Implementation of acoustic, radiofrequency and microwave rotating fields in analytical plasma sources

Four helium plasma sources operating at atmospheric pressure have been developed for analytical emission spectrometry by applying a synchronically rotating field with three or more phases operating at 1 kHz, 27 MHz or 2.45 GHz. The plasma takes the form of a disk and has minimum field strength at the axis. Thus, a channel is formed at the center through which the sample in the form of wet aerosol or a chemically generated vapor of halogen may be introduced. A dual-flow concentric ceramic injector was used to supply helium plasma gas and the sample to the plasma. The helium plasma operated at low power levels (40-300 W) and low gas flow rates of below 3 L min^− 1 and was self-igniting. The acoustic, radio-frequency (rf) and microwave-driven plasmas can withstand wet aerosol loadings of 5, 30 and 100 mg min^− 1, respectively, generated by an ultrasonic nebulizer without a desolvation unit. The plasma physical characteristics were compared at these three frequencies under otherwise similar operating conditions. The helium excitation temperature, OH rotational temperature and electron number density increased with increasing frequency in ranges of 2800-4000 K, 1100-3200 K and 0.1-7 × 10¹⁴ cm^− 3, respectively. To demonstrate the effect of frequency on the plasma excitation efficiency the emission intensity from halogen ions was evaluated using chemical vapor generation with continuous sampling without desiccation. Using 3-phase microwave, 6-phase microwave, 4-phase rf and 1 kHz helium plasma sources the detection limits (3σ) for chlorine at 479.40 nm were 26, 60, 230 and 1200 ng mL^− 1, respectively. The microwave-driven plasma was the densest and had the highest excitation potential toward chlorine and bromine ions.     

Physical and analytical characteristics of an atmospheric pressure argon–helium radiofrequency capacitively coupled plasma

A very low power radiofrequency capacitively coupled plasma (13.56 MHz, 5–70 W), was generated in our laboratory on a sharp Kanthal tip without any counter electrode, as an intrinsic part of RLC series resonant circuit. Physical characteristics of this plasma obtained in Ar–He mixture, were studied as function of observation height or gas mixture composition. The excitation temperature of Ar (1500–2100 K), He (3000–3500 K) and H (2500–3200 K), the rotational temperature of the OH band (1300–2900 K), the electron temperature (5500–6500 K) and the electron number density (8 · 10¹³–2 · 10¹⁴ cm^− 3) were determined. The evolution of several atomic emission lines or molecular bands was studied in order to investigate the fundamental processes that take place in such plasma. From the point of view of analytical applications it was found that the optimum conditions of excitation (most intense emission lines and lowest detection limits) are met for a 42% He in the gas mixture and an observation height of 1 mm above the electrode. The optimum atomic emission analysis parameters were established for 7 elements (Na, Li, Ca, K, Cd, Zn and Hg) using pneumatically nebulized liquid solutions. It was found that the presence of He in the plasmogenic gas has an enhancing effect on the emission intensities and detection limits.     

Quenching of the OH and nitrogen molecular emission by methane addition in an Ar capacitively coupled plasma to remove spectral interference in lead determination by atomic fluorescence spectrometry

A new method is proposed to remove the spectral interference on elements in atomic fluorescence spectrometry by quenching of the molecular emission of the OH radical (A²Σ⁺ → X²Π) and N₂ second positive system (C³Π_u → B³Σ_g) in the background spectrum of medium power Ar plasmas. The experiments were carried out in a radiofrequency capacitively coupled plasma (275 W, 27.12 MHz) by CH₄ addition. The quenching is the result of the high affinity of OH radical for a hydrogen atom from the CH₄ molecule and the collisions of the second kind between nitrogen excited molecules and CH₄, respectively. The decrease of the emission of N₂ second positive system in the presence of CH₄ is also the result of the deactivation of the metastable argon atoms that could excite the nitrogen molecules. For flow rates of 0.7 l min^− 1 Ar with addition of 7.5 ml min^− 1 CH₄, the molecular emission of OH and N₂ was completely removed from the plasma jet spectrum at viewing heights above 60 mm. The molecular emission associated to CH and CH₂ species was not observed in the emission spectrum of Ar/CH₄ plasma in the ultraviolet range. The method was experimented for the determination of Pb at 283.31 nm by atomic fluorescence spectrometry with electrodeless discharge lamp and a multichannel microspectrometer. The detection limit was 35 ng ml^− 1, 2–3 times better than in atomic emission spectrometry using the same plasma source, and similar to that in hollow cathode lamp microwave plasma torch atomic fluorescence spectrometry.     

