Boundaries in digital spaces

[EN] Intuitively, a boundary in an N-dimensional digital space is a connected component of the (N − 1)-dimensional surface of a connected object. In this paper we make these concepts precise, and show that the boundaries so specified have properties that are intuitively desirable. We provide some efficient algorithms for tracking such boundaries. We illustrate that the algorithms can be used, in particular, for computer graphic display of internal structures (such as the skull and the spine) in the human body based on the output of medical imaging devices (such as CT scanners). In the process some interesting mathematical results are proven regarding “digital Jordan boundaries,” such as a specification of a local condition that guarantees the global condition of “Jordanness.”The research of the author is currently supported by NIH grant HL070472 and NSF grant DMS0306215.Herman, GT. (2007). Boundaries in digital spaces. Applied General Topology. 8(1):93-149. doi:10.4995/agt.2007.1918.SWORD931498

Faceted nanomaterial synthesis, characterizations and applications in reactive electrochemical membrane filtration

Facet engineering of nanomaterials, especially metals and metal oxides has become an important strategy for tuning catalytic properties and functions from heterogeneous catalysis to electrochemical catalysis, photocatalysis, biomedicine, fuel cells, and gas sensors. The catalytic properties are highly related to the surface electronic structures, surface electron transport characteristics, and active center structures of catalysts, which can be tailored by surface facet control. The aim of this doctoral dissertation research is to study the facet-dependent properties of metal or metal oxide nanoparticles using multiple advanced characterization techniques. Specifically, the novel atomic force microscope-scanning electrochemical microscope (AFM-SECM) and density functional theory (DFT) calculations were both applied to both experimentally and theoretically investigate facet dependent electrochemical properties, molecular adsorption, and dissolution properties of cuprous oxide and silver nanoparticles. To promote the facet engineered nanomaterials for environmental engineering apparitions, our research has evaluated the performances of electrochemically reactive membranes that were prepared with novel 2D nanomaterials with surface functioal modifications to enable electrochemical advanced oxidation processes (EAOPs) in membrane filtration process. Our results demonstrated many advantages such as tunable reactivity, tailored surface reactions, antifouling features, and feasibility of large-scale continuous operations. Specifically, this dissertation will introduce our electrochemical membrane synthesis, reactivity, aging, byproducts formation and electrochemical adsorption and desorption, oxidation of pollutants such as two typical per-and poly-fluoroalkyl substances (PFAS), perfluorooctanoic Acid (PFOA) and perfluorobutanoic acid (PFBA)

Local Structure in Hard Particle Self-Assembly and Assembly Failure

The relationship between local order and global structure is not often a straightforward one in systems on the nano- and microscale in which interactions are usually weak and thermal fluctuations drive self-assembly. Moreover, structure in systems for which particle symmetry is broken is difficult to describe theoretically on any level higher than a pairwise one, due to the prohibitively high-dimensional nature of the relevant configuration space. However, a thorough understanding of local structure in all phases of soft matter systems is necessary to gain a complete picture of the physics of these systems and to leverage them for technological and materials science applications. In this dissertation, I investigate local structure in systems of anisotropic particles mediated exclusively by entropy maximization. Specifically, I explore the role of local structure in crystallization and its failure by tackling two related lines of inquiry. First, I study the interplay between particle shape and spherical confinement in systems of hard polyhedral particles, to examine locally dense clusters of anisotropic particles and their possible connection to preferred local structures during unconfined self-assembly. I use Monte Carlo simulation methods to find putative densest clusters of the Platonic solids in spherical confinement, for up to N = 60 constituent particles. I find that a spherical boundary suppresses the packing influence of particle shape and produces a robust class of common cluster structures. I also find a range of especially dense clusters at so-called "magic numbers" of constituent particles, and discover that a magic-number cluster of tetrahedra is a prominent motif in the self-assembled structure of tetrahedra, the dodecagonal quasicrystal. Second, I explore the influence of local structure in systems of hard polyhedral particles that fail to crystallize. I use a shape landscape, or a two-dimensional space of particles that are continuously interrelated by a set of shape perturbations, to investigate why slight changes to particle shape sometimes result in the vitrification rather than crystallization of dense monatomic systems of these particles. I show that assembly failure in these systems arises from a multiplicity of competing local structures, each of which is prevalent in ordered phases crystallized by particles that are only slightly different in shape. Thus, systems that fail to assemble do so because they cannot crystallize into any one ordered phase. Third, I demonstrate that fragility in these systems, a technologically relevant measure of glass-forming ability, can be tuned by slight changes to particle shape. I relate this finding to simulations of molecular systems in which fragility is linked to intermolecular bond angle. Finally, I detail the methods and applications of software I developed to detect multi-particle local structure in real space. This software is open-source and in current use, and has already been utilized for local structure detection in several papers by myself and others. I conclude this dissertation by providing an outlook on the implications and future directions of my work.PHDApplied PhysicsUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttps://deepblue.lib.umich.edu/bitstream/2027.42/147721/1/erteich_1.pd

