Search Results

Synthesis and Characterization of Crystalline Assemblies of Functionalized Hydrogel Nanoparticles

Description: Two series monodispersed nanoparticles of hydroxylpropyl cellulose (HPC) and functionalized poly-N-isopropylamide (PNIPAM) particles have been synthesized and used as building blocks for creating three-dimensional networks, with two levels of structural hierarchy. The first level is HPC nanoparticles were made from methacrylated or degradable cross-linker attached HPC. These nanoparticles could be stabilized at room temperature by residual methacrylate or degradable groups are present both within and on the exterior of HPC nanoparticles. Controlled release studies have been performed on the particle and networks .The nearly monodispersed nanoparticles have been synthesized on the basis of a natural polymer of hydropropylcellulose (HPC) with a high molecular weight using the precipitation polymerization method and self-assembly of these particles in water results in bright colors. The HPC nanoparticles can be potential using as crosslinkers to increase the hydrogels mechanical properties, such as high transparency and rapid swelling/de-swelling kinetics. The central idea is to prepare colloidal particles containing C=C bonds and to use them as monomers - vinylparticles, to form stable particle assemblies with various architectures. This is accomplished by mixing an aqueous suspension of hydrogel nanoparticles (PNIPAM-co-allylamine) with the organic solvent (dichloromethane) to grow columnar crystals. The hydrogels with such a unique crystal structure behavior not only like the hydrogel opals, but also have a unique property: anisotropy.
Access: This item is restricted to UNT Community Members. Login required if off-campus.
Date: December 2005
Creator: Cai, Tong
Partner: UNT Libraries

Polymer hydrogel nanoparticles and their networks

Description: The thermally responsive hydroxypropyl cellulose (HPC) hydrogel nanoparticles have been synthesized and characterized. The HPC particles were obtained by chemically crosslinking collapsed HPC polymer chains in water-surfactant (dodecyltrimethylammonium bromide) dispersion above the lower critical solution temperature (LCST) of the HPC. The size distributions of microgel particles, measured by dynamic light scattering, have been correlated with synthesis conditions including surfactant concentration, polymer concentration, and reaction temperature. The swelling and phase transition properties of resultant HPC microgels have been analyzed using both static and dynamic light scattering techniques. By first making gel nanoparticles and then covalently bonding them together, we have engineered a new class of gels with two levels of structural hierarchy: the primary network is crosslinked polymer chains in each individual particle, while the secondary network is a system of crosslinked nanoparticles. The covalent bonding contributes to the structural stability of the nanostructured gels, while self-assembly provides them with crystal structures that diffract light, resulting in colors. By using N-isopropylacrylamide copolymer hydrogel nanoparticles, we have synthesized nanoparticle networks that display a striking iridescence like precious opal but are soft and flexible like gelatin. This is in contrast to previous colored hydrogels, which were created either by adding dyes or fluorescent, or by organic solvent or by embedding a colloidal crystal array of polymer solid spheres . Creating such periodic 3D structures in materials allows us to obtain useful functionality not only from the constituent building blocks but also from the long-range ordering that characterizes these structures. Hydroxypropyl cellulose (HPC) and poly (acrylic acid ) (PAA) complexes were studied using turbidity measurement and laser light scattering. The phase transition temperature of the complexes is found to depend on pH and molecular weights of PAA and HPC. The driving force for this phenomenon is due to the hydrogen bonding and hydrophobic interaction ...
Date: August 2002
Creator: Lu, Xihua
Partner: UNT Libraries

Quantum-Confined CdS Nanoparticles on DNA Templates

Description: As electronic devices became smaller, interest in quantum-confined semiconductor nanostructures increased. Self-assembled mesoscale semiconductor structures of II-VI nanocrystals are an especially exciting subject because of their controllable band gap and unique photophysical properties. Several preparative methods to synthesize and control the sizes of the individual nanocrystallites and the electronic and optical properties have been intensively studied. Fabrication of patterned nanostructures composed of quantum-confined nanoparticles is the next step toward practical applications. We have developed an innovative method to fabricate diverse nanostructures which relies on the size and a shape of a chosen deoxyribonucleic acid (DNA) template.
Date: May 1998
Creator: Rho, Young Gyu
Partner: UNT Libraries

Synthesis and characterization of crystalline assembly of poly Nisopropylacry-lamide)-co-acrylic acid nanoparticles.

