Nanotechnology is a term used to describe nanometer scaled systems. This thesis presents various nanomaterials and systems for the investigation of biologically relevant analytes in general, and in particular for their detection, decontamination, or destruction. The validation of short peptide fragments as models for protein aggregation is initially discussed through applying spectroscopic and microscopic techniques to Langmuir monolayer surface chemistry. Following this validation, the use of nanogold as a photoablative material for the destruction of aggregated protein is investigated. Subsequently, the versatility of nanotechnology is shown by investigating a different form of nanogold; namely, gold quantum dots and the interesting phenomenon that arise when dealing with materials on a nanoscale. Experiments involving a complex between these gold quantum dots and an antibody are performed for the detection of an immunoglobulin in solution. The power of this analytical technique is highlighted by the capability of detecting the analyte at nanomolar concentrations. Finally, a limitation-the multiple synthetic steps necessary for imparting biological activity-- of quantum dots is addressed: a single step reaction is studied that allows for direct stabilization and conjugation of quantum dots with proteins and enzymes. As a representative application of the above mentioned procedure, the detection and decontamination of an organophosphorus compound is explored. In general, methods for overcoming limitations of nanoparticles and nanocrystals are discussed.

Invented in the 1950s, gel electrophoresis has now become a routine analytical method to verify the size of nucleic acids and proteins in molecular biology labs. Conventional gel electrophoresis can successfully separate DNA fragments from several base pairs to a few tens of kilo base pairs, beyond which a point is reached that DNA molecules cannot be resolved due to the size independent mobility. In this case, pulsed field gel electrophoresis (PFGE) was introduced to extend the range of DNA fragment sizes that can be effectively separated. But despite the incredible success of PFGE techniques, some important drawbacks remain. First, separation time is extremely long, ranging from several hours to a few days. Second, detection methods still rely on staining the gel after the run. Real time observation and study of band migration behavior is impossible due to the large size of the PFGE device. Finally, many commercial PFGE instruments are relatively expensive, a factor that can limit their accessibility both for routine analytical and preparative use as well as for performing fundamental studies. In this research, a miniaturized PFGE device was constructed with dimension 2cm x 2.6cm, capable of separating DNA fragments ranging from 2.5kb to 32kb within three hours using low voltage. The separation process can be observed in real time under a fluorescence microscope mounted with a cooled CCD camera. Resolution and mobility of the sample were measured to test the efficiency of the device. We also explored manipulating DNA fragments by end labeling DNA molecules with quantum dot nanocrystals. The quantum dot-DNA conjugates can be further modified through binding interactions with biotinylated single-stranded DNA primers. Single molecule visualization was performed during gel electrophoresis and the extension length, entanglement probability and reorientation time of different conjugates were measured to study their effect on DNA migration through the gel. Finally, electrophoresis of DNA conjugates was performed in the miniaturized PFGE device, and shaper bands were observed compared with the non end-labeled sample. Furthermore, by end-labeling DNA with quantum dots, the migration distance of shorter fragments is reduced, providing the possibility of separating a wider range of DNA fragment sizes on the same gel to achieve further device miniaturization.

Quantum dots are inorganic nanocrystals of semiconductor metals that have unique light emitting properties. Due to their tunable and narrow emission profile, broad absorption spectra, resistance to photobleaching and high level of brightness they have emerged as inorganic fluorophores and numerous applicabilities for in vitro, in situ as well as in vivo studies are present. The chemical nature of the quantum dot surface needs to be altered in order to make the inorganic nanoparticles applicable to biological systems. Water soluble and biocompatible particles that limit unspecific binding to proteins can be obtained through functionalization of the surface coating with appropriate molecules.   In this pilot study, two surface modification strategies were performed upon two commercially available quantum dots in order to attach the zwitterionic molecules L-cysteine and thiolated sulfobetaine methacrylate, both shown to create non-fouling and biocompatible surfaces.   A biphasic exchange method was successfully used to perform ligand exchange of Qdot® ITK™ Organic Quantum Dots (QD-Organic) in order to exchange the structurally unknown, native lipophilic coating to one consisting of the amino acid L-cysteine (QD-Cysteine). The quantum dots transferred from the organic to the aqueous phase after the natively hydrophobic coating was changed to the hydrophilic L-cysteine. A characteristic mass fragment of protonated trioctylphosphine oxide (TOPO) was found for QD-Organic, using TOF-SIMS, suggesting TOPO is a part of the native coating. Further, the mentioned mass fragment was no longer present after the exchange. The C (1s) XPS-spectrum showed a new peak for carboxylic carbon, characteristic for L-cysteine, and expected changes in elemental composition were consistent with measured changes for all relevant elements. Large amounts of buffer remained after purification, suggesting the purification protocol needs further evaluation. Traces of the native coating were found in the C (1s) XPS-spectrum for QD-Cysteine, indicating not all ligands were exchange.      Additionally, a strategy for surface functionalization of Qdot® 655 ITK™ amino (PEG) quantum dots (QD-PEG-NH2) with L-cysteine and thiolated sulfobetaine methacrylate was outlined and performed, using Michael addition and the heterobifunctional linker 3-Maleimidobenzoic acid N-hydroxysuccinimide ester. Unfortunately, no indications of successful attachment of the linker to the quantum dot have been found, neither by TOF-SIMS nor XPS, and thus functionalization with L-cysteine and tSBMA was not achieved. In theory, the proposed coupling chemistry used during the pilot study is promising, but further experiments are needed to obtain a successful and optimized protocol for the functionalization.

