Diaminonaphthalene functionalized LUS-1 as a fluorescence probe for simultaneous detection of Hg2+ and Fe3+ in Vetiver grass and Spinach.

One of the important problems in the environment is heavy metal pollution, and fluorescence is one of the best methods for their detection due to its sensitivity, selectivity, and relatively rapid and easy operation. In this study, 1,8-diaminonaphthalene functionalized super-stable mesoporous silica (DAN-LUS-1) was synthesized and used as a fluorescence probe to identify Hg2+ and Fe3+ in food samples. The TGA and FT-IR spectra illustrated that 1,8-diaminonaphthalene was grafted into LUS-1. XRD patterns verified that the LUS-1 and functionalized mesoporous silica have a hexagonal symmetrical array of nano-channels. SEM images showed that the rod-like morphology of LUS-1 was preserved in DAN-LUS-1. Also, surface area and pore diameter decreased from 824 m2 g⁻1 and 3.61 nm for the pure LUS-1 to 748 m2 g⁻1 and 3.43 nm for the DAN-LUS-1, as determined by N2 adsorption-desorption isotherms. This reduction demonstrated that 1,8-diaminonaphthalene immobilized into the pore of LUS-1. The DAN-LUS-1 fluorescence properties as a chemical sensor were studied with a 340/407 nm excitation/emission wavelength that was quenched by Hg2+ and Fe3+ ions. Hg2+ and Fe3+ were quantified using the fluorescence response in the working range 8.25-13.79 × 10-6 and 3.84-10.71 × 10-6 mol/L, with detection limits of 8.5 × 10-8 M and 1.3 × 10-7 M, respectively. Hg2+ and Fe3+ were measured in vetiver grass and spinach. Since the Fe3+ quenching can move in the opposite direction with sodium hexametaphosphate (SHMP) as a hiding compound for Fe3+, consequently, the circuit logic system was established with Fe3+, Hg2+, and SHMP as inputs and the fluorescent quench as the output.

Magnetic Poly(Amidoamine) Dendrimer for the Dispersive Solid Phase Extraction of Nitrophenols from Environmental Water Samples.

A fast and simple dispersive solid phase extraction method is described for nitrophenols determination in water samples by using gas chromatography-nitrogen phosphorous detector. Firstly, the Poly(amidoamine) grafted Fe3O4 magnetic nanoparticles were synthesized in different generations by successive addition of butyl acrylate and ethylenediamine. After characterization, the prepared dendrimer was utilized as an adsorbent for magnetic solid phase extraction of 2-nitrophenol, 3-nitrophenol, and 4-nitrophenol to benefit large number of surface amine interaction sites. The effects of the different parameters influencing the sample preparation efficiency were investigated. The proposed method showed linearity in the ranges of 0.04-700 and 0.05-700 µg/dm3 for nitrophenols. The obtained limits of detection and quantification under optimized conditions were 0.01-0.02 and 0.04-0.05 µg/dm3, respectively. The relative standard deviations (n = 5) were less than 3.8% (at 10 µg/dm3). Moreover, the calculated enrichment factors were above 200. In addition, the relative recoveries for a spiked river water sample were satisfactory.

Development of Solid-Phase Extraction Coupled with Dispersive Liquid-Liquid Microextraction Method for the Simultaneous Determination of Three Benzodiazepines in Human Urine and Plasma.

A new pretreatment method termed solid-phase extraction (SPE) which is combined with dispersive liquid-liquid microextraction (SPE-DLLME) has been developed for the determination of oxazepam, alprazolam and diazepam in urine and plasma samples. The analytes were extracted from biological samples using SPE followed by DLLME. Various parameters that affect the efficiency of the two extraction techniques have been optimized. The calibration plots were linear in the range of 2.5-500 µg L(-1) for oxazepam, alprazolam and 1.0-500 µg L(-1) for diazepam with detection limits of 0.7 µg L(-1) for oxazepam, alprazolam and 0.4 µg L(-1) for diazepam in plasma sample. The results confirm the suitability of the SPE-DLLME-HPLC-UV as a sensitive method for the analysis of the targeted analytes in urine and plasma samples.

Molecularly imprinted polymer on a SiO2 -coated graphene oxide surface for the fast and selective dispersive solid-phase extraction of Carbamazepine from biological samples.

