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Description
Locomotion of microorganisms is commonly observed in nature and some aspects of their motion can be replicated by synthetic motors. Synthetic motors rely on a variety of propulsion mechanisms including auto-diffusiophoresis, auto-electrophoresis, and bubble generation. Regardless of the source of the locomotion, the motion of any motor can be characterized

Locomotion of microorganisms is commonly observed in nature and some aspects of their motion can be replicated by synthetic motors. Synthetic motors rely on a variety of propulsion mechanisms including auto-diffusiophoresis, auto-electrophoresis, and bubble generation. Regardless of the source of the locomotion, the motion of any motor can be characterized by the translational and rotational velocity and effective diffusivity. In a uniform environment the long-time motion of a motor can be fully characterized by the effective diffusivity. In this work it is shown that when motors possess both translational and rotational velocity the motor transitions from a short-time diffusivity to a long-time diffusivity at a time of pi/w. The short-time diffusivities are two to three orders of magnitude larger than the diffusivity of a Brownian sphere of the same size, increase linearly with concentration, and scale as v^2/2w. The measured long-time diffusivities are five times lower than the short-time diffusivities, scale as v^2/{2Dr [1 + (w/Dr )^2]}, and exhibit a maximum as a function of concentration. The variation of a colloid's velocity and effective diffusivity to its local environment (e.g. fuel concentration) suggests that the motors can accumulate in a bounded system, analogous to biological chemokinesis. Chemokinesis of organisms is the non-uniform equilibrium concentration that arises from a bounded random walk of swimming organisms in a chemical concentration gradient. In non-swimming organisms we term this response diffusiokinesis. We show that particles that migrate only by Brownian thermal motion are capable of achieving non-uniform pseudo equilibrium distribution in a diffusivity gradient. The concentration is a result of a bounded random-walk process where at any given time a larger percentage of particles can be found in the regions of low diffusivity than in regions of high diffusivity. Individual particles are not trapped in any given region but at equilibrium the net flux between regions is zero. For Brownian particles the gradient in diffusivity is achieved by creating a viscosity gradient in a microfluidic device. The distribution of the particles is described by the Fokker-Planck equation for variable diffusivity. The strength of the probe concentration gradient is proportional to the strength of the diffusivity gradient and inversely proportional to the mean probe diffusivity in the channel in accordance with the no flux condition at steady state. This suggests that Brownian colloids, natural or synthetic, will concentrate in a bounded system in response to a gradient in diffusivity and that the magnitude of the response is proportional to the magnitude of the gradient in diffusivity divided by the mean diffusivity in the channel.
ContributorsMarine, Nathan Arasmus (Author) / Posner, Jonathan D (Thesis advisor) / Adrian, Ronald J (Committee member) / Frakes, David (Committee member) / Phelan, Patrick E (Committee member) / Santos, Veronica J (Committee member) / Arizona State University (Publisher)
Created2013
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Description
The objective of this research is to develop a biocompatible scaffold based on dextran and poly acrylic acid (PAA) with the potential to be used for soft tissue repair. In this thesis, physical and chemical properties of the scaffold were investigated. The scaffolds were made using electrospinning and cross-linked under

The objective of this research is to develop a biocompatible scaffold based on dextran and poly acrylic acid (PAA) with the potential to be used for soft tissue repair. In this thesis, physical and chemical properties of the scaffold were investigated. The scaffolds were made using electrospinning and cross-linked under high temperature. After heat treatment, Scanning Electron Microscope (SEM) was used to observe the structures of these scaffolds. Fourier transform infrared spectroscopy (FTIR) was used to measure the cross-linking level of scaffold samples given different times of heat treatment by detecting and comparing the newly formed ester bonds. Single-walled carbon nanotubes (SWCNT) were added to enhance the mechanical properties of dextran-PAA scaffolds. Attachment of NIH-3T3 fibroblast cells to the scaffold and the response upon implantation into rabbit vaginal tissue were also evaluated to investigate the performance of SWCNT dextran-PAA scaffold. SEM was then used to characterize morphology of fibroblast cells and rabbit tissues. The results suggest that SWCNT could enhance cell attachment, distribution and spreading performance of dextran-PAA scaffold.
ContributorsLiu, Chongji (Author) / Massia, Stephen (Thesis advisor) / Pizziconi, Vincent (Committee member) / Pauken, Christine (Committee member) / Arizona State University (Publisher)
Created2014
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Description
Processed pyro-gel contains castor oil with solid component of boehmite (Al-OOH). The pyro-gel is synthesized by heat to convert boehmite to gamma-Al2O3 and to a certain extent alpha-Al2O3 nano-particles and castor oil into carbon residue. The effect of heat on pyro-gel is analyzed in a series of experiments using two