This thesis presents results of time-resolved photoluminescence experiments conducted on several different self-assembled InGaAs/GaAs and InAs/GaAs semiconductor quantum dot (QD) structures. Depending on the application in mind, different structural, electronic or optical properties have a different weight of importance. Fast carrier capture and relaxation is critical for QD based lasers, for example. In this thesis, the influence of surplus carriers, introduced through modulation-doping, is studied. It is shown that carrier capture is essentially unaffected whereas the intradot relaxation mechanisms, at least at low carrier concentrations, are fundamentally different. The phonon mediated cascade relaxation found in the undoped reference sample is replaced by efficient scattering with the built-in carriers in the case of the doped structures. Moreover, spin relaxation also depends on presence of extra carriers. During energy relaxation via carrier-carrier scattering, the spin polarization is preserved whereas in the undoped sample the strong interaction of relaxing carriers with LO phonons causes spin relaxation. The decay of the ground state spin polarization proceeds at the same rate for doped and undoped structures and is shown to be caused by acoustic phonons, even up to 300 K. While optimizing QD growth for specific applications, it is imperative to evaluate the influence of nonradiative recombination, which is most often detrimental. While misfit dislocations, deliberately introduced in the substrate, lead to the formation of laterally ordered, uniform dots, these samples are found to suffer from strong nonradiative recombination. Structures with different barrier thicknesses and numerical simulations indicate defects in the vicinity of the QDs as main origin of fast carrier trapping. On the other hand, it is shown that direct dot doping, compared to barrier doping or undoped structures, causes only minor degradation of the optical properties. Directly doped dots even exhibit a significantly weaker photoluminescence quenching with temperature, making them prospective for devices operating at room temperature. Finally, the superior proton radiation hardness of QD structures compared to quantum wells is demonstrated, which is due to the three-dimensional confinement. The increase of photoluminescence intensity at low to moderate doses is interpreted as an enhanced carrier transfer into the dots via the defects introduced into the material by the protons. / QC 20100920

Multijunction solar cells made from a combination of CQDs of differing sizes and thus bandgaps are a promising means by which to increase the energy harvested from the Sun’s broad spectrum. In this dissertation, we first report the systematic engineering of 1.6 eV PbS CQD solar cells, optimal as the front cell responsible for visible wavelength harvesting in tandem photovoltaics. We rationally optimize each of the device’s collecting electrodes—the heterointerface with electron accepting TiO2 and the deep-work-function hole-collecting MoO3 for ohmic contact—for maximum efficiency. Room-temperature processing enables flexible substrates, and permits tandem solar cells that integrate a small-bandgap back cell atop a low thermal-budget larger-bandgap front cell. We report an electrode strategy that enables a depleted heterojunction CQD PV device to be fabricated entirely at room temperature. We develop a two-layer donor-supply electrode (DSE) in which a highly doped, shallow work function layer supplies a high density of free electrons to an ultrathin TiO2 layer via charge-transfer doping. Using the DSE we build all-room-temperature-processed small-bandgap (1 eV) colloidal quantum dot solar cells suitable for use as the back junction in tandem solar cells. We further report in this work the first efficient CQD tandem solar cells. We use a graded recombination layer (GRL) to provide a progression of work functions from the hole-accepting electrode in the bottom cell to the electron-accepting electrode in the top cell. The recombination layers must allow the hole current from one cell to recombine, with high efficiency and low voltage loss, with the electron current from the next cell. We conclude our dissertation by presenting the generalized conditions for design of efficient graded recombination layer solar devices. We demonstrate a family of new GRL designs experimentally and highlight the benefits of the progression of dopings and work functions in the interlayers.

