Sharif Digital Repository

The approach of this thesis is to develop and simplify robust microextraction techniques and apply these developed methods to real samples and complex matrices. Firstly, 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. The evaluation results demonstrated that the calibration curve showed linearity in the range of 1.0–130.0 ng/mL which covers therapeutic window and even lower amounts which is... 

In this study, a newly designed needle trap device (NTE) containing modified nanosilica as sorbent is used for sampling and preconcentration of some polycyclic aromatic hydrocarbons (PAHs) from headspace of aqueous solutions. An inexpensive modifier, cis-9-octadecenoic acid (oleic acid), which contains a long chain, was used to modify the surface of the nano-scaled silica particles. The hydrophobic interaction between oleic acid and aromatic compounds was the preliminary evidence for extraction of these compounds. After adsorption of selected compounds, thermal desorption was, subsequently, employed to transfer the extracted analytes into a GC–FID. Extraction time and temperature, flow rate... 

Novel electrospun nanofibers and their applications as the microextractionsorbents are the centre of this research. Polymeric nanofibers with diameter in the scale of nano-to-micro were prepared by the electrospinning method and employed for microextraction purposes. Two major microextraction methods included solid phase microextraction (SPME) and micro-Solid phase extraction (µ-SPE). In the first work, a novel SPME fiber was fabricated by electrospinning method. A thin stainless steel wire was coated by the network of polymeric nanofibers. The polymeric nanofiber coating on the wire was mechanically stable due to the fine and continuous nanofibers formation around the wire with a three... 

A simple, fast and sensitive method based on microextraction in packed syringe (MEPS), a new format of solid-phase extraction (SPE), as a sample preparation technique in off-line combination with gas chromatography-mass spectrometry (GC-MS) was developed. Polyaniline (PANI) nanowire network was synthesized and used as sorbent of MEPS for the multiresidue determination of selected analytes from triazine, organochlrorine and organophosphorous pesticides in aqueous samples. The PANI nanowires network was prepared using soft template technique and its characterization was studied by scanning electron microscopy (SEM). The use of micelles in this methodology has an important role in the shape of... 

In this study new magnetic solid phase extraction (MSPE) methods based on Fe3O4 magnetic nanoparticles (NPs) for extraction and preconcentration of oxadiargyl and fuoxetine from aqueous and biological samples were developed. In the first work, Fe3O4 NPs was successfully used as a magnetic nano-sorbent in magnetic micro-solid phase extraction (M-µ-SPE) of oxadiargyl, a newly used pesticide, from environmental water samples prior to gas chromatography-mass spectrometry determination. Oxadiargyl in mild acidic condition has tendency to be adsorbed on Fe3O4 NPs surfaces. Most important parameters that affect the extraction efficiency were also studied. Under optimized condition, the proposed... 

A novel Fe3O4/poly (aniline-naphthylamine) (ANI-NA)-based nanocomposite was synthesized by chemical oxidative polymerization process as a magnetic sorbent for magnetic solid phase extraction. The extraction efficiency of this sorbent was examined by isolation of rhodamine B (RhB), a mutagenic and carcinogenic dye from aquatic media in dispersion mode. The efficiency of the synthesized Fe3O4/copolymer composite was examined and compared with Fe3O4/polyaniline (PANI) and Fe3O4/polynaphthylamine (PNA) by quantification of RhB using spectrofluorimetry. Among them, Fe3O4/poly (ANI-NA) nanocomposite showed a prominent efficiency. The scaning electron microscopy (SEM) image of the synthesized... 

Electrospinning is a simple and versatile technique for producing polymeric and ceramic nanofibers. The conventional procedure for fabrication of ceramic nanofibers is a combination of sol-gel techniques and electrospinning. The main challenge is the spin polymer nanofiber in fabricate of fibers with diameter from 1 to 100 nm, while their standard deviation are as low as possible. Uniform beads free polyamidenanofibers with lower diameter were fabricated.A 18% w/w of polyamide in formic acid was chosen and the effect of magnetic field, adding magnetic ionic liquid surfactant, auxiliary electrode on the main fiber were investigated. They termsfiber 1 to fiber 5. The mean diameters of 489,... 