Plasma diagnostic on a low-flow plasma for inductively coupled plasma optical emission spectrometry

In order to elucidate the fundamental properties of a low-flow inductively coupled plasma (ICP) operated under total Ar consumption of 0.6 L min^− 1, excitation temperatures, rotational temperatures, ionization temperatures, electron temperatures, and electron number densities were studied with optical emission based methods. The plasma was operated in the SHIP torch (Static High Sensitivity ICP), which was designed for optical emission spectrometric detection.     

Time-resolved optical emission spectroscopic measurements of He plasma induced by a high-power CO2 pulsed laser

Laser-induced breakdown spectroscopy of helium plasma, initially at room temperature and pressures ranging from 12 to 101 kPa was investigated using a transverse excitation atmospheric CO₂ pulsed laser (λ = 9.621 and 10.591 μm, a full width at half maximum of 64 ns, and an intensity from 1.5 to 5.36 GW cm⁻²). The helium breakdown spectrum is mainly due to electronic relaxation of excited He, He⁺ and H. Plasma characteristics were examined in detail on the emission lines of He and He⁺ by the time-integrated and time-resolved optical emission spectroscopy technique. Optical breakdown threshold intensities, ionization degree and plasma temperatures were obtained. An auxiliary metal mesh target was used to analyze the temporal evolution of the species in the plasma. The results show a faster decay of the continuum emission and He⁺ species than in the case of neutral He atoms. The velocity and kinetic energy distributions for He and He⁺ species were obtained from time-of-flight measurements. Electron density in the laser-induced plasma was estimated from the analysis of spectral data at various times from the laser pulse incidence. Temporal evolution of electron density has been used for the estimation of the three-body electron-ion recombination rate constant.     

Temporally resolved laser induced plasma diagnostics of single crystal silicon — Effects of ambient pressure

Laser-Induced Breakdown Spectroscopy of silicon was performed using a nanosecond pulsed frequency doubled Nd:YAG (532 nm) laser. The temporal evolution of the laser ablation plumes in air at atmospheric pressure and at an ambient pressure of ∼ 10^− 5 mbar is presented. Electron densities were determined from the Stark broadening of the Si (I) 288.16 nm emission line. Electron densities in the range of 6.91 × 10¹⁷ to 1.29 × 10¹⁹ cm^− 3 at atmospheric pressure and 1.68 × 10¹⁷ to 3.02 × 10¹⁹ cm^− 3 under vacuum were observed. Electron excitation temperatures were obtained from the line to continuum ratios and yielded temperatures in the range 7600–18,200 K at atmospheric pressure, and 8020–18,200 K under vacuum. The plasma morphology is also characterized with respect to time in both pressure regimes.     

Development of a methodology to quantify tamoxifen and endoxifen in breast cancer patients by micellar liquid chromatography and validation according to the ICH guidelines

