Nanotechnology has enormous potential to transform a wide variety of sectors, e.g., energy, electronics, healthcare, and environmental sustainability. At the same time, there are concerns about the health and environmental impacts of nanotechnology and uncertainties about the fate and toxicity of nanomaterials. Life cycle assessment (LCA), a quantitative framework for evaluating the cumulative environmental impacts associated with all stages of a material or process, has emerged as a decision-support tool for analyzing the environmental burdens of nanotechnology. The objective of this research was to combine laboratory techniques with LCA modeling to reduce the life cycle impacts of gold nanoparticle (AuNP) production. The LCA studies were focused on three aspects of AuNP synthesis: 1) the use of bio-based ("green") reducing agents; 2) the potential for recycling gold from nanomaterial waste; and, 3) the reduction of the life cycle impacts of AuNP production by conducting the synthesis at reduced temperature. The LCA models developed for AuNPs can inform future nanotechnology-focused LCA studies. Comparative LCA showed that in some cases, the environmental impacts associated with green synthesis methods may be worse than those of conventional synthesis approaches. The main driver of the environmental burdens associated with AuNP synthesis is the large embodied energy of gold, and so-called green synthesis methods do not offset those impacts. In addition, the reaction yield, which is seldom reported in the literature for green synthesis of nanomaterials, was found to greatly influence the life cycle impacts of AuNP synthesis. Gold from nanomaterial waste was successfully recovered by using host-guest inclusion complex formation facilitated by alpha-cyclodextrin. This recycling approach involved room temperature conditions and did not require the toxic cyanide or mercury commonly used in the selective recovery of gold. A major advantage offered by this approach for selective gold recovery over conventional approaches is that the recovery does not involve the use of toxic cyanide or mercury. To reduce the energy footprint of citrate-reduced AuNP synthesis, the synthesis was conducted at room temperature. LCA models showed significant reduction in the energy footprint. The findings of this research can inform future LCAs of other nanomaterials. / Ph. D.

Background: Photothermal therapy is an actively researched cancer treatment alternative to chemotherapy and resection due to its potential as a minimally invasive treatment with fewer health complications than high energy radiation therapies. The effectiveness of photothermal therapy may be enhanced with the use of photoabsorbtive nanoparticles by increasing heat generation and improving spatial selectivity. While photothermal therapy is a spatially distributed treatment, traditional experimental analysis methods used to assess photothermal therapy have either lacked spatial assessment such as is the case with standard viability assays of cell monolayers, or they only provide macroscopic treatment information, such as the measurement of the diameters of implanted mice flank tumors post-treatment. Goals: This work aims to accomplish two major goals. The first is to determine the therapeutic impact of combining Single Walled Carbon Nanohorns (SWNHs) with photothermal therapy. The second is to advance the measurement tools used to assess photothermal therapy by developing viability measurement methods which incorporate detailed quantitative spatial information Methods: Photothermal therapy was tested with and without SWNHs in in vitro cell monolayers, in vitro tissue phantoms, and ex-vivo tissue. Digital image analysis methods were developed which allowed for the use of viability assays and histological information to be identified and organized spatially. These methods were then used to compare the impact of cellular microenvironment and heating method on Arrhenius parameters. Results: The inclusion of SWNHs dramatically increased the temperatures reached in each experiment. Digital image analysis methods were shown to quantify spatial viability with a high degree of accuracy and precision in 2D and 3D. Experimental data indicated that there were areas of collateral damage (partially treated tissue) surrounding areas of completely treated tissue ranging which were between 46% and 78% of the completely treated volume. In each case the heat transfer properties of the experimental system had a large impact on the area of treatment. Variation in the temperature and viability response of photothermal therapy for specific laser and nanoparticle treatment parameters was quantified. Conclusions: This research has brought an experimental cancer treatment procedure from experiments in cell monolayers to tests in ex-vivo tissue to analyze viability response. The strengths of photothermal therapy such as its minimally invasive nature, and effectiveness at killing cells were experimentally demonstrated. This research has also developed the tools necessary to assess the spatial impact in vitro and lay the foundations for assessing spatial impact in vivo. These tools may be used to assess other treatments beyond photothermal therapy, and serve as a basis for improving the analysis of biological systems both in vitro and in vivo. / Ph. D.

