The aim of this work is to make electrochemical metal nanowire growth a competitive method, being up to par with more standardized procedures, like e.g. lithography. This includes on the one hand the production of nanowires as reliable and reproducible parts, potentially suited for nanoelectronic circuit design. Therefore, this work presents a systematic investigation of the causes of nanowire branching, the necessary conditions to achieve straight growth and the parameters affecting the diameter of the wires. The growth of ultrathin (down to 15 nm), straight and unbranched platinum nanowires assembly is demonstrated. On the other hand, it is the objective to go beyond purely electronic applications. An examination of the crystallography of the wires reveals nanoclusters inside the wire with a common crystallographic orientation. The versatility of the wires is illustrated by implementing them into an impedimetric sensor capable of the detection of single nanoscaled objects, such as bacteria. / Die Zielstellung der vorliegenden Arbeit ist es, die elektrochemische Herstellung von metallischen Nanodrähten zu einer wettbewerbsfähigen Methode zu machen, die sich mit standardisierten Prozessen, wie z. B. der Lithographie messen kann. Dies beinhält auf der einen Seite die Produktion der Nanodrähte als zuverlässige und reproduzierbare Bauteile, die im nanoelektrischen Schaltungsdesign Verwendung finden können. Daher befasst sich diese Arbeit mit einer systematischen Untersuchung der Ursachen für die Verzweigung von Nanodrähten, den notwendigen Bedingungen um gerades Wachstum zu erlangen und mit den Parametern, die Einfluss auf den Durchmesser der Drähte haben. Der Wuchs von sehr dünnen (bis zu 15 nm), geraden und unverzweigten Nanodrähten aus Platin wird gezeigt. Auf der anderen Seite ist es erklärtes Ziel, über rein elektronische Anwendungen hinaus zu gehen. Eine Untersuchung der Kristallographie der Nanodrähte zeigt, dass die Drähte aus Nanopartikeln bestehen, die eine gemeinsame kristallographische Orientierung aufweisen. Die Vielseitigkeit der Drähte wird anhand einer Sensoranwendung gezeigt, mit der es möglich ist, einzelne nanoskalige Objekte (wie z. B. Bakterien) zu detektieren.

The aim of this work is to make electrochemical metal nanowire growth a competitive method, being up to par with more standardized procedures, like e.g. lithography. This includes on the one hand the production of nanowires as reliable and reproducible parts, potentially suited for nanoelectronic circuit design. Therefore, this work presents a systematic investigation of the causes of nanowire branching, the necessary conditions to achieve straight growth and the parameters affecting the diameter of the wires. The growth of ultrathin (down to 15 nm), straight and unbranched platinum nanowires assembly is demonstrated. On the other hand, it is the objective to go beyond purely electronic applications. An examination of the crystallography of the wires reveals nanoclusters inside the wire with a common crystallographic orientation. The versatility of the wires is illustrated by implementing them into an impedimetric sensor capable of the detection of single nanoscaled objects, such as bacteria. / Die Zielstellung der vorliegenden Arbeit ist es, die elektrochemische Herstellung von metallischen Nanodrähten zu einer wettbewerbsfähigen Methode zu machen, die sich mit standardisierten Prozessen, wie z. B. der Lithographie messen kann. Dies beinhält auf der einen Seite die Produktion der Nanodrähte als zuverlässige und reproduzierbare Bauteile, die im nanoelektrischen Schaltungsdesign Verwendung finden können. Daher befasst sich diese Arbeit mit einer systematischen Untersuchung der Ursachen für die Verzweigung von Nanodrähten, den notwendigen Bedingungen um gerades Wachstum zu erlangen und mit den Parametern, die Einfluss auf den Durchmesser der Drähte haben. Der Wuchs von sehr dünnen (bis zu 15 nm), geraden und unverzweigten Nanodrähten aus Platin wird gezeigt. Auf der anderen Seite ist es erklärtes Ziel, über rein elektronische Anwendungen hinaus zu gehen. Eine Untersuchung der Kristallographie der Nanodrähte zeigt, dass die Drähte aus Nanopartikeln bestehen, die eine gemeinsame kristallographische Orientierung aufweisen. Die Vielseitigkeit der Drähte wird anhand einer Sensoranwendung gezeigt, mit der es möglich ist, einzelne nanoskalige Objekte (wie z. B. Bakterien) zu detektieren.

