defects produced during implantation and it was difficult for Si1-xCx alloys to form during annealing at 850-950 degreesC. With the increase of implanted C concentration, almost all implanted carbon atoms would occupy substitution positions to form Si1-xCx alloys, but only part of implanted carbon atoms would occupy the substitution position to form Si1-xCx alloys as the implanted dose increased to 1.5 %. Most Si1-xCx alloy phases would vanish as the annealing temperature was increased higher.

Polycrystalline silicon films prepared by improved pulsed rapid thermal annealing

An improved pulsed rapid thermal annealing (PRTA) has been used for the solid-phase crystallization (SPC) of a-Si films prepared by PECVD. The SPC can be completed with time-temperature budgets such as 10 cycles of 60-s 550 degrees C thermal bias/1-s 850 degrees C thermal pulse. The microstructure and surface morphology of the crystallized films are investigated by X-ray diffraction (XRD). The results indicate that this PRTA is a suitable post-crystallization technique for fabricating large-area poly-Si films on low-cost substrate. (C) 2000 Elsevier Science B.V. All rights reserved.

Hard magnetic properties of Sm3Fe26.7VxN4 and Sm3Fe26.7VxCy

Sm3Fe26.7V2.3N4 nitrides and Sm3Fe26.7V2.3Cy carbides have been synthesized by gas-solid phase reaction. Their hard magnetic properties have been investigated by means of additional ball-milling at room temperature. The saturation magnetization of Sm3Fe26.7V2.3N4 almost decreases linearly with increasing ball-milling time t, but that of Sm3Fe26.7V2.3Cy has no obvious change when the ball-milling time increases from t = 1 to 28 h. As a preliminary result, the maximum remanence B-r of 0.94 and 0.88 T, the coercivity mu(0i)H(C) of 0.75 and 0.25 T, and the maximum energy product (BH) of 108.5 and 39.1 kJ/m(3) for their resin-bonded permanent magnets are achieved, respectively, by ball-milling at 293 K. (C) 1999 Published by Elsevier Science B.V. All rights reserved.

Ge related defect energy and microcavity effect in GaN epitaxial layer

Using solid-phase regrowth technique, Pd/Ge contact has been made on the GaN layer, and very good ohmic behavior was observed for the contact. The Photoluminescence (PL) spectra for different structures formed by the Pd/Ge contact, GaN layer, sapphire substrate, and mirror were studied, and a defect-assisted transition was found at 450 nm related to Ge impurity. The results show that the microcavity effect strongly influences the PL spectra of the band-gap and defect-assisted transitions.

CERIUM SILICIDE FORMATION IN THIN CE SI MULTILAYER FILMS

Alternating layers of Si(200 angstrom thick) and Ce(200 angstrom thick) up to 26 layers altogether were deposited by electron evaporation under ultrahigh vacuum conditions on Si(100) substrate held at 150-degrees-C. Isothermal, rapid thermal annealing has been used to react these Ce-Si multilayer films. A variety of analytical techniques has been used to study these multilayer films after annealing, and among these are Auger electron spectroscopy, Rutherford backscattering, X-ray diffraction, and high resolution transmission electron microscopy. Intermixing of these thin Ce-Si multilayer films has occurred at temperatures as low as 150-degrees-C for 2 h, when annealed. Increasing the annealing temperature from 150 to 400-degrees-C for 1 h, CeSi2 forms gradually and the completion of reaction occurs at approximately 300-400-degrees-C. During the formation of CeSi2 from 150-400-degrees-C, there is some evidence for small grains in the selected area diffraction patterns, indicating that CeSi2 crystallites were present in some regions. However, we have no conclusive evidence for the formation of epitaxial CeSi2 layers, only polycrystals were formed when reacted in the solid phase even after rapid thermal anneal at 900-degrees-C for 10 s. The formation mechanism has also been discussed in combining the results of the La-Si system.