Materials & Nanotechnology Doctoral Work

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Dynamic 3D In Vitro Bone Metastatic Testbeds for Prostate and Breast Cancer
(North Dakota State University, 2022) Jasuja, Haneesh
Metastatic prostate cancer spreads preferentially to the bone, causing skeletal complications associated with significant morbidity and a poor prognosis, despite current therapeutic approaches. Increasing evidence suggests the synergistic role of biochemical and biophysical cues in cancer progression at metastases. However, the mechanism underlying the crosstalk between interstitial flow-induced mechanical stimuli and prostate cancer progression in the bone microenvironment remains poorly understood. To this end, we have developed 3D in vitro dynamic models of prostate cancer bone metastasis using perfusion bioreactor and horizontal flow bioreactor to delineate the role of flow-induced shear stress on prostate cancer progression and migration, respectively at metastases. Using a perfusion bioreactor, we observed changes in the expressions of MET biomarkers and the tumoroid morphologies of prostate cancer cells under dynamic culture. Evaluation of cell adhesion proteins indicated that the altered cancer cell morphologies resulted from the constant force pulling due to increased E-cadherin and FAK proteins under shear stress. Using a horizontal flow bioreactor, we demonstrated that the percent cell migration rate of prostate cancer cells was increased in the presence of bone under dynamic conditions. The results showed that interstitial fluid flow did not alter the CXCR4 level, but bone upregulated CXCR4 levels, leading to increased MMP-9 levels. In addition, both αvβ3 integrins and MMP-9 levels were upregulated by fluid flow conditions, contributing to an increased migration rate under dynamic conditions. Breast cancer cells also tend to preferentially disseminate to bone and colonize within the remodeling bone site to cause bone metastases. We have previously developed a 3D in vitro breast cancer bone metastasis model using hMSCs and commercial breast cancer cells (MCF-7 and MDAMB231), recapitulating late-stage breast cancer metastasis to bone. In the present study, we have validated our model using patient-derived breast cancer cell lines- NT013 and NT023, exhibiting hormone-positive and triple-negative characteristics, respectively that showed MET and formed tumors in the presence of bone. In addition, the results showed ET-1 (NT013) and DKK-1 (NT023) mediated stimulation and abrogation of the osteogenesis via Wnt/β catenin pathway, in line with our previous results with MCF-7 and MDAMB231 cell lines.
Study of New Functionalized Nanomaterials for Non-Invasive Point-of-Care Biosensor Devices
(North Dakota State University, 2021) Johnson, Michael
Early disease detection and in-time health monitoring via novel sensing systems is highly demanded for modern medicine and health management. Recent development in nanotechnology and nanomaterials such as functionalized nanostructured metal-oxide semiconductors and newly discovered two-dimensional Ti3C2 MXenes have offered exciting areas of research as nanomaterial-based biomedical sensing devices. In this thesis, two major nanomaterials, KWO for application in diabetes and MXene for cancer management and further improvement of the KWO diabetes sensor, are intensively researched. KWO shows great potential as a breath acetone sensor, which can be utilized to monitor and diagnose diabetes. It also shows the unique ferroelectric property, which allows for a room-temperature sensing operation. Synthesis methods and characterization are done to further the understanding of KWO as an acetone sensor and further improve its capability towards becoming the cornerstone of a handheld biomedical sensor that is non-invasive, portable, and easy-to-use. Continuing, Ti3C2 MXenes are studied and characterized under various synthesis conditions to create both accordion-like structures with varying gap widths, and single-to-few layered nanosheets created by the intercalation of Li+ ions. Additionally, a new sensor based on 2D nanosheets, Ti3C2 MXene, has been designed and used for the sensing response to 8-HOA and PGE2 in lung cancer cells. The preliminary results indicate an important conclusion: this new Ti3C2-based sensor can provide a convenient and simple method for anti-cancer treatment guidance. Finally, a nanocomposite is synthesized using both KWO and Ti3C2 MXenes to improve the acetone sensor’s sensitivity and selectivity by majorly reducing humidity cross-interference.