Doctor of Philosophy / Department of Chemistry / Stefan H. Bossmann / Cancer is a group of diseases that are characterized by uncontrolled growth and spread of cells. In order to treat cancer successfully, it is important to diagnose cancers in their early stages, because survival often depends on the stage of cancer detection. For that purpose, highly sensitive and selective methods must be developed, taking advantage of suitable biomarkers. The expression levels of proteases differ from one cancer type to the other, because different cancers arise from different cell types. According to the literature, there are significant differences between the protease expression levels of cancer patients and healthy people, because solid tumors rely on proteases for survival, angiogenesis and metastasis. Development of fluorescence-based nanobiosensors for the early detection of pancreatic cancer and non-small-cell lung cancer is discussed in this thesis. The nanobiosensors are capable of detecting protease/arginase activities in serum samples over a broad range. The functionality of the nanobiosensor is based on Förster resonance energy transfer and surface energy transfer mechanisms. The nanobiosensors for protease detection feature dopamine-coated Fe/Fe₃O₄ nanoparticles, consensus (cleavage) peptide sequences, meso-tetra(4-carboxyphenyl)porphine (TCPP), and cyanine 5.5. The consensus peptide sequences were synthesized by solid-supported peptide synthesis. In this thesis, improved consensus sequences were used, which permit faster synthesis and higher signal intensities. TCPP, which is the fluorophore of the nanoplatform, was connected to the N-terminal end of the oligopeptides while it was still on the resin. After the addition of TCPP, the TCPP-oligopeptide was cleaved off the resin and linked to the primary amine groups of Fe/Fe₃O₄-bound via a stable amide bond. In the presence of a particular protease, the consensus sequences attached to the nanoparticle can be cleaved and release TCPP to the aqueous medium. Upon releasing the dye, the emission intensity increases significantly and can be detected by fluorescence spectroscopy or, similarly, by using a fluorescence plate reader. In sensing of arginase, posttranslational modification of the peptide sequence will occur, transforming arginine to ornithine. This changes the conformational dynamics of the oligopeptide tether, leading to the increase of the TCPP signal. This is a highly selective technology, which has a very low limit of detection (LOD) of 1 x 10⁻¹⁶ molL⁻¹ for proteases and arginase. The potential of this nanobiosensor technology to detect early pancreatic and lung cancer was demonstrated by using serum samples, which were collected from patients who have been diagnosed with pancreatic cancer and non-small cell lung cancer at the South Eastern Nebraska Cancer Center (lung cancer) and the University of Kansas Cancer Center (pancreatic cancer). As controls, serum samples collected from healthy volunteers were analyzed. In pancreatic cancer detection, the protease/arginase signature for the detection of pancreatic adenocarcinomas in serum was identified. It comprises arginase, MMPs -1, - 3, and -9, cathepsins -B and -E, urokinase plasminogen activator, and neutrophil elastase. For lung cancer detection, the specificity and sensitivity of the nanobiosensors permit the accurate measurements of the activities of nine signature proteases in serum samples. Cathepsin -L and MMPs-1, -3, and -7 permit detecting non-small-cell lung-cancer at stage 1.