Description: In this study, crystalline poly(N-isopropylacrylamide-co-acrylic acid) (PNIPAm-co-AAc) nanoparticle network in organic solvents was obtained by self assembling precursor particles in acetone/epichlorohydrin mixture at room temperature followed by inter-sphere crosslinking at ~98 °C. The crystals thus formed can endure solvent exchanges or large distortions under a temporary compressing force with the reoccurrence of crystalline structures. In acetone, the crystals were stable, independent of temperature, while in water crystals could change their colors upon heating or changing pH values. By passing a focused white light beam through the crystals, different colors were displayed at different observation angles, indicating typical Bragg diffraction. Shear moduli of the gel nanoparticle crystals were measured in the linear stress-yield ranges for the same gel crystals in both acetone and water. Syntheses of particles of different sizes and the relationship between particle size and the color of the gel nanoparticle networks at a constant solid content were also presented. Temperature- and pH- sensitive crystalline PNIPAm-co-AAc hydrogel was prepared using osmosis crosslinking method. Not only the typical Bragg diffraction phenomenon was observed for the hydrogel but also apparent temperature- and pH- sensitive properties were performed. The phase behavior of PNIPAm nanoparticles dispersed in water was also investigated using a thermodynamic perturbation theory combined with lightscattering and spectrometer measurements. It was shown how the volume transition of PNIPAM particles affected the interaction potential and determined a novel phase diagram that had not been observed in conventional colloids. Because both particle size and attractive potential depended on temperature, PNIPAM aqueous dispersion exhibited phase transitions at a fixed particle number density by either increasing or decreasing temperature. The phase transition of PNIPAm-co-AAc colloids was also studied. The results from the comparison between pure PNIPAm and charged PNIPAm colloids showed that the introducing of carboxyl (-COOH) group not only contributed to the synthesis ...
Date: December 2004
Creator: Zhou, Bo
Partner: UNT Libraries

Nanoparticles Engineered to Bind Serum Albumin: Microwave Assisted Synthesis, Characterization, and Functionalization of Fluorescently-Labeled, Acrylate-Based, Polymer Nanoparticles

Description: The potential use of polymeric, functionalized nanoparticles (NPs) as drug delivery vectors was explored. Covalent conjugation of albumin to the surface of NPs via maleimide chemistry proved problematic. However, microwave assisted synthesis of NPs was not only time efficient, but enabled the exploration of size control by changing the following parameters: temperature, microwave power, reaction time, initiator concentration, and percentage of monomer used. About 1.5 g of fluorescently-labeled, carboxylic acid-functionalized NPs (100 nm diameter) were synthesized for a total cost of less than $1. Future work will address further functionalization of the NPs for the coupling of albumin (or other targeted proteins), and tests for in vivo biodistribution.
Date: August 2010
Creator: Hinojosa, Barbara R.
Partner: UNT Libraries

Edge energies and shapes of nanoprecipitates.

Description: In this report we present a model to explain the size-dependent shapes of lead nano-precipitates in aluminum. Size-dependent shape transitions, frequently observed at nanolength scales, are commonly attributed to edge energy effects. This report resolves an ambiguity in the definition and calculation of edge energies and presents an atomistic calculation of edge energies for free clusters. We also present a theory for size-dependent shapes of Pb nanoprecipitates in Al, introducing the concept of ''magic-shapes'' defined as precipitate shapes having near zero elastic strains when inserted into similarly shaped voids in the Al matrix. An algorithm for constructing a complete set of magic-shapes is presented. The experimental observations are explained by elastic strain energies and interfacial energies; edge energies play a negligible role. We replicate the experimental observations by selecting precipitates having magic-shapes and interfacial energies less than a cutoff value.
Date: January 1, 2006
Creator: Hamilton, John C.
Partner: UNT Libraries Government Documents Department

