[Truncated abstract] In the past decade, the synthesis of superparamagnetic iron oxide nanoparticles (SPIONs) has received considerable attention due to their potential applications in biomedical fields. However, success in size and shape control of the SPIONs has been mostly achieved through organic routes using large quantities of toxic or/and expensive precursors in organic reaction medium at high reaction temperature. This has limited the biomedical applications of SPIONs and therefore, development of a synthetic method under aqueous condition that is reproducible, scalable, environmentally benign, and economically feasible for industrial production is of paramount importance in order to fully realise their practical applications. Spinning Disc Processing (SDP) has been used to synthesise superparamagnetic magnetite (Fe3O4) nanoparticles at room temperature via a modified chemical precipitation method under continuous flow condition and offer a potential alternative to be applied to SPIONs production. SDP has extremely rapid mixing under plug flow conditions, effective heat and mass transfer, allowing high throughput with low wastage solvent efficiency. The synthesis process involves passing ammonia gas over a thin aqueous film of Fe2+/3+ which is introduced through a jet feed close to the centre of a rapidly rotating disc (500-2500 rpm). Synthetic parameters such as precursor concentrations, temperature, flow rate, disc speed, and surface texture influence the particle sizes. ... Magnetic silica microspheres are receiving great attention for possible applications in magnetic targeting drug delivery, bioseparation and enzyme isolation. However, the current available methods for preparation suffer from the setback of low loading of Fe3O4 nanoparticles in the silica microsphere, which result in low magnetic moment, thereby limiting their practical applications. Therefore it is of considerable importance to develop new alternative synthetic methods for fabricating magnetic silica microspheres with high magnetic nanoparticles loading. Superparamagentic Fe3O4 nanoparticles (8-10 nm diameter) and curcumin have been encapsulated in mesoporous silica in a simple multiplestep self assembly approach process with high Fe3O4 nanoparticles loading (37%). The synthesis involves loading of curcumin in the Cetyltrimethylammonium bromide (CTAB) micellar rod in the presence of superparamagnetic Fe3O4 nanoparticles via a parallel synergistic approach. The synthesised magnetic mesoporous silica composite material is stable, superparamagnetic with high saturation magnetisation before and after curcumin leaching experiment. Under physiological pH in phosphate buffer, the curcumin is slowly released over several days. These magnetic mesoporous silica are expected to have great potential as targeted drug delivery systems.

Thesis (Ph. D.)--State University of New York at Binghamton, Department of Chemistry, 2008. / Includes bibliographical references.

>Magister Scientiae - MSc / Supercapacitors are one of the important subjects concerning energy storage which has proven to be a challenge in this country. Currently, the electrodes of most commercial supercapacitor are made of carbon which is known to be inexpensive and has high resistance to corrosion. These carbon based supercapacitors operate under EDLC. They offer fast charging/discharging rates and have the ability to sustain millions of cycles without degrading. With their high power densities, they bridge the gap between batteries which offer high energy densities but are slow in charging/discharging and conventional dielectric capacitors which are very fast but having very low energy densities. The objective of this work was to develop a high performance supercapacitor using polyanilino-graphene oxide intercalated with platinum group metal nanocomposites. Specific capacitance of each material was investigated with the objective of ascertaining the material that has the best capacitance. In this work, GO was functionalized with aniline and intercalated with Pt, Pd and Pd-Pt nanocomposites. The nanomaterials were characterized with FTIR, Ultravioletvisible (UV-visible) spectroscopy, high resolution scanning electron microscopy (HRSEM), high resolution transmission electron microscopy (HRTEM), energy dispersive x-ray microanalysis (EDS) and X-ray diffraction (XRD) analysis. The composites were tested for possible application as supercapacitor materials using potentiostatic-galvanostatic constant current charge/discharge. The synthesized materials had good electronic, mechanical, optical, physical etc. properties as proven by the various characterization techniques but they proved not to be ideal for application as supercapacitor materials. The materials tested negative when tested for both anodic and cathodic materials therefore we can conclude that the materials are not good supercapacitor materials and therefore cannot be used in application as novel as supercapacitors.