Liquid-liquid-liquid microextraction (LLLME) is a new miniaturized liquid extraction to preconcentrate and purify for ionizable analytes. In LLLME firstly analytes extracted in an organic phase, and subsequently back-extracted into a second aqueous phase. Main advantages of LLME are their speed, simplicity, negligible volume of solvents, analytical precision, short sample preparation and low cost. This technique was shown to be an efficient preconcentration method for the extraction of estrone and estriol from biological samples. A basic microdrop in the tip of microsyringe was fixed in the organic layer over the sample solution. After extraction for a preset time, the microdrop was... 

A novel application of diazonium salts for grafting the sol-gel based sorbents was sucessfully introduced. Preparation of unbrekable sorbents has been on highly demand and sough after by many researches for several years. However, there are a few achivements in this regard, but it still remains as a big challenge.Regarding to this issue, diazonium salts were sucessfully applied for functionalizing the different substrates, in which there is no limitation in selection of substrates. Different substrates, metallic and non metallic, such as copper, brass, stailess steel and PTFE were chosen to be functionalized by chemical or electrochemical reduction of 4-Amino phenyl acetic acid. Then,... 

An on-line solid phase extraction (SPE) method coupled with high performance liquid chromatography (HPLC) was developed using electrospun polyamide (PA) nanofibers as the extractin medium for trace determination of clodinafop propargyl herbicide in environmental aqueous samples. The sufficient numbers of disc sheets were cut from the electrospun PA mat and used as packing material in a cartridge. The homogeneity and the porosity of the prepared PA sheet were studied using the scanning electron microscopy (SEM) and the observed nanofiber diameters and lengths proved that the prepared sorbent possess a high aspect ratio. Major parameters affecting the extraction efficiency were optimized. The... 

In this study, a novel electrospun modified polyamide (PA) based nanofibers were synthesized and employed as fibers coating for rapid determination of chlorophenols. The major polymer solution contained PA along with polyethylene glycol (PEG), acting as a side low molecular weight polymer. After production of the PA−PEG fiber coating, PEG was subsequently removed and modified by water which was confirmed by Fourier transform infra-red spectrometry.The scanning electron microscopy images showed anaverage diameter of 640 and 148 nmforPA and PA−PEG coatings, respectively while the latter coating structure was homogeneous and porous.The extraction efficiency of unmodified and modified coatings... 

In the present work, the combination of single drop liquid phase microextraction and gas chromatography-mass detector (GC-MS) was used for determination of pesticides, Clodinafop, Haloxyfop and Fenoxyprop in natural water samples. a novel techniques based on SDME for develop in which solvents with higher density than water was successfully used. this technique could overcome some limitations of conventional SDME such as instability of organic droplet and limited stirrer rate in which result increasing the mass transfer rate and extraction efficiency. Experimental liquid phase microextraction (LPME) conditions, such as extracting solvent, stirring rate, micro drop volume, extraction time, pH... 

A method for determination of estrogens in biological samples was developed. This method was based on high performance liquid chromatography using online micro-solid phase extraction with 25 mg sorbent synthesized by electrospining of silica/PVA nanofibers. Poly (vinyl alcohol) (PVA) is an easily electrospun polymer with unique properties such as biocompatibility, processability, and hydrophilicity. Silica is biocompatible, thermally stable, and comparatively inert. Incorporation of silica with PVA produces hybrids with enhanced thermal and chemical stability in sample media and elution solvents without relinquishing the biocompatibility of PVA. The sufficient numbers of disc sheets were cut... 

