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Interplay of Molecular and Nanoscale Behaviors in Biological Soft Matter
Title
Interplay of Molecular and Nanoscale Behaviors in Biological Soft Matter.
Creator
Ciaffone, Nicholas, Tetard, Laurene, Kang, Hyeran, Santra, Swadeshmukul, University of Central Florida
Abstract / Description
The complexity of biological soft matter at the sub-micrometer level is fundamentally correlated to the functionalities at the larger scale. Reflecting the level of heterogeneities in the properties of systems remains challenging when probing small scales, due to the mismatch between the area surveyed with the tools offering nanoscale resolution, such as atomic force microscopy (AFM), and the scale of natural variations inherent to biology. Hence, to understand the physiological and...
Show moreThe complexity of biological soft matter at the sub-micrometer level is fundamentally correlated to the functionalities at the larger scale. Reflecting the level of heterogeneities in the properties of systems remains challenging when probing small scales, due to the mismatch between the area surveyed with the tools offering nanoscale resolution, such as atomic force microscopy (AFM), and the scale of natural variations inherent to biology. Hence, to understand the physiological and mechanical alterations that occur within a single cell relative to a cell population, a multiscale approach is necessary. In this work we show that it is possible to observe molecular, chemical and physical alterations in both plant and human cells with a multiscale approach. Biophysical and biochemical traits of cell populations are studied with Fourier Transform infrared spectroscopy (FTIR) and in turn, guide higher resolution discovery with Raman spectroscopy and nanoscale infrared spectroscopy using AFM (NanoIR) to access finer details. We illustrate this with three examples of biological soft matter systems: 1) a preliminary study of cellular interactions with naturally occurring vehicles applicable to human health, 2) a qualitative examination of antibiotics and new pesticide treatments in food crop systems, and 3) a fundamental investigation of the deconstruction mechanisms of plant cells during pre-treatments in preparation for biofuel production.
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Date Issued
2018
Identifier
CFE0007395, ucf:52058
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0007395
Optically Induced Forces in Scanning Probe Microscopy
Title
Optically Induced Forces in Scanning Probe Microscopy.
Creator
Kohlgraf-Owens, Dana, Dogariu, Aristide, Christodoulides, Demetrios, Kik, Pieter, DeWilde, Yannick, University of Central Florida
Abstract / Description
The focus of this dissertation is the study of measuring light not by energy transfer as is done with a standard photodetector such as a photographic film or charged coupled device, but rather by the forces which the light exerts on matter. In this manner we are able to replace or complement standard photodetector-based light detection techniques. One key attribute of force detection is that it permits the measurement of light over a very large range of frequencies including those which are...
Show moreThe focus of this dissertation is the study of measuring light not by energy transfer as is done with a standard photodetector such as a photographic film or charged coupled device, but rather by the forces which the light exerts on matter. In this manner we are able to replace or complement standard photodetector-based light detection techniques. One key attribute of force detection is that it permits the measurement of light over a very large range of frequencies including those which are difficult to access with standard photodetectors, such as the far IR and THz. The dissertation addresses the specific phenomena associated with optically induced force (OIF) detection in the near-field where light can be detected with high spatial resolution close to material interfaces. This is accomplished using a scanning probe microscope (SPM), which has the advantage of already having a sensitive force detector integrated into the system. The two microscopies we focus on here are atomic force microscopy (AFM) and near-field scanning optical microscopy (NSOM). By detecting surface-induced forces or force gradients applied to a very small size probe ( diameter), AFM measures the force acting on the probe as a function of the tip-sample separation or extracts topography information. Typical NSOM utilizes either a small aperture ( diameter) to collect and/or radiate light in a small volume or a small scatterer ( diameter) in order to scatter light in a very small volume. This light is then measured with an avalanche photodiode or a photomultiplier tube.These two modalities may be combined in order to simultaneously map the local intensity distribution and topography of a sample of interest. A critical assumption made when performing such a measurement is that the distance regulation, which is based on surface induced forces, and the intensity distribution are independent. In other words, it is assumed that the presence of optical fields does not influence the AFM operation. However, it is well known that light exerts forces on the matter with which it interacts. This light-induced force may affect the atomic force microscope tip-sample distance regulation mechanism or, by modifying the tip, it may also indirectly influence the distance between the probe and the surface. This dissertation will present evidence that the effect of optically induced forces is strong enough to be observed when performing typical NSOM measurements. This effect is first studied on common experimental situations to show where and how these forces manifest themselves. Afterward, several new measurement approaches are demonstrated, which take advantage of this additional information to either complement or replace standard NSOM detection. For example, the force acting on the probe can be detected while simultaneously extracting the tip-sample separation, a measurement characteristic which is typically difficult to obtain. Moreover, the standard field collection with an aperture NSOM and the measurement of optically induced forces can be operated simultaneously. Thus, complementary information about the field intensity and its gradient can be, for the first time, collected with a single probe. Finally, a new scanning probe modality, multi-frequency NSOM (MF-NSOM), will be demonstrated. In this approach, the tuning fork is driven electrically at one frequency to perform a standard tip-sample distance regulation to follow the sample topography and optically driven at another frequency to measure the optically induced force. This novel technique provides a viable alternative to standard NSOM scanning and should be of particular interest in the long wavelength regime, e.g. far IR and THz.
