GC determination of nicotine in subcutaneous adipose tissue obtained by minimal trauma tissue biopsy

Summary Nicotine has been analyzed by gas chromatography nitrogen-phosphorus detection in tissue samples obtained by repeated minimal trauma tissue biopsies from human subcutaneous adipose tissue. For sample preparation, a single extraction step of the tissue samples with chloroform was performed at 30–45°C. Calibration curves generated with spiked porcine subcutaneous adipose tissue were linear over a concentration range from 0.20 to 100 μg g⁻¹, therefore, the limit of quantification was fixed at 0.20 μg g⁻¹. The limit of detection was found to be 0.05 μg g⁻¹ adipose tissue. The recovery of nicotinespiked porcine subcutaneous adipose tissue by chloroform extraction was 100±8%. The performance of the assay was not affected by the complex lipid matrix. The method was employed for analysis in a clinical study on nicotine penetration from a transdermal delivery system through the skin of moderate smokers. Presented at Balaton Symposium on High Performance Separation Methods, Siófok, Hungary, September 1–3, 1999.     

Simultaneous determination of cocaethylene and cocaine in blood by gas chromatography with surface ionization detection

Summary Cocaethylene together with cocaine spiked in human whole blood has been found measurable at high sensitivities by capillary gas chromatography with surface ionization detection. The drugs could be rapidly extracted by Sep-Pak C₁₈ cartridges with recovery of more than 60%. The calibration curves for both cocaethylene and cocaine using cocapropylene as internal standard were linear in the range 50–300 pmol mL⁻¹ of whole blood. The detection limits of cocaethylene and cocaine were 5–10 pmol mL⁻¹ (0.1–0.2 pmol on column if recovery is 100%). Cocaethylene could be determined for whole blood obtained from rats (ca. 200 g body wt.), which had received subcutaneous injection of 10 mg cocaine hydrochloride and 2.0 mL of 30% (v/v) ethanol 3 h before sampling; the mean levels of cocaethylene and cocaine were 101 and 1230 pmol mL⁻¹, respectively.     

Determination of heterocyclic aromatic amines (HAA) in commercially available meat products and fish by high performance liquid chromatography—Electrospray tandem mass spectrometry (HPLC-ESI-MS-MS)

Summary Ten heterocyclic aromatic amines (HAA) (1)–(10) were analyzed in commercially available meat products and fish. After sample preparation by Extrelut treatment and subsequent solid phase extraction applying propylsulphonic and C₁₈ silica cartridges, HPLC-ESI-MS-MS using selected reaction monitoring (SRM) and d₃-PhIP and d₃-MeIQx as internal and external standards, respectively, revealed the widely distributed presence of PhIP (8) and MeIQx (4), ranging from 0.1 to 5.3 ng g⁻¹ and 0.1 to 5.2 ng g⁻¹, respectively. Lower amounts were found for 4,8-DiMeIQx (5) and 7,8-DiMeIQx (6), ranging from 0.2 to 2.0 ng g⁻¹ and 0.1 to 0.2 ng g⁻¹, respectively. The other HAA under study, i.e. IQ, MeIQ, 4,7,8-TriMeIQx, Glu-P-1, and Glu-P-2 were not determinable under the experimental conditions used (determination limit 0.1 ng g⁻¹).     

Microwave-assisted extraction followed by headspace solid-phase microextraction and gas chromatography with mass spectrometry detection (MAE-HSSPME-GC-MS/MS) for determination of polybrominated compounds in aquaculture samples

This paper describes the first validated method for the extraction, purification and determination of trace levels of a number of pollutants of growing concern, including polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs), in aquaculture feeds and products. The new procedure comprises microwave-assisted extraction (MAE; optimized, using a central composite experimental design, to 15 min at 85 °C in 14 mL of 1:1 hexane/dichloromethane), and concentration by headspace solid-phase microextraction (HSSPME), and separation/quantification by gas chromatography with mass spectrometry detection (GC-MS/MS). The method was validated on the reference materials IAEA-406 and WMF-01. Limits of detection for fourteen of the fifteen analytes considered range from 10 to 600 pg g⁻¹, and limits of quantification from 50 pg g⁻¹ to 1.9 ng g⁻¹. Linear ranges, accuracies and precisions are reported.     