A simple micellar liquid chromatographic procedure is described to determine tamoxifen and endoxifen in plasma. For the analysis, tamoxifen and endoxifen solutions were diluted in water and UV-irradiated for 20 min to form the photocycled derivative with a phenanthrene core which shows intense fluorescence. Samples were then directly injected, thus avoiding long extraction and experimental procedures. The resolution from the matrix was performed using a mobile phase containing 0.15 mol L⁻¹ SDS-7% n-butanol at pH 3, running at 1.5 mL min⁻¹ through a C18 column at 40 °C. Detection was carried out by fluorescence, and the excitation and emission wavelengths were 260 and 380 nm, respectively. The chromatographic analysis time was 20 min. The analytical methodology was validated following the International Conference on Harmonisation of Technical Requirements for Registration of Pharmaceuticals for Human Use (ICH) guidelines. The response of the drugs in plasma was linear in the 0.5-15 μg mL⁻¹ range, with r² > 0.99. Accuracy and precision were <14% in both cases. Limits of detection and quantification (ng mL⁻¹) in plasma were 75 and 250 for endoxifen, and 50 and 150 in tamoxifen. The method developed herein does not show interferences by endogenous compounds. Finally the analytical method was used to determine the amount of tamoxifen and endoxifen in several plasma samples of breast cancer patients from a local hospital.     

Development of a miniature dielectric barrier discharge–optical emission spectrometric system for bromide and bromate screening in environmental water samples

Dielectric barrier discharge (DBD) at atmospheric pressure provides an efficient radiation source for the excitation of bromine and it is used for the first time for optical emission spectrometric (OES) detection of bromide and bromate. A portable DBD–OES system is developed for screening potential pollution from bromide and bromate in environmental waters. Bromide is on-line oxidized to bromine for in-situ generation of volatile bromine. Meanwhile, a helium stream carries bromine into the DBD micro-plasma for its excitation at a discharging voltage of 3.7 kV and optical emission spectrometric detection with a QE65000 charge-coupled device (CCD) spectrometer in the near-infrared spectral region. Similarly, the quantification of bromate is performed by its pre-reduction into bromide and then oxidized to bromine. The spectral characteristics and configuration of the DBD micro-plasma excitation source in addition to the oxidation vapor generation of bromine have been thoroughly investigated. With a sampling volume of 1 mL, a linear range of 0.05–10.0 mg L⁻¹ is obtained with a detection limit of 0.014 mg L⁻¹ by measuring the emission at 827 nm. A precision of 2.3% is achieved at 3 mg L⁻¹ bromide. The system is validated by bromine detection in certified reference material of laver (GBW10023) at mg L⁻¹ level, giving rise to satisfactory agreement. In addition, it is further demonstrated by screening trace bromide and bromate as well as spiking recoveries in a series of environmental water samples.     

Analysis of four alkaloids of Coptis chinensis in rat plasma by high performance liquid chromatography with electrochemical detection

A sensitive and precise high performance liquid chromatography (HPLC)-electrochemical detection (ECD) method has been developed for the simultaneous determination of four isoquinoline alkaloids including berberine, jatrorrhizine, coptisine and palmatine in Chinese medicine Coptis chinensis. The typical HPLC analysis was performed on WondaSil^® C18-WR column (250 × 4.6 mm, 5 μm) with the mobile phase comprising 40 mM phosphate buffer (pH 7.0)–acetonitrile (40:60, v/v) at the flow rate of 0.8 mL min⁻¹. The electrochemical detection employed a three electrode system with a bare glassy carbon electrode at +1.3 V versus the Ag/AgCl reference electrode. The limits of detection (LODs) of four alkaloids ranged from 0.01 to 0.03 μmol L⁻¹ and the LOD of berberine was 80 times lower than LOD obtained by UV detection. The rat plasma samples were assayed after oral administration of the traditional Chinese medicine Coptis chinensis by the proposed HPLC-ECD method. The recoveries of this method were ranging from 88.0 to 116%, with the relative standard deviation lower than 3.1% for intra-day precision and 5.7% for inter-day precision. These results show that HPLC-ECD is a useful tool for the quality control of herbal medicine Coptis chinensis and also for pharmacokinetic studies.     