Synthesis of Novel Organic Chromophores and Their Characterization

Description: Nonlinear organic liquids that exhibit two-photon absorption (TPA) function as good optical limiters for sensor protection from laser pulses. L34 (4-butyl-4'-propyl-diphenylethyne) is a liquid organic compound exhibiting nonlinear optical absorption. A thiol- derivatized analog of L34 (“thiol-L34”) was prepared to bind the molecules to the surface of gold nanoparticles. Surface binding is necessary to investigate synergy between nonlinear optical absorption of gold nanoparticles and thiol-L34. Thiol-L34 was prepared in a six-step organic synthesis starting from 3-(4-bromophenyl) propionic acid. Au nanoparticles with <15 nm diameter have been prepared and sensitized with the thiol-L34 compound for assessment of their nonlinear optical behavior. Diazolylmethenes a class of metal-coordinating dyes that are similar to dipyrrins with some substitutions of nitrogen atoms in place of carbon atoms. Modification in the framework of dipyrrinoid dyes via this replacement of nitrogen for carbon atoms may lead to compounds that serve as effective agents for bioimaging and/or photodynamic therapy. Several routes to the synthesis of di-(1,2,3)-triazolylmethenes, di-(1,2,4)-triazolylmethenes, and ditetrazolylmethenes are presented.
Date: December 2014
Creator: Pokharel, Sundari D.
Partner: UNT Libraries

Determination of critical length scales for corrosion processes using microelectroanalytical techniques.

Description: A key factor in our ability to produce and predict the stability of metal-based macro- to nano-scale structures and devices is a fundamental understanding of the localized nature of corrosion. Corrosion processes where physical dimensions become critical in the degradation process include localized corrosion initiation in passivated metals, microgalvanic interactions in metal alloys, and localized corrosion in structurally complex materials like nanocrystalline metal films under atmospheric and inundated conditions. This project focuses on two areas of corrosion science where a fundamental understanding of processes occurring at critical dimensions is not currently available. Sandia will study the critical length scales necessary for passive film breakdown in the inundated aluminum (Al) system and the chemical processes and transport in ultra-thin water films relevant to the atmospheric corrosion of nanocrystalline tungsten (W) films. Techniques are required that provide spatial information without significantly perturbing or masking the underlying relationships. Al passive film breakdown is governed by the relationship between area of the film sampled and its defect structure. We will combine low current measurements with microelectrodes to study the size scale required to observe a single initiation event and record electrochemical breakdown events. The resulting quantitative measure of stability will be correlated with metal grain size, secondary phase size and distribution to understand which metal properties control stability at the macro- and nano-scale. Mechanisms of atmospheric corrosion on W are dependent on the physical dimensions and continuity of adsorbed water layers as well as the chemical reactions that take place in this layer. We will combine electrochemical and scanning probe microscopic techniques to monitor the chemistry and resulting material transport in these thin surface layers. A description of the length scales responsible for driving the corrosion of the nanocrystalline metal films will be developed. The techniques developed and information derived from this work will ...
Date: March 1, 2004
Creator: Zavadil, Kevin Robert & Wall, Frederick Douglas
Partner: UNT Libraries Government Documents Department

Decomposition of contaminants using photochemically active nanoparticles.

Description: Abstract Not Provided
Date: April 1, 2006
Creator: Zifer, Thomas; Kemp, Richard Alan (Sandia National Laboratories, Albuquerque, NM); Jennison, Dwight Richard (Sandia National Laboratories, Albuquerque, NM); Spangler, Scott W. (Sandia National Laboratories, Albuquerque, NM); Simmons, Blake Alexander; Morse, Daniel H. et al.
Partner: UNT Libraries Government Documents Department

Functionalized nanoparticles for sensor applications.

Description: We will describe our work on functionalized arrays of nanoparticles crosslinked with short conducting molecules that contain sensing functionalities. These bridging ligands modulate their conductivity based on their interaction with analytes. This functionalized nanoparticles organic ligand composite material once it is assembled between nanogaps electrodes will provide nanosized sensors that can be easily interrogated. These nanogap sensors will be engineered so that they can be fabricated into arrays of different sensor elements. This project consists of a number of different requirements that must be met in order to enable the use of functionalized nanoparticles for sensor applications. The first requirement is the appropriately functionalized nanoparticle. The second is a method to assemble the particles. The third requirement is the generation of a nanogap to contain the nanoparticles. The successes in each of these areas will be discussed as will the sensing behavior of the final films.
Date: September 1, 2005
Creator: Simonson, Robert Joseph; Childs, Kenton David; Howell, Stephen Wayne; Dirk, Shawn M. & Wheeler, David Roger
Partner: UNT Libraries Government Documents Department