Síntesis y ensamblaje de nanoestructuras plasmónicas de oro uniformes para aplicaciones en biomedicina

Tesis de la Universidad Complutense de Madrid, Facultad de Ciencias Químicas, Departamento de Química Física I, leída el 30-06-2017Se espera de la nanociencia y la nanotecnología que hagan frente a muchos de los retos que amenazan nuestro futuro, desde el almacenamiento de energía hasta la cura de enfermedades. En este contexto, las nanopartículas de oro se encuentran entre los sistemas que están a la cabeza de esta lucha, ofreciendo una combinación única de propiedades ópticas modulables (resonancias plasmónicas superficiales localizadas, LSPRs) y alta estabilidad química con reactividad controlable. Entre la gran variedad de campos de aplicación cubiertos por las nanopartículas de oro, su uso en la detección, el diagnóstico y el tratamiento de enfermedades humanas pueden ser de las que produzcan un mayor impacto en la sociedad. En esta tesis titulada "Síntesis y Ensamblaje de Nanoestructuras Plasmónicas de Oro Uniformes para Aplicaciones en Biomedicina", hemos trabajado en el desarrollo de enfoques novedosos para la síntesis de nanoestructuras plasmónicas que puedan utilizarse para el diagnóstico y tratamiento de diversas enfermedades humanas. Específicamente, los aspectos fundamentales en ella tratados son la síntesis de nanopartículas de oro con propiedades ópticas específicas y su subsiguiente funcionalización y/o auto-ensamblaje, con el objetivo de explotarlas para estudiar y detectar el proceso de amiloidogénesis, así como su aplicación en terapia fototérmica. Una de las principales innovaciones de este trabajo es la implementación de los láseres pulsados como herramientas valiosas para controlar algunos de los aspectos anteriormente mencionados. Como primera estrategia se han sintetizado nanoesferas de oro con elevada monodispersidad y se han auto-ensamblado sobre sustratos usando plantillas piramidales, mediante funcionalización con polietilenglicol tiolado y en presencia de pequeñas concentraciones de un surfactante catiónico. Siguiendo con el concepto de síntesis y funcionalización racionales, se fabricaron nanovarillas de oro y se estabilizaron con el modelo prionoide RepA-WH1. Este enfoque nos permitió inducir la formación de oligómeros amiloides, especies tóxicas que juegan un papel clave en la etiología de una serie de devastadoras enfermedades humanas degenerativas. Además, aprovechamos la sensibilidad de las LSPR y las propiedades de las nanopartículas plasmónicas para incrementar la señal Raman de moléculas (SERS) para monitorizarlo. En una segunda aproximación, aprovechamos la fuerte interacción de las nanopartículas plasmónicas con pulsos láser de femtosegundos para el auto-ensamblaje de nanopartículas de oro anisótropas, así como para su uso en terapia fototérmica...Depto. de Química FísicaFac. de Ciencias QuímicasTRUEunpu