M. Tech (Department of Chemistry, Faculty of Applied and Computer Sciences) Vaal University of Technology. / Water is a limited resource and pollution has become an increasing problem due to industrialization. Aromatic organic pollutants are resistant to biodegradation, and thus chemical methods like the Fenton reaction is required for degradation. The Fenton reaction is catalyzed by cobalt oxide. This study aims to investigate the effect of size and shape of cobalt oxide nanoparticles on the catalytic activity. Methylene blue (MB) was used as a model pollutant. The size and shape of nanoparticles are known to influence the activity of catalysts. The study used a precipitation method to prepare spherical and cubic-shaped cobalt oxide nanoparticles of different sizes using preparation parameters like cobalt precursor, amount and type of oxidant and time of reaction. The XRD patterns of all the prepared cobalt oxide nanoparticles showed a pure cubic Co3O4 phase. The shape of the nanoparticles changed from spherical to cubic when the cobalt precursor was changed from cobalt nitrate to cobalt acetate. The size of the nanoparticles increased when lower amounts of hydrogen peroxide and longer reaction times were used. Nanoparticles between 4.6 to 19.5 nm for spherical particles and between 6.6 and 43.3 nm for cubic particles were prepared. FTIR spectra analysis showed the presence of both nitrate and acetate ions on the surface of cobalt oxide nanoparticles. The TGA results indicated that the adsorption of the acetate ions is stronger than the nitrate ions on the surface of the cobalt oxide nanoparticles. The rate of degradation of methylene blue, the pseudo first order rate constant and the amount of leaching increased with a decrease in the nanoparticles size. The Turn Over Frequency (TOF), which is the moles of methylene blue converted per mole of surface cobalt atoms, decreased with a decrease in the size for both the spherical and cubic nanoparticles. The TOF for the spherical and cubic nanoparticles were similar indicating that the catalytic activity may not be dependent on the shape of the nanoparticles. FTIR analyses showed that degradation occurred, and that methylene blue was not just decolourised to leuco methylene blue.

In this paper, the electrochemical behaviors of a single gold nanoparticle attached on a nanometer sized electrode have been studied. The single nanoparticle was characterized by using electrochemical methods. Since there is only one nanoparticle on the electrode, unarguable information for that sized particle could be obtained. Our preliminary results show that it becomes more difficult to oxidize gold nanoparticle or reduce gold nanoparticle oxide as the radius of the particle becomes smaller. Also, the peak potential of the reduction of gold nanoparticle oxide is proportional to the reciprocal of the radius of the particle.

No description available.

Multicomponent ligand interactions are involved in essentially all nanoparticle (NP) applications. However, the ligand conformation and ligand binding mechanisms on NPs are highly controversial. The research reported here is focused on deepening the fundamental understanding of multicomponent ligand interactions with gold and silver nanoparticles (AuNPs and AgNPs) in water. We demonstrated that AuNPs passivated by saturated layer of poly(ethylene glycol) (PEG-SH) have large fractions of AuNP surface area available for ligand adsorption and exchange. The fraction of AuNP surface area passivated by PEG-SH with molecular weights of 2000, 5000, and 30000 g/mol was calculated to be ~ 25%, ~20%, and ~9% using 2-mercaptobenzimidazole and adenine as model ligands. The effect of both reduced and oxidized protein cysteine residues on protein interactions with AgNPs was investigated. The model proteins included wild-type and mutated GB3 variants with 0, 1, or 2 reduced cysteine residues. Bovine serum albumin containing 34 oxidized (disulfide-linked) and 1 reduced cysteine residues was also included. Protein cysteine content that were found to have no detectable effect on kinetics of protein/AgNP binding. However, only proteins that contain reduced cysteine induced significant AgNP dissolution. We further demonstrated that organothiols can induce both AgNP disintegration and formation under ambient conditions by simply mixing organothiols with AgNPs or AgNO3, respectively. Surface plasmon- and fluorescence-active AgNPs formed by changing the concentration ratio between Ag+ and organothiol. Organothiols also induced AuNP formation by mixing HAuCl4 with organothiols, but no AuNP disintegration occured. Finally, we proposed that multicomponent ligand binding to AuNPs can be highly dependent on the sequence of ligand mixing with AuNPs. Quantitative studies revealed that competitive adenine and glutathione adsorption onto both as-synthesized and PEG-SH functionalized AuNPs is predominantly a kinetically controlled process. Besides providing new insights on multicomponent ligand interactions with colloidal AuNPs and AgNPs, this study opens a new avenue for fabrication of novel nanomaterials in biological/biomedical applications.