Optical emission spectroscopy diagnostics of inductively-driven plasmas in argon gas at low pressures

An optical emission spectroscopy method for determination of electron temperature, electron density and gas temperature is developed and applied for diagnostics of inductively-driven argon discharges in a cylindrical geometry. The discharges are maintained at frequency 27 MHz, applied power varied in the limits P = (90 – 160) W and gas pressure in the range p = (1.1 – 117.3) Pa. The method combines measurements of emission spectral line intensities and profile broadenings with a collisional-radiative model of argon plasma at low pressure. The model is employed for investigation of the plasma kinetics governing the population densities of 3p⁵4s and 3p⁵4p argon configuration levels, treated separately. In the numerical calculations the electron density and electron temperature are varied whereas the values of the third plasma parameter — the gas temperature — are involved as obtained data from the experiments. Comparison of the experimental results of the line-intensity ratios with those calculated by the model yields the values of the electron density and temperature. The dependence of the electron temperature, electron density and gas temperature on the discharge conditions is obtained and discussed in the study.     

Trace element determination using static high-sensitivity inductively coupled plasma optical emission spectrometry (SHIP-OES)

A low-flow air-cooled inductively coupled plasma (ICP) design for optical emission spectrometry (OES) with axial plasma viewing is described and an evaluation of its analytical capabilities in trace element determinations is presented. Main advantage is a total argon consumption of 0.6 L min⁻¹ in contrast to 15 L min⁻¹ using conventional ICP sources.The torch was evaluated in trace element determinations and studied in direct comparison with a conventional torch under the same conditions with the same OES system, ultrasonic nebulization (USN) and single-element optimization. A variety of parameters (x-y-position of the torch, rf power, external air cooling, gas flow rates and USN operation parameters) was optimized to achieve limits of detection (LOD) which are competitive to those of a conventional plasma source.Ionic to atomic line intensity ratios for magnesium were studied at different radio frequency (rf) power conditions and different sample carrier gas flows to characterize the robustness of the excitation source. A linear dynamic range of three to five orders of magnitude was determined under compromise conditions in multi-element mode. The accuracy of the system was investigated by the determination of Co, Cr, Mn, Zn in two certified reference materials (CRM): CRM 075c (Copper with added impurities), and CRM 281 (Trace elements in rye grass). With standard addition values of 2.44 ± 0.04 and 3.19 ± 0.21 μg g⁻¹ for Co and Mn in the CRM 075c and 2.32 ± 0.09, 81.8 ± 0.4, 32.2 ± 3.9 for Cr, Mn and Zn, respectively, were determined in the samples and found to be in good agreement with the reported values; recovery rates in the 98-108% range were obtained. No influence on the analysis by the matrix load in the sample was observed.     

Towards the reduction of matrix effects in inductively coupled plasma mass spectrometry without compromising detection limits: The use of argon-nitrogen mixed-gas plasma

The multivariate optimization of a mixed-gas plasma was conducted in an attempt to find conditions minimizing matrix effects without sacrificing the detection limits that are observed with an all argon plasma optimized for maximum sensitivity in inductively coupled plasma mass spectrometry. Compared to the latter, where 49.1 ± 7.1% (n = 17) analyte signal suppression resulted in the presence of 0.1 M Na, 3.8 ± 3.2% suppression (and 2.8 ± 2.1% enhancement in some cases) was observed in the optimized mixed-gas plasma with 0.13% v/v N₂ in the plasma gas and 0.11% in the central channel as a sheath gas around the nebulizer gas flow. Furthermore, improved detection limits were observed for Al, Co, Pd, and V with the optimized mixed-gas plasma compared to an argon plasma at maximum sensitivity. The robustness of this mixed-gas plasma was further demonstrated through the accurate determination of U and Mo in NASS-5 seawater certified reference material using a simple external calibration, without matrix-matching or internal standardization. Indeed, the result obtained for Mo (9.1 ± 1.9 μg/L) was within the 95% confidence interval of the certified value of 9.6 ± 1.0 μg/L, while that obtained for U (3.0 ± 0.2 μg/L) was close to the information value of 2.6 μg/L. Spatial profiling results suggest better energy transfer between the toroidal zone and the central channel in the mixed-gas plasma.     