다성분 나노 구조체의 정밀한 조성 및 구조에 관한 연구

학위논문 (박사)-- 서울대학교 대학원 : 자연과학대학 화학부, 2019. 2. Nam, Jwa Min.현재의 나노 기술과 정교한 첨단 나노 장치 사이의 격차를 줄이기 위한 하나의 큰 도전은 나노 수준에서 물질의 조성, 차원 및 기능성을 정밀하게 조절하는 것입니다. 정밀한 조성과 구조적 제어성을 갖는 다성분 나노 구조를 설계하고 합성함으로써 다양한 구성 요소 간의 전기적, 광학적, 그리고 화학적 상호 작용을 이해할 수 있으며, 여러 구성 요소의 커플링에 의한 강한 시너지 효과와 메커니즘을 밝힐 수 있습니다. 다양한 재료 중 특히 금속 및 반도체 나노 구성 요소는 전자, 광학 및 촉매 특성이 두드러집니다. 금속 나노 구성 요소들 중 특히 귀금속은 높은 전자 이동도, 활성 플라즈몬 및 이종 촉매의 특성을 갖고, 반도체 나노 복합체는 온도 의존적전도도, 광 유도 전하 분리 및 도핑 성과 같은 독특한 광전자 특성을 갖습니다. 다중 금속 구조와 금속-반도체 헤테로 구조의 정밀한 제어는 여러 분야에서 특별한 연구 관심 대상입니다. 그러나 헤테로 계면에서의 표면 에너지 및 계면 에너지 차이로 인해 헤테로 접합 부분의 정밀한 제어와 다양한 구성 요소 사이의 구조를 규정하는 것은 여전히 어려운 문제로 남아있습니다. 이러한 문제를 극복하기 위해서는 나노 구조체가 성장하는 동안 표면 에너지와 계면 에너지의 변화에 각별한 주의를 기울일 필요가 있습니다. 표면 에너지 및 계면 에너지에 대한 이해는 복잡한 나노 구조의 합성에서 유용하게 활용 될 수 있을 것입니다. 이 논문에서는 헤테로 계면 형성을 방해하는 계면 에너지를 정밀한 조성 및 구조를 갖는 헤테로 구조의 합성에 효과적인 추진력으로 바꾸기 위한 몇 가지 합성 전략을 소개하였습니다. 전략은 1차 나노 구조상의 표면 에너지 분포를 균일하게 유지하고, 2차 나노 구조의 조성과 리간드와 성장 동력학 등에 의한 계면 에너지를 미세하게 조절하는 것입니다. 계면 에너지의 변화에 따른 헤테로 계면의 변화는 나노 구조체의 형태를 결정하게 됩니다. 이러한 전략으로 나노 구조체의 모양, 크기, 조성과 함께 가장 중요한 요소인 여러 구성 요소들의 구조적인 형태를 조절할 수 있습니다. 1장에서는 다성분 나노 구조의 합성 원리 및 전략에 대한 근래의 연구 동향을 살펴 보았습니다. 단일 성분으로 합성할 때와 다성분으로 합성할 때의 차이점과 다성분 나노 구조의 구조에 따른 성질의 관계를 정리하였습니다. 에피 택셜 성장, 리간드 기반 선택성 및 열역학적 제어와 동력학적 제어의 경쟁 등과 같은 일반적인 경험과 전략들은 단일 성분 합성에 관한 도구 상자에서 부분적으로 끌어올 수 있지만, 본래 정밀하게 제어되는 단일 나노 구조의 대부분이 단결정 방식으로 개발되기 때문에, 다성분 나노 구조체를 이루는 여러 구성 요소 간의 고유한 차이는 단결정 방식의 효율성을 크게 제한하게 됩니다. 반면에 다성분 나노구조체에 존재하는 헤테로 계면 및 격자 부정합은 단일 성분으로 달성할 수 없는 새로운 합성 방법을 발견하는 기회를 제공하였습니다. 이 새로운 합성 전략과 방법으로 우리는 다성분 나노 구조체의 새로운 시너지 효과와 새로운 물리 화학적 성질을 얻게 되었습니다. 2장에서는 격자 불일치도가 11.4%나 되는 금과 구리 간의 헤테로 에피 택셜 성장을 이루기 위해 개발한 결정 구조 공학을 소개하였습니다. 단결정과 5겹 트윈 두 가지 유형의 결정 구조가 구리 2차 구조에서 합성되었으며, 이는 각각의 결정 구조로 합성된 금 시드로부터 유도되었다. 헤테로 에피 택셜 성장의 결과로, 단결정의 경우 입방형 구리가 형성되었고, 5겹 트윈의 경우는 테이퍼 형의 구리가 얻어졌다. 이는 결정 구조 공학이 격자 불일치가 크더라도 2차 나노 구조에 추가적인 구조 제어성을 제공 할 수 있음을 보여주었습니다. 이러한 대칭성의 파괴는 금과 구리 사이에 강한 전자기 에너지의 전달을 가능케 하므로 금-구리 팁-테이퍼 나노 입자의 팁 부분에서 전기장이 크게 증폭됩니다. 국지화 되고 증폭된 전자기장으로 화학 반응이 금 팁에서 활성화 될 수 있으며 향상된 표면 강화 된 라만 스펙트럼 (SERS) 신호를 얻을 수 있었습니다. 3장에서는 구리-금-은 다성분 이방성 나노 입자 (MAPs)에서 정밀하게 제어된 헤테로 접합을 얻기 위해, 결정 구조가 보정된 금-구리 나노 구조체에 균일하게 분포된 표면 에너지와 동력학적으로 제어된 갈바니 치환이 함께 이용되었습니다. 두 가지의 잘 정의된 MAPs (변형 가능한 금@구리-은 MAP 및 구리-금-은 MAP)를 고수율로 합성할 수 있었으며, 이들의 구조 및 플라즈몬 특성을 고도로 제어 할 수 있음을 보여 주었습니다. 이 접근법은 단일 MAP 내에서 서브-나노 구성 요소의 독특한 표면 플라즈몬 공명 특성의 효율적인 통합과 결합을 가능하게 하며, 플라즈몬 증강을 이용하는 다양한 응용분야에서 플라즈몬 증강을 더할 수 있는 큰 가능성을 보여주었습니다. 또한, 세 가지 물질로 이루어진 nm 규모의 헤테로 접합 공학과 '닫힌 목 접합부'에서 '열린 목 접합부'로의 조절 가능성 및 MAP의 원거리장 및 근거리장 특성의 조절 가능성이 플라즈몬 제어와 증강의 기회를 제공하여 다양한 금속 및 반도체 기반의 에너지 응용 분야 및 확산 기반의 촉매 응용 분야에 사용될 수 있을 것으로 전망됩니다. 4 장에서는 금속-반도체 Ag-Ag2S NP를 모델로 사용하여 Heterointerfacial strain equilibrium (HSE) 전략을 연구했다. Ag-Ag2S 나노입자를 HSE-directed time-resolved HRTEM와 XRD 측정하여 Ag와 Ag2S의 상전이를 보였다. 또한, Ag-Ag2S 나노입자는 산화가 잘되지 않고, 열역학적으로 안정한 것으로 밝혀졌다. 이 특징은 Ag를 다양한 금속 (M)-Ag2S (M=Au, Pd, Pt) 나노 구조로 site-specific galvanic exchange하는 데 추가로 사용데 도움이 되었다. 5 장에서는 HSE 전략에 추가로 Pt/Ag2S 헤테로 계면을 도입함으로써 cubic Ag-Pt/Ag2S metal-semiconductor nanoframe (MSF)의 one-pot 합성을 개발하였다. 