Development of a non-labeled immunosensor for the herbicide trifluralin via optical waveguide lightmode spectroscopic detection

A highly sensitive immunosensor using optical waveguide lightmode spectroscopy (OWLS) was developed for the detection of the herbicide trifluralin. OWLS as an in situ and label free method of detection, based on the measurement of the diffraction of a linearly polarized laser beam (He-Ne laser, 632.8 nm) on a diffraction grating in a thin waveguide layer (SiO₂-TiO₂), offered means to produce immunosensors utilizing immobilized antibodies raised against trifluralin allowing a non-competitive biosensor, or immobilized trifluralin conjugate allowing a competitive biosensor for this analyte. Immobilization of molecules sensitizing the sensor was undertaken on amino silanized waveguide surfaces in a two-step procedure using glutaraldehyde. Within the immobilized antibody (Ab) based immunosensor the signal measured was proportional to the trifluralin content in the samples, but the method allowed detection of trifluralin only above 100 ng ml⁻¹ due to the small molecular size of the antigen (Ag). In the immobilized antigen based immunosensor, a trifluralin-bovine serum albumin (BSA) conjugate was covalently linked to the waveguide surface. During measurements the standard solutions and samples were mixed in 1:1 ratio with antiserum, containing constant amounts of antibodies. The amount of free antibodies bound to the surface was inversely proportional to the trifluralin content of the solutions measured. The immobilized antigen based method allowed detection of trifluralin in the concentration range of 2×10⁻⁷ to 3×10⁻⁵ ng ml⁻¹. Results of trifluralin determinations were compared to those obtained in parallel enzyme-linked immunosorbent assay (ELISA) tests and in gas chromatorgraphic-mass spectrometric (GC-MS) analyses, and indicated an increase of six orders of magnitude in the limit of detection (LOD).     

Mechanisms for negative reactant ion formation in an atmospheric pressure corona discharge

In an effort to better understand the formation of negative reactant ions in air produced by an atmospheric pressure corona discharge source, the neutral vapors generated by the corona were introduced in varying amounts into the ionization region of an ion mobility spectrometer/mass spectrometer containing a ⁶³Ni ionization source. With no discharge gas the predominant ions were O₂ ⁻, however, upon the introduction of low levels of discharge gas the NO₂ ⁻ ion quickly became the dominant species. As the amount of discharge gas increased the appearance of CO₃ ⁻ was observed followed by the appearance of NO₃ ⁻. At very high levels, NO₃ ⁻ species became effectively the only ion present and appeared as two peaks in the IMS spectrum, NO₃ ⁻ and the NO₃ ⁻·HNO₃ adduct, with separate mobilities. Since explosive compounds typically ionize in the presence of negative reactant ions, the ionization of an explosive, RDX, was examined in order to investigate the ionization properties with these three primary ions. It was found that RDX forms a strong adduct with both NO₂ ⁻ and NO₃ ⁻ with reduced mobility values of 1.49 and 1.44 cm²V⁻¹ s⁻¹, respectively. No adduct was observed for RDX with CO₃ ⁻ although this adduct has been observed with a corona discharge mass spectrometer. It is believed that this adduct, although formed, does not have a sufficiently long lifetime (greater than 10 ms) to be observed in an ion mobility spectrometer.     

Suitability of a Novel Circulating Cooling SPME for Analysis of Organophosphorous Pesticides in Tomatoes

The feasibility of circulating cooling-solid phase microextraction (CC-SPME) combined with gas chromatography-nitrogen phosphorous detector (GC-NPD) for the determination of five organophosphorous pesticides (OPPs) in tomato samples is evaluated. By heating the sample while cooling the fiber coating, the developed method provides better performance in terms of sensitivity, linearity and recovery than that of traditional headspace-solid phase microextraction (HS-SPME). The extraction capacities of activated carbon fiber (ACF) and three commercially available fibers were compared. ACF is found to be the most suitable fiber for the analysis of OPPs in tomatoes. The main factors affecting the CC-SPME process such as adsorption time, adsorption temperature and ionic strength were investigated and optimized. The matrix effect was evaluated, and concluded that addition of water is required to reduce the matrix effect. Good linearity (R ² > 0.992) is observed in the 1–200 ng g⁻¹ concentration range with satisfactory RSD (%) values of 5.6–8.5%. The limits of detection obtained using the proposed method range from 0.2 to 0.5 ng g⁻¹, and the recoveries for CC-SPME are in the range of 82.5–90.0% with RSDs lower than 8.7%. Experimental results confirm the usefulness of the proposed method for the analysis of OPPs in tomato samples.     

Quantitative analysis of temazepam in plasma by capillary gas chromatography: Application to pharmacokinetic studies in rats

Summary A sensitive method was developed for the determination of temazepam in plasma using capillary gas chromatography. After the extraction into dichloromethane-pentane (1∶1), temazepam was quantitated as its O-trimethylsilyl derivative on a capillary column with a⁶³Ni electron capture detector using prazepam as internal standard. The detector response was found to be linear in the concentration range 0.031 to 8 μg mL⁻¹. The detection limit was about 3.5 ng mL⁻¹. The intraday and inter-day coefficients of variation were below 9%. The method was used to determine the pharmacokinetic profile of temazepam in rats after intravenous administration.     