The investigation of argon plasma surface modification to polyethylene: Quantitative ATR-FTIR spectroscopic analysis

This paper studied the surface modification of argon plasma to polyethylene by using ATR-FTIR analysis. The mass loss ratio has maximum value at discharge time of 70-120 s or discharge power of 62 W by using argon plasma treatment for polyethylene. New surface structure was formed after polyethylene was treated by argon plasma. The peroxide bond peak area also has maximum value at discharge time of 70-120 s or discharge power of 62 W. The CC nonsaturated double bond absorb peaks were appeared at 1640 cm⁻¹, 1549 cm⁻¹ and 1528 cm⁻¹ after polyethylene treated by argon plasma. The CC nonsaturated double bond absorb peak area has minimum value at discharge time of 60-70 s and the power of 65 W. The CC nonsaturated double bond absorb peak area has maximum value at discharge power of 62-72 W and the discharge time of 2 min. The absorption peak intensity of 2916 cm⁻¹ methylene nonsymmetry stretch vibration, 2848 cm⁻¹ methylene symmetry stretch vibration, 1463 cm⁻¹ methylene nonsymmetry changing angle vibration, and 719 cm⁻¹ methylene swing in plane vibration was decreased greatly. The four absorption peaks intensity has maximum value at discharge time of 120 s or discharge power of 62 W.     

Combination of cool plasma and collision-reaction interface for correction of polyatomic interferences on copper signals in inductively coupled plasma quadrupole mass spectrometry

Inductively coupled plasma mass spectrometry (ICP-MS) is an important instrumental technique for elemental analysis. However, some elements suffer from spectral interferences caused by ions derived from argon plasma gas and matrix components. The determination of copper isotopes is affected by ⁴⁰Ar²³Na⁺ and ⁴⁰Ar²⁵Mg⁺. The performance of an ICP-MS with a collision reaction interface (CRI) and cool plasma conditions for correction of spectral interferences was evaluated here. The efficiency of the CRI was studied introducing H₂ or He through sampler and skimmer cones. Gas introduction through the sampler cone was ineffective. Complete elimination of spectral interferences was reached when introducing 60 or 80 mL min⁻¹ of H₂ in the skimmer cone, but sensitivity losses were as large as 99%. Further, the effect of interferences was checked when the argon plasma was operated under cool plasma conditions. The effects of the applied radiofrequency (0.6, 0.8, 0.9, and 1.0 kW), sampling depth (5.5, 8.5 and 11.5 mm), and dwell time (25 and 50 ms) were studied considering interference reduction and sensitivities. Best conditions were reached at 0.8 kW. Subsequently, both CRI and cool plasma conditions were combined to evaluate their performance on reduction of polyatomic Na and Mg argide interferences. Spectral interferences were eliminated using a CRI with 20 mL min⁻¹ H₂ introduced through the skimmer cone, cool plasma conditions at 0.8 kW and sampling depth of 8.5 mm. This work demonstrated the feasibility of combining CRI and cool plasma for circumventing some spectral interferences on Cu determination by ICP-QMS.     

Determination of dioxin-like polychlorinated biphenyls in 1 mL whole blood using programmable temperature vaporization large volume injection coupled to gas chromatogram and high-resolution mass spectrometry

A sensitive method based on programmable temperature vaporization large volume injection coupled to gas chromatogram and high-resolution mass spectrometry (PTV-GC–HRMS) has been developed for the determination of ultra trace levels of dioxin-like polychlorinated biphenyls (DL PCBs) in small amounts of human blood. Blood samples (1 mL) were first extracted by column extraction and then purified with column chromatorgraphies. Final extracts (20 μL) were introduced to the PTV injector under the solvent vent mode and detected by GC–HRMS (SIM mode). PTV parameters were observed by changing one factor at a time (practical conditions: vent flow: 50 mL min⁻¹, vent pressure: 0 kPa and vent time: 0.1 min), recoveries of most PCB congeners ranged from 55.1% to 108%, and method detection limits were in the range of 0.11–1.63 pg g⁻¹.     