이 방법을 통해 매우 오목한 Pt/Ag/Ag2S 금속 - 반도체 나노 큐브 metal-semiconductor concave nanocube (MSC) 를 만들 수 있었으며, 이는 self-etching 효과에 의해 hollow MSF로 변환되었다. MSF구조는 Pt/S 전구체 비율을 변경함으로써 정사면체 프레임에서 다양한 edge-to-body diameter ratios를 갖는 입방면체 구조로 간단하게 조정할 수있어 구조조절이 용이하다.One grand challenge in current nanotechnology is the increasingly stringent criteria on compositionality, dimensionality and functionality of materials at the nanometer scale. Elaborate design and controllable syntheses of multicomponent nanostructures with precise composition and delicate structure are especially desired for in-depth exploration of the electrical, optical and chemical interactions between these different components. Among various nanomaterials, metal and semiconductor nanocomponents are prominent candidates for these researches due to the strong electromagnetic (EM) and photoelectronic interactions between these nanoparticles (NPs). Metal nanocomponents, especially plasmonic metals (such as Au and Ag), are featured with high electron mobility, strong EM field localization capability and high photocatalytic activity, while semiconductor nanocomposites possess unique photoelectronic properties such as temperature-dependent conductivity, photo-induced charge separation and dopability. The combination of them into metal-semiconductor heterostructures is thus of great interest in many different research fields, including nanoantena, photocatalysis, optoelectronic devices and various plasmonic-enhanced applications. Due to the structure-dependent plasmonic property and the short lifetime of photogenerated hot carriers, the performance of nanodevices and nanosystems that supported by these heterostructures is highly sensitive to their structural nuances at the nanoscale. However, the precise compositional and structural engineering of these heterostructures remain challenging due to the lack of understanding on their surface/ interfacial energy and the lattice strain induced by the heterointerface. In this thesis, we focused on the exploration of synthetic tools aiming to promote the precise controllability and structure tunability in heterointerface and multicomponent nanostructures. Special attentions were paid to the heterointerface and the accompanying lattice strain, which were further adopted as a thermodynamic driven force to guide structural evolution. The strategies we developed here were to minimize the interfacial energy/lattice strain under slow growth kinetic, either by crystal structure engineering of seeds in seed-mediated methods, or co-nucleation and simultaneous growth of multiple components to promote in-situ strain equilibrium. In Chapter 1, recent advances in the synthetic strategy and property exploration of multicomponent structures, especially multimetallic and metal-semiconductor nanostructures, have been summarized. The difference between single component synthesis and multicomponent synthesis, and the structure-property relationship in multicomponent nanostructures were discussed. Some general experience and strategies such as epitaxial growth, ligand-based selectivity and thermodynamic verse kinetic control can partially explain some phenomena in multicomponent synthesis. However, the intrinsic difference induced by heterointerface largely limits the efficiency of the synthetic tools developed in single-component systems. On the other hand, there were also new opportunities in the multicomponent synthesis due to the existence of heterointerface and lattice strain, which can be used to develop new synthetic methods that cannot be achieved in single component cases. In Chapter 2, crystal structure engineering has been developed to perform heteroepitaxial growth between largely-lattice-mismatched gold and copper (with a degree of 11.4 %). Two types of crystal structures, including single crystalline and five-fold twin have been demonstrated in the copper secondary structure, induced by the crystal structure-engineered gold seeds, respectively. As a result