The military potential of nanotechnology was anticipated by its proponents from the early stages of its development, and explicit programmes for this purpose are now well established. However, the impact of nanotechnology on arms control is very unlikely to be merely additive. Instead, it threatens to undermine the arms control paradigm, for reasons explored in this paper. These include the place of nanoscience and nanotechnology as the principal enablers of technological convergence; the extension from dual-use to multiple-use dilemmas arising from new materials and processes, and their integration into economic development and competitiveness; low entry-level infrastructural requirements (already a feature of biotechnology); and a blurring of the distinction between offensive arms and capabilities likely to be viewed as threatening.

The steady downscaling of CMOS technology has led to the development of devices with nanometer dimensions. Contemporaneously, maturity in technologies such as chemical self-assembly and DNA scaffolding has influenced the rapid development of non-CMOS nanodevices including vertical carbon nanotube (CNT) transistors and molecular switches. One main problem in manufacturing defect-free nanodevices, both CMOS and non-CMOS, is the inherent variability in nanoscale fabrication processes. Compared to current CMOS devices, nanodevices are also more susceptible to signal noise and thermal perturbations. One approach for developing robust digital systems from such unreliable nanodevices is to introduce defect- and fault-tolerance at the architecture level. Structurally redundant architectures, reconfigurable architectures and architectures that are a hybrid of the previous two have been proposed as potential defect- and fault-tolerant nanoscale architectures. Hence, the design of reliable nanoscale digital systems will require detailed architectural exploration. In this dissertation, we develop probabilistic methodologies and CAD tools to expedite the exploration of defect- and fault-tolerant architectures. These methodologies and tools will provide nanoscale system designers with the capability to carry out trade-off analysis in terms of area, delay, redundancy and reliability. During execution, the next state of a digital system is only dependent on the present state and the digital signals propagate in discrete time. Hence, we have used Markov processes to analyze the reliability of nanoscale digital architectures. Discrete Time Markov Chains (DTMCs) have been used to analyze logic architectures and Markov Decision processes (MDPs) have been used to analyze memory architectures. Since structurally redundant and reconfigurable nanoarchitectures may consist of millions of nanodevices, we have applied state space partitioning techniques and Belief propagation to scale these techniques. We have developed three toolsets based on these Markovian techniques. One of these toolsets has been specifically developed for the architectural exploration of molecular logic systems. The toolset can generate defect maps for isolating defective nanodevices and provide capabilities to organize structurally redundant fault-tolerant architectures with the non-defective devices. Design trade-offs for each of these architectures can be computed in terms of signal delay, area, redundancy and reliability. Another tool called HMAN (Hybrid Memory Analyzer) has been developed for analyzing molecular memory systems. Besides analyzing reliability-redundancy trade-offs using MDPs, HMAN provides a very accurate redundancy-delay trade-off analysis using HSPICE. SETRA (Scalable, Extensible Tool for Reliability Analysis) has been specifically designed for analyzing nanoscale CMOS logic architectures with DTMCs. SETRA also integrates well with current industry-standard CAD tools. It has been shown that multimodal computational models capture the operation of emerging nanoscale devices such as vertical CNT transistors, instead of the bimodal Boolean computational model that has been used to understand the operation of current electronic devices. We have extended an existing multimodal computational model based on Markov Random Fields (MRFs) for analyzing structurally redundant and reconfigurable architectures. Hence, this dissertation develops multiple probabilistic methodologies and tools for performing nanoscale architectural exploration. It also looks at different defect- and fault-tolerant architectures and explores different nanotechnologies. / Ph. D.

Biological force microscopy (BFM) was developed to quantitatively measure pico- to nano-Newton forces (10-9 to 10-12 N) as a function of the nanoscale distance (nanometers) between living bacteria and mineral surfaces, in aqueous solution. Native cells were linked to a force-sensing probe, which was used in a force microscope to measure attractive and repulsive forces as a mineral surface approached, made contact with, and subsequently withdrew from a bacterium on the probe. The resulting data were used to interpret the interactive dynamics operative between bacteria and mineral surfaces under environmentally relevant conditions. BFM was used to study bacterial adhesion to mineral surfaces. In the case of Escherichia coli interactions with goethite, graphite, and muscovite, attractive and repulsive forces were detected at ranges up to 400 nanometers, the magnitude and sign depending on the ionic strength of the intervening solution and the mineral surface charge and hydrophobicity. Adhesion forces, up to several nanoNewtons in magnitude and exhibiting various fibrillation dynamics, were also measured and reflect the complex interactions of structural and chemical functionalities on the bacteria and mineral surfaces. In the study of Burkholderia cepecia interactions with mica, it was found that the physiological condition of the cell affected the observed adhesion forces. Cells grown under oligotrophic conditions exhibited an increased affinity for the mineral surface as opposed to cells grown under eutropic conditions. BFM was also used to characterize the transfer of electrons from biomolecules on Shewanella oneidensis to Fe(III) in the structure of goethite. Force measurements with picoNewton resolution were made in aqueous solution under aerobic and anaerobic conditions. Energy values (in attoJoules) derived from these measurements show that the affinity between S. oneidensis and goethite rapidly increases by two to five times under anaerobic conditions where electron transfer from bacterium to mineral is expected. Specific signatures in the force curves, analyzed with the worm-like chain model of protein unfolding, suggest that the bacterium recognizes the mineral surface such that a 150 kDa putative, iron reductase is quickly mobilized within the outer membrane of S. oneidensis and specifically interacts with the goethite surface to facilitate the electron transfer process. / Ph. D.