In-Silico Investigation of Geological and Biological Materials by Molecular Dynamics Simulations
(North Dakota State University, 2021) Faisal, H M Nasrullah
Molecular dynamics (MD) simulation is a computational technique that predicts the time-dependent behavior of a molecular system utilizing molecular mechanics. MD simulations are extensively employed in the scientific arena to investigate a wide range of material systems at the nanoscale (atoms and molecules), including organics, inorganics, polymer, composites, biomacromolecules, etc. This work investigates the properties of a range of geological (Green River oil shale and swelling clays) and biological materials (coronaviral proteins) at the molecular level using MD simulations. Oil shale, a sedimentary rock containing organic crude oil precursor named kerogen trapped in an inorganic mineral matrix, has long been considered an alternative source of petroleum. Molecular dynamics simulation of Green River oil shale Type I kerogen has been performed in the proximity of predominantly present calcite and quartz minerals to identify their binding interactions with trapped kerogen from the mineral matrix for efficient crude oil production. Sodium-montmorillonite (Na-MMT), a member of the smectite group, is one of the swelling clay minerals components that find various geo-environmental and industrial applications due to its high swelling capacity. Steered molecular dynamics (SMD) simulations have been performed to determine the nanomechanical properties of both dry and hydrated Na-MMT clay tactoid. Besides the geological materials, MD and SMD simulations have also been used to computationally inspect the coronaviral protein-ACE2 protein interactions to elucidate the potential reasons why COVID-19 results in significantly more infections and deaths compared to other coronaviruses. The coronaviral attachment to host cell through spike-ACE2 interactions and coronaviral replication mechanism through tri non-structural protein (nsp12-nsp7-nsp8) interactions have been simulated to understand the differences between SARS-CoV and SARSCoV-2 (COVID-19). The major findings obtained from coronaviral protein interactions may point towards the underlying reasons behind the severity of COVID-19. Moreover, the potency of different phytochemicals has been examined for breast cancer treatment. Compounds commonly found in Rhodiola, and Oregano plants extracts have been targeted against a series of breast cancer proteins utilizing molecular docking to determine the most potent phytochemical for breast cancer treatment.
Enhanced Bone Tissue Regeneration Enabled with Tissue-Engineered Interlocking Nanoclay Scaffolds and Bone Morphogenic Proteins
(North Dakota State University, 2022) Kundu, Krishna
About 6 million bone fractures occur annually in the US; 30% require bone grafting transplants to aid bone healing. Well-established clinical therapy techniques for bone regeneration suffer from limited availability, higher infection risk, donor site morbidity, and poor transplant integration. Delay in healing or nonunion of critical-sized defects is another concern in orthopedics. This dissertation focuses on constructing an interlocking scaffold structure to speed bone regeneration. In this thesis, a BMP-2 & 7 coated PCL-nanoclay-hydroxyapatite interlocking scaffold was developed to accelerate bone regeneration. Developed nano clay polymer interlocking scaffolds retain the scaffold's structural integrity and provide a large surface area while allowing for media interaction. Mesenchymal stem cells (MSCs) and osteoblast cells seeded at a 1:1 ratio boost cell viability and enable calcium deposition on day three and collagen production on day 7 with BMP-2 and BMP-7 coated scaffolds. In addition, BMPs, interlocking, and co-culturing of osteoblasts and MSCs promote osteogenic differentiation. In this dissertation, The long-term effect of BMP-2/BMP-7 on in-vitro utilizing interlocking scaffold blocks was evaluated. Changes to the nanomechanical properties of scaffolds and bone tissue during osteogenesis with the progression of ECM formation were reported. Gene expression results and Alizarin Red S staining images indicate a significant increase in mineralized bone nodules with BMPs coated samples compared with uncoated samples. Results suggest BMPs played a critical role in mineralized ECM production, which increased the scaffolds' elastic modulus. This research provides valuable insight into understanding how BMPs affect bone growth. In this dissertation, polymer clay nanocomposites fibers were constructed utilizing a pressured gyration setup and observed improved cell viability, osteogenic differentiation, ECM development, and collagen formation for PCL HAP MMT-Clay nanocomposite fiber scaffolds compared to pure PCL fibers. In this dissertation, the in-silico design of the unnatural amino acids modified clays and fabricated unnatural amino acids modified scaffolds were reported for application as cancer testbeds. This dissertation also reported the design of the in situ hydroxy apatite and tri-calcium phosphate incorporated nano clays polymer scaffolds for bone tissue engineering applications. These studies represent a new opportunity to design manufacturable composite nanoclay polymer scaffolds for bone tissue engineering applications.
Manipulation and Isolation of Biomolecules Using Dielectrophoretic and Hydrodynamic Methods
(North Dakota State University, 2021) Oh, Myungkeun
Novel particle manipulation techniques are developed to separate, isolate, and control a wide range biomolecules from DNA to cells in complex solution such as whole blood. First, we show that integrating an insulating tip with dielectrophoresis allows us to trap, carry, reposition, and relocate nanoscale objects, which can be used as molecular tweezers without fouling, electrolysis, and joule heating issues associated with conventional dielectrophoretic methods. In addition, we find that two theoretical force calculations (Clausius-Mossotti model and counter ion fluctuation model) result in a factor of 2-40 difference, but the magnitude of both is 4 orders stronger than the thermal force, which is strong enough to manipulate objects in the medium. Second, we perform sedimentation and size-based particle separation methods in a microfluidic device configuration. Using polydimethylsiloxane and its high gas solubility, we demonstrate a sedimentation-based, blood cell separation method. To further isolate small biomarkers such as exosomes utilizing a deterministic lateral displacement principle, we fabricate nanoscale pillar structures on a silicon wafer using multiple nanolithography processes and explore possibilities for size-dependent particle separation on the device.