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Date Issued
2013
Identifier
CFE0004705, ucf:49829
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0004705
Nanoscale Spectroscopy in Energy and Catalytic Applications
Title
Nanoscale Spectroscopy in Energy and Catalytic Applications.
Creator
Ding, Yi, Tetard, Laurene, Challapalli, Suryanarayana, Zhai, Lei, Thomas, Jayan, Lyakh, Arkadiy, Blair, Richard, University of Central Florida
Abstract / Description
Emerging societal challenges such as the need for more sustainable energy and catalysis are requiring more sensitive and versatile measurements at the nanoscale. This is the case in the design and optimization of new materials for energy harvesting (solar cells) and energy storage devices (batteries and capacitors), or for the development of new catalysts for carbon sequestration or other reactions of interest. Hence, the ability to advance spectroscopy with nanoscale spatial resolution and...
Show moreEmerging societal challenges such as the need for more sustainable energy and catalysis are requiring more sensitive and versatile measurements at the nanoscale. This is the case in the design and optimization of new materials for energy harvesting (solar cells) and energy storage devices (batteries and capacitors), or for the development of new catalysts for carbon sequestration or other reactions of interest. Hence, the ability to advance spectroscopy with nanoscale spatial resolution and high sensitivity holds great promises to meet the demands of deeper fundamental understanding to boost the development and deployment of nano-based devices for real applications. In this dissertation, the impact of nanoscale characterization on energy-related and catalytic materials is considered. Firstly an introduction of the current energy and environmental challenges and our motivations are presented. We discuss how revealing nanoscale properties of solar cell active layers and supercapacitor electrodes can greatly benefit the performance of devices, and ponder on the advantages over conventional characterization techniques. Next, we focus on two dimensional materials as promising alternative catalysts to replace conventional noble metals for carbon sequestration and its conversion to added-value products. Defect-laden hexagonal boron nitride (h-BN) has been identified as a good catalyst candidate for carbon sequestration. Theoretically, defects exhibit favorable properties as reaction sites. However, the detailed mechanism pathways cannot be readily probed experimentally, due to the lack of tools with sufficient sensitivity and time resolution. A comprehensive study of the design and material processes used to introduce defects in h-BN in view of improving the catalytic properties is presented. The processing-structure-property relationships are investigated using a combination of conventional characterization and advanced nanoscale techniques. In addition to identifying favorable conditions for defect creation, we also report on the first signs of local reactions at defect sites obtained with nanoscale spectroscopy. Next, we explore avenues to improve the sensitivity and time-resolution of nanoscale measurements using light-assisted AFM-based nanomechanical spectroscopy. For each configuration, we evaluate the new system by comparing its performance to the commercial capabilities.Lastly, we provide a perspective on the opportunities for state-of-the-art characterization to impact the fields of catalysis and sustainable energy, as well as the urge for highly sensitive functional capabilities and time-resolution for nanoscale studies.
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Date Issued
2018
Identifier
CFE0007751, ucf:52387
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0007751
Asteroid Surfaces: The Importance of Cohesive Forces
Title
Asteroid Surfaces: The Importance of Cohesive Forces.
Creator
Jardine, Keanna, Dove, Adrienne, Tetard, Laurene, Britt, Daniel, University of Central Florida
Abstract / Description
Adhesive forces play a significant role on airless bodies due to their weak gravities. Investigating adhesion at the surface of asteroids and their constituent components is vital to understanding their formation and evolution. Previous research has been done to understand the interaction of micron-sized spheres to planar surfaces and sphere-to-sphere interactions, which have been used to develop models of asteroid surfaces. Our investigation experimentally investigates adhesion through...
