Sharif Digital Repository

The main approach of this thesis is to study the performance and efficiency of agricultural biomass derived extractive phases in sample preparation methods. In this regard, different types of agricultural biomasses and various important factors in the production of biochar from biomass were studied by two physical and chemical methods. Accordingly, different types of biochars have been made and applied in different extraction setups along with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) and gas chromatography-electron capture (GC-ECD) to detect agricultural pesticides. Also, validated developed methods were used to investigate the safety of some highly... 

Progress in analysis of multicomponent mixtures and processes focused on the interpretation of the multivariate responses, rely on the combination of sophisticated instrumental techniques and suitable chemometric methods. Among the present chemometric method, curve resolution techniques have a wide application in the analysis of multicomponent mixtures and processes. Chemometric resolution techniques are used in the present work. At the first, Essential oil of green and black cardamoms was extracted by hydrodistillation and was analyzed by gas chromatography–mass spectrometry (GC-MS). Due to the fact that the essential oils are complex mixtures, strong overlap is observed between the peaks.... 

In this thesis, a new approach was developed to achieve mechanical and chemical resistant capillary microextraction (CME) in on-line combination with high performance liquid chromatography (HPLC) based on sol-gel technology. This thesis is divided into three chapters:
First chapter contains of two parts. Overcoming the lack of mechanical stability of the substrate of CME by replacing the fused silica by copper tubings was the main objective of the first part. Self-assembled monolayers technique was employed to functionalize the copper tube followed by chemical bonding of the sorbent on the inner surface of the copper tube by sol-gel technology. The prepared copper tube containing the... 

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... 

Factor analysis based methods are one of the applied methods in the Chemometrics. In this regard, some modifications on one of the factor analysis based method named fixed size moving window evolving factor analysis were done and two new methods named variable size moving window evolving factor analysis and preselected variable size moving window evolving factor analysis were introduced. The performance of the new introduced methods were examined and compared by the fixed size moving window evolving factor analysis.
Pure variable selection methods are useful for curve resolution methods which need to define an initial estimate from chromatographic profile or spectra. In this aspect the... 

Considering principles of both micro-solid phase extraction (µ-SPE) and stir-bar sorptive extraction (SBSE) techniques, in this study a microextraction technique was developed using a polypropylene sheet as extracting device for isolation of fluoxetine from biological samples. Being rather inexpensive and simple to prepare extracting device, elimination of time consuming sorbent synthesis step and memory effect are some of the advantages of the proposed method. The extraction process was performed using a polypropylene sheet as extracting device. Solvent desorption was performed in a microvial and then extractant was injected into HPLC system. The effect of various parameters including pH,... 

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... 

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... 

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... 

A green aerogel was prepared by synthesizing amine-modified lignin from sugarcane bagasse and further modification by CS2 and subsequent freeze drying. This aerogel was implemented as an extractive phase in a home-made online micro solid phase extraction-high performance liquid chromatography (μSPE-HPLC) setup for analyzing cardiovascular drugs (valsartan and losartan) in urine samples. To study the effect of functionalization, bare or functionalized lignin powders were mixed with graphene oxide (GO) at different ratios while functionalized lignin showed the highest efficiency. The prepared aerogel was analyzed using CHNS elemental analysis, and FT-IR spectrometry. Effects of influencing... 

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... 

One of the considerable issues in fullereneresearch is low yield of endohedral fullerene production.In this project, synthesis and optimization of endohedral metallofullereneproduction was undertaken byarc reactor applying vertical graphite electrodes, using vaporizing composite lanthanum-oxide-graphite-dopped rod. Increasing the efficiency of endohedral fullerrene production in sootwas followed applyingcarbide formation in electrode which was studied by X-ray diffraction(XRD), thermogravimetric analysis(TGA) and infrared (IR) spectroscopy. In addition, as a simple and fast method, the liquid column chromatography was applied in separation and purification of fullerenes as well as endohedral... 

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 research project, the aim was to investigate the potential of olive leaf extract as an eco-friendly inhibitor for enhancing the corrosion resistance of reinforcing steel in simulated geopolymer concrete pore solution (GCP) containing chloride ions. The inhibitory effects of olive leaf extract were evaluated using various electrochemical techniques as well as scanning electron microscopy. The main phenolic compounds present in olive leaf extract were identified using high performance liquid chromatography (HPLC). Moreover, the elements and chemical bonds present in the surface passive film of the steel bar immersed in the olive leaf inhibiting system were characterized using... 

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... 

Thiomersal is an organomercury compound. This compound is a well established antiseptic and antifungal agent. It has been used as a preservative in vaccines, immuno-globulin preparations, skin test antigens, antivenins, ophthalmic and nasal products, and tattoo inks. Thiomersal is very toxic by inhalation, ingestion, and in contact with skin, with a danger of cumulative effects. It is also very toxic to aquatic organisms and may cause long-term adverse effects in aquatic environments.
Thiomersal's main use is as an antiseptic and antifungal agent in vaccines. In multidose injectable drug delivery systems, it prevents serious adverse effects such as the Staphylococcus infection that,... 

The main goal of this thesis was to develop μ-solid extraction techniques using electrspun nanofibers under the influence of magnetic field along with flow injection system. The thesis is divided into two sections:The first chapter deals with the use of magnetic field for improving μ-solid phase extraction efficiencies. After preparing the magnetic-based electrospun nanofibers (PBt/MNPs), sufficient numbers of disc from the prepared electrospun composite mat were cut and used as packing materials in a cartridge. The prepared system was coupled on-line to liquid chromatography for microextraction of selected drugs of furosemide, naproxene, diclofenac and clobetasol propionate. The homogeneity... 

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,... 

This thesis deals with the synthesis and characterization of some nanostructured conductive polymers and their applications toward microextraction of drugs, environmental pollutants and pesticides from aqueous and biological samples. In chapters 3–6, silver nanoparticles and their relevant nanocomposites were applied as the desired extracting media while in the last chapter, a polyaniline nanocomposite, containing titanium oxide nanoparticles, was synthesized and employed as an efficient medium for the extraction purposes. In the first work, a nanocomposite based on polyaniline-silver nanoparticles (PANI-Ag NPs) was synthesized and used as an extraction medium for microextraction in packed...