Adhesion With Slender Structures: Tape Loops, Crumples, and Origami
(North Dakota State University, 2021) Elder, Theresa Marie
The desire for improved adhesive systems led us to examine three geometries: tape loops, crumples, and origami shapes. The tape loop is mechanically interesting because it is stable in more than one configuration. For example, the first configuration is a circular loop. The second is an elongated oval shape that occurs after the loop is pushed into a surface. In this work we examined this cycle and derive a simple mathematical model. We found a solution to the model that only needs one input measurement, that of the loop radius, to determine a tape loop’s adhesion. We explored how a sticky but crumpled film adhered to smooth and rough surfaces. To do this we crumpled inextensible sheets because crumples have been shown to maintain a high compliance while increasing contact area through deforming around obstacles. We found that there was no significant difference in the adhesive behavior of the crumples on rough surfaces compared to flat surfaces. Finally, we designed a switchable adhesive based on thin film origami. We examined a unit cell of the Ron Resch pattern which had two different configurations (open and closed) aided by a 3-D printed device In the closed state the device had a high pull off force, and in the open state a different style of peel off occurred, lowering the peak force. We present promising results that show this to be the case.
Lead Halide Perovskite Nanocrystals: Photophysical and Photochemical Dynamics
(North Dakota State University, 2021) Forde, Aaron Arthur
Lead halide perovskites nanocrystals (LHP NCs) are a recent novel material of ‘high-defect tolerance’ that has been synthesized which have provided a new platform for opto-electronic devices, such as photovoltaics and light-emitting diodes. Development of these materials for commercial devices requires a thorough understanding of their photo-physical properties. A comprehensive understanding of photo-physical properties involves studying the interplay between light-matter interactions, which produce photo-excited charge carriers and govern radiative recombination mechanism, carrier-lattice interactions, which play a dominate role in non-radiative dynamics such as hot-carrier cooling and recombination, and the NC surface chemistry which plays an important role in passivating surface sites which can potentially act as non-radiative recombination centers. In chapter 1 a review of the photo-physical phenomena and electronic processes which occur in materials is established and the motivation for incorporating nanomaterials into opto-electronic devise is provided. Chapter 2 describes in formal details the theoretical methods used to compute electronic structure, light-matter interactions, and carrier-lattice interactions are. Chapter 3 overviews simple physical models, such as particle-in-a-box photo-physics and two-level Redfield theory, which give intuition on how to understand the results of the research. Finally chapters 4-7 are devoted to original research on charge-carrier dynamics within a LHP NC atomistic model as free carriers, bound polarons, in the presence of surface defects, and finally in the presence of transition metal dopants. Chapter 4 provides computational evidence of slow electron cooling due to strong electronic confinement and large spin-orbit coupling contributed from Pb2+ 6p orbitals. Chapter 5 considers the effect of polaron formation on hot-carrier dynamics with the prediction of low efficiency polaron infrared photoluminescence. Chapter 6 provides mechanism for ‘defect tolerance’ due to bright electron surface trap states that form due to polaron reorganization. Chapter 7 models dual exciton-dopant luminescence due to Mn2+ doping.
Tissue-Engineered Nanoclay-Based Bone-Mimetic 3D In Vitro Testbed for Studying Breast Cancer Metastasis to Bone
(North Dakota State University, 2020) Kar, Sumanta
Breast cancer shows a high affinity towards the bone, causing bone-related complications leading to poor clinical prognosis. Approximately 80% of breast cancer patients die within five years after primary cancer has metastasized to the bones. The tumor stage strongly influences the survival rates of patients with breast cancer that has spread to bone at the time of diagnosis. There are currently no effective therapeutics available for bone metastases due to the failure of animal models and the scarcity of human bone metastasized samples, as most patients with advance stages of cancer are already in palliative care. Therefore, it is imperative to develop translational models to elucidate disease mechanisms at the cellular and molecular level. Here, we report the development of tissue-engineered nanoclay-based bone-mimetic three-dimensional (3D) in vitro model for studying later stages of cancer pathogenesis at the metastatic bone site using osteogenically-differentiated human mesenchymal stem cells (MSCs) and human breast cancer cells (MDA-MB-231 and MCF-7). This 3D model provides an ideal microenvironment suitable for cell-cell and cell-matrix interactions while retaining the behavior of breast cancer cells with different metastatic potential along with mimicking mesenchymal to epithelial transition (MET) of breast cancer cells. Sequential cultures of MSCs with MCF-7 gave rise to tumoroids, while sequential cultures of MSCs with MDA-MB-231 formed disorganized clusters of cells with poor cell-cell adhesion. We further evaluated how cancer-derived factors and cytokines affect bone leading to up to metastasis and conferring drug resistance, respectively. Results showed that Wnt/β-catenin and interleukin-6 (IL-6) mediated IL-6/STAT3 pathways are responsible for bone-related complications and conferring drug resistance, respectively. Furthermore, we have utilized the 3D in vitro model to develop methods for non-invasive and rapid prediction of cancer progression using various biophysical techniques such as spectroscopy and nanoindentation. Spectroscopy methods showed significant contributions of proteins, lipids, and nucleic acids, while the nanoindentation method showed F-actin mediated softening of cancer cells during cancer progression at the metastatic bone site, respectively. Collectively, 3D in vitro model provides an ideal platform for studying the molecular mechanism of breast cancer progression at the metastatic bone site, drug development, and discovery of biomarkers for cancer progression.