This thesis describes the synthesis and assembly of metal and semiconductor nanoparticles (NPs). The two research topics include i) hetero-assembly of metal and semiconductor NPs, ii) effect of ionic strength on homo-assembly of gold nanorods (GNRs). First, we present hetero-assembly of GNRs and semiconductor quantum dots (QDs) in a chain using biotin-streptavidin interaction. We synthesized alloyed CdTeSe QDs and modified them with mercaptoundecanoic acid to render them water-soluble and to attach streptavidin. We synthesized GNRs by a seed-mediated method and selectively modified the ends with biotin. Hetero-assembly of QDs and GNRs depended on the size, ligands, and ratio of QDs and GNRs. Second, we controlled the rate of homo-assembly of GNRs by varying the ionic strength of the DMF/water solution. The solubility of polystyrene on the ends of GNRs depended on the ionic strength of the solution, which correlated with the rate of assembly of GNRs into chains.

This thesis describes the synthesis and assembly of metal and semiconductor nanoparticles (NPs). The two research topics include i) hetero-assembly of metal and semiconductor NPs, ii) effect of ionic strength on homo-assembly of gold nanorods (GNRs). First, we present hetero-assembly of GNRs and semiconductor quantum dots (QDs) in a chain using biotin-streptavidin interaction. We synthesized alloyed CdTeSe QDs and modified them with mercaptoundecanoic acid to render them water-soluble and to attach streptavidin. We synthesized GNRs by a seed-mediated method and selectively modified the ends with biotin. Hetero-assembly of QDs and GNRs depended on the size, ligands, and ratio of QDs and GNRs. Second, we controlled the rate of homo-assembly of GNRs by varying the ionic strength of the DMF/water solution. The solubility of polystyrene on the ends of GNRs depended on the ionic strength of the solution, which correlated with the rate of assembly of GNRs into chains.

No description available.

This thesis investigates the biodistribution and toxicological effects of amphiphilic polymer coated CdSe/ZnS quantum dots (QDs) in two aquatic species, Daphnia magna (daphnia) and Danio rerio (zebrafish). The use of QDs in the life sciences has become common practice over the past decade. In addition QDs are being incorporated in commercially available light emitting diodes and photovoltaic solar cells. As the widespread commercial use of QDs increases, environmental release is inevitable, and water will contain the highest environmental concentrations based on life cycle assessments. Despite increased attention to the aquatic toxicology of nanomaterials in recent years, little information exists on the biological fate of QDs in aquatic organisms. Quantitative data on the uptake and excretion of QDs from daphnia and zebrafish were collected using fluorescence imaging paired with metal analysis. First, daphnia were examined after aqueous and dietary exposure to amphiphilic polymer coated CdSe/ZnS QDs. Surface coating influenced QD acute toxicity and high particle aggregation correlated with daphnia mortality. QDs were readily ingested by daphnia and accumulated in the intestines. High body burdens of 150-200 μg/g were found in the daphnia, with intestinal QD concentrations significantly elevated above the exposure media concentration. The slow elimination observed in daphnia suggested that trophic transfer of QDs to higher organisms may occur. Using daphnia and zebrafish as a model food chain revealed that QDs can transfer to zebrafish through dietary exposure with body burdens of 8-9.5 μg/g found. However, no biomagnification between daphnia and zebrafish was observed and the biomagnification factor (BMF = 0.04) was significantly less than one. This work demonstrates that aqueous and dietary exposures to QDs can result in high total body concentrations in aquatic organisms with little to no gross toxicity. The low acute toxicity observed for some surface coated QDs encourages further design optimization to improve the biocompatibility and reduce the environmental impact of QDs.

In the quantum dot implementation of an intermediate band solar cell presented in this thesis, the offset of the intermediate band with respect to the conduction band is approximated by the ground state energy of a single electron in a single quantum dot heterojunction. The ground state energy is calculated with the radial Schrodinger equation with a Hamiltonian whose potential is composed from the step-like conduction band offset of the quantum dot heterojunction and the 1/r electrostatic potential of the hydrogenic impurity. The position of the intermediate band is tuned by adjusting the radius of the quantum dots. By assuming that the centrally located impurities are ionized, the location of the Fermi energy is guaranteed to be within the intermediate band. An intermediate band solar cell contains three bands: a conduction band, a valence band; and an intermediate band. The addition of an intermediate band augments the photogeneration of carriers. These additional carriers allow for an increased theoretical efficiency as compared to a conventional homojunction solar cell. The challenges in implementing an intermediate band solar cell involve centering the intermediate band at an energy level matched to the solar spectrum and aligning the Fermi energy within the intermediate band. The latter is necessary to ensure both a supply of electrons capable of photon induced transition to the conduction band as well as a large population of holes that allow photon induced electrons to transition from the valence band to the intermediate band. This thesis presents a novel material system, InPAs quantum dots enveloped in AlGaAs barriers grown on GaAs substrates, with which to implement an optimized QD-IBSC. This novel material system is selected based upon a refined set of design rules that include a requirement that the quantum dot/barrier pair offer a negligible valence band offset. With such a design rule the existence of hole levels is avoided, thus reducing bandgap narrowing at the valence band edge and the existence of minibands below the intermediate band.