Superconducting Transition-Edge Sensor Physics

Despite record-setting performance demonstrated by superconducting Transition Edge Sensors (TESs) and growing utilization of the technology, a theoretical model of the physics governing TES devices superconducting phase transition has proven elusive. Earlier attempts to describe TESs assumed them to be uniform superconductors. Sadleir et al. 2010 shows that TESs are weak links and that the superconducting order parameter strength has significant spatial variation. Measurements are presented of the temperature T and magnetic field B dependence of the critical current Ic measured over 7 orders of magnitude on square Mo/Au bilayers ranging in length from 8 to 290 microns. We find our measurements have a natural explanation in terms of a spatially varying order parameter that is enhanced in proximity to the higher transition temperature superconducting leads (the longitudinal proximity effect) and suppressed in proximity to the added normal metal structures (the lateral inverse proximity effect). These in-plane proximity effects and scaling relations are observed over unprecedentedly long lengths (in excess of 1000 times the mean free path) and explained in terms of a Ginzburg-Landau model. Our low temperature Ic(B) measurements are found to agree with a general derivation of a superconducting strip with an edge or geometric barrier to vortex entry and we also derive two conditions that lead to Ic rectification. At high temperatures the Ic(B) exhibits distinct Josephson effect behavior over long length scales and following functional dependences not previously reported. We also investigate how film stress changes the transition, explain some transition features in terms of a nonequilibrium superconductivity effect, and show that our measurements of the resistive transition are not consistent with a percolating resistor network model.

Applications of functional nucleic acids in imaging, sensing and drug delivery and investigations of DNAzyme-metal interactions

Functional nucleic acids (FNA), including nucleic acids catalysts (ribozymes and DNAzymes) and ligands (aptamers), have been discovered in nature or isolated in a laboratory through a process called in vitro selection. They are nucleic acids with functions similar to protein enzymes or antibodies. They have been developed into sensors with high sensitivity and selectivity; it is realized by converting the reaction catalyzed by a DNAzyme/ribozyme or the binding event of an aptamer to a fluorescent, colorimetric or electrochemical signal. While a number of studies have been reported for in vitro sensing using DNAzymes or aptamers, there are few reports on in vivo sensing or imaging. MRI is a non-invasive imaging technique; smart MRI contrast agents were synthesized for molecular imaging purposes. However, their rational design remains a challenge due to the difficulty to predict molecular interactions. Chapter 2 focuses on rational design of smart T1-weighted MRI contrast agents with high specificity based on DNAzymes and aptamers. It was realized by changing the molecular weight of the gadolinium conjugated DNA strand with the analytes, which lead to analyte-specific water proton relaxation responses and contrast changes on an MRI image. The designs are general; the high selectivity of FNA was retained. Most FNA-based fluorescent sensors require covalent labeling of fluorophore/quencher to FNAs, which incurrs extra expenses and could interfere the function of FNAs. Chapter 3 describes a new sensor design avoiding the covalent labeling of fluorophore and quencher. The fluorescence of malachite green (MG) was regulated by the presence of adenosine. Conjugate of aptamers of MG and adenosine and a bridge strand were annealed in a solution containing MG. The MG aptamer did not bind MG because of its hybridization to the bridge strand, resulting in low fluorescence signal of MG. The hybridization was weakened in the presence of adenosine, leading to the binding of MG to its aptamer and a fluorescence increase. The sensor has comparable detection limit (20 micromolar) and specificity to its labeled derivatives. Enzymatic activity of most DNAzymes requires metal cations. The research on the metal-DNAzyme interaction is of interest and challenge to scientists because of the lack of structural information. Chapters 4 presents the research on the characterization of the interaction between a Cu2+-dependent DNAzyme and Cu2+. Electron paramagnetic resonance (EPR) and UV-Vis spectroscopy were used to probe the binding of Cu2+ to the DNAzyme; circular dichroism was used to probe the conformational change of the DNAzyme induced by Cu2+. It was proposed that the conformational change by the Cu2+ binding is important for the activity of the DNAzyme. Chapter 5 reports the dependence of the activity of 8-17 DNAzyme on the presence of both Pb2+ and other metal cations including Zn2+, Cd2+ and Mg2+. It was discovered that presence of those metal cations can be cooperative or inhibitive to 8-17 activity. It is hypothesized that the 8-17 DNAzyme had multiple binding sites for metal cations based on the results. Cisplatin is effective killing tumor cells, but with significant side effects, which can be minimized by its targeted delivery. Chapter 6 focuses on the effort to functionalize liposomes encapsulating cisplatin by an aptamer that selectively bind nucleolin, an overexpressed protein by breast cancer cells. The study proved the selective cytotoxicity to breast cancer cells of the aptamer-functionalized liposome.