of heteroepitaxial growth, a cubic shaped copper sub-NP was found in the single crystalline case, while a taper shaped copper sub-NP was obtained in the five-fold twin case. Such symmetry breaking results in a dramatically different electromagnetic communication between gold and copper, where strong enhancement was found in the gold-copper tip-taper nanoparticle. In Chapter 3, the crystal structure corrected gold-copper nanostructures together with kinetic-controlled galvanic replacement have been utilized to obtain precise heterojunction controllability in copper-gold-silver multicomponent anisotropic nanoparticles (MAPs). We showed that two series of well-defined MAPs (transformative gold@copper-silver MAP and copper-gold-silver MAP) can be synthesized in a high yield, and their structures and plasmonic properties are highly controllable. The nm-scale heterojunction engineering capability with three different components, the tunability over the confined-neck junction to open-neck junction and the fine balancing of far-field and near-field properties in MAPs offer great opportunity for plasmonic control and enhancement in various metal and semiconductor-based energy applications as well as diffusion-based catalytic applications. In Chapter 4, heterointerfacial strain equilibrium (HSE) strategy was explored using metal-semiconductor Ag-Ag2S NP as a model. The HSE-directed growth of Ag-Ag2S NPs was studied by time-dependent HRTEM and XRD measurements, evidencing the phase transition of Ag and Ag2S. Moreover, the Ag-Ag2S NPs were found to possess remarkable thermodynamic stability against chemical oxidation and long term storage. This feature was further used for the site-specific galvanic exchange of Ag into various metal (M)-Ag2S (M=Au, Pd, Pt) nanostructures. In Chapter 5, the one-pot synthesis of cubic Ag-Pt/Ag2S metal-semiconductor nanoframe (MSF) was developed by introducing the Pt/Ag2S heterointerface as an additional strain source in the HSE strategy. It led to the formation of highly concave Pt/Ag/Ag2S metal-semiconductor nanocube (MSC), which further transformed into a hollow MSF by self-etching effect. The MSF structures can be easily tuned from tetrahedron frames to cubic frames with different edge-to-body diameter ratios, simply by altering the Pt/S precursor ratio, indicating high structure tunability.Contents Abstracts i Contents v List of Figures vii List of Tables xvii Chapter 1: Introduction 1.1 Introduction 1 1.2 Principles and strategies in nanosynthesis 1 1.3 Challenges and opportunities in multicomponent synthesis 6 1.4 Recent advances in multicomponent synthesis 8 1.5 Plasmonic enhancement of multicomponent nanostructures 13 1.6 Hot electron-driven water splitting reactions 19 Chapter 2: Crystal Structure Engineering in Symmetry Breaking of Bimetallic Nanoparticles 2.1 Introduction 32 2.2 Experimental section 33 2.3 Results and Discussion 36 2.4 Conclusion 42 Chapter 3: Precise Compositional Engineering and Optical Tuning in Multi-metallic Nanoantenna 3.1 Introduction 52 3.2 Experimental section 54 3.3 Results and Discussion 56 3.4 Conclusion 64 Chapter 4: Synthesis of Monodisperse Ag-Ag2S NPs as Platform for Metal-Semiconductor Nanostructures 4.1 Introduction 77 4.2 Experimental section 79 4.3 Results and Discussions 81 4.4 Conclusion 87 Chapter 5: Synthesis and Structure Engineering of Cubic Metal-Semiconductor Nanoframes 5.1 Introduction 100 5.2 Experimental section 103 5.3 Results and Discussions 104 5.4 Conclusion 108 Bibliography 117Docto

