Hamed Piri-Moghadam

An unbreakable on-line approach towards sol-gel capillary microextraction

In this work a novel unbreakable sol-gel-based in-tube device for on-line solid phase microextraction (SPME) was developed. The inner surface of a copper tube, intended to be used as a high performance liquid chromatography (HPLC) loop, was electrodeposited by metallic Cu followed by the self assembled monolayers (SAM) of 3-(mercaptopropyl) trimethoxysilane (3MPTMOS). Then, poly (ethyleneglycol) (PEG) was chemically bonded to the -OH sites of the SAM already covering the inner surface of the copper loop using sol-gel technology. The homogeneity and the porous surface structure of the SAM and sol-gel coatings were examined using the scanning electron microscopy (SEM) and adsorption/desorption porosimetry (BET). The prepared loop was used for online in-tube SPME (capillary microextraction) of some selected polycyclic aromatic hydrocarbons (PAHs), as model compounds, from the aquatic media. After extraction, the HPLC mobile phase was used for on-line desorption and elution of the extracted analytes from the loop to the HPLC column. Major parameters affecting the extraction efficiency including the sample flow rate through the copper tube, loading time, desorption time and sample volume were optimized. For investigating the sorbent efficiency, four loops based on the copper tube itself, the copper tube after electrodeposition with Cu and the tubes with the SAMs and SAMs-sol-gel coating were made and compared. The SAMs-sol-gel coated loop clearly shows a prominently lead of at least 20-100 times of higher efficiency. The linearity for the analytes was in the range of 0.01-500 μg L(-1). Limit of detection (LOD) was in the range of 0.005-0.5 μg L(-1) and the RSD% values (n=5) were all below 8.3% at the 5 μg L(-1) level. The developed method was successfully applied to real water samples while the relative recovery percentages obtained for the spiked water samples were from 90 to 104%. The prepared loop exhibited long life time due to its remarkable solvent and mechanical stability. Different solvents such as methanol, acetonitrile and acetone were passed through the loop for many days and it was also used for more than 100 extractions/desorption of the selected analytes and no decrease in the peak areas was observed.

Role of precursors and coating polymers in sol–gel chemistry toward enhanced selectivity and efficiency in solid phase microextraction

To evaluate the selectivity and efficiency of solid phase microextraction (SPME) fiber coatings, synthesized by sol-gel technology, roles of precursors and coating polymers were extensively investigated. An on-line combination of capillary microextraction (CME) technique and high performance liquid chromatography (HPLC) was set up to perform the investigation. Ten different fiber coatings were synthesized in which five of them contained only the precursor and the rests were prepared using both the precursor and coating polymer. All the coatings were chemically bonded to the inner surface of copper tubes, intended to be used as the CME device and already functionalized by self-assembly monolayers of 3-(mercaptopropyl)trimethoxysilane (3MPTMOS). The selected precursors included tetramethoxysilane (TMOS), 3-(trimethoxysilyl)propylmethacrylate (TMSPMA), 3-(triethoxysilyl)-propylamine (TMSPA), 3MPTMOS, [3-(2,3-epoxypropoxy)-propyl]-trimethoxysilane (EPPTMOS) while poly(ethyleneglycol) (PEG) was chosen as the coating polymer. The effects of different precursors on the extraction efficiency and selectivity, was studied by selecting a list of compounds ranging from non-polar to polar ones, i.e. polycyclic aromatic hydrocarbon, herbicides, estrogens and triazines. The results from CME-HPLC analysis revealed that there is no significant difference between precursors, except TMOS, in which has the lowest extraction efficiency. Most of the selected precursors have rather similar interactions toward the selected analytes which include Van der Walls, dipole-dipole and hydrogen bond while TMOS has only dipole-dipole interaction and therefore the least efficiency. TMOS is silica but the other sorbents are organically modified silica (ORMOSIL). Our investigation revealed that it is rather impossible to prepare a selective coating using conventional sol-gel methodologies. The comparison study performed among the fiber coatings contained only a precursor and those synthesized by a precursor along with coating polymer proved that the extraction efficiency obtained for all coatings are the same. This is an indication that by selecting the appropriate precursor there is no need to use any coating polymer. In overall, a fiber coating in sol-gel process could be synthesize with no coating polymer which leads to faster, easier, cheaper and more controllable synthesis.