Molecular nanotechnology has matured in the last thirty-nine years from the germ of an idea by a Nobel Laureate physicist to a rapidly growing international research site with more than $1 billion dollars in annual investment. Although only recently accepted as "mainstream" by the R&D community, nanotechnology research is now populated by eminent researchers in such fields as physics, chemistry, molecular biology, and computer science. Refereed journal articles appear with increasing frequency. The National Academy of Sciences, the RAND Corporation, the Department of Defense, and the National Science Foundation have recently issued reports calling for more structure and organization in nanotechnology research to improve synergy and research efficiency. Others insist that centralization would restrict independent approaches, one of which might be the best path to follow. This thesis addresses the following issues for the emerging field of molecular nanotechnology: • The field is extensive, growing, and in need of policy review. • The parties responsible for strategic science and technology policy in the United States as well as the current infrastructure for R&D funding are identified. • External evaluators have appraised our current policy and found it lacking in some key respects. • There are substantive issues that might be considered by American policymakers in assessing nanotechnology policy strategies. • We need to find a way to reconcile the sometimes conflicting aims of peer review and interdisciplinarity. • A workable framework for a national nanotechnology program is identified. / Master of Science

Kinetically controlled isothermal growth is fundamental to biological development, but it remains challenging to rationally design molecular systems that self-assemble isothermally into complex geometries via prescribed assembly and disassembly pathways. By exploiting the programmable chemistry of base pairing, sophisticated spatial and temporal control have both been demonstrated in DNA self-assembly, but largely as separate pursuits. This dissertation extends a new approach, called developmental self-assembly, that integrates temporal with spatial control by using a prescriptive molecular program to specify the kinetic pathways by which DNA molecules isothermally self-assemble into well-defined three-dimensional geometries. / Chemistry and Chemical Biology

<p>Biological systems have inspired interest in developing artificial molecular self-assembly techniques that imitate nature's ability to harness chemical forces to specifically position atoms within intricate assemblies. Of the biomolecules used to mimic nature's abilities, nucleic acids have gained special attention. Specifically, deoxyribonucleic acid is a stable molecule with a readily accessible code that exhibits predictable and programmable intermolecular interactions. These properties are exploited in the revolutionary structural DNA nanotechnology method known as scaffolded DNA origami. For DNA origami to establish itself as a widely used method for creating self-assembling, complex, functional materials, current limitations need to be overcome and new methods need to be established to move forward with developing structures for diverse applications in many fields. The limitations discussed in this dissertation include 1) pushing the scale of well-formed, fully-addressable origami to two and seven times the size of conventional origami, 2) testing cost-effective staple strand synthesis methods for producing pools of oligos for a specified origami, and 3) engineering mechanical properties using non-natural nucleotides in DNA assemblies. After accomplishing the above, we're able to design complex DNA origami structures that incorporate many of the current developments in the field into a useful material with applicability in wide-ranging fields, namely cell biology and photonics.</p> / Dissertation

Published Article / In the era of open innovation, the capability to conduct collaborative research and development has become a key indicator of absorptive capacity and innovation competitiveness. However, the literature addressing open innovation has a focus on developed economies. New evidence from the South African National R&D Survey, together with supplementary data, make it possible to gain a greater understanding of the structure of open innovation in nanotechnology, biotechnology and open source software in the South African context. Findings from a comparative analysis include: the identification of collaboration-intensive R&D networks whose structures are influenced by the characteristics of each technological platform; linkages between localized innovation networks and global innovation networks; and distinct patterns of expenditure, sectoral distribution and geographical location characterizing each of these technologies. The paper concludes with some suggestions for policy applications for these findings as well as directions for further research.