The deep structure of Gaussian scale space images

In order to be able to deal with the discrete nature of images in a continuous way, one can use results of the mathematical field of 'distribution theory'. Under almost trivial assumptions, like 'we know nothing', one ends up with convolving the image with a Gaussian filter. In this manner scale is introduced by means of the filter's width. The ensemble of the image and its convolved versions at al scales is called a 'Gaussian scale space image'. The filter's main property is that the scale derivative equals the Laplacean of the spatial variables: it is the Greens function of the so-called Heat, or Diffusion, Equation. The investigation of the image all scales simultaneously is called 'deep structure'. In this thesis I focus on the behaviour of the elementary topological items 'spatial critical points' and 'iso-intensity manifolds'. The spatial critical points are traced over scale. Generically they are annihilated and sometimes created pair wise, involving extrema and saddles. The locations of these so-called 'catastrophe events' are calculated with sub-pixel precision. Regarded in the scale space image, these spatial critical points form one-dimensional manifolds, the so-called critical curves. A second type of critical points is formed by the scale space saddles. They are the only possible critical points in the scale space image. At these points the iso-intensity manifolds exhibit special behaviour: they consist of two touching parts, of which one intersects an extremum that is part of the critical curve containing the scale space saddle. This part of the manifold uniquely assigns an area in scale space to this extremum. The remaining part uniquely assigns it to 'other structure'. Since this can be repeated, automatically an algorithm is obtained that reveals the 'hidden' structure present in the scale space image. This topological structure can be hierarchically presented as a binary tree, enabling one to (de-)select parts of it, sweeping out parts, simplify, etc. This structure can easily be projected to the initial image resulting in an uncommitted 'pre-segmentation': a segmentation of the image based on the topological properties without any user-defined parameters or whatsoever. Investigation of non-generic catastrophes shows that symmetries can easily be dealt with. Furthermore, the appearance of creations is shown to be nothing but (instable) protuberances at critical curves. There is also biological inspiration for using a Gaussian scale space, since the visual system seems to use Gaussian-like filters: we are able of seeing and interpreting multi-scale

