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1.
A new device for carbonyl compounds based on coupling on-line and miniaturizing both, sample pretreatment and chromatographic separation, is reported. Two capillary columns, a GC capillary column (95% methyl-5% phenyl substituted backbone, 70 cm × 0.32 mm i.d., 3 μm film thickness) in the injection valve for in-tube solid-phase microextraction (IT-SPME) and a Zorbax SB C18 (150 mm × 0.5 mm i.d., 5 μm particle diameter) LC capillary column were employed. Different combinations of IT-SPME and derivatization using 2,4-dinitrophenylhydrazine (DNPH) were examined for mixtures containing 15 carbonyl compounds (aliphatic, aromatic and unsaturated aldehydes and ketones). A screening analysis of aqueous extracts of atmospheric particulate PM(10) was carried out. Moreover, the possibility of coupling IT-SPME and conventional liquid chromatography is also tested. Derivatization solution and IT-SPME coupled to capillary liquid chromatography provided the best results for achieving the highest sensitivity for carbonyl compounds in atmospheric particulate analysis. Detection limits (LODs) using a photodiode array detector (DAD) were ranged from 30 to 198 ng L(-1), improving markedly those LODs reported by conventional SPME-LC-DAD.  相似文献   

2.
Fan Y  Feng YQ  Da SL  Wang ZH 《Talanta》2005,65(1):111-117
A configuration of in-tube solid-phase microextraction (SPME) coupled to HPLC was constructed by using a pump and a six-port valve combined with a PEEK tube as the pre-extraction segment. The extraction capillary was fixed directly on the HPLC six-port valve to substitute for the sample loop. The whole system could be handled easily to perform accurate on-line extraction, and the possible inaccurate quantification caused by sample/mobile phase mixing when using an autosampler could be eliminated.A β-cyclodextrin coated capillary, prepared by sol-gel method, was used as the extraction capillary for in-tube SPME. Three non-steroidal anti-inflammatory drugs, ketoprofen, fenbufen and ibuprofen, were employed to evaluate the extraction performance of the capillary. After optimizing the extraction conditions, satisfactory extraction efficiency was obtained and detection limits for ketoprofen, fenbufen and ibuprofen in diluted urine samples were 38, 18 and 28 ng/mL, respectively. The extraction reproducibility was evaluated with intra-day and inter-day precision, and the R.S.D.s obtained were lower than 4.9 and 6.9%, respectively. The capillary was proved to be reusable and the extraction efficiency did not decrease after 250 extractions.  相似文献   

3.
Odorous emissions from wastewater collection systems and treatment facilities affecting quality of life have given local populations reasons to complain for decades. In order to characterise the composition of such malodorous emissions, a method based on headspace solid-phase microextraction (HS-SPME) and gas chromatography coupled to mass spectrometry (GC-MS) has been developed to determine a list of compounds belonging to different chemical families, which have been previously described as potentially responsible for odour complaints, in wastewater matrices. Some parameters affecting the chromatographic behaviour of the target compounds were studied (e.g. splitless time). Experimental conditions affecting the extraction process (temperature, time and salt content) were evaluated by applying a factorial design at two levels. Using a DVB/CAR/PDMS fibre and the optimised HS-SPME conditions, calibration curves were constructed with detection limits in the range of 0.003-0.6 μg L(-1). Recovery values higher than 70% and relative standard deviation values between 5 and 16% (n=5) were obtained for all compounds and found to be satisfactory. In wastewater samples, a decrease in the concentration of the analysed compounds through the different treatments was observed. Most of the target analytes were found in influent samples while only octanal and carvone were detected in samples from the plant effluent.  相似文献   