Sensitive determination of herbicide trifluralin on the surface of copper nanowire electrochemical sensor

A novel voltammetric method for the determination of trifluralin is proposed based on a composit of carbon paste and copper nanowire as a sensitive sensor. The presence of copper nanowire in the composite film enhance the conductivity and as a result increased the electron transfer rate constant and so the current will increase. The composite exhibits a promising higher electrocatalytic activity towards the oxidation of trifluralin in pH 4.0 aqueous solution. The reduction peak currents of trifluralin increased remarkably and the reduction peak potential shifted positively at the nanostructuring electrode, compared with that at a bare CPE which show the enhanced effect of nanowire. The support electrolyte to provide a more defined and intense peak current for trifluraline determination was 0.05 mol L⁻¹ phosphate buffer at pH 4.0. The fast Fourier transform square wave voltammetry was used as a new electrochemical technique in flow injection system to abtain more sensitivity by application of discrete fast Fourier transform method by background subtraction and two-dimensional integration of the electrode response over a selected potential range and time window, the signal-to-noise ratio has significantly increased and made the sensivity to be higher than other methods. The effective parameters such as frequency, amplitude, and pH were optimized to get the best sensitivity. As a result, the sensor showed a valuable response in linear concentration range of 100–0.02 nmol L⁻¹ with a (limit of detection) LOD of 0.008 nmol L⁻¹ and (limit of quantification) LOQ of 0.15 nmol L⁻¹ for trifluralin. A good recovery was obtained for assay spiked urine samples and a good quantification of trifluralin was achieved in soil samples.     

Detection limits of Au using fast and thermal neutron activation analyses

The applicability of fast and thermal neutron activation analyses for the determination of gold in rock samples has been studied. Using a Ge/Li/ detector limit of 0.45 mg g⁻¹ was obtained for a fast neutron flux of 8.10⁷ n cm⁻².s⁻¹. With a thermal neutron flux of 6.10⁵ n cm⁻².s⁻¹ and the same detector a value of 35 μg g⁻¹ was obtained. Using a NaI/Tl/ crystal a sensitivity of 14 μg g⁻¹ was attained at the same thermal flux. This work was supported in part by the Hungarian Academy of Sciences.     

Determination of the food carcinogen 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) in human hair by solid-phase extraction and gas chromatography-mass spectrometry

Summary A method for the determination of the food mutagen 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) in human hair has been developed and validated. Hair samples (200 mg) were dissolved in NaOH (1 M) and PhIP was isolated by successive solid-phase extraction on a polystyrene-divinylbenzene column and on a silica-based mixed-mode column with C₈ and-SO₃ ⁻ functional groups. Quantification was performed by gas chromatography-electron-impact ionization high-resolution mass spectrometry in selected-ion-monitoring mode. The method was validated for determination of PhIP in the concentration range 0.5–25 ng g⁻¹ hair with [²H₃]PhIP as internal standard. The limit of quantification was 0.26 ng g⁻¹ hair. Within-day and between-day precision were in the ranges 1–27% and 2–15% relative standard deviation, respectively. The hair sample used for method validation was found to contain 0.26 ng PhIP g⁻¹ hair.     

Electrochemical study of Meldola's blue,methylene blue and toluidine blue immobilized on a SiO<Subscript>2</Subscript>/Sb<Subscript>2</Subscript>O3 binary oxide matrix obtained by the sol-gel processing method

SiO₂/Sb₂O₃ (SiSb), having a specific surface area, S _BET, of 788 m² g⁻¹, an average pore diameter of 1.9 nm and 4.7 wt% of Sb, was prepared by the sol-gel processing method. Meldola's blue (MeB), methylene blue (MB) and toluidine blue (TB) were immobilized on SiSb by an ion exchange reaction. The amounts of the dyes bonded to the substrate surface were 12.49, 14.26 and 22.78 μmol g⁻¹ for MeB, MB and TB, respectively. These materials were used to modify carbon paste electrodes. The midpoint potentials (E _m) of the immobilized dyes were −0.059, −0.17 and −0.18 V vs. SCE for SiSb/MeB, SiSb/MB and SiSb/TB modified carbon paste electrodes, respectively. A solution pH between 3 and 7 practically did not affect the midpoint potential of the immobilized dyes. The electrodes presented reproducible responses and were chemically stable under various oxidation-reduction cycles. Among the immobilized dyes, MeB was the most efficient to mediate the electron transfer for NADH oxidation in aqueous solution at pH 7. In this case, amperometric detection of NADH at an applied potential of 0 mV vs. SCE gives linear responses over the concentration range of 0.1–0.6 mmol L⁻¹, with a detection limit of 7 μmol L⁻¹.     