In this thesis I present a novel coarse-grained model of deoxyribonucleic acid (DNA). The model represents single-stranded DNA as a chain of rigid nucleotides, and includes potentials to represent chain connectivity, excluded volume, hydrogen-bonding and base stacking interactions. The parameterization of these interactions is justified by comparing the model's representation of a range of physical phenomena to experimental data. In particular, the geometrical structure and elastic moduli of duplex DNA, and the flexibility of single-stranded DNA, are shown to be physically reasonable. Additionally, the thermodynamics of single-stranded stacking, duplex hybridization, hairpin formation and more complex motifs are shown to agree well with experimental data. The model is optimized for capturing the thermodynamic and mechanical changes associated with duplex formation from single strands. Considerable attention is therefore given to ensuring that single-stranded DNA behaves physically, an approach which differs from previous attempts to model DNA. As a result, the model is the first in which an explicit stacking transition is present in single strands, and also the only coarse-grained model to date to capture both hairpin formation within a single strand and duplex formation between strands. The scope of the model is demonstrated by simulating DNA tweezers, an iconic nanodevice -- the first time that coarse-grained modelling has been applied to dynamic DNA nanotechnology. The simulations suggest that branch migration during toehold-mediated strand displacement -- a central feature of many nanomachines -- does not have a flat free-energy profile, as is generally assumed. This finding may help to explain the observed dependence of displacement rate on toehold length. Finally, the operation of a two-footed DNA walker on a single-stranded DNA track is considered. The model suggests that several aspects of the walker will reduce its efficiency, including a tendency to bind to an undesired site on the track. Several design modifications are suggested to improve the operation of the walker.

Nowadays, nanotechnology is becoming an inescapable part of everyday life. The big barrier in front of its rapid growth is our incapability of producing nanoscale materials in a reliable and cost-effective way. In fact, the current yield of nano-devices is very low (around 10 %), which makes fabrications of nano-devices very expensive and uncertain. To overcome this challenge, the first and most important step is to investigate how to control nano-structure synthesis variations. The main directions of reliability research in nanotechnology can be classified either from a material perspective or from a device perspective. The first direction focuses on restructuring materials and/or optimizing process conditions at the nano-level (nanomaterials). The other direction is linked to nano-devices and includes the creation of nano-electronic and electro-mechanical systems at nano-level architectures by taking into account the reliability of future products. In this dissertation, we have investigated two topics on both nano-materials and nano-devices. In the first research work, we have studied the optimization of one of the most important nanowire growth processes using statistical methods. Research on nanowire growth with patterned arrays of catalyst has shown that the wire-to-wire spacing is an important factor affecting the quality of resulting nanowires. To improve the process yield and the length uniformity of fabricated nanowires, it is important to reduce the resource competition between nanowires during the growth process. We have proposed a physical-statistical nanowire-interaction model considering the shadowing effect and shared substrate diffusion area to determine the optimal pitch that would ensure the minimum competition between nanowires. A sigmoid function is used in the model, and the least squares estimation method is used to estimate the model parameters. The estimated model is then used to determine the optimal spatial arrangement of catalyst arrays. This work is an early attempt that uses a physical-statistical modeling approach to studying selective nanowire growth for the improvement of process yield. In the second research work, the reliability of nano-dielectrics is investigated. As electronic devices get smaller, reliability issues pose new challenges due to unknown underlying physics of failure (i.e., failure mechanisms and modes). This necessitates new reliability analysis approaches related to nano-scale devices. One of the most important nano-devices is the transistor that is subject to various failure mechanisms. Dielectric breakdown is known to be the most critical one and has become a major barrier for reliable circuit design in nano-scale. Due to the need for aggressive downscaling of transistors, dielectric films are being made extremely thin, and this has led to adopting high permittivity (k) dielectrics as an alternative to widely used SiO₂ in recent years. Since most time-dependent dielectric breakdown test data on bilayer stacks show significant deviations from a Weibull trend, we have proposed two new approaches to modeling the time to breakdown of bi-layer high-k dielectrics. In the first approach, we have used a marked space-time self-exciting point process to model the defect generation rate. A simulation algorithm is used to generate defects within the dielectric space, and an optimization algorithm is employed to minimize the Kullback-Leibler divergence between the empirical distribution obtained from the real data and the one based on the simulated data to find the best parameter values and to predict the total time to failure. The novelty of the presented approach lies in using a conditional intensity for trap generation in dielectric that is a function of time, space and size of the previous defects. In addition, in the second approach, a k-out-of-n system framework is proposed to estimate the total failure time after the generation of more than one soft breakdown.

