Compared with traditional radioimmunoassay and fluoroimmunoassay for early diseases detection, the magnetic immunoassay utilizing magnetic nanoparticles as bio-labels and magnetic signal sensors as detectors has remarkable advantages because most biological samples exhibit no magnetic background and highly sensitive measurements can be performed. This thesis presents the development of biodetection platform taking advantage of the physical-and chemical-stability, low-toxicity, and environmentally-safety of magnetic iron oxide nanoparticles (IONPs) and the high-sensitivity, low-cost, and portable capabilities of magnetoresistive (MR) sensors. The first part explained why a magnetic biodetection platform is desirable, and what advantages it possesses. Then the magnetism of IONPs utilized in this detection system was introduced, followed by the introduction of main synthesis methods to obtain the desirable IONPs. The working principle of MR sensor was explained, and the recent advances about the biodetection platforms with various magnetoresistive sensors and magnetic IONPs labeling was reviewed. A brief summary of new contributions reported in this thesis was summarized. Then the establishment of home-made measurement setups for the characterization of MR sensor was described. The MR loops of MR sensors can be obtained with the instrument using two-point probe measurement, four-point probe measurement, or Wheatstone bridge measurement. The single MTJ sensor, MTJs array sensor, and the GMR spin valve sensor in Wheatstone bridge were characterized here. The magnetic IONPs were prepared through co-precipitation method and thermal decomposition method, and then surface-functionalized using citric acid and fatty acids to acquire carboxyl groups for the binding ability with biomolecules. The physical and chemical properties, sterilizing-treatment tolerability and biocompatibility of nanoparticles were studied. Furthermore, two new synthesis methods were developed to obtain novel magnetic gold/iron oxide nanocomposites for their potential use as magnetic bio-labels. A magnetic detection platform was built, and the detection of 10-nm superparamagnetic IONPs with MR sensor was first realized here. The output signal of the giant magnetoresistive (GMR) sensor in Wheatstone bridge exhibited log-linear function of the concentration of IONPs, making our sensing system suitable for use when ultra-small bio-labels are needed. The biodetection platform with MR sensor and IONPs was successfully developed and applied for the detection of antigen biomolecules. The feasibility of magnetic biodetection system, based on magnetic tunneling junction (MTJ) sensors and carboxyl-group functionalized IONPs, to detect AFP antigens (liver cancer biomarker) and p24 antigens (HIV biomarker) was demonstrated here for the first time. By taking advantages of its high sensitivity, low power consumption, low cost, and feasibility to be miniaturized, the development of magnetoresistive biodetection platform will bring revolutionary impact on the biodetection techniques for clinical early diseases diagnosis. / published_or_final_version / Electrical and Electronic Engineering / Doctoral / Doctor of Philosophy

Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2009. / Committee Chair: Z. John Zhang; Committee Member: Angus Wilkinson; Committee Member: C P Wong; Committee Member: E. Kent Barefield; Committee Member: Mostafa El-Sayed. Part of the SMARTech Electronic Thesis and Dissertation Collection.

No description available.

The magnetic spinel ferrite nanoparticle is exceptionally intriguing nanocrystal system due to the industrial importance of various technical applications and the scientific significance of studying the quantum origin of magnetism. Studies of quantum influences upon magnetic properties have revealed that the spin-orbit coupling and the net magnetization greatly affect the net magnetic properties of each spinel ferrite system differently. In case of cobalt ferrite where spin-orbit coupling is relatively large, increasing Cr3+ doping concentration, which has smaller magnetic moment and zero angular moment, decreases blocking temperature, saturation magnetization, remnant magnetization and coercivity. However, in case of manganese ferrite where spin-orbit coupling is relatively small, increasing Cr3+ doping concentration, reduces all the magnetic parameters except coercivity. The coercivity increases due to smaller magnetocrystalline anisotropy energy constant which forces the coercivity to increase as saturation magnetization decreases in accordance with Stoner-Wohlfarth theory. In order to improve product quality and quantity, synthesis routes in hot oleylamine and aminolytic reaction were developed. Both methods were proven to be extremely effective, environmental friendly, inexpensive, and simple routes in the synthesis of a variety of spinel ferrite systems including CoFe2O4, MnFe2O4, NiFe2O4, and ZnFe2O4 from a single source metal precursor.