Show moreAdhesive forces play a significant role on airless bodies due to their weak gravities. Investigating adhesion at the surface of asteroids and their constituent components is vital to understanding their formation and evolution. Previous research has been done to understand the interaction of micron-sized spheres to planar surfaces and sphere-to-sphere interactions, which have been used to develop models of asteroid surfaces. Our investigation experimentally investigates adhesion through atomic force microscopy (AFM) measurements between JSC-1 simulant particles and several AFM tips, including a typical pyramidal gold tip and microspheres of sizes 2 (&)#181;m and 15 (&)#181;m. The samples of JSC-1 consist of three size ranges: (<) 45 (&)#181;m, 75-125 (&)#181;m, and 125-250 (&)#181;m. For each sample we looked at the magnitude and distribution of the measured adhesive forces. Results show that the pyramidal tip produced larger forces than the spherical tips generally, and the sample that produced larger forces and a larger distribution of those force was the smaller, more powder-like sample with sizes (<)45 (&)#181;m.
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Date Issued
2018
Identifier
CFE0007755, ucf:52377
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0007755
PROBING THE NANOSCALE INTERACTION FORCES AND ELASTIC PROPERTIES OF ORGANIC AND INORGANIC MATERIALS USING FORCE-DISTANCE (F-D) SPECTROSCOPY
Title
PROBING THE NANOSCALE INTERACTION FORCES AND ELASTIC PROPERTIES OF ORGANIC AND INORGANIC MATERIALS USING FORCE-DISTANCE (F-D) SPECTROSCOPY.
Creator
Vincent, Abhilash, Seal, Sudipta, University of Central Florida
Abstract / Description
Due to their therapeutic applications such as radical scavenging, MRI contrast imaging, Photoluminescence imaging, drug delivery, etc., nanoparticles (NPs) have a significant importance in bio-nanotechnology. The reason that prevents the utilizing NPs for drug delivery in medical field is mostly due to their biocompatibility issues (incompatibility can lead to toxicity and cell death). Changes in the surface conditions of NPs often lead to NP cytotoxicity. Investigating the role of NP surface...
Show moreDue to their therapeutic applications such as radical scavenging, MRI contrast imaging, Photoluminescence imaging, drug delivery, etc., nanoparticles (NPs) have a significant importance in bio-nanotechnology. The reason that prevents the utilizing NPs for drug delivery in medical field is mostly due to their biocompatibility issues (incompatibility can lead to toxicity and cell death). Changes in the surface conditions of NPs often lead to NP cytotoxicity. Investigating the role of NP surface properties (surface charges and surface chemistry) on their interactions with biomolecules (Cells, protein and DNA) could enhance the current understanding of NP cytotoxicity. Hence, it is highly beneficial to the nanotechnology community to bring more attention towards the enhancement of surface properties of NPs to make them more biocompatible and less toxic to biological systems. Surface functionalization of NPs using specific ligand biomolecules have shown to enhance the protein adsorption and cellular uptake through more favorable interaction pathways. Cerium oxide NPs (CNPs also known as nanoceria) are potential antioxidants in cell culture models and understanding the nature of interaction between cerium oxide NPs and biological proteins and cells are important due to their therapeutic application (especially in site specific drug delivery systems). The surface charges and surface chemistry of CNPs play a major role in protein adsorption and cellular uptake. Hence, by tuning the surface charges and by selecting proper functional molecules on the surface, CNPs exhibiting strong adhesion to biological materials can be prepared. By probing the nanoscale interaction forces acting between CNPs and protein molecules using Atomic Force Microscopy (AFM) based force-distance (F-D) spectroscopy, the mechanism of CNP-protein adsorption and CNP cellular uptake can be understood more quantitatively. The work presented in this dissertation is based on the application of AFM in studying the interaction forces as well as the mechanical properties of nanobiomaterials. The research protocol employed in the earlier part of the dissertation is specifically aimed to understand the operation of F-D spectroscopy technique. The elastic properties of thin films of silicon dioxide NPs were investigated using F-D spectroscopy in the high force regime of few 100 nN to 1 µN. Here, sol-gel derived porous nanosilica thin films of varying surface morphology, particle size and porosity were prepared through acid and base catalyzed process. AFM nanoindentation experiments were conducted on these films using the F-D spectroscopy mode and the nanoscale elastic properties of these films were evaluated. The major contribution of this dissertation is a study exploring the interaction forces acting between CNPs and transferrin proteins in picoNewton scale regime using the force-distance spectroscopy technique. This study projects the importance of obtaining appropriate surface charges and surface chemistry so that the NP can exhibit enhanced protein adsorption and NP cellular uptake.
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Date Issued
2010
Identifier
CFE0003079, ucf:48305
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0003079
Advanced Nanoscale Characterization of Plants and Plant-derived Materials for Sustainable Agriculture and Renewable Energy
Title
Advanced Nanoscale Characterization of Plants and Plant-derived Materials for Sustainable Agriculture and Renewable Energy.