4.
We report a new device for the estimation of the content of chlorophyll a pigment in water samples as an indicator of water quality. The extraction of the pigment from water was also optimized. 10 mL of water was filtered through a nylon filter (45 μm pore size and 13 mm of diameter), after the chlorophylls were dissolved by immersing the filter in 1 mL of a low non-hazardous solvent as ethanol. An in-valve in-tube SPME device coupled to capillary liquid chromatography with diode array detection was designed. A capillary column of 70 cm in length (0.32 mm i.d. coated with 5% diphenyl-95% polydimethylsiloxane, 3 μm coating thickness) was used as the loop of the injection valve for preconcentration and a Zorbax SB C18 (SiO2-based) 150 mm × 0.5 mm i.d., 5 μm column (Agilent) was used as analytical column. The achieved detection limit was 0.05 μg L−1 and the working range of concentrations was 0.1-1 μg L−1. % RSD values between 2 and 11 were obtained. Chlorophyll a in several water matrices was determined with good results in presence of other pigments such as chlorophyll b, pheophytin a and pheophytin b.  相似文献   

5.
Summary Al2O3-PLOT columns are used with great advantage for the analysis of volatiles, because of the increased capacity ratio and selectivity compared to WCOT-columns. Their applicability is limited to relatively non-polar components with relatively low boiling points i. e. eluting before n-decane.In the analysis of the halocarbons in stratospheric air, the decomposition of certain compounds was observed. In this study the stability of a number of volatile organic compounds was determined in function dependence of the column temperature using a two-dimensional GC-system.A possible reaction mechanism for the decomposition is proposed and confirmed for several chlorinated ethanes.  相似文献   

6.
A novel Fe3O4/graphene/polypyrrole nanocomposite has been successfully synthesised via a simple chemical method and applied as a new magnetic solid-phase extraction (MSPE) sorbent for the separation and pre-concentration of trace amounts of Pt (IV) in environmental samples followed by flame atomic absorption spectrometric (FAAS) detection. The nanocomposite has been characterised by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Fourier transform infrared (FTIR) spectroscopy. Seven important parameters, affecting the extraction efficiency of Pt (IV), including pH, adsorption time, desorption solvent type and concentration, desorption time, elution volume and sample volume, were investigated. Under the optimised conditions, the calibration graph was linear in the range of 50–1500 μg L?1 (R = 0.993). The detection limit and pre-concentration factor (PF) for Pt (IV) were found to be 16 μg L?1 and 112.5, respectively. Under the optimised solid-phase extraction (SPE) conditions, the adsorption isotherm and the adsorption capacity of the nanocomposite for Pt (IV) were studied. Pt (IV) adsorption equilibrium data were fitted well to the Langmuir isotherm and the maximum adsorption capacity of the magnetic sorbent was calculated from the Langmuir isotherm model as 416.7 mg g?1. The precision of the method was studied as intraday and interday variations. A relative standard deviation percentage (RSD%) value less than 3.0 indicates that the method is precise. Also, the accuracy of the method was tested by the analysis of the standard reference material (NIST SRM 2556) and by recovery measurements on spiked real samples. It was also shown that the optimised method was suitable for the analysis of trace amounts of Pt (IV) in roadside soil, tap water and wastewater samples.  相似文献   

7.
Before coal processing such as pyrolysis, liquefaction, gasification and combustion, it is very crucial to monitor the trace element concentration levels as that determines the coal quality. Therefore, the current study describes the development of microwave-assisted acid extraction (MW-AAE) method for extraction of 15 trace elements in coal samples prior to their determination using inductively coupled plasma-mass spectrometry. Diluted HNO3-H2O2 was used in order to reduce reagents amount used, eliminate matrix interferences caused by concentrated acids and to decrease waste produced in analytical laboratories. The optimisation of the proposed extraction method was carried out by using a full factorial design (24) involving four factors; that is, temperature, extraction time, HNO3 and H2O2 concentrations. The optimum conditions for the MW-AAE procedure were found to be 200°C, 5 min, 5 mol L?1 and 2 mol L?1 for temperature, extraction time, HNO3 and H2O2 concentrations, respectively. Under optimum conditions, the accuracy of the MW-AAE method was examined by analysing three coal certified reference materials (SARM 18, 19 and 20) and recoveries of 80–115% were achieved for V, Mn, Co, Ni, Cu, Zn, Ga, Ge, As, Sr, Zr, Cs, Ba, Pb and U, except for Ti (10–25%) and Hf (27–70%). In addition, the precision of the proposed method, expressed in terms of relative standard deviation (SD) (n = 15), was within the accepted range (≤3.5%). The method detection limits of 0.001–0.57 µg g?1 for all trace elements under the investigation were similar to the literature reported work, except for Ti (4.00 µg g?1).  相似文献   