No description available.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2009. / Please refer to full text to view abstract

Magnetic nanoparticles and molecules, in particular ferromagnetic noble metal nanoparticles, molecular magnet and single-molecule magnets (SMM), are perfect examples to investigate the role of quantum mechanics at the nanoscale. For example, SMMs are known to reverse their magnetization by quantum tunneling in the absence of thermal excitation and show a number of fundamental quantum mechanical manifestations, such as quantum interference effects. On the other hand, noble metal nanoparticles are found to behave ferromagnetically for diameters below a few nanometers. Some of these manifestations are still intriguing, and novel research approaches are necessary to advance towards a more complete understanding of these exciting nanoscale systems. In particular, the ability to study an isolated individual nanoscale system (i.e just one molecule or nanoparticle) is both challenging technologically and fundamentally essential. It is expected that accessing to the energy landscape of an isolated molecule/nanoparticle will allow unprecedented knowledge of the basic properties that are usually masked by collective phenomena when the systems are found in large ensembles or in their crystal form. Several approaches to this problem are currently under development by a number of research groups. For instance, some groups are developing deposition techniques to create patterned thin films of isolated magnetic nanoparticles and molecular magnets by means of optical lithography, low-energy laser ablation, or pulsed-laser evaporation or specific chemical functionalization of metallic surfaces with special molecular ligands. However, it is still a challenge to access the properties of an individual molecule or nanoparticle within a film or substrate. iv I have studied molecular nanomagnets and ferromagnetic noble metal nanoparticles by means of a novel experimental approach that mixes the chemical functionalization of nano-systems with the use of single-electron transistors (SETs). I have observed the Coulomb-blockade single-electron transport response through magnetic gold nanoparticles and single-molecule magnet. In particular, Coulomb-blockade response of a Mn4-based SET device recorded at 240 mK revealed the appearance of two diamonds (two charge states) with a clear switch between one and the other is indicative of a conformational switching of the molecule between two different states. The excitations inside the diamonds move with magnetic field. The curvature of the excitations and the fact of having them not going down to zero energy for zero magnetic field, indicated the presence of magnetic anisotropy (zero-field splitting) in the molecule. In addition, the high magnetic field slope of the excitations indicates that transitions between charge states differ by a net spin value equal to 9 (|∆S| = 9), as expected from the behavior of Mn4 molecules in their crystalline form. Anticrossings between different excitations are indicative of quantum superpositions of the molecular states, which are observed for the first time in transport measurements through and individual SMM.

Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: Living chains prepared by RAFT polymerization and NMP reactions using Z-carboxylate and Z-phosphate RAFT agents, and X-phosphate NMP initiators, were efficiently attached to the surface of magnetic nanoparticles (MNPs) and used for the separation of dead chains formed in these polymerization reactions prior to the attachment of the RAFT agents and NMP initiators to the surface of MNPs. All the living chains that attach selectively to the surface of MNPs contained RAFT or NMP functionalities, had a low polydispersity index (PDI), and could be reactivated to form new polymer extensions or block copolymers with no detectable deviation from 100% efficiency. RAFT chains prepared by RAFT polymerization using the Z-carboxylate RAFT agent and an excess of free radical initiator were also attached to the surface of MNPs and separated in the presence of an external magnetic field. Separated RAFT-functional chains contained no dead chains formed by combination or disproportionation reactions, but a substantial amount of cross-terminated by-product with a low UV absorbance at 320 nm. The cross-termination of the intermediate radical formed in the RAFT polymerization reactions was also investigated in the monomer-excluded free radical reaction model of polystyryl benzyl-(4-carboxyl dithiobenzoate) and polystyryl ethyl-2-bromoisobutyrate. The Z-carboxylate 3- and 4-arm star polymers (formed by cross-termination reactions) were then efficiently attached to the surface of MNPs and separated from the remainder of the polymer solution. They were separated from MNPs and characterized by 1H and 13C-NMR spectroscopy, and MALDI-ToF-MS. Living chains prepared by a RAFT miniemulsion polymerization reaction using Z-carboxylate RAFT agent were attached to the surface of MNPs and used for the separation of all dead chains and uncontrolled high molecular weight polymer of secondary particle formations occur during a miniemulsion polymerization reaction prior to the attachment. Separated dead chains had high PDI values and contained a significant fraction of uncontrolled high molecular weight polymer that lacked RAFT functionality. Initiator-derived chains formed in RAFT polymerization reactions of styrene (St) and methyl methacrylate (MMA) using phosphate free radical (PFR) initiator were selectively attached to the surface of MNPs and separated from R-group-derived polymer chains in the presence of an external magnetic field. All separated initiator-derived chains contained large fractions of dead chains with weak UV absorbance, and which lacked RAFT functionality, and small fractions of RAFT polymer chains. The separated initiator-derived chains had higher PDI values than the as-prepared polymer in the polymerization of St, but lower PDI values than the as-prepared polymer in the polymerization of MMA. RAFT agents attached to the surface of MNPs by the Z group were used as mediating agents for the synthesis of polymers grafted to the surface of MNPs. The polymers grafted to the surface of MNPs were separated from the solution of the free polymer by applying an external magnetic field. The amounts of the polymers grafted to the surface of MNPs greatly increased as the number of RAFT agents attached to the surface of MNPs decreased. When ethyl acetate was used as solvent, it reached 65% by weight and 50% by number of chains. Separated polymers grafted to the surface of MNPs had high PDI values and contained RAFT functionality. Investigations into the kinetics of the RAFT-mediated polymerization reaction on the surface of MNPs revealed that the polymerization reaction mediated using a RAFT agent attached by its Z group to the surface of MNPs had a faster polymerization rate than that mediated using a free Z group RAFT agent. The molecular weight of the grafted polymer increased linearly with conversion, and the reaction rate was pseudo-first-order. / AFRIKAANSE OPSOMMING: Lewende polimeerkettings, berei deur middel van RAFT-beheerde polimerisasie en NMP reaksies waarin Z-karboksilaat en Z-fosfaat RAFT-verbindings en 'n X-fosfaat NMP afsetter gebruik is, is geheg aan die oppervlaktes van magnetisenanopartikels (MNPs), en gebruik vir die skeiding van dooie kettings wat tydens die RAFT en NMP reaksies gevorm is. Alle lewende kettings wat aan die oppervlakte van die MNPs geheg is, is geskei van die oorblywende polimeeroplossing deur die aanwending van ‗n eksterne magnetise veld. Alle kettings wat selektief aan die oppervlaktes van die MNPs gekoppel is met RAFT of NMP funksionaliteit, het ‗n laë poliverspreidingswaarde (PDI) gehad en kon heraktiveer word om ‗n nuwe polimeerverlengings of blokkopolimere te vorm met geen merkbare afwyking van 100% doeltreffendheid nie. RAFT-kettings wat gedurende RAFT-polimerisasie met 'n Z-karboksilaat RAFT-agent en oormaat vrye-radikaalafsetter berei is, is ook geheg aan die oppervlaktes van MNPs en geskei in die teenwoordigheid van 'n eksterne magnetiese veld. Die geskeide RAFT-funksionele kettings het geen dooie kettings bevat nie (gevorm deur kombinasie reaksies), maar 'n aansienlike hoeveelheid ongekontroleerde hoë molekulêremassa polimeer (met lae UV absorpsie by 320 nm). Die kruis-beëindiging van die intermediêre radikaal wat gevorm is tydens die RAFT-proses is ondersoek in die monomeer-uitsluitende vrye-radikaalreaksiemodel van polistirielbensiel-4-karboksielditiobensoaat en polistirieletiel-2-bromoisobutiraat. Die Z-karboksilaat 3- en 4-arm sterpolimere (gevorm a.g.v. kruis-terminasiereaksies) is effektief geheg aan die oppervlaktes van MNPs en geskei van die res van die polimeeroplossing, en daarna gekarakteriseer met behulp van 1H en 13C KMR, en MALDI-ToF-MS. Lewende kettings, berei m.b.v. RAFT miniemulsiepolimerisasies met 'n Z-karboksilaat RAFT-agent, is geheg aan die oppervlaktes van MNPs en gebruik vir die skeiding van alle dooie kettings en sekondêre partikels wat tydens die reaksie voor die aanhegting gevorm het. Die geskeide dooie kettings wat agtergebly het, het 'n wye PDI getoon en het 'n aansienlike hoeveelheid ongekontroleerde hoë molekulêremassa polimeer, met geen RAFT-funksionaliteit nie, bevat. Afsetterafkomstigekettings wat gevorm is tydens die RAFT polimerisasiereaksies van stireen (St) en metielmetakrilaat (MMA) met 'n fosfaat-vrye vrye-radikaalafsetter is selektief geheg aan die oppervlaktes van MNPs en geskei van R-groep-afkomstige polimeerkettings in die teenwoordigheid van 'n eksterne magnetise veld. Alle geskeide afsetter-afkomstige kettings het 'n groot hoeveelheid dooie kettings gehad (met swak UV absorpsie) en met geen RAFT-funksionalilteit nie, en klein fraksies van RAFT-polimeerkettings. Die geskeide afsetter-afkomstige kettings het hoër PDI waardes gehad as die ('as-prepared') polimeer in die polimerisasie van St, maar laer PDI waardes as die ('as-prepared') polimeer in die polimerisasie van MMA. RAFT-verbindings wat aan die oppervlaktes van die MNPs geheg is deur middel van die Z-groep is as bemiddellingsagente (Eng: mediating agents) gebruik vir die sintese van polimere wat geënt is aan die oppervlakte aan MNPs. Die polimere wat aan die oppervlakte van die MNPs geënt is is geskei van die res van die polimeeroplossing deur die aanwending van ‗n eksterne magnetise veld. Die hoeveelhede van die polimere wat aan die oppervlaktes van die MNPs geënt is het sterk toegeneem namate die aantal RAFT-agente wat aan die oppervlaktes van MNPs geheg is afgeneem het. Wanneer etielasetaat as oplosmiddel gebruik is, was die waardes 55% m.b.t. gewig en 45% m.b.t. die aantal kettings. Die geskeide polimere wat aan die oppervlaktes van MNPs geënt is het hoë PDI getoon en het RAFT-funksionaliteit bevat. Die kinetika van die RAFT-beheerde polimerisasiereaksies van St, wat gebruik maak van ‗n RAFT-agent wat aan die oppervlakte van die MNPs geheg is deur middel van die Z-groep, is ook ondersoek. Die tempo van polimerisasie was vinniger in die geval waarin die RAFT-agent geheg is deur sy Z-groep aan die oppervlakte van die MNPs as die reaksie met 'n RAFT agent met 'n vrye Z-groep. Die molekulêremassas van die entpolimere het liniêr toegeneem met omsetting, en die reaksie was pseudo-eerste-orde.