Processed pyro-gel contains castor oil with solid component of boehmite (Al-OOH). The pyro-gel is synthesized by heat to convert boehmite to gamma-Al2O3 and to a certain extent alpha-Al2O3 nano-particles and castor oil into carbon residue. The effect of heat on pyro-gel is analyzed in a series of experiments using two burning chambers with the initial temperature as the main factor. The obtained temperature distribution profiles are studied and it is observed that the gel behaves very close to the theoretical prediction under heat. The carbon residue with Al2O3 is then processed for twelve hours and then analyzed to obtain the pore distribution of the Al2O3 nano-particles and the relation between the pore volume and the pre-heat temperature is analyzed. The obtained pore distribution shows the pore volume of Al2O3 nano-particles has direct relation to the pre-heat temperature. The experimental process involving the cylindrical reactor is simulated by using a finite rate chemistry eddy-dissipation model in a non-premixed and a porous mesh. The temperature distribution profile of the processed gel for both the meshes is obtained and a comparison is done with the data obtained in the experimental analysis. The temperature distribution obtained from the simulations show they follow a very similar profile to the temperature distribution obtained from experimental analysis, thus confirming the accuracy of both the models. The variation in numerical values between the experimental and simulation analysis is discussed. A physical model is proposed to determine the pore formation based on the temperature distribution obtained from experimental analysis and simulation.
ContributorsSagi, Varun (Author) / Lee, Taewoo (Thesis advisor) / Phelan, Patrick (Committee member) / Chen, Kangping (Committee member) / Arizona State University (Publisher)
Created2010
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Description
Aqueous solutions of temperature-responsive copolymers based on N-isopropylacrylamide (NIPAAm) hold promise for medical applications because they can be delivered as liquids and quickly form gels in the body without organic solvents or chemical reaction. However, their gelation is often followed by phase-separation and shrinking. Gel shrinking and water loss is

Aqueous solutions of temperature-responsive copolymers based on N-isopropylacrylamide (NIPAAm) hold promise for medical applications because they can be delivered as liquids and quickly form gels in the body without organic solvents or chemical reaction. However, their gelation is often followed by phase-separation and shrinking. Gel shrinking and water loss is a major limitation to using NIPAAm-based gels for nearly any biomedical application. In this work, a graft copolymer design was used to synthesize polymers which combine the convenient injectability of poly(NIPAAm) with gel water content controlled by hydrophilic side-chain grafts based on Jeffamine® M-1000 acrylamide (JAAm). The first segment of this work describes the synthesis and characterization of poly(NIPAAm-co-JAAm) copolymers which demonstrates controlled swelling that is nearly independent of LCST. The graft copolymer design was then used to produce a degradable antimicrobial-eluting gel for prevention of prosthetic joint infection. The resorbable graft copolymer gels were shown to have three unique characteristics which demonstrate their suitability for this application. First, antimicrobial release is sustained and complete within 1 week. Second, the gels behave like viscoelastic fluids, enabling complete surface coverage of an implant without disrupting fixation or movement. Finally, the gels degrade rapidly within 1-6 weeks, which may enable their use in interfaces where bone healing takes place. Graft copolymer hydrogels were also developed which undergo Michael addition in situ with poly(ethylene glycol) diacrylate to form elastic gels for endovascular embolization of saccular aneurysms. Inclusion of JAAm grafts led to weaker physical crosslinking and faster, more complete chemical crosslinking. JAAm grafts prolonged the delivery window of the system from 30 seconds to 220 seconds, provided improved gel swelling, and resulted in stronger, more elastic gels within 30 minutes after delivery.
ContributorsOverstreet, Derek (Author) / Caplan, Michael (Thesis advisor) / Massia, Stephen (Committee member) / Mclaren, Alexander (Committee member) / Vernon, Brent (Committee member) / McLemore, Ryan (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Electronic devices based on various stimuli responsive polymers are anticipated to have great potential for applications in innovative electronics due to their inherent intelligence and flexibility. However, the electronic properties of these soft materials are poor and the applications have been limited due to their weak compatibility with functional materials.