8.
In this paper, an ordered mesoporous alumina coating was prepared and applied to capillary microextraction (CME) of trace Co, Ni and Cd for the first time. The coated capillary was used for on-line coupling CME with inductively plasma mass spectrometry (ICP-MS) for the determination of trace metals of Co, Ni and Cd. The porous structure of Al2O3 coating was examined by SEM and TEM. The effects of the extraction parameters including pH, sample flow rate and volume, elution solution and interfering ions on the recovery of analytes have been investigated and optimized. Under the optimized conditions, the limits of detection were 0.33, 1.5 and 1.4 ng L−1 for Co, Ni and Cd, respectively, with a preconcentration factor of 10 times. The precisions for all investigated elements were 2.7, 4.1 and 2.5% (c = 0.05 ng L−1, n = 7), for Co, Ni and Cd, respectively, and the sample frequency was 8 h−1.The proposed method was successfully applied for the analysis of trace metals in water, rice and urine samples with the recovery of 94-105%. In order to validate the proposed method, two certified reference materials of GBW 0913 human urine and NIES No.10-b rice flour were analyzed, and the determination values are in good agreement with the certified values. The ordered mesoporous Al2O3 coated capillary can be used more than 20 times without decreasing the extraction efficiency.  相似文献   

9.
TiO2 photocatalysts were synthesized by a hydrothermal method from tetraisopropyl orthotitanate (TPOT) in the presence of NH4F with different NH4F/Ti molar ratios (0, 0.25, and 1). The formation of a well-crystallized anatase phase of TiO2 and the suppression of phase transition to rutile were observed, even at high calcination temperature, owing to the effects of NH4F. The TiO2 synthesized hydrothermally with NH4F exhibited absorption with a shift to the longer wavelengths of the visible-light region. The hydrothermally synthesized TiO2 with a moderate amount of NH4F exhibited high photocatalytic activity for the degradation of alcohol diluted in water under both UV-light and visible-light irradiations.  相似文献   

10.
The composite of carboxyl-modified multi-walled carbon nanotubes (MWNT-COOH) and TiO2 nanoparticles was prepared in a solvothermal process. The x-ray diffraction (XRD), transmission electron microscope (TEM) and UV-vis spectrum were used to characterize the products. The results showed that the MWNT-COOH was dispersed uniformly in the composite and coated with TiO2 nanoparticles. The photo-reduction of Cr(VI) to Cr(III) in water catalyzed by the composite was investigated at room temperature. The photocatalytic activity of the composite markedly increased by a factor of approximately 2.2 in comparison with pure TiO2 (P25). Furthermore, the mechanism of the photocatalytic activity enhancement of the MWNT-COOH/TiO2 nanoparticles composite for the photo-reduction of Cr(VI) was discussed.  相似文献   