Non-Thermal Plasma Synthesis of Luminescent Silicon Nanocrystals from Cylclohexasilane
(North Dakota State University, 2019) Pringle, Todd Andrew
In this report we establish cyclohexasilane (CHS) as a reliable precursor for non-thermal plasma synthesis of high quality photoluminescent silicon nanocrystals (SiNCs). We demonstrate that this synthesis approach can produce high quality, size tunable silicon quantum dots with quantum yields exceeding 60% as synthesized (subsequent work in our group has measured over 70% quantum yield after density gradient ultracentrifugation size purification).After a brief background on non-thermal plasma synthesis, the characterization methods used in this study, and an overview of CHS, we report at length on our development of the apparatus used, and our exploration of the controllable processing parameters of the synthesis method. We describe our successes and challenges with size tuning, sample collection, and passivation. Finally, we discuss preliminary studies we performed to identify promising future research areas. Novel reactor designs, blue light passivation, and magnetic confinement of plasma are described briefly to entice future researchers.
Flexible Nanocomposite Thin Films for Electronic Devices
(North Dakota State University, 2019) Alzaid, Meshal Mufleh
Electronic technology is moving towards flexible, durable, and smaller devices with multifunctional capability. To accelerate this movement, creating materials with outstanding properties is critical. Nanocomposites based on single wall carbon nanotubes (SWCNTs) have received considerable attention because of their unique mechanical and electrical properties. When SWCNTs are formed as a sheet, they provide large contact area and ease of control, especially when incorporated into a flexible format. However, when SWCNT films are adhered to an elastic substrate, there are challenges with their use in flexible electronics, such as a reduction Young’s modulus under deformation. SWCNT films can undergo plastic behavior at even a small strain because individual SWCNTs slide past each other in response to deformation. To address these challenges, a strain-induced elastic buckling instability for mechanical measurements (SIEBIMM) method was used to query SWCNT film mechanics. The buckling wavelength and the film thickness are two main factors that influence the mechanics of nanocomposite thin films adhered to elastomeric substrates. SWCNT films coated with a second nanomaterial, such as a polymer thin film or nanocrystals (NCs), have shown a significant enhancement in elasticity. The studies described in this dissertation demonstrate that polymer thin film can reduce the strain softening of SWCNT films, where both yield strain and Young’s modulus increase with the introduction of SWCNT-polymer layers. Specifically, the films started to exhibit a strong synergy between SWCNT and polymer at a film thickness of around 20 nm, which is attributed to the thickness approaching the characteristic interfacial width between the two materials. Both a ‘passive’ polymer thin film (for example, polystyrene-PS) and an ‘active’ polymer thin film, the conducting polymer poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate)(PEDOT:PSS), were investigated, spanning a bilayer to the bulk limit of SWCNT-polymer multilayers. In addition, ultrathin SWCNT films coated with colloidal NCs have also been investigated. We have utilized two approaches to coat SWCNT films with NCs: Langmuir-Blodgett (LB) and spray coating. Both Si and CdSe nanocrystals showed a roughly two-fold enhancement in film elasticity, which was attributed to an excluded volume effect that prevents the SWCNT rearrangement under an applied strain.