Electronic devices based on various stimuli responsive polymers are anticipated to have great potential for applications in innovative electronics due to their inherent intelligence and flexibility. However, the electronic properties of these soft materials are poor and the applications have been limited due to their weak compatibility with functional materials. Therefore, the integration of stimuli responsive polymers with other functional materials like Silicon is strongly demanded. Here, we present successful strategies to integrate environmentally sensitive hydrogels with Silicon, a typical high-performance electronic material, and demonstrate the intelligent and stretchable capability of this system. The goal of this project is to develop integrated smart devices comprising of soft stimuli responsive polymeric-substrates with conventional semiconductor materials such as Silicon, which can respond to various external stimuli like pH, temperature, light etc. Specifically, these devices combine the merits of high quality crystalline semiconductor materials and the mechanical flexibility/stretchability of polymers. Our innovative system consists of ultra-thin Silicon ribbons bonded to an intelligently stretchable substrate which is intended to interpret and exert environmental signals and provide the desired stress relief. As one of the specific examples, we chose as a substrate the standard thermo-sensitive poly(N-isopropylacrylamide) (PNIPAAm) hydrogel with fast response and large deformation. In order to make the surface of the hydrogel waterproof and smooth for high-quality Silicon transfer, we introduced an intermediate layer of poly(dimethylsiloxane) (PDMS) between the substrate and the Silicon ribbons. The optical microscope results have shown that the system enables stiff Silicon ribbons to become adaptive and drivable by the soft environmentally sensitive substrate. Furthermore, we pioneered the development of complex geometries with two different methods: one is using stereolithography to electronically control the patterns and build up their profiles layer by layer; the other is integrating different multifunctional polymers. In this report, we have designed a bilayer structure comprising of a PNIPAAm hydrogel and a hybrid hydrogel of N-isopropylacrylamide (NIPAAm) and acrylic acid (AA). Typical variable curvatures can be obtained by the hydrogels with different dimensional expansion. These structures hold interesting possibilities in the design of electronic devices with tunable curvature.
ContributorsPan, Yuping (Author) / Dai, Lenore (Thesis advisor) / Jiang, Hanqing (Thesis advisor) / Lind, Mary Laura (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Gels are three-dimensional polymer networks with entrapped solvent (water etc.). They bear amazing features such as stimuli-responsive (temperature, PH, electric field etc.), high water content and biocompatibility and thus find a lot of applications. To understand the complex physics behind gel's swelling phenomenon, it is important to build up fundamental

Gels are three-dimensional polymer networks with entrapped solvent (water etc.). They bear amazing features such as stimuli-responsive (temperature, PH, electric field etc.), high water content and biocompatibility and thus find a lot of applications. To understand the complex physics behind gel's swelling phenomenon, it is important to build up fundamental mechanical model and extend to complicated cases. In this dissertation, a coupled large deformation and diffusion model regarding gel's swelling behavior is presented. In this model, free-energy of the total gel is constituted by polymer stretching energy and polymer-solvent mixing energy. In-house nonlinear finite element code is implemented with fast computational capability. Complex phenomenon such as buckling and healing of cracked gel by swelling are studied. Due to the wide coverage of polymeric materials and solvents, solvent diffusion in gels not only follows Fickian diffusion law where concentration map is continuous but also follows non-Fickian diffusion law where concentration map shows high gradient. Phenomenological model with viscoelastic polymer constitutive and concentration dependent diffusivity is created. The model well captures this special diffusion phenomenon such as sharp diffusion front and distinctive swollen and unswollen region.
ContributorsZhang, Jiaping (Author) / Jiang, Hanqing (Thesis advisor) / Peralta, Pedro (Committee member) / Dai, Lenore (Committee member) / Rajan, Subramaniam D. (Committee member) / Chawla, Nikhilesh (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Environmentally responsive microgels have drawn significant attention due to their intrinsic ability to change volume in response to various external stimuli such as pH, temperature, osmotic pressure, or electric and magnetic fields. The extent of particle swelling is controlled by the nature of the polymer-solvent interaction. This thesis focuses on