Doctor of Philosophy / Department of Chemistry / Jun Li / Reduction in electrode size down to nanometers dramatically enhances the detection sensitivity and temporal resolution. Here we explore nanoelectrode arrays (NEAs) and nanoparticles in building high performance biosensors. Vertically aligned carbon nanofibers (VACNFs) of diameter ~100 nm were grown on a Si substrate using plasma enhanced chemical vapor deposition. SiO[subscript]2 embedded CNF NEAs were then fabricated using techniques like chemical vapor deposition, mechanical polishing, and reactive ion etching, with CNF tips exposed at the final step. The effect of the interior structure of CNFs on electron transfer rate (ETR) was investigated by covalently attaching ferrocene molecules to the exposed end of CNFs. Anomalous differences in the ETR were observed between DC voltammetry (DCV) and AC voltammetry (ACV). The findings from this study are currently being extended to develop an electrochemical biosensor for the detection of cancerous protease (legumain). Preliminary results with standard macro glassy carbon electrodes show a significant decrease in ACV signal, which is encouraging. In another study, NEA was employed to capture and detect pathogenic bacteria using AC dielectrophoresis (DEP) and electrochemical impedance spectroscopy (EIS). A nano-DEP device was fabricated using photolithography processes to define a micro patterned exposed active region on NEA and a microfluidic channel on macro-indium tin oxide electrode. Enhanced electric field gradient at the exposed CNF tips was achieved due to the nanometer size of the electrodes, because of which each individual exposed tip can act as a potential DEP trap to capture the pathogen. Significant decrease in the absolute impedance at the NEA was also observed by EIS experiments. In a final study, we modified gold nanoparticles (GNPs) with luminol to develop chemiluminescence (CL) based blood biosensor. Modified GNPs were characterized by UV-Vis, IR spectroscopy and TEM. We have applied this CL method for the detection of highly diluted blood samples, in both intact and lysed forms, which releases Fe[superscipt]3[superscript]+ containing hemoglobin to catalyze the luminol CL. Particularly, the lysed blood sample can be detected even after 10[superscript]8 dilution (corresponding to ~0.18 cells/well). This method can be readily developed as a portable biosensing technique for rapid and ultrasensitive point-of-care applications.

<p>In this thesis, I present the electrochemical studies of three dendrimeric polypropylene imine (PPI) nanomaterials and their applications as a platform in the development of a novel label free DNA nanobiosensor based on electrochemical impedance spectroscopy. Cyclic voltammetry (CV), differentia pulse voltammetry (DPV), square wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) techniques were used to study and model the electrochemical reactivities of the nanomaterials on glassy carbon electrode (GCE) as the working electrode.</p>

<p>In this thesis, I present the electrochemical studies of three dendrimeric polypropylene imine (PPI) nanomaterials and their applications as a platform in the development of a novel label free DNA nanobiosensor based on electrochemical impedance spectroscopy. Cyclic voltammetry (CV), differentia pulse voltammetry (DPV), square wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) techniques were used to study and model the electrochemical reactivities of the nanomaterials on glassy carbon electrode (GCE) as the working electrode.</p>

Philosophiae Doctor - PhD / In this thesis, I present the electrochemical studies of three dendrimeric polypropylene imine (PPI) nanomaterials and their applications as a platform in the development of a novel label free DNA nanobiosensor based on electrochemical impedance spectroscopy. Cyclic voltammetry (CV), differentia pulse voltammetry (DPV), square wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) techniques were used to study and model the electrochemical reactivities of the nanomaterials on glassy carbon electrode (GCE) as the working electrode. / South Africa

No description available.

<p>In this thesis, I present a simple, sensitive and low cost electrochemical nanobiosensor for quantitative determination of the herbicides glufosinate, glyphosate and its metabolite aminomethylphosphonic acid (AMPA). Firstly, the nanostructured poly(2,5-dimethoxyaniline) (PDMA) materials were synthesized on gold electrode by the electrochemical &ldquo / soft template&rdquo / method using poly(4-styrenesulfonic acid) (PSS) as the dopant and structure-directing molecule. Fourier transform infrared (FTIR) spectroscopy, UV-Vis Spectroscopy, Transmission electron microscopy (TEM) and Scanning electron microscopy (SEM) studies inferred successful doping of the nanostructured PDMA film by PSS and that the template PSS directed the synthesis of both nanotubes and nanoparticles of PDMA with diameters less than 100 nm.</p>

<p>In this thesis, I present a simple, sensitive and low cost electrochemical nanobiosensor for quantitative determination of the herbicides glufosinate, glyphosate and its metabolite aminomethylphosphonic acid (AMPA). Firstly, the nanostructured poly(2,5-dimethoxyaniline) (PDMA) materials were synthesized on gold electrode by the electrochemical &ldquo / soft template&rdquo / method using poly(4-styrenesulfonic acid) (PSS) as the dopant and structure-directing molecule. Fourier transform infrared (FTIR) spectroscopy, UV-Vis Spectroscopy, Transmission electron microscopy (TEM) and Scanning electron microscopy (SEM) studies inferred successful doping of the nanostructured PDMA film by PSS and that the template PSS directed the synthesis of both nanotubes and nanoparticles of PDMA with diameters less than 100 nm.</p>