11.
In this work, a capillary electrophoresis (CE) procedure was developed for the simultaneous determination of a pharmaceutical drug and its counter-ion, namely labetalol hydrochloride. For this purpose, an uncoated fused-silica capillary, a low conductivity background electrolyte (BGE) and a capacitively coupled contactless conductivity detector (C4D) were employed. This detection system is highly sensitive and enables detection of inorganic as well as organic ions unlike with direct UV detection. Moreover, to be able to simultaneously analyze the cationic drug (labetalol+) and its anionic counter-ion (Cl) in the same electrophoretic run without the need of a coated capillary, a dual-opposite end injection was performed. In this technique, the sample is hydrodynamically injected into both ends of the capillary. This method is simple and easy to perform since the different injection steps are automated by the CE software.This novel CE-C4D procedure with dual-opposite end injection has been successfully validated and applied for the analysis of chloride content in an adrenergic antagonist (labetalol hydrochloride). Thus, the hereby developed method has been shown to enable fast (analysis time < 10 min), precise (repeatability of migration times < 0.7% and of corrected-peak areas < 3.3%; n = 6) and rugged analyses for the simultaneous determination of a pharmaceutical drug and its counter-ion.  相似文献   

12.
Ying Gao  Yuanhong Xu  Jing Li 《Talanta》2009,80(2):448-453
CE/Ru(bpy)32+ electrochemiluminescence (ECL) system with the assistance of ionic liquids (ILs) was successfully established for sensitive determination of verticine and verticinone in Bulbus Fritillariae for the first time. Migration behavior of alkaloid largely relies on the hydrogen bonding interactions between alkyl imidazolium cations in ILs and the alkaloids. Running buffer containing 40 mmol/L 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF4) IL-8 mmol/L phosphate resulted in significant changes in separation selectivity for alkaloids with similar structures. The highest sensitivity of the detection was obtained by maintaining the detection potential at 1.2 V. Under the optimized conditions, relative standard derivations of the ECL intensity and the migration time were 3.27 and 2.84% for verticine and 4.42 and 1.69% for verticinone, respectively. The standard curves were linear between 1 × 10−8 and 1 × 10−6 mol/L for verticine and between 5 × 10−8 and 1 × 10−6 mol/L for verticinone, respectively. Detection limits of 1.25 × 10−10 mol/L for verticine and 1 × 10−10 mol/L for verticinone were obtained (S/N = 3). Developed method was successfully applied to determine the amounts of alkaloids in Bulbus Fritillariae.  相似文献   

13.
Analytical derivatization either in pre or post column modes is one of the most widely used sample pretreatment techniques coupled to liquid chromatography. In the present review article we selected to discuss the post column derivatization mode for the analysis of organic compounds. The first part of the review focuses to the instrumentation of post-column setups including not only fundamental components such as pumps and reactors but also less common parts such as static mixers and back-pressure regulators; the second part of the article discusses the most popular “chemistries” that are involved in post column applications, including reagent-less approaches and new sensing platforms such as the popular gold nanoparticles. Some representative recent applications are also presented as tables.  相似文献   

14.
Chai Y  Ding H  Zhang Z  Xian Y  Pan Z  Jin L 《Talanta》2006,68(3):610-615
A new photocatalytic system, nano-TiO2-Ce(SO4)2 coexisted system, which can be used to determine the low chemical oxygen demand (COD) is described. Nano-TiO2 powders is used as photocatalyst in this system. The measuring method is based on direct determination of the concentration change of Ce(IV) resulting from photocatalytic oxidation of organic compounds. The mechanism of the photocatalytic oxidation for COD determination was discussed and the optimum experimental conditions were investigated. Under the optimum conditions, a good calibration graph for COD values between 1.0 and 12 mg l−1 was obtained and the LOD value was achieved as low as 0.4 mg l−1. When determining the real samples, the results were in good agreement with those from the conventional methods.  相似文献   

