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21.
Gas‐phase photolysis of trimethoxysilane, achieved for the first time by focused ArF laser radiation at 193 nm, yields C1,2 hydrocarbons, methanol and carbon monoxide along with ultrafine nanostructured silicone powder possessing ? SiO3 and SiO4 configurations and Si? H and Si? OCH3 bonds. The photolytic process, resulting in efficient removal of the methyl groups, is explained as a multitude of steps involving cleavages of all the available bonds. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   
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Polybrominated diphenyl ethers (PBDEs) are flame retardants, which due to their widespread use are frequently present as pollutants in the environment. In the EU Water Framework Directive (WFD) six PBDE congeners (BDE 28, BDE47, BDE 99, BDE 100, BDE 153 and BDE 154) are listed as priority substances. The uncertainty of the analytical method used for their determination in water samples at environmental quality standard (EQS) level (0.5 ng L−1 for the ΣPBDEs) should be equal or less than 50% and the limit of quantification (LOQ) for ΣPBDEs below 0.15 ng L−1. To meet these requirements, an analytical procedure for the determination of these six PBDEs in environmental water samples by gas chromatography–inductively coupled plasma mass spectrometry (GC–ICP-MS) was developed. The acidification of water samples to pH 2 maintained the stability of PBDEs for at least 20 days. The use of Tris–citrate buffer enabled efficient desorption of PBDEs from suspended particulate matter (SPM) and humic acids (HA), and their further quantitative solvent extraction into 2 mL of iso-octane. When 300 mL of water sample was used for analysis and the organic phase concentrated to 25 μL, the expanded uncertainty for determination of PBDEs at EQS level was found to be around 40% (a coverage factor for a confidence level of 95%, k = 2), and the LOQ for the ΣPBDEs 0.109 ng L−1. Finally, to demonstrate the applicability of the newly developed GC–ICP-MS procedure, PBDEs were determined in river and sea water samples.  相似文献   
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Polybrominated diphenyl ethers (PBDEs) are flame retardants. As a consequence of their widespread use, they have been released into the environment. PBDEs are lipophilic organic contaminants that enter wastewater treatment plants (WWTPs) from urban, agricultural and industrial discharges. Because of their low aqueous solubility and resistance to biodegradation, up to 90% of the PBDEs are accumulated in the sewage sludge during the wastewater treatment. To assess the possibilities for sludge re-use, a reliable determination of the concentrations of these PBDEs is of crucial importance. Six PBDE congeners (BDE 28, BDE 47, BDE 99, BDE 100, BDE 153 and BDE 154) are listed as priority substances under the EU Water Framework Directive. In the present work a simple analytical method with minimal sample-preparation steps was developed for a sensitive and reliable determination of the six PBDEs in sewage sludge by the use of gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS). For this purpose an extraction procedure was optimised. Different extracting agents (methanol (MeOH), acetic acid (AcOH)/MeOH mixture (3:1) and 0.1 mol L−1 hydrochloric acid (HCl) in MeOH) followed by the addition of a Tris-citrate buffer (co-extracting agent) and iso-octane were applied under different modes of extraction (mechanical shaking, microwave- and ultrasound-assisted extraction). Mechanical shaking or the microwave-assisted extraction of sewage sludge with 0.1 mol L−1 HCl in MeOH and the subsequent addition of the Tris-citrate buffer and the iso-octane extracted the PBDEs from the complex sludge matrix most effectively. However, due to easier sample manipulation during the extraction step, mechanical shaking was used. The PBDEs in the organic phase were quantified with GC-ICP-MS by applying a standard addition calibration method. The spike recovery test (recoveries between 95 and 104%) and comparative analyses with the species-specific isotope-dilution (ID) GC-ICP-MS confirmed the accuracy of the developed analytical procedure. The procedure is sensitive (limits of detection (LODs) for PBDEs congeners between 0.2 and 0.3 ng g−1), repeatable and reproducible (RSDs 2.2–5.7%) and was applied for the determination of PBDEs in sewage sludge samples collected three times at the municipal WWTP over a period of 16 years.  相似文献   
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This paper deals with the results of indoor radon and thoron concentrations and exposure doses obtained for 63 dwellings out of the 14 rural communities of Central Kosovo, North Kosovo and Prizren region. These research activities are part of overall radiological research that has systematically been carried out since 1986, particularly in Kosovo and Metohija regions. Passive radon/thoron discriminative detectors, exposed for three months, were used. The arithmetic mean concentrations of indoor radon and thoron are CRn = 429 Bq m?3 CTn = 85 Bq m?3.  相似文献   
27.
A series of novel 1,2,3-triazolyl nucleoside analogues was synthesized via the CuAAC reaction of N1-alkynyl uracil, 6-methyluracil, 3,6-dimethyl uracil, thymine and quinazolin-2,4-dione with protected azido β-d-ribofuranose. The obtained compounds differ in both the nature of the pyrimidine-2,4-dione fragment and the length of the polymethylene linker connecting it with the β-d-ribofuranosyl-1,2,3-triazol-4-yl moiety. The 1,2,3-triazolyl nucleoside analogues were evaluated for their cytotoxicity in vitro.  相似文献   
28.
