Sharif Digital Repository

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... 

Corrosion is caused through chemical interactions between metal and gases in the surrounding environment. Conductive polymers are used for corrosion protection, polyaniline is the most environmentally stable out of all the conductive polymers, the most studied of this materials, is highly stable, synthesized easily, highly conducting, and readily converted between its various oxidation states.
In this study we prepared nanoporous polyaniline coating on carbon steel to corrosion protection. Coating was included nanopouros polyaniline with doping molybdate (PANI-MoO_4^(-2)). To increase adhesion between steel and PANI-MoO_4^(-2) layer, oxalic acid was used. Polystyrene nanoparticle layer... 

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... 

In this study, gelatin/polyvinylpyrrolidone semi interpenetrating polymer network scaffold was synthesized in presence of glutaraldehyde as a cross linker and a porous structure was obtained by freeze drying method. The biocompatible network with properties like huge porosity, good thermal stability and establishing different interactions, was employed as an extractive phase in needle trap device and used for evaluation of benzene, toluene, ethylbenzene and xylene (BTEX) in conjugation with gas chromatography-flame ionization detector. For investigating semi interpenetrating polymer network efficiency, Different ratios of gelatin and polyvinylpyrrolidone (gelatin/polyvinylpyrrolidone: 1:0,... 

Porous materials using polymers have been developed for a variety of industrial applications. These structures mostly contain well-aligned microchannels and exhibit good mechanical properties and high porosity.There are several ways to prepare porous polymeric structures, such as sintering, stretching, track etching and phase separation processes. In this work Phase separation method using anti-solvent of selected polymer in liquid nitrogen was used to fabricate the porous structures. Considering physical and chemical peroperties of polycyclic aromatic hydrocarbons, porous polystyrene make to be good sorbents. Solvent supported microextraction technique was applied to extract polycyclic... 

The main focus of this thesis is based on surface modification of polystyrene in order to prepare extractive phases appropriate for extraction of analytes with a wide polarity range. This goal was achieved by increasing surface polarity. In fact, improved wettability and the possibility of interaction with polar analytes after addition of functional groups on polystyrene surface were the main reason for increased extraction capacity. In the first research, different functional groups including amine, nitro, carboxyl and acetyl were added on polystyrene particles by chemical bonding and to investigate their influence on extraction process, 22 analytes with a wide polarity range (LogP=-2 to... 

The main purpose of this dissertation was to synthesize nanostructured adsorbents based on the sol–gel and electrospinning methods and implement them to the trace determination of the desired analytes from different matrices. In the first and second chapters, a summary of the sol–gel and electrospinning methods along with a glance on extraction methods are presented. Then, the implemented projects are presented in the consecutive chapters.In the first work, third chapter, silica nanofibers were successfully produced using electrospinning method. In this process, sol–gel was formed during electrospinning and then, the backbone polymer was removed by heating. To obtain a thin layer of silica... 

In this work, a biocompatible sorbent based on halloysite nanotubes-zein bionanocomposite for direct-immersion thin film microextraction (DI-TFME) is introduced. Zein as a biodegradable, low cost and accessible polymer was used to prepare a flexible thin film with the possession of different interactions and good adsorption capacity. To improve the mechanical and chemical resistance of the film, halloysite nanotubes were combined with zein to prepare the thin film sorbent. The film was used for TFME of 16 pesticides from different chemical classes, including organochlorines and organophosphates followed by gas chromatography with electron capture detector (GC-ECD). To achieve the maximum... 

The aim of this study was to develop a method to determine the trace residual amounts of nonsteroidal anti-inflammatory drugs in meat-related samples and to study the effect of different cooking methods and storage conditions of meat before cooking as an effective factor on the fate of these drugs. To proceed this goal, a nanocomposite was prepared from polycaprolactone nanofiber/silica mesopores as green sorbent by electrospinning. The synthesized nanocomposite was implemented for micro-solid phase extraction of the desired drugs in conjunction with high performance liquid chromatography. Polycaprolactone, due to its excellent physical properties, availability, biodegradability,... 

Several metal-organic frameworks based on chromium metal salt and terephthalic acid were synthesized by the solvo-thermal method and modified directly using amino acids or their imidazole derivatives. Suitable characteristics of the synthesized novel MOFs led to their use as novel extracting phases for sample preparation. The sorbent’s performance in extracting anti-hypertension drugs such as eprosartan, losartan and valsartan was tested using the magnetic solid phase extraction which is a form of μ-SPE, followed by HPLC analysis. Different parameters effecting the extraction and desorption procedures were optimized to achieve the highest performance of extraction and sensitivity. Said... 

Coordination polymers are a wide range of metal-organic polymers that have good potential for use as extraction phase in solid phase extraction and solid phase microextraction. Also, these polymers can be synthesized in various morphologies such as nanorods, microspheres, nanofibers, etc. to demonstrate the effect of morphology on extraction efficiency.In this study, the extraction efficiency of a coordination polymer with two morphologies (nanorods and microspheres) and different nitrogen percentages was investigated in needle trap device using gas chromatography-mass spectrometry to measure polycyclic aromatic hydrocarbons as model analytes.PAHs were measured in conventional cigarette... 

In this study, a 1,2,3-triazole-containing ligand and the subsequent zinc-based MOF were synthesized. Then, in order to investigate the role of structural similarity of analytes and sorbent on sorption efficiency, the sorption capability of triazole-containing MOF along with several other well-known sorbents toward selected triazole fungicides were tested using dispersive micro solid phase extraction (d-μSPE). In order to further investigate the role of structural similarity on the sorption efficiency, the performance of synthesized MOF in the extraction of other compounds such as triazine herbicides, organochlorine, and organophosphorous pesticides was also evaluated. As expected, the... 

The main focus of this thesis was on fluorescence sensors development based on carbon dots and deep eutectic solvents. Accordingly, an attempt was made to synthesize carbon dots and modified with deep eutectic solvents as biocompatible sensors. Eventually, development and application of these sensors in analytical systems ultimately led to satisfactory and comparable results with previous methods. In the first project, a rapid and miniaturized fluorescent probe based on the ultrasound‒assisted formation of carbon dots (CDs) in a metallic deep eutectic solvent (MDES) was developed and conveniently implemented to detect 4-MeI in commercial dark soft drinks. In-situ synthesis of CDs-chelated... 

Reducing fossil fuels and increasing urban air pollution, has made the automotive industry to reduce the fuel consumption of their engines by various approaches. Removing the compressor of air conditioning system by replacing the absorption chiller instead of inverse rankin cycle is a shortcut to reduce the fuel consumption which at the same time reduces costs of using air conditioning system for occupants. Design of a 3 kW lithium bromide-water absorbent chiller has verified based on environmental conditions and car space limitations and using the combustion products as the heat source of system. K4M engine of L90 sedan Car as an internal combustion engine sample’s exhaust manifold has been...