Nanoparticle based devices are becoming of great interest because of their single-electron transport behavior, and high surface charge density. Nanoparticle based devices operate at low power, and are potentially highly stable and extremely robust. Making interconnections to nanoparticle devices, however, has been an impending issue. Also percolating/conductive array of nanoparticles is not easy to build since repulsion between the charged nanoparticles causes them to deposit at distance significantly larger for electron tunneling. In this study, we resolve these challenges to make nanoparticle based electronic devices. Using biological (bacteria) or physical (polyelectrolyte fiber) scaffolds, we selectively deposited percolating array of 30 nm Au nanoparticles, to produce a highly versatile nanoparticle-organic hybrid device. The device is based on electron tunneling phenomena, which is highly sensitive to change in inter-particle distance and dielectric constant between nanoparticles. The key to building this structure is the molecular brushes on the surface of the scaffold, which shield the charge on nanoparticle to allow for percolating deposition. The electrostatic attraction for such a deposition on bacteria was measured to be so strong (0.038 N/m) that it could bend a 400 nm long and 25 nm wide gold nanorod. Once the device is built, the hygroscopic scaffolds were actuated by humidity, to modulate the electron tunneling barrier width (or height) between the metallic nanoparticles. A decrease in inter-particle separation by < 0.2 nm or a change in the dielectric constant from ~ 40 to 3 (for humidity excursion from 20% to ~0%), causes a 40-150 fold increase in electron tunneling current. The coupling between the underlying scaffold and the Au particle structure is essential to achieving such a high and robust change in current. In contrast to most humidity sensors, the sensitivity is extremely high at low humidity. This device is >10-fold better than standard microelectronic and MEMS technology based humidity sensors. After the deposition, the "live" bacterial scaffold retains its biological construct, providing an avenue for active integration of biological functions with electronic transport in nanoparticle device. Such hybrids will be the key to conceptually new electronic devices that can be integrated with power and function of microorganisms, on flexible plastic-like substrates using simple beaker chemistry. The technology has broad potential based on variety of nanoparticles (for example, magnetic, metallic and semi-conducting) to make electro-optical and inorganic devices, bringing a prominent advancement in the present technology. Our work is published in, Angewandte Chemie, JACS and Nano Letters, and featured in places such as, Discover Magazine, Science News and Nature. / Ph. D.

No / The convergence of several technological systems (especially nanotechnology, biotechnology, information technology, and robotics) has now been adopted as a strategic goal by several countries, most notably the United States and those of the European Union. The anticipated benefits and related fears of competitive disadvantage have brought together a wide range of interested parties, governmental and nongovernmental. In the rush to enter and/or dominate this arena, the benign promise of converging technologies (CT) are highlighted, although a range of risks and less welcome (if difficult to quantify) implications are at best understated. What, then, are the prospects for exercising governance over the technological systems we are busy creating¿and the uses to which they might be put? What will it mean to speak of "global governance" in a world in which the technological promise of CT has been fulfilled?

Electrostatic self-assembly was used to fabricate several samples of polymers known to have non-linear optical behavior. These samples characteristics were measured with interferometry and their electro-optic coefficients determined to be on the order that of LiNbO3. The self-assembled samples are shown to have an enhanced polar order compared to that of more traditional poled polymers. Furthermore, this polar order is intrinsic and thus doesn't require electric field poling and does not decay with time. The self-assembly process is therefore shown to possess great potential for the fabrication of high-speed electro-optic modulators for commercial and military applications. / Master of Science