The applicability of an anion-exchange fast protein liquid chromatographic-electrothermal atomic absorption spectrometric procedure (FPLC-ETAAS) was investigated for the determination of Cr(VI) in welding fumes after alkaline extraction of aerosols loaded on filters. Gas tungsten arc welding (GTAW) of stainless steel was applied. Samples of welding fumes were collected during regular welding on polycarbonate membrane filters of 8 microm and 0.4 microm pore size (inhalable and respirable aerosols). Alkaline extraction (2% NaOH-3% Na2CO3) of filters in a heated ultrasonic bath was applied to leach Cr from the airborne particulate matter. 0.5 cm3 of sample extract was then injected onto an anion-exchange FPLC column. Tris-HCl buffer (0.005 mol dm(-3), pH 8.0) and the same buffer with NaCl (0.5 mol dm(-3)) were employed in gradient elution (15 min, flow rate 1 cm3 min(-1)). The separated Cr species were determined "off line" by ETAAS in 0.5 cm3 fractions. Cr(VI) was reproducibly and quantitatively eluted from 12.0 to 13.0 min with a maximum peak at 12.5 min. Good repeatability of measurement (+/-3.0%) of alkaline extracts was obtained for Cr(VI). The LOD (3s) was found to be 0.035 microg m(-3) Cr(VI), when 2 m3 of aerosols were collected on the filter. Validation of the procedure was performed by spiking alkaline extracts and by the analysis of standard reference material CRM 545, Cr(VI) in welding dust loaded on a filter. The technique was successfully applied for the determination of Cr(VI) in welding fumes.  相似文献   
29.
Temperature-programmed desorption coupled with mass spectrometer as a detector (TPD), IR and 13C NMR measurements are used to study the adsorption of n-hexane on hydrated HZSM-5 and NH4ZSM-5 zeolites. The 13C NMR measurements show that n-hexane can access the pore structure of ZSM-5 zeolites previously saturated with water. TPD spectra of n-hexane are monitored in the temperature region 50–300°C, in the case of fully or partially hydrated samples; two-stage desorption of n-hexane is found. Simultaneous desorption of water and n-hexane in the same temperature region are found, in all investigated samples.  相似文献   
30.
Scancar J  Milacic R  Benedik M  Krizaj I 《Talanta》2003,59(2):355-364
Total metal concentrations were determined in the serum of 12 continuous ambulatory peritoneal dialysis (CAPD) patients and in fresh and spent CAPD fluids by electrothermal and flame atomic absorption spectrometry (ETAAS, FAAS). Concentrations of Cu in serum of CAPD patients ranged from 720 to 1780 ng cm−3, Rb from 128 to 346 ng cm−3, Al from 10 to 72 ng cm−3, Fe from 800 to 2300 ng cm−3 and Zn from 659 to 1310 ng cm−3. The accuracy of the analytical procedure was checked by the analysis of the reference material Seronom™, Trace Elements in Serum. Good agreement between the certified and determined values was obtained for Al, Cu, Fe and Zn. The data on the total metal concentrations in CAPD fluids indicated that during CAPD fluid exchange the losses of Cu from 5.0 to 35 ng cm−3, of Rb from 50 to 110 ng cm−3 and of Al from 3.0 to 14.0 ng cm−3 occurred through the peritoneal membrane. Although fresh CAPD fluids contained traces of Fe (3.0-5.0 ng cm−3), the transfer of this element took place through the peritoneal membrane into spent CAPD fluid (13.0-38.0 ng cm−3). Zn concentrations were in general lower in spent (20.0-80 ng cm−3) than in fresh CAPD fluids (∼100 ng cm−3). To follow the mechanisms of the transfer of trace elements through the peritoneal membrane of CAPD patients, fractionation of metals was carried out in spent CAPD fluids by size exclusion chromatography with UV and AAS detection, applying Superdex HR 10/30 column. The chromatographic run was followed at 278 nm and separated metal species also determined ‘off line’ in 1 cm3 fractions by ETAAS or FAAS. From the UV chromatograms and AAS analysis of trace elements in the separated fractions it was demonstrated that Cu, Al, Fe and Zn were bound to proteins and only partially to low molecular weight (LMW) species, while Rb was associated exclusively with LMW species. For characterisation of the high molecular weight (HMW) binding proteins, fractions containing trace elements were subjected to SDS-PAGE electrophoresis. Al and Fe were presumably bound to transferrin, but due to its low concentration in spent CAPD fluids, it was not possible to confirm its presence in the separated fractions. About 10% of Al and 15% of Fe corresponded to LMW species. A fraction of HMW proteins of Cu in spent CAPD fluids was most probably bound to albumin and Zn to albumin and globulins. About 50% of Cu and Zn existed in LMW proteins, while Zn was also found partially in ionic form.  相似文献   
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