A surface carbamazepine-imprinted polymer was grafted and synthesized on the SiO2 /graphene oxide surface. Firstly SiO2 was coated on synthesized graphene oxide sheet using the sol-gel technique. Prior to polymerization, the vinyl group was incorporated on to the surface of SiO2 /graphene oxide to direct selective polymerization on the surface. Methacrylic acid, ethylene glycol dimethacrylate and ethanol were used as monomer, cross-linker and porogen, respectively. Nonimprinted polymer was also prepared for comparison. The properties of the molecularly imprinted polymer were characterized using field-emission scanning electron microscopy and Fourier-transform infrared spectroscopy. The surface molecularly imprinted polymer was utilized as an adsorbent of dispersive solid-phase extraction for separation and preconcentration of carbamazepine. The effects of the different parameters influencing the extraction efficiency, such as sample pH were investigated and optimized. The specificity of the molecular imprinted polymer over the nonimprinted polymer was examined in absence and presence of competitive drugs. The carbamazepine calibration curve showed linearity in the ranges 0.5-500 µg/L. The limits of detection and quantification under the optimized conditions were 0.1 and 0.3 µg/L, respectively. The within-day and between-day relative standard deviations (n = 3) were 3.6 and 4.3%, respectively. Furthermore, the relative recoveries for spiked biological samples were above 85%.

Synthesis of a graphene-based nanocomposite for the dispersive solid-phase extraction of vancomycin from biological samples.

The approach of this work was to study the capability of graphene-based materials in the field of biological sample preparation. A polypyrrole/graphene composite was synthesized and characterized. The potential of the nanocomposite was investigated as a sorbent in dispersive solid-phase extraction followed by high-performance liquid chromatography with UV detection for vancomycin as a model drug. The effect of different parameters influencing extraction efficiency such as sample pH and sample volume, ionic strength, extraction time, type, and volume of desorption solvent and desorption time were investigated. A comparison study was also conducted between polypyrrole/graphene and some different novel and classic sorbents. Under optimized conditions, the calibration curve for vancomycin showed linearity in the range of 0.05-10 µg/mL. In addition, limits of detection, and quantification were 0.003 and 0.01 µg/mL, respectively. The intraday and interday relative standard deviations at a concentration of 0.05 µg/mL (n = 3) were 1.6 and 2.1%, respectively. Furthermore, the proposed method was successfully applied for the determination of vancomycin in plasma and urine samples. The relative recoveries indicated the feasibility of graphene-based sorbents in biological sample analysis.

Membrane protected conductive polymer as micro-SPE device for the determination of triazine herbicides in aquatic media.

A micro-SPE technique was developed by fabricating a rather small package including a polypropylene membrane shield containing the appropriate sorbent. The package was used for the extraction of some triazine herbicides from aqueous samples. Solvent desorption was subsequently performed in a microvial and an aliquot of extractant was injected into GC-MS. Various sorbents including aniline-ortho-phenylene diamine copolymer, newly synthesized, polypyrrole, multiwall carbon nanotube, C18 and charcoal were examined as extracting media. Among them, conductive polymers exhibited better performance. Influential parameters including extraction and desorption time, desorption solvent and the ionic strength were optimized. The developed method proved to be rather convenient and offers sufficient sensitivity and good reproducibility. The detection limits of the method under optimized conditions were in the range of 0.01-0.04 ng/mL. The RSDs at a concentration level of 0.1 ng/mL were obtained between 4.5 and 9.3% (n=5). The calibration curves of analytes showed linearity in the range of 0.05-10 ng/mL. The developed method was successfully applied to the extraction of selected triazines from real water samples. The whole procedure showed to be conveniently applicable and quite easy to manipulate.

Optimization of some experimental parameters in the electro membrane extraction of chlorophenols from seawater.

