Chemistry & Biochemistry Theses and Dissertations
Permanent URI for this collectionhttp://hdl.handle.net/1903/2752
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Item Solution Processing of Long Carbon Nanotubes: from Fundamentals to Applications(2019) Wang, Peng; Wang, YuHuang; Chemistry; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Single-walled carbon nanotubes (SWCNTs) are one of the most intensively studied nanomaterials due to their extraordinary mechanical, electrical, and optical properties. Attaining aqueous solutions of individual SWCNTs is the critical first step for harnessing their outstanding properties and applying them in many applications and further processing, such as sorting, imaging, and sensing. However, the current ultrasonication-then-ultracentrifugation approach inevitably introduces defects to SWCNTs and cuts the nanotubes into smaller pieces, compromising the electrical and mechanical properties of this otherwise remarkable material. In this dissertation, we introduce an unexpectedly simple approach that completely eliminates the need for ultrasonication, and nondestructively disperses SWCNTs in aqueous solution, so that the synthetic lengths of SWCNTs can be preserved. The dispersion is achieved by using surfactants to wrap and stabilize the protonated SWCNTs by simple acid-base neutralization reactions. The result is that the protons on SWCNTs are replaced by surfactants, and thus, we name this method “superacid-surfactant exchange (S2E).” In chapters 2-4, we demonstrate the length of dissolved SWCNTs by S2E can be 4-10 times longer than the sonicated controls, thereby significantly improving the optical, electrical and electromechanical properties. We further find that by tuning the concentrations of SWCNTs in this S2E process, short nanotubes can be selectively extracted out, allowing separation of the long carbon nanotubes (>10 µm). In chapter 5, we show that long SWCNTs can behave like mechanical reinforcing structures that enhance the mechanical strength of graphene through π-π interactions without sacrificing much of the outstanding transparency of graphene. This fact has enabled the fabrication of the mechanically strong yet ultrathin graphene/SWCNTs hybrid structure (G+T) for operando probing of the electrical double layer at the electrode-electrolyte interface by X-ray photoelectron. Finally, as a ramification result from the S2E process, chapter 6 describes the scalable synthesis of organic-color-center tailored SWCNTs.Item Electrical Properties of a Tube-in-a-Tube Semiconductor(2016) Ng, Allen Lee; Wang, YuHuang; Chemistry; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)Tube-in-a-tube (Tube^2) nanostructures were synthesized through the outer-wall selective covalent functionalization of double-walled carbon nanotubes (DWCNTs) at high functional densities. Upon functionalization, the properties of individual walls within the structure decouple resulting in an electrically insulating functional outer tube while the inner tube retains exceptional CNT properties. The exceptional electrical properties of Tube^2 semiconductor structures were demonstrated for applications that include molecular and biological sensors and patterning of CNTbased structures with electronic type specificity. Tube^2 thin film transistor (TFT) sensors exhibited simultaneous ultrahigh sensitivity and selectivity towards chemical and biological targets. Carboxylic acid terminated Tube^2 sensors displayed an NH3 sensitivity of 60 nM, which is comparable with small molecule aqueous solution detection using state-of-the-art TFT sensors while simultaneously attaining 6,000 times higher chemical selectivity towards a variety of amine containing analyte molecules over carboxylic acids. Similarly, 23-base ii oligonucleotide terminated Tube^2 sensors demonstrated concomitant sensitivity down to 5 nM towards their complementary sequence without amplification techniques and single mismatch selectivity without the use of a gate electrode. Unique sensor architectures can be designed with the requirement of a gate electrode, such as the creation of millimeter-scale point sensors. The optical features and unique structural features of Tube^2 thin films were also exploited to address the challenge of patterning CNT nanostructures with electronic type specificity. Patterned dot arrays and conductive pathways were created on an initially insulating Tube^2 thin film by tuning the resonance of the direct-writing laser with the electronic type of the inner tube (i.e., metallic or semiconducting). The successful patterning of Tube^2 thin films was unambiguously confirmed with in situ Raman spectral imaging and electrical characterization. Furthermore, a hybrid 2-D carbon nanostructure comprised of a functionalized graphene that covers a semiconducting (6,5) SWCNT network (fG/sSWCNT) was developed. The hybrid fG/sSWCNT nanostructure exhibits similar structural and electrical properties as a semiconducting Tube^2 thin film, but possesses a transconductance that is an order of magnitude larger than Tube^2 and ON/OFF ratios as high as 5400 without the useful of further processing steps such as electrical breakdown.Item MANIPULATION OF DNA TOPOLOGY USING AN ARTIFICIAL DNA-LOOPING PROTEIN(2012) Gowetski, Daniel; Kahn, Jason D; Biochemistry; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)DNA loop formation, mediated by protein binding, plays a broad range of roles in cellular function from gene regulation to genome compaction. While DNA flexibility has been well investigated, there has been controversy in assessing the flexibility of very small loops. We have engineered a pair of artificial coiled-coil DNA looping proteins (LZD73 and LZD87), with minimal inherent flexibility, to better understand the nature of DNA behavior in loops of less than 460 bp. Ring closure experiments (DNA cyclization) were used to observe induced topological changes in DNA upon binding to and looping around the engineered proteins. The length of DNA required to form a loop in our artificially rigid system was found to be substantially longer than loops formed with natural proteins in vivo. This suggests the inherent flexibility of natural looping proteins plays a substantial role in stabilizing small loop formation. Additionally, by incrementally varying the binding site separation between 435 bp and 458 bp, it was observed that the LZD proteins could predictably manipulate the DNA topology. At the lengths evaluated, the distribution of topological products correlates to the helical repeat of the double helix (10.5 bp). The dependence on binding site periodicity is an unequivocal demonstration of DNA looping and represents the first application of a rigid artificial protein in this capacity. By constructing these DNA looping proteins, we have created a platform for addressing DNA flexibility in regards to DNA looping. Future applications for this technology include a vigorous study of the lower limits of DNA length during loop formation and the use of these proteins in assembling protein:DNA nanostructures.