Over the past few decades, tremendous efforts have been made to develop nanomaterials for biotechnological applications such as therapeutics. Understanding and engineering interfaces between biomacromolecules and nanomaterials is a key to the creation of successful therapeutic systems. My research has been oriented toward developing therapeutic systems using gold nanoparticles (AuNPs) incorporating material science, organic synthesis, and biology. For this purpose, mixed monolayer protected AuNPs (~2 nm core size) with various functional groups have been employed for triggering therapeutic effects. Several strategies have been accomplished using anticancer drugs that non-covalently and covalently incorporate onto AuNPs as a drug delivery carrier. Alternatively, AuNPs were developed by regulating host-guest complexation processes inside the cell, allowing control of the therapeutic effect of the AuNP. In addition, by using host-guest chemical events on the AuNPs, exocytosis of the AuNPs was controlled, enabling their prolonged retention inside of the cells, providing new strategies for improving conventional drug delivery systems. Therefore, engineering of the AuNP surface can afford new pathways for designing and improving therapeutics.

Air pollution is increasingly recognised as an important and modifiable risk factor for cardiovascular disease. Exposure is associated with a range of adverse cardiovascular events including hospital admissions with angina and myocardial infarction, and with cardiovascular death. The main arbiter of these adverse health effects appears to be combustion-derived nanoparticles that incorporate reactive organic and transition metal components. Through the induction of cellular oxidative stress and pro-inflammatory pathways, these nanoparticles exert detrimental effects on platelets, vasculature and myocardium, and can augment the development and progression of atherosclerosis. Over the last 10 years there has been remarkable progress in the development of targeted engineered nanoparticles as contrast agents to enhance cellular and molecular imaging. Ultra-small paramagnetic iron oxide (USPIO) nanoparticles (<100 nm) produce disruptions in the magnetic field of magnetic resonance imaging (MRI) scanners, and a decrease in image intensity in areas where the particles accumulate. USPIO particles are phagocytosed by cells of the monocyte-macrophage system throughout the body including within atheromatous plaques. USPIOs have regulatory approval in the United Kingdom for imaging lymph nodes in breast and prostate cancer as well as FDA approval for parenteral iron-replacement therapy in chronic kidney disease. There is great interest in developing USPIO and other nanoparticle contrast agents for imaging atherosclerosis. The delivery of engineered nanoparticles (ENPs) directly into the bloodstream to provide enhanced imaging of the unstable atheromatous plaque may assist in the diagnosis of plaque rupture and may ultimately permit targeted delivery of therapies directly to the site of vascular injury. However, these particles once blood-borne may alter monocyte-macrophage function and activate circulating platelets with adverse effects on clinical outcomes. Previously it has been shown that inhalation of combustion-derived nanoparticles results in increases in platelet-monocyte aggregation and thrombus formation in healthy volunteers. These combustion derived nanoparticles share structural similarities with engineered nanoparticles designed for intravascular infusion. This raises an obvious paradoxical question: can engineered nanoparticles designed for medical use mediate similar effects to combustion derived nanoparticles in susceptible populations? My thesis addresses this question and describes a series of complimentary experimental and clinical studies to investigate the effects of engineered nanoparticles on platelet function and thrombogenesis using commercial and clinically available nanoparticles. I found that cationic nanoparticles caused platelet activation and aggregation in vitro, whereas, anionic nanoparticles caused inflammation and up-regulated adhesion molecule ICAM-1 in monocyte derived macrophages indicating that nanoparticles have different toxicological properties in different biological conditions. Using an ex vivo model of thrombus formation, the Badimon chamber, I observed that USPIO nanoparticles added to flowing native whole blood in an extra-corporeal circuit increased platelet rich thrombus formation under high shear conditions compared to saline control in healthy volunteers. These studies were repeated in patients with abdominal aortic aneurysms who received intra-venous systemic infusions of USPIO to enhance MRI imaging. I demonstrated up-regulation in markers of platelet activation and more platelet rich thrombus formation in the Badimon chamber one hour following systemic delivery of USPIO. In summary I have demonstrated that medical nanoparticles influence platelet activation in patients with cardiovascular disease and have pro-thrombotic effects in an ex-vivo model of in both healthy persons and susceptible patients. In light of this data and to ensure the safe future development of engineered nanoparticles for medical use platelet activation assays and follow-up monitoring of patients should be considered routine in both the developmental and clinical stages of engineered nanoparticle use.