HPLC quantification of formaldehyde, as formaldemethone, in plants and plant-like organisms

Summary Formaldehyde, as its dimedone adduct formaldemethone, has been detected and quantified in all the tested species of angiosperms, gymnosperms, pteridophytes, lichens and fungi, as well as in the two species tested of cyanobacteria and the one species of charophyte. Yields ranged from<10μg g⁻¹ to 6940 μg g⁻¹ fresh weight, calculated as formaldemethone (equivalent to <1 μg g⁻¹ to 713 μg g⁻¹ fresh weight, calculated as formaldehyde). An HPLC procedure was used for quantification of formaldemethone. A linear relationship was found between 20 and 2160 μg g⁻¹ and the statistical limit of detection was calculated as 48 μg g⁻¹.     

A study of the adsorption properties of the hypercross-linked polystyrene sorbents Styrosorb by gas chromatography. Effect of the conditioning temperature

The effect of the conditioning temperature of the hypercross-linked polystyrene sorbents Styrosorb on the retention ofn-hexane, benzene. and acetone was studied by gas chromatography. The rigid but mobile structure of 100% cross-linked polymers with a specific surface area of 300–500 m² g⁻¹ prepared in cyclohexane slightly shrinks by conditioning above 200 °C. This results in a significant increase in the specific retention volumes of the adsorbates. The commercial hypercross-linked sorbents MN-100 and MN-200 with specific surface areas of −1000 m² g⁻¹ retain their structure up to 250 °C. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1502–1506, August. 1999.     

Aqueous colloidal sol–gel route to synthesize nanosized ceria-doped titania having high surface area and increased anatase phase stability

Nanocrystalline sol–gel derived titania doped with ceria (1, 2, 5 and 10-mole%) has been prepared from titanyl oxysulphate. The titania doped with 5-mole% CeO₂ after calcining to 500 °C, possesses specific surface area of 97 m² g⁻¹ and has anatase phase stability up to 900 °C. Moreover it retains a surface area of 37 m² g⁻¹ at 700 °C. In comparison, the undoped calcined material has anatase stability only up to 700 °C and specific surface area only 48 m² g^-1 and 6 m² g^-1 at 500 °C and 700 °C, respectively. The diffuse reflectance spectra show that, as the cerium content increases, the absorption undergoes a red shift and reaches the visible range. The exceptionally high phase stability, crystallinity and high surface area are due to the extremely fine particle size and effective doping achieved by the specific synthesis method. The results based on X-ray diffraction, specific surface area and diffuse reflectance spectra indicated that the maximum threshold limit of doping is up to a value of 5-mole%.     

Purity testing of organometallic catalysts by micro liquid chromatography-electron ionization mass spectrometry

Summary A micro liquid chromatography-mass spectrometry system utilizing 100 μm i. d. packed capillary columns has been used for purity testing of organometallic catalysts. The total effluent, 1 μLmin⁻¹ from the column, was introduced directly into the ion source of a bench-top quadrupole mass spectrometer and electron ionization mass spectra were acquired. In full scan mode a mass limit of detection of 10–15 ng was achieved for the organometallic compounds investigated. The catalysts dimethyl pentamethylcyclopentadienyl iridium dimethylsulphoxide (Cp^*Ir(DMSO)Me₂) and di(pentamethylcyclopentadienyl dichloro iridium) ((Cp^*IrCl₂)₂) were purity tested and their electron ionization mass spectra recorded. Impurities present down to 1% of the main compound could be determined using large volume injection.     

Electrophoretic deposition of polyaniline nanofibers on a stainless steel wire as an adsorbent for determination of tamoxifen by SPME/GC–FID in urine samples