Magnetic and electric field assisted electrospun polyamide nanofibers for on-line μ-solid phase extraction and HPLC

The effects of applied magnetic and electric fields on electrospinning were investigated to produce more efficient nanofibers. Considering the previous extensive studies, polyamide nanofibers were prepared by a conventional approach and under auxiliary electric and magnetic fields. The first sorbent was synthesized by electrospinning of a solution of 18% polyamide in formic acid. The second and third types of polyamide were prepared similarly while the electrospinning processes were assisted by an electric and a magnetic field. The third type of polyamide contained a magnetic ionic liquid (MIL) to induce sufficient magnetic susceptibility in the polymeric solution. The SEM images revealed that the application of auxiliary electric and magnetic fields led to the aligned nanofibers with mean diameters of 200 and 90 nm, respectively while for the conventional electrospun non-woven nanofibers the mean diameter was 500 nm. To evaluate the extraction efficiency of the prepared nanofibers, they were removed from the collector electrode and packed into the μ-solid phase extraction (μ-SPE) cartridge, coupled on-line with high performance liquid chromatography (HPLC). Apart from the influence of the assisted fields on electrospinning, the effects of size of the nanofibers and the ionic liquid content on the μ-SPE of imidacloprid, metribuzin, ametryn and chlorpyrifos were investigated. The highest extraction efficiency was achieved for the third sorbent due to its higher aspect ratio. After preparation of five sets of nanofibers, it was revealed that the presence of MIL dopant up to 10% in a solution of 18% polyamide exhibited the most satisfactory results. The linearity for the analytes was in the range of 1–500 μg L−1. The limit of detection (LOD) was in the range of 0.4–4 μg L−1 and the RSD% values (n = 5) were all satisfactory at the 20 and 200 μg L−1 levels. The applicability of the developed on-line μ-SPE-HPLC method was examined by analyzing real water samples obtained from spiked Zayandeh rood river and Caspian Sea and the relative recovery percentages were from 84 to 108% at 20 and 200 μg L−1 levels.

Grafting the sol-gel based sorbents by diazonium salts: a novel approach toward unbreakable capillary microextraction.

The present work deals with a novel approach for grafting a sol-gel based sorbent, using diazonium salts for preparation of an unbreakable capillary microextraction (CME) device in on-line combination with high performance liquid chromatography (HPLC). The use of diazonium salts modifier allowed all types of metallic and non-metallic substrates to be used without any limitation. Substrates including copper, brass, stainless steel and polytetrafluoroethylene (PTFE) were chosen to be functionalized by chemical or electrochemical reduction of 4-amino phenyl acetic acid. Then, 3-(trimethoxysilyl)propylamine (3TMSPA) was selected as the precursor and the only reagent for preparation of the desired surface chemical bonded sorbent. The presence of chemical bond between substrate, diazonium salts and 3TMSPA is more probably responsible for thermal and solvent stability and long lifetime of the prepared sorbent. Characterization of the aryl group formation on the various substrates along with the prepared sorbents was thoroughly investigated by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and thermogravimetry analysis (TGA). Typically, one of the prepared sorbents, deposited on the inner surface of the copper tube, was selected for assessing the developed method. The CME device was used for on-line extraction of atrazine, ametryn and terbutryn, as model compounds, from the aquatic media. After extraction, the HPLC mobile phase was used for on-line desorption and elution of the extracted analytes from the CME loop, containing the grafted sol-gel based sorbent, through the HPLC column. Figures of merit of the developed method were also obtained in which the linearity for the analytes was in the range of 30-1000μgL(-1). The value of LOD (S/N=3) for all analytes was 10μgL(-1) and the RSD% values (n=5) were all below 9.4% at the 500μgL(-1) level. Applicability of the developed method was examined by analyzing some real water samples in which the relative recovery percentage ranged from 75 to 95%.