Evaluating Mechanisms of Metastasis of Prostate Cancer to Bone Using 3D Bone-Mimetic Tissue Engineered Scaffolds
(North Dakota State University, 2018) Molla, MD Shahjahan
The complex nature of cancer metastasis necessitates the development of a cancer model based on specific metastatic stages. In this dissertation, we report a polymer-nanoclay based in vitro tumor model which recapitulates early stage of prostate cancer skeletal metastasis. A unique cell culture system termed as ‘sequential culture’ has been applied to create a bone-mimetic niche for colonization of prostate cancer cells. Sequentially cultured MDA PCa 2b cells with MSCs formed self-organized multicellular tumoroids with distinct tight cellular junctions and hypoxic core regions. Further, the sequentially cultured PC-3 cell formed multicellular tumoroid like clusters. We performed immunocytochemical confocal microscopy, qRT-PCR, ELISA assays, nanomechanical evaluation and SEM imaging to characterize our tumor model. We observed that in the in vitro model that MSCs differentiated to matured osteoblasts, EMT (epithelial to mesenchymal transition) was inhibited, MET was enhanced, and hypoxia increased angiogenesis when prostate cancer cells were sequentially cultured with MSCs. We also studied the effect of prostate cancer metastasis on bone microenvironment using different prostate cancer cell lines. We found that the less metastatic MDA PCa 2b cells inhibited mineralized collagen formation whereas, highly metastatic PC-3 cells enhanced mineralized collagen formation. All the experimental results indicated osteoblastic bone formation by PC-3 cells and osteolytic bone resorption by MDA PCa 2b cells. Cancer metastasis is a complex process requiring dramatic remodeling of the cell cytoskeleton. Bone metastasis is characterized by complex biochemical, morphological, pathophysiological, and genetic changes to cancer cells as they colonize at remote bone sites. These changes can be captured in sum by changes to nanomechanical properties of cancer cells during metastasis. Using a specially designed nanoindentation apparatus, we observed significant softening of prostate cancer cells during MET and then further softening during the disease progression at the metastatic site. We observed a substantial reduction in elastic modulus of prostate cancer cells during MET arising from actin reorganization and depolymerization. This is the first study that reveals changes to nanomechanical characteristics of prostate cancer cells with correlation to cytoskeletal changes during MET and progression of the disease at the metastatic bone site.
Lattice Gases with Molecular Dynamics Collision Operator
(North Dakota State University, 2018) Parsa, Mohammad Reza
The purpose of this dissertation is to provide a direct microscopic underpinning for lattice Boltzmann (and lattice gas) methods. Lattice gases are idealized discrete models that conserve mass and momentum. These conservation laws imply, through the formalism of kinetic theory, that on a macroscopic scale these methods recover the continuity and Navier-Stokes equations. As part of the kinetic theory approach, an ensemble average of the lattice gas is taken leading to a lattice Boltzmann equation. These lattice Boltzmann equations can be implemented directly leading to the new how ubiquitous lattice Boltzmann methods. In this dissertation we step away from justifying lattice Boltzmann methods and the ability of recovering suitable macroscopic equations. Rather, their correspondence to coarse-grained Molecular Dynamics simulations is examine and can be cast in the form of a lattice gas evolution equation. We call this lattice gas the Molecular Dynamic Lattice Gas (MDLG). We use this MDLG to derive the exact formulation for lattice Boltzmann equilibrium distributions, relaxation parameters, and fluctuating properties.
An Electron Energy-Loss Spectroscopic Investigation of Molecular Interactions at Hydroxyapatite-Collagen Interfaces in Healthy and Diseased (Osteogenesis Imperfecta) Human Bone and Biomineralized Tissue-Engineered Bone
(North Dakota State University, 2018) Payne, Scott Andrew
At its primary level (nm scale) bone is a nanocomposite consisting of a mineral (hydroxyapatite) phase which gives bone its strength and an organic (type I collagen) phase giving bone its fracture toughness. Hydroxyapatite, (HAP) Ca10(PO4)6(OH)2, is the most abundant mineral in the human body. Bone tissue has a complex hierarchical structure spanning multiple length scales (cm to nm). Characterization of mineral composition in biomineralized tissues such as bone at their primary level, is very challenging and requires instrumentation with nanometer-scale spatial resolution. Transmission electron microscopy (TEM) combines high spatial resolution with visual correlation of diffraction and elemental-composition data. Electron energy-loss spectroscopy (EELS) is a sensitive technique used to probe electronic structure at the molecular level. TEM-based EELS is the only available technique that can provide information about the chemical and coordination environment of minerals with nm scale spatial resolution. Prior studies in our group has developed a method to create biomimetic HAP using biomineralization routes inside the clay galleries of montmorillonite clay modified with amino acids (in-situ HAPclay). Incorporation of in-situ HAPclay into polymer scaffolds and seeding with human mesenchymal stem cells has enabled the cells towards differentiation into osteoblastic lineages without differentiating media. Because of the importance of these materials for bioengineering applications, TEM-EELS was used to evaluate differences and similarities among HAP, biomimetic in-situ HAPclay, modified MMT clay, and β-tricalcium phosphate. Osteogenesis imperfecta (OI), also known as brittle bone disease, is an inheritable disease characterized by increased bone fragility, low bone mass, and bone deformity caused primarily by mutation in collagen type I genes and is expressed as changes in structure and mechanics at the macrostructural level of bone. Therefore the mineralization of HAP in OI bone and the molecular basis of OI bone disease makes this an interesting system for molecular-level investigations. Small changes in the valence band and outer electronic structures of the diseased bone have been revealed through EELS. These small changes observed in the electron energy-loss spectra of the OI bone appear to play important biological roles towards development of the disease.