Self-assembled monolayers (SAMs) were investigated with regard to their application as templates to control processes down to the nanometre length scale. With applications of SAM for electrochemical nanotechnology in mind, the range of aspects studied comprises patterning on different length scales, behaviour of SAMs under the conditions of electrochemical metal deposition, and the influence of the head and tail groups on formation and structure of SAMs. On a micrometre scale, laser scanning lithography (LSL) was used to pattern SAM covered Au surfaces. With this technique, localized regions of a SAM are desorbed by scanning the focal spot of a laser beam. Thermal desorption occurs as a result of the high substrate temperature produced by the laser pulses. Patterns with line width as small as 0.9 µm were produced by LSL. It is demonstrated that SAM can not only be patterned by laser radiation but can also be rendered more passive as revealed by electrochemical metal deposition. Such blocking effect is explained by annealing of defects upon irradiation at the appropriate laser energy. This effect can block deposition of bulk copper particles, but does not prevent the underpotential deposition. Based on this passivation effect, large passivation areas can be created, which can be used as substrate for further nano/micro fabrication. The combination of SAM patterning and electrochemical metal deposition was also demonstrated to be an effective way to prepare superhydrophobic surfaces, exhibiting a contact angle of 165° (water droplet). Aiming for the generation of smaller structures, scanning tunneling microscopy (STM) is used as a tool to pattern SAMs. Several phenomena observed in STM based manipulation of SAMs are addressed. The first one is sweeping effect. Deposited metal particles on top of SAM and SAMs are swept by STM tip by choosing appropriate I/V parameters. The closer the tip (higher current, lower bias), the more effective it is. Molecularly resolved images confirm that after sweeping, the scanned area is still covered by SAM molecules. This is explained by diffusion. The sweeping process can be repeated, thus, resulting in a layer by layer etching. The second effect is field-induced desorption. Applying a positive voltage (2.5-5V), a SAM is damaged beneath the area of the tip. The damage depends not only on the bias applied, but also on the current setpoint right before applying the bias. The third effect is nanografting. Nanografting was observed that a SAM having a stronger assembling ability can replace the weaker one (matrix layer) in hexadecane solution by STM scanning under normal I/V parameters combination that are usually used for imaging. It is found that longer chain can replace the shorter chain thiol, alkanethiol can replace biphenyl thiol. This method can be applied to pattern SAM. Defects (punched holes) were created purposely on the SAMs covered Au surface and in situ STM was used to investigate the process of Under-Potential Deposition (UPD) and bulk metal deposition. Bulk metal deposition on punched holes depends on the size. Small scale patterning by punching is sufficient for applications based on UPD but not for bulk metal deposition. Several SAMs assembled on Au(111) surface (1-mercaptoundecanoic acid (MUA), Dodecyl Thiocyanate (C12SCN) and bis(pyrazol-1-yl)pyridine-substituted thiol (bpp-SH) and thiocyanate (bpp-SCN)) were investigated with the aim to expand the type of SAMs that can be used as template for further application, such as metal coordination. High quality thiolate monolayers formed by cleavage of the S-CN bond can be obtained on Au(111). Thus, organothiocyanates appear to be a promising alternative to thiols. Well-ordered MUA monolayers are formed in a few hours at the temperature range of 323-363 K by Physical Vapour Deposition (PVD). Self-assembled monolayers of bpp-SH and bpp-SCN on Au(111)/mica were studied with STM. Preparation conditions such as temperature, solvent, and contamination affect the formation of SAMs on Au(111) much more than other common thiols such as alkanethiols and biphenythiols.

Nanotechnology is an emerging field of engineering. Awareness needs to be fostered in the K-12 education system in order to sustain its expansion. As a current Algebra 1 teacher, I participated in the NASCENT research program to further my education in nanotechnology and find ways to integrate this content and practices in my Science Technology Engineering and Math (STEM) based Algebra 1 curriculum. During the research, I learned about surface tension of solids and liquids and its effects on materials' wetting properties. After completing the research program, I created a 2-week long project where students will replicate my experiences during this research. The purpose of this report is to investigate the need for the integration of nanotechnology in STEM classes and find ways to turn my research experience into real-world learning opportunities for my students. / text