An electro membrane extraction (EME) methodology was utilized to study the isolation of some environmentally important pollutants, such as chlorophenols, from aquatic media based upon the electrokinetic migration process. The analytes were transported by application of an electrical potential difference over a supported liquid membrane (SLM). A driving force of 10V was applied to extract the analytes through 1-octanol, used as the SLM, into a strongly alkaline solution. The alkaline acceptor solution was subsequently analyzed by high performance liquid chromatography-ultraviolet (HPLC-UV) detection. The parameters influencing electromigration, including volumes and pH of the donor and acceptor phases, the organic solvent used as the SLM, and the applied voltage and its duration, were investigated to find the most suitable extraction conditions. Since the developed method showed a rather high degree of selectivity towards pentachlorophenol (PCP), validation of the method was performed using this compound. An enrichment factor of 23 along with acceptable sample clean-up was obtained for PCP. The calibration curve showed linearity in the range of 0.5-1000ng/mL with a coefficient of estimation corresponding to 0.999. Limits of detection and quantification, based on signal-to-noise ratios of 3 and 10, were 0.1 and 0.4ng/mL, respectively. The relative standard deviation of the analysis at a PCP concentration of 0.5ng/mL was found to be 6.8% (n=6). The method was also applied to the extraction of this contaminant from seawater and an acceptable relative recovery of 74% was achieved at a concentration level of 1.0ng/mL.

Immersed sol-gel based amino-functionalized SPME fiber and HPLC combined with post-column photochemically induced fluorimetry derivatization and fluorescence detection of pyrethroid insecticides from water samples.

A method based on direct immersion solid-phase microextraction (DI-SPME) coupled with high performance liquid chromatography combined with post-column photochemically induced fluorimetry derivatization and fluorescence detection (HPLC-PIF-FD) was developed to extract three pyrethroid insecticides, i.e. cyfluthrin, cypermethrin, and flumethrin from water samples. A sol-gel based coating fiber using 3-(trimethoxysilyl propyl) amine as precursor was prepared and used for the extraction of the pyrethroids from groundwater samples. A post-column photochemical reactor was designed and constructed for the derivatization of these environmentally important pollutants to increase their fluorescence sensitivity and determination in HPLC. The parameters affecting extraction process (extraction time and temperature, pH, salt addition, and co-solvent) and desorption step (solvent, desorption time, and temperature) of the analytes from the sol-gel-based fiber, along with photochemical reaction conditions were investigated. The developed method proved to be relatively rapid, simple, and easy and offers high sensitivity and reproducibility. Linear dynamic ranges (LDR) for these insecticides were ranged between 0.25 to 50 microg/L. The regression coefficients were satisfactory (R(2) > 0.984) for these pyrethroids. The limits of detection and limits of quantification varied between 0.09 and 0.35 microg/L and 0.25 and 1.00 microg/L, respectively. Relative standard deviation RSDs values varied between 4.41% and 6.20%. Relative recoveries obtained from analysis of Jajroud river water sample ranged between 94% and 104%.

An interior needle electropolymerized pyrrole-based coating for headspace solid-phase dynamic extraction.

A headspace solid-phase dynamic extraction (HS-SPDE) technique was developed by the use of polypyrrole (PPy) sorbent, electropolymerized inside the surface of a needle, as a possible alternative to solid-phase microextraction (SPME). Thermal desorption was subsequently, employed to transfer the extracted analytes into the injection port of a gas chromatography-mass spectrometry (GC-MS). The PPy sorbent including polypyrrole-dodecyl sulfate (PPy-DS) was deposited on the interior surface of a stainless steel needle from the corresponding aqueous electrolyte by applying a constant deposition potential. The homogeneity and the porous surface structure of the coating were examined using the scanning electron microscopy (SEM). The developed method was applied to the trace level extraction of some polycyclic aromatic hydrocarbons (PAHs) from aqueous sample. In order to enhance the extraction efficiency and increase the partition coefficient of analytes, the stainless steel needle was cooled at 5 degrees C, while the sample solution was kept at 80 degrees C. Optimization of influential experimental conditions including the voltage of power supply, the time of PPy electrodeposition, the extraction temperature, the ionic strength and the extraction time were also investigated. The detection limits of the method under optimized conditions were in the range of 0.002-0.01 ng mL(-1). The relative standard deviations (R.S.D.) at a concentration level of 0.1 ng mL(-1) were obtained between 7.54 and 11.4% (n=6). The calibration curves of PAHs showed linearity in the range of 0.01-10 ng mL(-1). The proposed method was successfully applied to the extraction of some selected PAHs from real-life water samples and the relative recoveries were higher than 90% for all the analytes.

Liquid-liquid-liquid microextraction followed by HPLC with UV detection for quantitation of ephedrine in urine.