Silicon Nanocrystals: Optical Properties and Self Assembly
(North Dakota State University, 2018) Brown, Samuel
Silicon nanocrystal’s (SiNCs) size dependent optical properties and nontoxic nature portend potential applications across a broad range of industries. With any of these applications, a thorough understanding of SiNC photophysics is desirable to tune their optical properties while optimizing quantum yield. However, a detailed understanding of the photoluminescence (PL) from SiNCs is convoluted by the complexity of the decay mechanisms, including a stretched-exponential relaxation and the presence of both nanosecond and microsecond decays. In this dissertation, a brief history of semiconductor nanocrystals is given, leading up to the first discovery of room temperature PL in SiNCs. This is then followed by an introduction to the various nanocrystal synthetic schemes and a discussion of quantum dot photophysics in general. Three different studies on the PL from SiNCs are then presented. In the first study, the stretched nature of the time dependent PL is analyzed via chromatically-resolved and full-spectrum PL decay measurements. The second study analyzes the size dependence of the bimodal PL decay, where the amplitude of the nanosecond and microsecond decay are related to nanocrystal size, while the third project analyzes the temperature and microstructure dependencies of the PL from SiNC solids. After an indepth look at the PL from SiNCs, this report examines preliminary results of SiNC and silver nanocrystal self-assembly. When compared to metal and metal chalcogenide nanoparticles, there is a dearth of literature on the self-assembly of SiNCs. To understand these phenomena, we analyze the size dependent ability of SiNCs to form a ‘superlattice’ and compare this with silver nanocrystals. Although the results on self-assembly are still somewhat preliminary, it appears that factors such as SiNC concentration and size dispersity play a key role in SiNC self-assembly, while suggesting intrinsic differences between the self-assembly of SiNCs and silver nanocrystals. Finally, at the end of this dissertation, a corollary project is presented on the computational analysis of fluorescent silver nanoclusters (AgNCs). Due to their small size and non-toxic nature, AgNCs are an ideal fluorophore for biological systems, yet there is a limited understanding of their photophysics, which is the focus of this part of the dissertation.
Synthesis, Characterization, and Modeling of New Molecule-Based Magnets
(North Dakota State University, 2015) Olson, Christopher Samuel
The chemical bond and its role as a mediator of magnetic exchange interaction remains an important aspect in the study of magnetic insulators and semiconductors. The M[TCNE] (M = transition metal, TCNE = tetracyanoethylene) class of organic-based magnets has attracted considerable interest since VII[TCNE]x (x ~ 2) exhibits one of the highest critical temperatures for its class – Tc ~ 400 K – in addition to highly spin-polarized conduction and valance bands (Eg ~ 0.5 eV), thus foreseeing potential spintronic application. The magneto-structural factors underlying this exceptional behavior remain elusive, however, due to the amorphous nature of the material. To address this, a novel synthetic route was utilized to produce new polycrystalline M[TCNE] solids (whose crystal structures have been resolved) with varying transition metal centers (Ni, Mn, Fe) and lattice dimensionality (2D-3D), exhibiting a wide range of Tc (40-170 K). Spectroscopic and magnetometric studies were performed and demonstrate that in 2D [MII(TCNE)(NCMe)2]X structures (M = Ni, Mn, Fe; X = diamagnetic anion), strong ligand-to-metal transfer of electron density from the organic TCNE radical plays a significant role in the formation of magnetic exchange pathways, while single-ion anisotropy strongly influences the critical temperature and below-Tc spin disorder for magnets in this material class. Additionally, using quantum-computational modeling, magnetic spin-density transfer trends, spin-polarized electronic structures, and electronic exchange coupling constants have been identified and interpreted in terms of 3d-orbital filling and dimensionality of magnetic interaction. These findings offer new perspectives on the stabilization of magnetic order in M[TCNE] solids.