15.
Photocatalytic degradation of propiconazole, a triazole pesticide, in the presence of titanium dioxide (TiO2) under ultraviolet (UV) illumination was performed in a batch type photocatalytic reactor. A full factorial experimental design technique was used to study the main effects and the interaction effects between operational parameters in the photocatalytic degradation of propiconazole in a batch photo-reactor using the TiO2 aqueous suspension. The effects of catalyst concentration (0.15–0.4 gL?1), initial pH (3–9), initial concentration (5–35 mg L?1) and light conditions were optimised at a reaction time duration of 90 min by keeping area/volume ratio constant at 0.919 cm2 mL?1. Photocatalytic oxidation of propiconazole showed 85% degradation and 76.57% mineralisation under UV light (365 nm/30 Wm?2) at pH 6.5, initial concentration 25 mg L?1 and constant temperature (25 ± 1 °C). The Langmuir–Hinshelwood kinetic model has successfully elucidated the effects of the initial concentration on the degradation of propiconazole and the data obtained are consistent with the available kinetic parameters. The photocatalytic transformation products of propiconazole were identified by using gas chromatography–mass spectrometry (GC/MS). The pathway of degradation obtained from mass spectral analysis shows the breakdown of transformation products into smaller hydrocarbons (m/z 28 and 39).  相似文献   

16.
<正>The electrochemical behavior of vitamin C(ascorbic acid or AA) is investigated on the surface of a carbon-paste electrode modified with TiO_2 nanoparticles and 2,2'-(1,2 butanediylbis(nitriloethylidyne))-bis-hydroquinone(BBNBH).The prepared modified electrode showed an efficient catalytic role in the electrochemical oxidation of AA,leading to remarkable decrease in oxidation overpotential and enhancement of the kinetics of the electrode reaction.This modified electrode exhibits well-separated oxidation peaks for AA and uric acid(UA).The modified electrode is successfully applied for the accurate determination of AA in pharmaceutical preparations.  相似文献   

17.
A method for the extraction of triethyl lead (TEL+), trimethyl lead (TML+), and Pb2+ from sand was developed using supercritical modified CO2-CH3OH extraction and in situ complexation with sodium diethyldithiocarbamate (NaDDTC) using a 25 factorial exploratory design is described. The screened variables were (i) pressure (69-193 bar), (ii) temperature (40-150 °C), (iii) ligand amount (0-100 mg), (iv) methanol volume (0.0-0.5 mL) and (v) static time (0-45 min). The optimum extraction conditions found were as follow: pressure, 193 bar; temperature, 40 °C; amount of NaDDTC, 100 mg; methanol volume, 0.5 mL; static time 45 min; and CO2 flow rate, 1 mL min−1. Under these conditions the following recoveries were obtained (TML+ 97 ± 2%, TEL+ 70 ± 5%, and Pb2+ 100 ± 4%). The presence of NaDDTC is not necessary for the extraction of TML+ and TEL+, but it is a very significative parameter for Pb2+. A second experimental design 22 + star for temperature and pressure was realized, but the results were not better than those of the first model. SFE extract derivatization was achieved with pentylmagnesium bromide, and target analyte determination was carried out by gas chromatography-mass spectrometry. Detection limits in the full-scan mode were 4, 10, and 39 pg as lead for TMPeL, TEPeL and PbPe4, respectively. The method was validated with urban dust containing TML+ (CRM 605. Pb 7.9 ±1.2 μg kg−1) and river sediment containing inorganic lead (GBW08301. Pb 79.0 ± 12.0 mg kg−1) as reference materials. The proposed method was applied to lead analysis in sand collected from an oil-polluted beach in Chile.  相似文献   