Comparison of two lab-made spray chambers based on MSIS™ for simultaneous metal determination using vapor generation-inductively coupled plasma optical emission spectroscopy

The objective of this study is to evaluate the performance of two lab-made systems based on the Multimode Introduction System (MSIS™) and the modified MSIS™, to generate and introduce vapors of Ag, Cu, Cd, Cu, Ni, Sn, Zn, and also Au in the ICP torch. An univariate procedure was used to select the optimized working conditions (Ar flow, sample, reductant and waste flows, and reagent concentrations). Optimum conditions for working with modified MSIS were: nitric acid concentration 0.35 M, 8-hydroxyquinoline concentration: 40 mg L⁻¹, sodium borohydride concentration: 1.75% (w/v) + 0.4% (w/v) NaOH, argon purge flow to sweep the vapors to the torch: 1.2 L min⁻¹, sample flow and sodium borohydride flows: 2.3 L min⁻¹; waste flow: 7.7 mL min⁻¹. For the optimum working conditions for lab-made MSIS in dual mode the concentration of 8-hydroxyquinoline was 225 mg L⁻¹, the Ar purge flow was 0.75 L min⁻¹, and the conventional nebulization flow was 2.3 L min⁻¹. The sensitivity obtained was higher using the lab-made MSIS than using the lab-made modified MSIS or a forced outlet gas–liquid separator. The limits of detection were better for Au, Cd, Sn than those obtained using conventional nebulization; the measurements were precise (RSDs ≤ 5% in dual mode) and a good accuracy was obtained in the determination of Cd, Cu, Ni and Zn in a wastewater reference material using aqueous calibration and the lab-made MSIS in dual mode.     

A spectroscopic study of laser-induced tin–lead plasma: Transition probabilities for spectral lines of Sn I

In this paper, we present transition probabilities for 97 spectral lines of Sn I, corresponding to transitions n(n = 6,7,8)s → 5p², n(n = 5,6,7)d → 5p², 5p³ → 5p², n(n = 7)p → 6s, determined by measuring the intensities of the emission lines of a Laser-induced breakdown (emission) spectrometry (LIBS). The optical emission spectroscopy from a laser-induced plasma generated by a 10 640 Å radiation, with an irradiance of 1.4 × 10¹⁰ Wcm^− 2 on an Sn–Pb alloy (an Sn content of approximately 20%), in vacuum, was recorded at 0.8 µs, and analysed between 1900 and 7000 Å. The population-level distribution and corresponding temperature were obtained using Boltzmann plots. The electron density of the plasma was determined using well-known Stark broadening parameters of spectral lines. The plasma under study had an electron temperature of 13,200 K and an electron number density of 2 × 10¹⁶ cm^− 3. The experimental relative transition probabilities were put on an absolute scale using the branching ratio method to calculate Sn I multiplet transition probabilities from available radiative lifetime data of their upper states and plotting the Sn I emission spectrum lines on a Boltzmann plot assuming local thermodynamic equilibrium (LTE) to be valid and following Boltzmann's law. The LTE conditions and plasma homogeneity have been checked. Special attention was paid to the possible self-absorption of the different transitions. The experimental results obtained have been compared with the experimental values given by other authors.     

A highly sensitive HPLC method with automated on-line sample pre-treatment and fluorescence detection for determination of reboxetine in human plasma