Environmentally responsive microgels have drawn significant attention due to their intrinsic ability to change volume in response to various external stimuli such as pH, temperature, osmotic pressure, or electric and magnetic fields. The extent of particle swelling is controlled by the nature of the polymer-solvent interaction. This thesis focuses on design and synthesis of environmentally responsive microgels and their composites, and encompasses methods of utilizing microgel systems in applications as vehicles for the adsorption, retention, and targeted delivery of chemical species. Furthermore, self-assembled microgel particles at ionic liquid (IL)-water interfaces demonstrate responsive colloidal lattice morphology. The thesis first reports on the fundamental aspects of synthesis, functionalization, and characteristic properties of multifunctional environmentally responsive microgels derived from poly(N-isopropylacrylamide) (PNIPAm) and other functional co-monomers. In particular, the uptake and release of active chemical species such as rheology modifiers into and from these ionic microgels is demonstrated. Moreover, a facile tunable method for the formation of organic-inorganic composites with Fe3O4 nanoparticles adsorbed and embedded within ionic microgel particles is explored. Additionally, the development of zwitterionic microgels (ZI-MG) is presented. These aqueous ZI-MG dispersions exhibit reversible parabolic swelling as a function of pH and display a minimum hydrodynamic diameter at a tunable isoelectric point (IEP). This study also elucidates the controlled uptake and release of surfactants from these particle systems. The extent of surfactant loading and the ensuing relative swelling/deswelling behaviors within the polymer networks are explained in terms of their binding interactions. The latter part of this thesis highlights the versatility of fluorescently labeled microgel particles as stabilizers for IL-water droplets. When the prepared particles form monolayers and equilibrate at the liquid-liquid interface, the colloidal lattice organization may re-order itself depending on the surface charge of these particles. Finally, it is shown that the spontaneously formed and densely packed layers of microgel particles can be employed for extraction applications, as the interface remains permeable to small active species.
ContributorsChen, Haobo (Author) / Dai, Lenore L (Committee member) / Chen, Kangping (Committee member) / Forzani, Erica (Committee member) / Lind, Mary Laura (Committee member) / Mu, Bin (Committee member) / Arizona State University (Publisher)
Created2015
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Description
New sol-gel routes based on peroxo complexes of early transition metals in a highly acidic medium were developed, to prepare metal oxide phosphates that feature structural protons. A sol-gel synthetic route was chosen because it allows atomic level mixing of precursors and lower heating temperatures, which are preferable in exploring

New sol-gel routes based on peroxo complexes of early transition metals in a highly acidic medium were developed, to prepare metal oxide phosphates that feature structural protons. A sol-gel synthetic route was chosen because it allows atomic level mixing of precursors and lower heating temperatures, which are preferable in exploring metastable phases. Titanium and molybdenum sol-gel chemistries were the focus of the initial studies and the synthesis of Ti1-xMoxP2O7 (x = 0 – 0.5) and Mo1-yTiyP2O8-y (y = 0 – 0.4) type metal oxide phosphates were explored. For the synthesis of the metal oxide phosphates, hydrogen peroxide was employed to prepare the respective precursor solutions. The peroxide ligand suppressed the immediate precipitation of metal cations in aqueous medium, by coordinating to Ti4+ and Mo6+ ions, and produced a soft wet-gel following polycondensation. Phosphoric acid was used to acidify the reaction medium and to provide protons and phosphate ions as structural components. From this synthetic route, a series of Ti1-xMoxP2O7 (x = 0 – 0.5) and Mo1-yTiyP2O8-y (y = 0 – 0.4) crystalline compounds, with various degrees of purity, were synthesized. For x = 0 and y = 0, the crystalline compounds TiP2O7 and MoP2O8 were produced, respectively, after calcining at 600 °C.