Closed-loop nanopatterning and characterization of polymers with scanning probes

There is a need to discover advanced materials to address the pressing challenges facing humanity, however there are far too many combinations of material composition and processing conditions to explore using conventional experimentation. One powerful approach for accelerating the rate at which materials are explored is by miniaturizing the scale at which experiments take place. Reducing the size of samples has been tremendously productive in biomedicine and drug discovery through standardized formats such as microwell plates, and while these formats may not be the most appropriate for studying polymeric materials, they do highlight the advantages of studying materials in ultra-miniaturized volumes. However, precise and controlled methods for handling diverse samples at the sub-femtoliter-scale have not been demonstrated. In this thesis, we establish that scanning probes can be used as a technique for realizing and interrogating sub-femtoliter scale polymer samples. To do this, we develop and apply methods for patterning materials with control over their size and composition and then use these methods to study material systems of interest. First, we develop a closed-loop method for patterning liquid samples using scanning probes by utilizing tipless cantilevers capable of holding a discrete liquid drop together with an inertial mass sensing scheme to measure the amount of liquid loaded on the probe. Using these innovations, we perform patterning with better than 1% mass accuracy on the pL-scale. While dispensing fluid with tipless cantilevers is successful for patterning pL-scale features and can be considered a candidate for robust nanoscale manipulation of liquids for high-throughput sample preparation, the minimum amount of liquid that can be transferred using this method is limited by number of factors. Thus, in the second section of this thesis, we explore ultrafast cantilevers that feature spherical tips and find them capable of patterning aL-scale features with in situ feedback. The development of methods of interrogating polymers at the pL-scale led us to explore how the mechanical properties of photocurable polymers depend on processing conditions. Specifically, we investigate the degree to which oxygen inhibits photocrosslinking during vat polymerization and how this effect influences the mechanical properties of the final material. We explore this through a series of macroscopic compression studies and AFM-based indentation studies of the cured polymers. Ultimately, the mechanical properties of these systems are compared to pL-scale features patterned using scanning probe lithography and we find that not only does oxygen prevent full crosslinking when it is present during the post-print curing, but the presence of oxygen during printing itself irreversibly softens the material. In addition to developing new methods for realizing ultra-miniaturized samples for study, the novel scanning probe methods in this work have led to new paradigms for rapidly evaluating complex interactions between material systems. In particular, we present a novel method to quantitatively investigate the interaction between the metal-organic frameworks (MOFs) and polymers by attaching a single MOF particle to a cantilever and studying the interaction force between this MOF and model polymer surfaces. Using this approach, we find direct evidence supporting the intercalation of polymer chains into the pores of MOFs. This work lays the foundation for directly characterizing the facet-specific interactions between MOFs and polymers in a high-throughput manner sufficient to fuel a data-driven accelerated material discovery pipeline. Collectively, the focus of this thesis is the development and utilization of novel scanning probe methods to collect data on extremely small systems and advance our understanding of important classes of materials. We expect this thesis to provide the foundation needed to transform scanning probe systems into instruments for performing reliable nanochemistry by combining controlled and quantitative sample preparation at the nanoscale and high-throughput characterization of materials. To conclude, we present an outlook about the necessary technological advancements and promising directions for materials innovations that stem from this work

Vision 21: Interdisciplinary Science and Engineering in the Era of Cyberspace

The symposium Vision-21: Interdisciplinary Science and Engineering in the Era of Cyberspace was held at the NASA Lewis Research Center on March 30-31, 1993. The purpose of the symposium was to simulate interdisciplinary thinking in the sciences and technologies which will be required for exploration and development of space over the next thousand years. The keynote speakers were Hans Moravec, Vernor Vinge, Carol Stoker, and Myron Krueger. The proceedings consist of transcripts of the invited talks and the panel discussion by the invited speakers, summaries of workshop sessions, and contributed papers by the attendees