Experimental Evaluation of Multiscale Behavior of Human Bone
(North Dakota State University, 2014) Gu, Chunju
Bone is the most important structural member of the human body. It has a unique hierarchical structure and its primary constituents, collagen molecules and hydroxyapatite, are arranged in a staggered pattern at nanometer scale. Osteogenesis imperfecta (OI) is an inheritable disease characterized by the fragility of bones and other tissues rich in the type I collagen. OI provides an interesting platform for investigating how alterations of collagen at the molecular level cause changes in the structure of bone. In this dissertation, multi-scale-, particularly nanometer and sub-micro scale-, behaviors of both normal and OI (putative type I) human bones have been evaluated experimentally. Since chemical treatment influences collagen or mineral structure, we have used ―undisturbed bone samples‖ that are not subjected to any chemicals as previously done in literature. Photoacoustic-Fourier transform infrared spectroscopy (PA-FTIR) experiments reveal orientational differences in stoichiometry of hydroxyapatite. FTIR, electron microscopy, scanning probe microscopy, and nanomechanical tests also show that the OI disease results in a distorted microstructure in bone and that the mineralization of hydroxyapatite in OI is also altered. Modulus mapping test displays the distribution of mineralized fibril and extrafibrillar mineral according to the spatial variation of elastic properties. Dynamic nanomechanical behaviors of OI bone and normal bone indicates that the viscoelasticity of intact bone is mostly determined by the mineral. Also investigated are molecular composition and nanomechanical properties of different anatomical positions in the diaphysis of an OI human tibia. Our study on OI bone describes unique differences in collagen as previously described but also elaborates on unique influence of the non-collagenous proteins on mineralization of bone in OI. The fundamental premise of this work is investigation of the molecular basis of this highly debilitating bone disease.
Optical Properties and Ensemble Characteristics of Size Purified Silicon Nanocrystals
(North Dakota State University, 2014) Miller, Joseph Bradley
Nanotechnology is at the forefront of current scienti c research and nanocrystals are being hailed as the `arti cial' atoms of the 21st century. Semiconducting silicon nanocrystals (SiNCs) are prime candidates for potential commercial applications because of silicon's already ubiquitous presence in the semiconductor industry, nontoxicity and abundance in nature. For realization of these potential applications, the properties and behavior of SiNCs need to be understood and enhanced. In this report, some of the main SiNC synthesis schemes are discussed, including those we are currently experimenting with to create our own SiNCs and the one utilized to create the SiNCs used in this study. The underlying physics that governs the unique behavior of SiNCs is then presented. The properties of the as-produced SiNCs are determined to depend strongly on surface passivation and environment. Size puri cation, an important aspect of nanomaterial utilization, was successfully performed on our SiNCs though density gradient ultracentrifugation. We demonstrate that the size-puri ed fractions exhibit an enhanced ability for colloidal self-assembly, with better aligned nanocrystal energy levels which promotes greater photostability in close-packed lms and produces a slight increase in photoluminescence (PL) quantum yield. The qualities displayed by the fractions are exploited to form SiNC clusters that exhibit photostable PL. An analysis of SiNC cluster (from individual nanocrystals to collections of more than one thousand) blinking and PL shows an improvement in their PL emitting `on' times. Pure SiNC lms and SiNC-polymer nanocomposites are created and the dependence of their PL on temperature is measured. For such nanocomposites, the coupling between the `co ee-ring' e ect and liquid-liquid phase separation is also examined for ternary mixtures of solvent, polymer and semiconducting nanocrystal. We discover that with the right SiNC-polymer concentration and polymer molecular weight, phase separation can be supressed; we use this to build a prototype nanocomposite printing device. Finally, the nanocrystals are PEGylated and introduced into an aqueous biological environment to demonstrate their potential for use in biological labelling and sensing devices. The development of superlattice structures from monodisperse SiNC fractions and their use in solid-state lighting and solar cell applications are also explored.
Laser-Assisted Advanced Assembly for MEMS Fabrication
(North Dakota State University, 2014) Atanasov, Yuriy Andreev
Micro Electro-Mechanical Systems (MEMS) are currently fabricated using methods originally designed for manufacturing semiconductor devices, using minimum if any assembly at all. The inherited limitations of this approach narrow the materials that can be employed and reduce the design complexity, imposing limitations on MEMS functionality. The proposed Laser-Assisted Advanced Assembly (LA3) method solves these problems by first fabricating components followed by assembly of a MEMS device. Components are micro-machined using a laser or by photolithography followed by wet/dry etching out of any material available in a thin sheet form. A wide range of materials can be utilized, including biocompatible metals, ceramics, polymers, composites, semiconductors, and materials with special properties such as memory shape alloys, thermoelectric, ferromagnetic, piezoelectric, and more. The approach proposed allows enhancing the structural and mechanical properties of the starting materials through heat treatment, tribological coatings, surface modifications, bio-functionalization, and more, a limited, even unavailable possibility with existing methods. Components are transferred to the substrate for assembly using the thermo-mechanical Selective Laser Assisted Die Transfer (tmSLADT) mechanism for microchips assembly, already demonstrated by our team. Therefore, the mechanical and electronic part of the MEMS can be fabricated using the same equipment/method. The viability of the Laser-Assisted Advanced Assembly technique for MEMS is demonstrated by fabricating magnetic switches for embedding in a conductive carbon-fiber metamaterial for use in an Electromagnetic-Responsive Mobile Cyber-Physical System (E-RMCPS), which is expected to improve the wireless communication system efficiency within a battery-powered device.