A fully automated, rapid and highly sensitive HPLC method with automated sample pre-treatment by column-switching system and fluorescence detection has been developed for the trace quantitative determination of the new antidepressant reboxetine (RBX) in human plasma. A simple pre-column derivatization procedure with 7-flouro-4-nitrobenzo-2-oxa-1,3-diazole (NBD-F) reagent was employed. Paroxetine (PXT) was used as an internal standard. Plasma samples containing both RBX and PXT, after filtration, were derivatized by heating with NBD-F in borate buffer of pH 8 at 70 °C for 30 min. The derivatized plasma samples were injected into the HPLC system where an on-line sample clean up was achieved on the pre-treatment column (Co-sense Shim-pack MAYI-ODS) with a washing mobile phase (acetonitrile:2% acetic acid; 40:60, v/v) at a flow rate of 5 mL min⁻¹ for 1 min. After an automated on-line column switching to the analytical Hypersil phenyl 120A column (250 mm × 4.6 mm, 5 μm), the separation of the derivatized RBX and PXT was performed using a mobile phase consisting of sodium acetate buffer (pH 3.5):tetrahydrofuran:acetonitrile (55:35:10, v/v/v) at a flow rate of 2.0 mL min⁻¹. The eluted derivatives were monitored by a fluorescence detector set at an excitation wavelength of 470 nm and an emission wavelength of 530 nm. Under the optimum chromatographic conditions, a linear relationship with good correlation coefficient (r = 0.9995, n = 5) was found between the peak area ratio of RBX to PXT and RBX concentration in the range of 2-500 ng mL⁻¹, with limits of detection and quantification of 0.5 and 1.7 ng mL⁻¹, respectively. The intra- and inter-day precisions were satisfactory; the relative standard deviations were 2.25 and 3.01% for the intra- and inter-day precisions, respectively. The accuracy of the method proved as the mean recovery values were 100.11 ± 2.24% and 100.99 ± 2.98% for the intra- and inter-day assay runs, respectively. The proposed method involved simple and minimum sample preparation procedure and short run-time (<12 min) and therefore it can be applied to the routine therapeutic monitoring and pharmacokinetic studies of RBX.     

Sensitive determination of fluoride in biological samples by gas chromatography–mass spectrometry after derivatization with 2-(bromomethyl)naphthalene

A gas chromatography–mass spectrometric method was developed in this study in order to determine fluoride in plasma and urine after derivatization with 2-(bromomethyl)naphthalene. 2-Fluoronaphthalene was chosen as the internal standard. The derivatization of fluoride was performed in the biological sample and the best reaction conditions (10.0 mg mL⁻¹ of 2-(bromomethyl)naphthalene, 1.0 mg mL⁻¹ of 15-crown-5-ether as a phase transfer catalyst, pH of 7.0, reaction temperature of 70 °C, and heating time of 70 min) were established. The organic derivative was extracted with dichloromethane and then measured by a gas chromatography–mass spectrometry. Under the established condition, the detection limits were 11 μg L⁻¹ and 7 μg L⁻¹ by using 0.2 mL of plasma or urine, respectively. The accuracy was in a range of 100.8–107.6%, and the precision of the assay was less than 4.3% in plasma or urine. Fluoride was detected in a concentration range of 0.12–0.53 mg L⁻¹ in six urine samples after intake of natural mineral water containing 0.7 mg L⁻¹ of fluoride.     

Validated liquid chromatographic-fluorescence method for the quantitation of gemifloxacin in human plasma

A highly selective, sensitive and rapid high performance liquid chromatographic method has been developed and validated to quantify gemifloxacin in human plasma. The gemifloxacin and internal standard (ciprofloxacin) were extracted by ultrafiltration technique followed by injection into chromatographic system. Chromatographic separation was achieved on a reversed phase C₁₈ column with a mobile phase of acetonitrile:0.1% trifluoroacetic acid (20:80, v/v) using isocratic elution (at flow rate 1 mL min⁻¹). The analytes were detected at 269 and 393 nm for excitation and emission, respectively. The assay exhibited a linear range of 25-5000 ng mL⁻¹ for gemifloxacin in human plasma. The lower limit of detection was 10 ng mL⁻¹. The method was statistically validated for linearity, accuracy, precision and selectivity following FDA guidelines. The intra- and inter-assay coefficients of variation did not exceed 7.6% deviation of the nominal concentration. The recovery of gemifloxacin from plasma was greater than 97.0%. Stability of gemifloxacin in plasma was excellent with no evidence of degradation during sample processing (auto-sampler) and at least 3 months storage in a freezer at −70 °C. This validation method is applied for clinical study of the gemifloxacin in human volunteers.