The main goals of this research were to fabricate magnetic cobalt nanoparticles and study their structural, crystal structure, optical, and magnetic properties. Cobalt nanoparticles with average particle size 8.7 nm were fabricated by the method of high temperature reduction of cobalt salt utilizing trioctylphosphine as a surfactant, oleic acid as a stabilizer, and lithium triethylborohydride as a reducing reagent. Energy-dispersive X-ray spectroscopy (EDX) analysis confirmed the formation of cobalt nanoparticles. High resolution transmission electron microscopy images show that Co NPs form both HCP and FCC crystal structure. The blocking temperature of 7.6 nm Co NPs is 189 K. Above the blocking temperature, Co NPs are single domain and hence showed superparamagnetic behavior. Below the blocking temperature, Co NPs are ferromagnetic. Cobalt nanoparticles with a single-domain crystal structure support a sharp plasmon resonance at 280 nm. Iron nanoparticles with average particle size 4.8 nm were fabricated using chemical reduction method show plasmon resonance at 266 nm. Iron nanoparticles are ferromagnetic at 6 K and superparamagnetic at 300 K.

D. Tech (Department of Chemistry, Faculty of Applied and Computer Sciences) Vaal University of Technology. / Trivalent arsenic (As(III)) and hexavalent chromium (Cr(VI)) toxicity have necessitated a great deal of research into the remediation of contaminated water. The techniques applied including oxidation, coagulation-flocculation and ion exchange have suffered drawbacks due to the high cost of materials and equipment, complex operations and secondary pollution among others. Adsorption, however, remains a cost-effective solution in the remediation of contaminated water. The use of biosorbent materials further lowers the cost of the adsorption process and improves its eco-friendliness. These biomaterials, however, suffer some drawbacks as poor porosity, low adsorption capacities and mechanical strength thus require modifications to improve their applicability as biosorbents. In this work pine cone powder, a waste from pine trees, was used as a biosorbent for the removal of As(III) and Cr(VI) from water. The powder was pre-treated with Fenton’s reagent to oxidize some of the functional groups and provide more binding sites. Iron oxide magnetic nanoparticles (magnetite) were incorporated into the pine cone matrix to form a magnetic composite with higher heavy metal affinity. The magnetite nanoparticles were also doped with manganese to improve their redox capacities and aid in the oxidation of the toxic As(III) to the less toxic As(V) and allow for improved binding. The adsorbents used in the study were therefore named as Fenton’s treated pine cone powder (FTP), pine cone -magnetite composite (FTP-MNP), magnetite nanoparticles (MNP), manganese doped magnetite nanoparticles (Mn MNP) and manganese doped pine cone-magnetite composite (Mn FTP-MNP). The prepared materials were fully characterized, and the adsorption process was optimized for both As(III) and Cr(VI) removal from aqueous solution. After modification the surface area of the particles increased in the order Mn MNP>MNP>Mn FTP-MNP>FTP-MNP>FTP. Surface and Xray analysis confirmed the formation of magnetite by the presence of both ferric and ferrous ion states on the surface and characteristic diffraction peaks for magnetite. The adsorption data was fitted into isotherm and kinetic models and the nature of adsorption was determined from the thermodynamic and kinetic parameters. Equilibrium studies indicated that the adsorption followed Langmuir isotherm for all adsorbents and was thus monolayer in nature, further analysis indicated that chemisorption was the predominant type of adsorption with ion exchange being the predominant mechanism of adsorption. Spent adsorbents were tested for reusability and displayed excellent adsorption capacities when used for up to three times. Adsorption mechanism was evaluated using characterization techniques and the ion-exchange mechanism inferred from thermodynamic data was confirmed spectroscopically with redox reactions aiding in the removal of the pollutants from water. The introduction of competing anions in solution, lowered the adsorption efficiency of both arsenic and chromium on the adsorbent indicating that there was competition for adsorption sites.