Biomimetic Nanoclay Scaffolds for Bone Tissue Engineering
(North Dakota State University, 2014) Ambre, Avinash Harishchandra
Tissue engineering offers a significant potential alternative to conventional methods for rectifying tissue defects by evoking natural regeneration process via interactions between cells and 3D porous scaffolds. Imparting adequate mechanical properties to biodegradable scaffolds for bone tissue engineering is an important challenge and extends from molecular to macroscale. This work focuses on the use of sodium montmorillonite (Na-MMT) to design polymer composite scaffolds having enhanced mechanical properties along with multiple interdependent properties. Materials design beginning at the molecular level was used in which Na-MMT clay was modified with three different unnatural amino acids and further characterized using Fourier Transform Infrared (FTIR) spectroscopy, X-ray diffraction (XRD). Based on improved bicompatibility with human osteoblasts (bone cells) and intermediate increase in d-spacing of MMT clay (shown by XRD), 5-aminovaleric acid modified clay was further used to prepare biopolymer (chitosan-polygalacturonic acid complex) scaffolds. Osteoblast proliferation in biopolymer scaffolds containing 5-aminovaleric acid modified clay was similar to biopolymer scaffolds containing hydroxyapatite (HAP). A novel process based on biomineralization in bone was designed to prepare 5-aminovaleric acid modified clay capable of imparting multiple properties to the scaffolds. Bone-like apatite was mineralized in modified clay and a novel nanoclay-HAP hybrid (in situ HAPclay) was obtained. FTIR spectroscopy indicated a molecular level organic-inorganic association between the intercalated 5-aminovaleric acid and mineralized HAP. Osteoblasts formed clusters on biopolymer composite films prepared with different weight percent compositions of in situ HAPclay. Human MSCs formed mineralized nodules on composite films and mineralized extracellular matrix (ECM) in composite scaffolds without the use of osteogenic supplements. Polycaprolactone (PCL), a synthetic polymer, was used for preparing composites (films and scaffolds) containing in situ HAPclay. Composite films showed significantly improved nanomechanical properties. Human MSCs formed mineralized ECM on films in absence of osteogenic supplements and were able to infiltrate the scaffolds. Atomic force microscopy imaging of mineralized ECM formed on composite films showed similarities in dimensions, arrangement of collagen and apatite with their natural bone counterparts. This work indicates the potential of in situ HAPclay to impart polymeric scaffolds with osteoinductive, osteoconductive abilities and improve their mechanical properties besides emphasizing nanoclays as cell-instructive materials.
Multicomponent Doped Barium Strontium Titanate Thin Films for Tunable Microwave Applications
(North Dakota State University, 2014) Alema, Fikadu Legesse
In recent years there has been enormous progress in the development of barium strontium titanate (BST) films for tunable microwave applications. However, the properties of BST films still remain inferior compared to bulk materials, limiting their use for microwave technology. Understanding the film/substrate mismatch, microstructure, and stoichiometry of BST films and finding the necessary remedies are vital. In this work, BST films were deposited via radio frequency magnetron sputtering method and characterized both analytically and electrically with the aim of optimizing their properties. The stoichiometry, crystal structure, and phase purity of the films were studied by varying the oxygen partial pressure (OPP) and total gas pressure (TGP) in the chamber. A better stoichiometric match between film and target was achieved when the TGP is high (> 30 mTorr). However, the O2/Ar ratio should be adjusted as exceeding a threshold of 2 mTorr in OPP facilitates the formation of secondary phases. The growth of crystalline film on platinized substrates was achieved only with a lower temperature grown buffer layer, which acts as a seed layer by crystallizing when the temperature increases. Concurrent Mg/Nb doping has significantly improved the properties of BST thin films. The doped film has shown an average tunability of 53%, which is only ~8 % lower than the value for the undoped film. This drop is associated with the Mg ions whose detrimental effects are partially compensated by Nb ions. Conversely, the doping has reduced the dielectric loss by ~40 % leading to a higher figure of merit. Moreover, the two dopants ensure a charge neutrality condition which resulted in significant leakage current reduction. The presence of large amounts of empty shallow traps related to NbTi localize the free carriers injected from the contacts; thus increase the device control voltage substantially (>10 V). A combinatorial thin film synthesis method based on co-sputtering of two BST sources doped with Mg/Nb and Ce, respectively, was applied. The composition and the dielectric properties of the deposited film were correlated and the optimal concentration of dopants corresponding to high tunability and low dielectric loss was determined in a timely fashion.

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