CMOS Technology has advanced for decades under the rule of Moore's law. But all good things must come to an end. Researchers estimate that CMOS will reach a lower limit on feature size within the next 10 to 15 years. In order to assure further progress in the field, new computing architectures must be investigated. These nanoscale architectures are many and varied. It remains to be seen if any will become a legitimate successor to CMOS. Single electron tunneling is a process by which electrons can be trans- ported (tunnel) across a thin insulating surface. A conducting island sepa rated by a pair of quantum tunnel junctions creates a Single Electron Transistor (SET). SETs exhibit higher functionality than traditional MOSFETs, and function best at very small feature sizes, in the neighborhood of 1nm. Many circuits must be developed before SETs can be considered a viable contender to CMOS technology. One important circuit is the Digital to Analog Converter (DAC). DACs are present on many microprocessors and microcontrollers in use today and are necessary in many situations. While other SET circuits have been proposed, including ADCs, no DAC design exists in open literature. We propose three possible SET DAC designs and characterize them with an HSPICE SET simulation model. The first design is a charge scaling architecture similar to what is frequently used in CMOS. The second two designs are based on a current steering architecture, but are unique in their implementation with SETs. / Master of Science

Yes / We report on the predicted structural disruption of an adenosine-binding DNA aptamer adsorbed via noncovalent interactions on aqueous graphene. The use of surface-adsorbed biorecognition elements on device substrates is needed for integration in nanofluidic sensing platforms. Upon analyte binding, the conformational change in the adsorbed aptamer may perturb the surface properties, which is essential for the signal generation mechanism in the sensor. However, at present, these graphene-adsorbed aptamer structure(s) are unknown, and are challenging to experimentally elucidate. Here we use molecular dynamics simulations to investigate the structure and analyte-binding properties of this aptamer, in the presence and absence of adenosine, both free in solution and adsorbed at the aqueous graphene interface. We predict this aptamer to support a variety of stable binding modes, with direct base−graphene contact arising from regions located in the terminal bases, the centrally located binding pockets, and the distal loop region. Considerable retention of the in-solution aptamer structure in the adsorbed state indicates that strong intra-aptamer interactions compete with the graphene−aptamer interactions. However, in some adsorbed configurations the analyte adenosines detach from the binding pockets, facilitated by strong adenosine−graphene interactions.

Yes / Peptides have demonstrated unique capabilities to fabricate inorganic nanomaterials of numerous compositions through noncovalent binding of the growing surface in solution. In this contribution, we demonstrate that these biomolecules can control all facets of Au nanoparticle fabrication, including Au3+ reduction, without the use of secondary reagents. In this regard using the AuBP1 peptide, the N-terminal tryptophan residue is responsible for driving Au3+ reduction to generate Au nanoparticles passivated by the oxidized peptide in solution, where localized residue context effects control the reducing strength of the biomolecule. The process was fully monitored by both time-resolved monitoring of the growth of the localized surface plasmon resonance and transmission electron microscopy. Nanoparticle growth occurs by a unique disaggregation of nanoparticle aggregates in solution. Computational modeling demonstrated that the oxidized residue of the peptide sequence does not impact the biomolecule’s ability to bind the inorganic surface, as compared to the parent peptide, confirming that the biomolecule can be exploited for all steps in the nanoparticle fabrication process. Overall, these results expand the utility of peptides for the fabrication of inorganic nanomaterials, more strongly mimicking their use in nature via biomineralization processes. Furthermore, these capabilities enhance the simplicity of nanoparticle production and could find rapid use in the generation of complex multicomponent materials or nanoparticle assembly. / Air Force Office of Scientific Research, grant FA9550-12-1-0226.

Yes / Peptide-mediated synthesis and assembly of nanostructures opens new routes to functional inorganic/organic hybrid materials. However, understanding of the many factors that influence the interaction of biomolecules, specifically peptides, with metal surfaces remains limited. Understanding of the relationship between peptide sequence and resulting binding affinity and configurations would allow predictive design of peptides to achieve desired peptide/metal interface characteristics. Here, we measured the kinetics and thermodynamics of binding on a Au surface for a series of peptide sequences designed to probe specific sequence and context effects. For example, context effects were explored by making the same mutation at different positions in the peptide and by rearranging the peptide sequence without changing the amino acid content. The degree of peptide-surface contact, predicted from advanced molecular simulations of the surface-adsorbed structures, was consistent with the measured binding constants. In simulations, the ensemble of peptide backbone conformations showed little change with point mutations of the anchor residues that dominate interaction with the surface. Peptide-capped Au nanoparticles were produced using each sequence. Comparison of simulations with nanoparticle synthesis results revealed a correlation between the colloidal stability of the Au nanoparticles and the degree of structural disorder in the surface-adsorbed peptide structures for this family of sequences. These findings suggest new directions in the optimization and design of biomolecules for in situ peptide-based nanoparticle growth, binding, and dispersion in aqueous media.