Liquid-liquid-liquid microextraction (LLLME) in combination with HPLC and UV detection has been used as a sensitive method for the determination of ephedrine in urine samples. Extraction process was performed in a homemade total glass vial without using a Teflon ring, usually employed. Ephedrine was first extracted from 3.5 mL of urine sample (pH 12) into a microfilm of toluene/benzene (50:50). The analyte was subsequently back extracted into an acidic microdrop solution (pH 2) suspended in the organic phase. The extract was then injected into the HPLC system directly. An enrichment factor of 137 along with a good sample clean-up was obtained under the optimized conditions. The calibration curve showed linearity in the range of 0.01-50 mg/L with regression coefficient corresponding to 0.998. The LODs and LOQs, based on a S/N of 3 and 10, were 5 and 10 microg/L, respectively. The method was eventually applied for the determination of ephedrine in urine sample after oral administration of 5 mg single dose of drug.

A novel sol-gel-based amino-functionalized fiber for headspace solid-phase microextraction of phenol and chlorophenols from environmental samples.

A novel amino-functionalized polymer was synthesized using 3-(trimethoxysilyl) propyl amine (TMSPA) as precursor and hydroxy-terminated polydimethylsiloxane (OH-PDMS) by sol-gel technology and coated on fused-silica fiber. The synthesis was designed in a way to impart polar moiety into the coating network. The scanning electron microscopy (SEM) images of this new coating showed the homogeneity and the porous surface structure of the film. The efficiency of new coating was investigated for headspace solid-phase microextraction (SPME) of some environmentally important chlorophenols from aqueous samples followed by gas chromatography-mass spectrometry (GC-MS) analysis. Effect of different parameters influencing the extraction efficiency such as extraction temperature, extraction time, ionic strength and pH was investigated and optimized. In order to improve the separation efficiency of phenolic compounds on chromatography column all the analytes were derivatized prior to extraction using acetic anhydride at alkaline condition. The detection limits of the method under optimized conditions were in the range of 0.02-0.05ngmL(-1). The relative standard deviations (R.S.D.) (n=6) at a concentration level of 0.5ngmL(-1) were obtained between 6.8 and 10%. The calibration curves of chlorophenols showed linearity in the range of 0.5-200ngmL(-1). The proposed method was successfully applied to the extraction from spiked tap water samples and relative recoveries were higher than 90% for all the analytes.

Modified solvent microextraction with back extraction combined with liquid chromatography-fluorescence detection for the determination of citalopram in human plasma.

A modified solvent microextraction with back extraction method (SME/BE) combined with high performance liquid chromatography and fluorescence detection (HPLC-FD) was developed for the determination of citalopram in human plasma. Extraction process was performed in a home-made total glass vial without using a teflon ring, usually employed in SME/BE. Citalopram was first extracted from 0.5 mL of plasma, modified with sodium hydroxide, into hexane. Back extraction step was then performed into 5.2 microL of 45 mM ammonium formate solution (pH 4) using a GC microsyringe. The extract was subsequently transferred into a liner-like vial and then injected into the HPLC system. An enrichment factor of 150 along with a good sample clean-up was obtained. The calibration curve showed linearity in the range of 1.0-130.0 ng mL(-1) with regression coefficient corresponding to 0.992. This range covers therapeutic window and even lower amounts which is important in pharmacokinetic studies. Limits of detection and quantification, based on a signal to noise ratio (S/N) of 3 and 10, were 0.3 and 0.8 ng mL(-1), respectively. The method was also applied for the determination of citalopram in plasma samples after oral administration of 40 mg single dose of citalopram.

Determination of fentanyl in human plasma by head-space solid-phase microextraction and gas chromatography-mass spectrometry.

A head-space solid-phase microextraction (HS-SPME) method coupled to GC-MS was developed to extract fentanyl from human plasma. The protein binding was reduced by acidification and, eventually, the sample was deproteinized with trichloroacetic acid. The parameters influencing adsorption (extraction time, temperature, pH and salt addition) and desorption (desorption time and temperature) of the analyte on the fibre were investigated and validated for method development. The developed method proved to be rapid, simple, easy and inexpensive and offers high sensitivity and reproducibility. Linear range was obtained from 0.1 ng/ml to 2 microg/ml. The limit of detection was 0.03 ng/ml while an inter-day precision of less than 5% (n=15) could be achieved. The method has been applied for the determination of fentanyl in plasma samples after application of 50 microg/h Duragesic fentanyl patch.