NPs are toxic to a wide range of organisms across trophic levels; gram-positive and gram-negative bacteria (Pseudomonas aeruginosa, Bacillus subtilis, Staphylococcus aureus and Escherichia coli), algae (Pseudokirchneriella subcapitata), crustaceans (Daphnia magna and Thamnocephalus platyurus), fish (rainbow trout, zebrafish, trout) and plants (Lactuca sativa L. and Raphanus sativus L). Due to their lack of target specificity, NPs may pose an environmental risk. The antibacterial properties of Ag and Cu nanoparticles (NP) are enhanced by their large reactive surface area, compared to bulk counterparts. Toxicity of NPs is attributed to their solubility and subsequent release of ions. However, the cytotoxic effects of NPs cannot always be attributed to the free ion fraction. The underpinning objective of this study was to link the response of microbial biosensors to detailed chemical analysis of NP dissolution products. NPs were suspended in Millipore water and in the presence of the steric stabiliser Na citrate and the resulting NP solubility characterised. Using chemical analysis this study quantified the flux of total dissolved metal (total [M]) and free metal ions [M+] from Ag and Cu NPs (Chapter 3). Two bioluminescent biosensors were used to assess the bioavailable metal fraction ([M]bio) of NP dissolution (Chapters 5 and 6). E. coli HB101 pUCD607 (bacterial) and M. citricolor (fungal) were chosen to represent NP toxicity across trophic levels using the same response mechanism. Additionally, the metal-induced bioreporter, P. fluorescens DF57-Cu15, was used to quantify the Cu bioavailability of Cu NP dissolution. By combining chemical and biological analysis this study inferred NP toxicity is not mass dependent, toxicity is dissolution dependent. Dissolution of Ag and Cu NPs in Millipore water was mostly in the [M+] form. This remained the case for Ag NPs in the presence of Na citrate. However, dissolution of Cu NPs in Na citrate was mostly as total [Cu]. This was due to Cu ions complexing readily with citrate. Toxicity of Ag NP dissolution in Millipore water was concentration dependent. Total [Ag] correlated with E. coli HB101 toxicity response. The addition of Na citrate reduced Ag NP dissolution and therefore reduced toxicity to E. coli HB101. M. citricolor was less sensitive than E. coli HB101 to the dissolution products of Ag NPs in Millipore water. However, the sensor was more sensitive to the dissolution of Ag NPs in Na citrate than E. coli HB101. Cu NPs were chemically stable in Millipore water. The bioreporter P. fluorescens DF57-Cu15 was not induced by Millipore suspensions and E. coli HB101 was not inhibited. However, M. citricolor responded to [Cu]bio of Millipore suspensions with a maximum 54% inhibition of bioluminescence. P. fluorescens DF57-Cu15 was induced by the dissolution products of Cu NPs with the addition of Na citrate, only at high NP concentrations (> 500 mg/L). [Cu]bio of the Na citrate suspensions was toxic to E. coli HB101. However, toxicity was greater for M. citricolor with a maximum biosensor inhibition of 83%. There was no correlation between total [Cu], [Cu2+] or [Cu]bio with the response of either biosensors nor the bioreporter. Interpretation of Ag and Cu NP toxicity was made possible by the combining of chemical and biological toxicity assessment. Dissolution of Ag NPs suspended in Millipore water could be attributed as the main factor in toxicity to E. coli HB101 because of the knowledge gained by chemical analysis. It also allowed the conclusion that NP dissolution was a key factor to toxicity in all cases but biological assessment attributed NP assimilation as a contributing factor. Biological assessment is vital as no chemical analysis can quantify [M]bio, especially when [M]bio was perceived differently by biosensors of different trophic levels and modes of action. Combining chemical and biological assessment in this study was essential for interpreting NP toxicity.