Polyaniline nanofiber films were fabricated on the surface of stainless steel wire via a controllable and simple electrophoretic deposition route from a nonaqueous colloidal suspension consisting of polyaniline nanofibers. The prepared coating material was then characterized by field emission scanning electron microscopy equipped with energy dispersive spectroscopy and elemental mapping analysis. The fabricated polyaniline film-coated stainless steel wire was then utilized as an effective and novel sorbent phase for solid-phase microextraction of tamoxifen for subsequent gas chromatography/flame ionization detection of this anticancer drug. Parameters consisting of the temperature, extraction time, salt concentration, agitation speed, pH, temperature and time of desorption were studied and optimized using a one-at-a-time strategy. Under the optimum conditions, detection limit (S/N = 3), the limit of quantification (10/3 limit of detection), linear dynamic range, repeatability and reproducibility values of 0.51 μg L⁻¹, 1.7 μg L⁻¹, 2–1,130 μg L⁻¹, 5.7% and 8.6% were attained, respectively. The prepared fiber can preserve 90% of its efficacy after 20 consecutive cycles, demonstrating the suitable thermal stability and cyclability of the proposed solid-phase microextraction coating material for the determination of tamoxifen by gas chromatography/flame ionization detection. The route was effectively utilized to determine tamoxifen in urine samples, with relative recoveries ranging from 89 to 106%.     

Development and validation of a gas chromatographic method for analysis of fosfomycin in chicken muscle samples

Summary A gas chromatographic method for the determination of residues of Fosfomycin in chicken muscle samples has been developed. Muscle samples were homogenised with TRIS buffer, containing phenylphosphonic acid (as internal standard) and Fosfomycin using a tissue homogenizer. Afterwards, the samples were ultrafiltered and the ultrafiltrate was evaporated to dryness. A silylation reagent for derivatization was used in order to reconstitute the residue. The linear concentration range of application was 10–150 μgg⁻¹, with a detection and quantitation limit of 3.11 and 10 μgg⁻¹, respectively. The method was efficient with a mean recovery of 87.83% from spiked muscle. The results obtained show that gas chromatography is a useful method for the determination of Fosfomycin residues in chicken muscle samples.     

Covalent Attachment of Some Phenol Derivatives to the Silica Surface by Use of Single-stage Aminomethylation

The reaction conditions and component ratios were established for the attachment of 4-(2-pyridylazo)resorcinol (PAR), 1-(2-pyridylazo)-2-naphthol (PAN) and 8-hydroxyquinoline (8-HQ) to the silica surface by means of a single-stage Mannich reaction. The modified sorbents that were synthesized were characterized by an adsorption method, and DRIFT and UV spectroscopies. The concentrations of PAR, PAN and 8-HQ grafted to the silica surface that were attained were 2.8×10⁻⁵, 8.5×10⁻⁵ and 2.7×10⁻⁴ mol g⁻¹, respectively. This revised version was published online in August 2006 with corrections to the Cover Date.     

Organosilica composite for preconcentration of phenolic compounds from aqueous solutions

A new adsorbent is proposed for the solid-phase extraction of phenol and 1-naphthol from polluted water. The adsorbent (TX-SiO₂) is an organosilica composite made from a bifunctional immobilized layer comprising a major fraction (91%) of hydrophilic diol groups and minor fraction (9%) of the amphiphilic long-chain nonionic surfactant Triton X-100 (polyoxyethylated isooctylphenol) (TX). Under static conditions phenol was quantitatively extracted onto TX-SiO₂ in the form of a 4-nitrophenylazophenolate ion associate with cetyltrimethylammonium bromide. The capacity of TX-SiO₂ for phenol is 2.4 mg g⁻¹ with distribution coefficients up to 3.4 × 10⁴ mL g⁻¹; corresponding data for 1-naphthol are 1.5 mg g⁻¹ and 3 × 10³ mL g⁻¹. The distribution coefficient does not change significantly for solution volumes of 0.025–0.5 L and adsorbent mass less than 0.03 g; 1–90 μg analyte can be easily eluted by 1–3 mL acetonitrile with an overall recovery of 98.2% and 78.3% for phenol and 1-naphthol, respectively. Linear correlation between acetonitrile solution absorbance (A ₅₄₀) and phenol concentration (C) in water was found according to the equation A ₅₄₀ = (6 ± 1) × 10⁻² + (0.9 ± 0.1)C (μmol L⁻¹) with a detection range from 1 × 10⁻⁸ mol L⁻¹ (0.9 μL g⁻¹) to 2 × 10⁻⁷ mol L⁻¹ (19 μL g⁻¹), a limit of quantification of 1 μL g⁻¹ (preconcentration factor 125), correlation coefficient of 0.936, and relative standard deviation of 2.5%. A solid-phase colorimetric method was developed for quantitative determination of 1-naphthol on adsorbent phase using scanner technology and RGB numerical analysis. The detection limit of 1-naphthol with this method is 6 μL g⁻¹ while the quantification limit is 20 μL g⁻¹. A test system was developed for naked eye monitoring of 1-naphthol impurities in water. The proposed test kit allows one to observe changes in the adsorbent color when 1-naphthol concentration in water is 0.08–3.2 mL g⁻¹.