Creator
Soliman, Mikhael, Tetard, Laurene, Vaidyanathan, Raj, Kang, Hyeran, Santra, Swadeshmukul, Zhai, Lei, Chumbimuni Torres, Karin, University of Central Florida
Abstract / Description
The need for nanoscale, non-invasive functional characterization has become more significant with advances in nano-biotechnology and related fields. Exploring the ultrastructure of plant cell walls and plant-derived materials is necessary to access a more profound understanding of the molecular interactions in the systems, in view of a rational design for sustainable applications. This, in turn, relates to the pressing requirements for food, energy and water sustainability experienced...
Show moreThe need for nanoscale, non-invasive functional characterization has become more significant with advances in nano-biotechnology and related fields. Exploring the ultrastructure of plant cell walls and plant-derived materials is necessary to access a more profound understanding of the molecular interactions in the systems, in view of a rational design for sustainable applications. This, in turn, relates to the pressing requirements for food, energy and water sustainability experienced worldwide.Here we will present our advanced characterization approach to study the effects of external stresses on plants, and resulting opportunities for biomass valorization with an impact on the food-energy-water nexus.First, the adaption of plants to the pressure imposed by gravity in poplar reaction wood will be discussed. We will show that a multiscale characterization approach is necessary to reach a better understanding of the chemical and physical properties of cell walls across a transverse section of poplar stem. Our Raman spectroscopy and statistical analysis reveals intricate variations in the cellulose and lignin properties. Further, we will present evidence that advanced atomic force microscopy can reveal nanoscale variations within the individual cell wall layers, not attainable with common analytical tools. Next, chemical stresses, in particular the effect of Zinc-based pesticides on citrus plants, will be considered. We will show how multiscale characterization can support the development of new disease management methods for systemic bacterial diseases, such as citrus greening, of great importance for sustainable agriculture. In particular, we will focus on the study of new formulations, their uptake and translocation in the plants following different application methods. Lastly, we will consider how plant reactions to mechanical and chemical stresses can be controlled to engineer biomass for valorization applications. We will present our characterization of two examples: the production of carbon films derived from woody lignocellulosic biomass and the development of nanoscale growth promoters for food crop. A perspective of the work and discussion of the broader impact will conclude the presentation.
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Date Issued
2018
Identifier
CFE0007415, ucf:52717
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0007415
SELF-ASSEMBLED LIPID TUBULES: STRUCTURES, MECHANICAL PROPERTIES, AND APPLICATIONS.
Title
SELF-ASSEMBLED LIPID TUBULES: STRUCTURES, MECHANICAL PROPERTIES, AND APPLICATIONS.
Creator
Zhao, Yue, Fang, Jiyu, University of Central Florida
Abstract / Description
Self-assembled lipid tubules are particularly attractive for inorganic synthesis and drug delivery because they have hollow cylindrical shapes and relatively rigid mechanical properties. In this thesis work, we have synthesized lipid tubules of 1,2-bis(tricosa-10,12-dinoyl)-sn-glycero-3-phosphocholine (DC8,9PC) by self-assembly and polymerization in solutions. We demonstrate for the first time that both uniform and modulated molecular tilt orderings exist in the tubule walls, which have been...
Show moreSelf-assembled lipid tubules are particularly attractive for inorganic synthesis and drug delivery because they have hollow cylindrical shapes and relatively rigid mechanical properties. In this thesis work, we have synthesized lipid tubules of 1,2-bis(tricosa-10,12-dinoyl)-sn-glycero-3-phosphocholine (DC8,9PC) by self-assembly and polymerization in solutions. We demonstrate for the first time that both uniform and modulated molecular tilt orderings exist in the tubule walls, which have been predicted by current theories, and therefore provide valuable supporting evidences for self-assembly mechanisms of chiral molecules. Two novel methods are developed for studying the axial and radial deformations of DC8,9PC lipid tubules. Mechanical properties of DC8,9PC tubules are systematically studied in terms of persistence length, bending rigidity, strain energy, axial and radial elastic moduli, and critical force for collapse. Mechanisms of recovery and surface stiffening are discussed. Due to the high aspect ratio of lipid tubules, the hierarchical assembly of lipid tubules into ordered arrays and desired architectures is critical in developing their applications. Two efficient methods for fabricating ordered arrays of lipid tubules on solid substrates have been developed. Ordered arrays of hybrid silica-lipid tubes are synthesized by tubule array-templated sol-gel reactions. Ordered arrays of optical anisotropic fibers with tunable shapes and refractive indexes are fabricated. This thesis work provides a paradigm for molecularly engineered structures.
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Date Issued
2007
Identifier
CFE0001918, ucf:47486
Format
Document (PDF)
PURL
http://purl.flvc.org/ucf/fd/CFE0001918