This thesis contains two major sections. The first section is dealing with the preparation of conductive polymers-based sorbents while the second section is mostly focused on the synthesizing nanocomposites by electrospinning. All the prepared sorbents and nanofibers have been utilized to isolate some organic compounds in environmental and biological samples. Section I:In the first chapter, an unbreakable solid phase microextraction fiber coating based on aniline-silica nanocomposite was electrodeposited on a stainless steel wire. The electropolymerization process was carried out at a constant deposition potential, applied to the corresponding aqueous electrolyte containing aniline and... 

Porosity and high surface area is a profound concept for creating advance materials. Nanofibers are an important class of nano materials which would be used as novel sorbents because of their high surface to volume ratio as a result of long lengths and nano-to-micro-scale diameters. Electrospining is a simple method for producing fine nanofibers from different meterials such as, polymers, composites and ceramics to prepare highly efficient sorbents. Moreover, electrospining has been developed for fabricating nanofibers with core-shell structures. These structures in compared with conventional fibers have gained higher attentions due to their high aspect ratios and flexiblity in surface... 

In this study, ananomagnetic polyamidoamine (PAMAM) dendrimer was synthesized as a novel SPME fiber coating and implemented to the determination of traces of chlorophenols in water samples. The synthesized magnetic PAMAM shows to have many polar groups with an enhanced internal porosity which is promising to be used as an efficient extracting medium. With this purpose, a thin stainless steel wire was coated by the network of dendritic PAMAM polymer through electrolysis and chemical reactions. The synthesized fiber is physical stable since it was chemically bonded to the substrate. Extraction efficiency of new coating was investigated by headspace SPME of chlorophenols from aqueous samples... 

In this project, melamine formaldehyde was chosen as initial substrate for its high porosity. Then for having superhydrophobic surface, surface functional groups were silanized and deactivated as a result. It was assumed that high porosity of prepared sorbent and its nonpolar nature, can increase extraction efficiency. To study extraction efficiency of the prepared sorbent, it was filled inside a needle and used for needle-trap head-space extraction of BTEX (abbreviation for Benzene, Toluene, Ethylbenzene and Xylenes). Needle packed with sorbent was held on headspace of sample containing BTEX and head- space was pumped with a peristaltic pump. Pumping introduces fresh sample to sorbent... 

In the past decades, electrospinning has been widely used for the production of micro/nanofibers. In spite of the simplicity and effectivity of the conventional electrospinning for fabricating nanofibers, compact structure and small pores of the nanofibers hinder the efficient penetration of analytes during the extraction process. In order to overcome this issue, an applicable strategy called wet electrospinnig has been employed to enlarge the pore size of the electrospun scaffolds. By applying this technique, a collector was placed at the bottom of a solvent bath and highly porous foam from polyamide nanofibers was produced immediately after freeze-drying (3D electrospinning).... 

In this project, silica and polystyrene based interpenetrating polymer networks (IPNs) were used as a sorbent for microextraction in packed sorbent for having both of the polymer’s properties at the same time. Interpenetrating polymer networks were synthesized with the simultaneous method and three different kind of interpenetrating polymer networks were prepared including full-interpenetrating polymer networks, covalent semi-interpenetrating polymer networks and non-covalent semi-interpenetrating polymer networks. To investigate extraction efficiency of prepared sorbents, 41 compounds including environmental pollutants and biomolecules were chosen. Studies showed that interpenetrating... 

Polyhedral oligomeric silsesquioxanes (POSSs) are 3D nanoscale structures with fascinating potential to be used as extractive phases in solid phase microextraction (SPME). Here, as a case study, the octaglycidyldimethylsilyl polyhedral oligomeric silsesquioxane (POSS–epoxy) network was fabricated on a stainless steel wire via sol–gel methodology and used as a SPME fiber coating. The uniform pore structure, high surface area, and hydrophobicity of POSS–epoxy, make it susceptible toward isolation of non– to semi–polar compounds. Performance of the POSS–epoxy fiber coating was examined considering three classes of typical environmental pollutants including chlorobenzenes (CBs), benzene...