18.
The reactions between Ln(AsF6)3 (Ln: lanthanide) and excess of XeF2 in anhydrous HF (aHF) as a solvent yield coordination compounds [Ln(XeF2)3](AsF6)3 or LnF3 together with Xe2F3AsF6 or mixtures of all mentioned products depending on the fluorobasicity of XeF2 and LnF3 along the series. XeF2 in a basic aHF is able to oxidize Pr3+ to Pr4+ besides Ce3+ to Ce4+ and Tb3+ to Tb4+. The tetrafluorides obtained are weaker fluorobases as XeF2 and are immediately exchanged with XeF2 yielding Xe2F3AsF6 and LnF4. The analogous reaction between Ln(BiF6)3 and XeF2 in aHF yields [Ln(XeF2)3](BiF6)3, Ln: La, Nd. Raman spectra of the compounds [Ln(XeF2)n](AF6)3 (A: As, Bi) show that no XeF+ salts are formed. The interaction of XeF2 with metal ion is covalent over the fluorine bridge. Analogous reactions of Ln(AsF6)3 with AsF3 in aHF yield [Ln(AsF3)3](AsF6)3 which are stable in a dynamic vacuum at temperatures lower than 233 K. In reactions between M(AF6)2 (M: alkaline earth metal and Pb, A: As, Sb) and XeF2 in aHF as a solvent, compounds of the type [M(XeF2)n](AF6)2 were synthesized. Analogous reactions with AsF3 yield coordination compounds of the type [M(AsF3)n](AsF6)2. During the preparation of Mx(AsF6)x (M: metal in oxidation state x+) by the reaction between metal fluoride and excess of AsF5 in aHF it was found that HF could also act as a ligand to the metal ions (e.g. Ca(HF)(AsF6)2).  相似文献   

19.
顾一丹  李继文  宋卫林  张祥民 《色谱》2014,32(2):204-209
采用离子色谱建立了合成气制烯烃(SGTO)水相产物和油相产物中C1~C6有机酸的测定方法。对分离条件进行了优化,使用标准样品测定了线性范围和工作曲线,考察了方法的精密度和准确度,确定了SGTO油相产物样品的碱洗条件,并对SGTO水相产物和油相产物样品进行了测定。结果表明:C1~C6有机酸的质量浓度在各自配制的质量浓度范围内呈现良好的线性关系,相关系数均大于0.99。标准溶液的回收率测定表明回收率在95.6%~104.3%之间,5次重复测定的相对标准偏差(RSD)在0.4%~3.6%之间,表明该方法具有良好的准确性和精密度。SGTO油相产物中的加标回收率在91.1%~96.8%之间,5次重复测定的RSD为0.7%~2.3%,准确性可以满足实际分析的需要。实际SGTO水相产物和油相产物中C1~C6有机酸的分析结果表明,SGTO水相产物中C2~C4有机酸含量较高,而SGTO油相产物中C4~C6有机酸含量较高。本研究对SGTO反应研究、催化剂制备、工艺优化以及设备材料的选择具有重要意义。  相似文献   

20.
The refinement of the crystal structure of Cu2O(SO4), dolerophanite, [a=9.370 (1) Å,b=6.319 (1) Å,c=7.639 (1) Å, =122.34 (1)°; space group C 2/m;Z=4;R=0.035] confirmed the trigonal dipyramidal coordination of one Cu(II) atom (mean distance Cu-O=2.025 Å). One O atom is tetrahedrally surrounded by four Cu(II) atoms; the mean Cu(II)-O distance of 1.918 Å compares well to [O Cu(II)4] tetrahedra found in inorganic crystal structures.de|Die Verfeinerung der Kristallstruktur von Cu2O(SO4), Dolerophanit, [a=9.370 (1) Å,b=6.319 (1) Å,c=7.639 (1) Å, =122.34 (1)°; Raumgruppe C 2/m;Z=4;R=0.035] bestätigte die trigonal dipyramidale Koordination des einen Cu(II)-Atoms (mittlerer Cu-O-Abstand=2.025 Å). Ein O-Atom ist tetraedrisch von vier Cu(II)-Atomen umgeben; der mittlere Cu(II)-O-Abstand von 1.918 Å entspricht den in ähnlichen [O Cu(II)4]-Tetraedern von anorganischen Kristallstrukturen gefundenen Werten.
Cu2O(SO4), Dolerophanit: Verfeinerung der Kristallstruktur mit einem Vergleich von [O Cu(II)4]-Tetraedern in anorganischen Verbindungen
  相似文献   

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