In pursuit of new metastable molybdenum oxide phosphate compounds, peroxo-molybdenum precursor mixtures with different molar ratios were treated gently by low-temperature heating. After controlled drying in a lab oven, MoO2(H2O)(HPO4) crystals were obtained as a highly crystalline pure product instead of a gel. The dissolution of MoO2(H2O)(HPO4) in water and precipitation with a CsCl solution produced a new crystalline compound with a cubic unit cell (a = 11.8(2) Å). Further studies will lead to crystal structure determination and elucidation of the aqueous chemistry of MoO2(H2O)(HPO4).
ContributorsAbeysooriya, Shanika (Author) / Seo, Dong K (Thesis advisor) / Chan, Candace K. (Committee member) / Trovitch, Ryan J (Committee member) / Arizona State University (Publisher)
Created2018
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Description
This report provides information concerning qualities of methylcellulose and how those properties affect further experimentation within the biomedical world. Utilizing the compound’s biocompatibility many issues, ranging from surgical to cosmetic, can be solved. As of recent, studies indicate, methylcellulose has been used as a physically cross-linked gel, which

This report provides information concerning qualities of methylcellulose and how those properties affect further experimentation within the biomedical world. Utilizing the compound’s biocompatibility many issues, ranging from surgical to cosmetic, can be solved. As of recent, studies indicate, methylcellulose has been used as a physically cross-linked gel, which cannot sustain a solid form within the body. Therefore, this report will ultimately explore the means of creating a non-degradable, injectable, chemically cross-linking methylcellulose- based hydrogel. Methylcellulose will be evaluated and altered in experiments conducted within this report and a chemical cross-linker, developed from Jeffamine ED 2003 (O,O′-Bis(2-aminopropyl) polypropylene glycol-block-polyethylene glycol-block-polypropylene glycol), will be created. Experimentation with these elements is outlined here, and will ultimately prompt future revisions and analysis.
ContributorsBundalo, Zoran Luka (Author) / Vernon, Brent (Thesis director) / LaBelle, Jeffrey (Committee member) / Overstreet, Derek (Committee member) / Barrett, The Honors College (Contributor) / Harrington Bioengineering Program (Contributor)
Created2013-05
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Description
Environmentally responsive hydrogels are one interesting class of soft materials. Due to their remarkable responsiveness to stimuli such as temperature, pH, or light, they have attracted widespread attention in many fields. However, certain functionality of these materials alone is often limited in comparison to other materials such as silicon; thus,

Environmentally responsive hydrogels are one interesting class of soft materials. Due to their remarkable responsiveness to stimuli such as temperature, pH, or light, they have attracted widespread attention in many fields. However, certain functionality of these materials alone is often limited in comparison to other materials such as silicon; thus, there is a need to integrate soft and hard materials for the advancement of environmental-ly responsive materials.

Conventional hydrogels lack good mechanical properties and have inherently slow response time, important characteristics which must be improved before the hydrogels can be integrated with silicon. In the present dissertation work, both these important attrib-utes of a temperature responsive hydrogel, poly(N-isopropylacrylamide) (PNIPAAm), were improved by adopting a low temperature polymerization process and adding a sili-cate compound, tetramethyl orthosilicate. Furthermore, the transition temperature was modulated by adjusting the media quality in which the hydrogels were equilibrated, e.g. by adding a co-solvent (methanol) or an anionic surfactant (sodium dodecyl sulfate). In-terestingly, the results revealed that, based on the hydrogels’ porosity, there were appre-ciable differences when the PNIPAAm hydrogels interacted with the media molecules.

Next, an adhesion mechanism was developed in order to transfer silicon thin film onto the hydrogel surface. This integration provided a means of mechanical buckling of the thin silicon film due to changes in environmental stimuli (e.g., temperature, pH). We also investigated how novel transfer printing techniques could be used to generate pat-terned deformation of silicon thin film when integrated on a planar hydrogel substrate. Furthermore, we explore multilayer hybrid hydrogel structures formed by the integration of different types of hydrogels that have tunable curvatures under the influence of differ-ent stimuli. Silicon thin film integration on such tunable curvature substrates reveal char-acteristic reversible buckling of the thin film in the presence of multiple stimuli.

Finally, different approaches of incorporating visible light response in PNIPAAm are discussed. Specifically, a chemical chromophore- spirobenzopyran was synthesized and integrated through chemical cross-linking into the PNIPAAm hydrogels. Further, methods of improving the light response and mechanical properties were also demonstrat-ed. Interestingly, such a system was shown to have potential application as light modulated topography altering system
ContributorsChatterjee, Prithwish (Author) / Dai, Lenore L. (Thesis advisor) / Jiang, Hanqing (Thesis advisor) / Lind, Mary Laura (Committee member) / Yu, Hongyu (Committee member) / Yu, Hongbin (Committee member) / Arizona State University (Publisher)
Created2015