Application of sol–gel based molecularly imprinted xerogel for on-line capillary microextraction of fentanyl from urine and plasma samples

A molecularly imprinted xerogel (MIX) for fentanyl was successfully prepared on the inner surface of a copper tube by sol–gel technology. Primarily, the tube was treated by self-assembly monolayers of 3-(mercaptopropyl) trimethoxysilane and then [3-(2,3-epoxypropoxy)-propyl]-trimethoxysilane was employed as a precursor for imprinting the template molecule in acidic conditions. During the sol–gel process influential parameters including volume and concentration of fentanyl were carefully investigated to obtain the most efficient and appropriate xerogel. In parallel, a non-imprinted xerogel (NIX) was synthesized in the absence of fentanyl. The extraction efficiencies achieved from MIX and NIX, showed some degree of selectivity for the MIX coating. Donepezil was used to estimate the selectivity of the imprinted xerogel with respect to the template molecule. The ratio of MIX/NIX, as a criterion of selectivity, was about 2.5 and 1.1 for fentanyl and donepezil, respectively. The linearity of the analyte was in the range of 5–5000 μg L−1. LOD was found to be 3 μg L−1 and the inter- and intra-day RSD% of 5.5 and 6.5 (n = 5) were obtained. The developed method was conveniently applied to plasma and urine samples spiked with the analyte, while the relative recovery percentages for the spiked samples were up to 85%.

Resorcinol–formaldehyde xerogel as a micro-solid-phase extraction sorbent for the determination of herbicides in aquatic environmental samples

In this study, organic aerogels were synthesized by the sol-gel polycondensation of mixed cresol with formaldehyde in a slightly basic aqueous solution. Carbon aerogels and xerogels are generated by pyrolysis of organic aerogels. The novel sol-gel-based micro-solid-phase extraction sorbent, resorcinol-formaldehyde xerogel, was employed for preconcentration of some selected herbicides. Three herbicides of the aryloxyphenoxypropionate group, clodinafop-propargyl, haloxyfop-etotyl, and fenoxaprop-P-ethyl, were extracted from aqueous samples by micro-solid-phase extraction and subsequently determined by gas chromatography with mass spectrometry. The effect of different parameters influencing the extraction efficiency of these herbicides including sample flow rate, sample volume, and extraction time were investigated and optimized. Under optimum conditions, linear calibration curves in the range of 0.10-500 ng/L with R(2) > 0.99 were obtained. The relative standard deviation at 50 μg/L concentration level was lower than 10% (n = 5) and detection limits were between 0.05 and 0.20 μg/L. The proposed method was successfully applied to the sampling and extraction of herbicides from Zayanderood and paddy water samples.

A combined micro-solid phase-single drop microextraction approach for trace enrichment of volatile organic compounds

An attempt was made to combine μ-solid phase extraction and headspace single drop microextraction techniques and use their advantages for trace determination of some volatile organic compounds in aqueous samples. After performing the two-step preconcentration approach, the desired analytes were determined by gas chromatography-mass spectrometry. A resorcinol-formaldehyde-based xerogel was used as the extraction medium in the μ-solid phase extraction (μ-SPE) method. Then, the extracted BTEX was eluted with a rather large amount of methanol. To remove the laborious process including solvent evaporation and further reconstitution, which is usually accompanied by loss of analytes and accuracy, headspace single drop microextraction (HS-SDME) was employed as the second orthogonal enrichment technique. The combination of these two techniques led to enrichment factors ranging from 118 to 504 for the extracted BTEX indicating the enhanced capability of the method towards aromatic compounds. Under optimum conditions, the limit of detection (LOD) varied from 0.03 to 0.1 μg L−1 and the linearity for the analytes was in the range of 0.1–100 μg L−1, while the RSD% values (n = 5) were all satisfactory at two concentration levels of 0.1 and 100 μg L−1. The applicability of the developed μ-SPE/HSSDME/GC-MS method was examined by analyzing river and paddy water samples and acceptable relative recovery percentages were obtained.