Microstructure and Electronic Structures of Er-Doped Si Nano-particles Synthesized by Vapor Phase Pyrolysis

Description: Si nanoparticles are new prospective optoelectronic materials. Unlike bulk Si cry-stals, Si nanoparticles display intriguing room-temperature photoluminescence. A major challenge in the fabrication of Si nanoparticles is the control of their size distribution. The rare-earth element Er has unique photo emission properties, including low pumping power, and a temperature independent, sharp spectrum. The emission wavelength matches the transmission window of optical fibers used in the telecommunications industry. Therefore, the study of Er-doped Si nanoparticles may have practical significance. The goals of the research described in this dissertation are to investigate vapor phase pyrolysis methods and to characterize the microstructure and associated defects, particles size distributions and photoluminescence efficiencies of doped and undoped Si nanoparticles using analytical transmission electron microscopy, high resolution electron microscopy, and optical spectroscopy. Er-doped and undoped Si nanoparticles were synthesized via vapor-phase pyrolysis of disilane at Texas Christian University. To achieve monodisperse size distributions, a process with fast nucleation and slow growth was employed. Disilane was diluted to 0.48% with helium. A horizontal pyrolysis oven was maintained at a temperature of 1000 °C. The oven length was varied from 1.5 cm to 6.0 cm to investigate the influence of oven length on the properties of the nanoparticles. The Si nanoparticles were collected in ethylene-glycol. The doped and undoped Si nanoparticles have a Si diamond cubic crystal structure. Neither Er precipitation, Er oxides or Er silicides were detected in any of the samples. The Er dopant concentration was about 2 atom% for doped samples from the 3.0 and 6.0 cm ovens as determined by quantitative analysis using X-ray energy dispersive spectroscopy. The average Si nanoparticle size increases from 11.3 to 15.2 nm in the doped samples and from 11.1 to 15.7 nm in the undoped samples as the oven length increases from 1.5 to 6.0 cm. HREM data ...
Access: This item is restricted to UNT Community Members. Login required if off-campus.
Date: May 2000
Creator: Chen, Yandong
Partner: UNT Libraries

Assembling semiconductor nanocomposites using DNA replication technologies.

Description: Deoxyribonucleic acid (DNA) molecules represent Nature's genetic database, encoding the information necessary for all cellular processes. From a materials engineering perspective, DNA represents a nanoscale scaffold with highly refined structure, stability across a wide range of environmental conditions, and the ability to interact with a range of biomolecules. The ability to mass-manufacture functionalized DNA strands with Angstrom-level resolution through DNA replication technology, however, has not been explored. The long-term goal of the work presented in this report is focused on exploiting DNA and in vitro DNA replication processes to mass-manufacture nanocomposite materials. The specific objectives of this project were to: (1) develop methods for replicating DNA strands that incorporate nucleotides with ''chemical handles'', and (2) demonstrate attachment of nanocrystal quantum dots (nQDs) to functionalized DNA strands. Polymerase chain reaction (PCR) and primer extension methodologies were used to successfully synthesize amine-, thiol-, and biotin-functionalized DNA molecules. Significant variability in the efficiency of modified nucleotide incorporation was observed, and attributed to the intrinsic properties of the modified nucleotides. Noncovalent attachment of streptavidin-coated nQDs to biotin-modified DNA synthesized using the primer extension method was observed by epifluorescence microscopy. Data regarding covalent attachment of nQDs to amine- and thiol-functionalized DNA was generally inconclusive; alternative characterization tools are necessary to fully evaluate these attachment methods. Full realization of this technology may facilitate new approaches to manufacturing materials at the nanoscale. In addition, composite nQD-DNA materials may serve as novel recognition elements in sensor devices, or be used as diagnostic tools for forensic analyses. This report summarizes the results obtained over the course of this 1-year project.
Date: November 1, 2005
Creator: Heimer, Brandon W.; Crown, Kevin K. & Bachand, George David
Partner: UNT Libraries Government Documents Department

Deleterious Synergistic Effects of Concurrent Magnetic Field and Superparamagnetic (Fe3O4) Nanoparticle Exposures on CHO-K1 Cell Line

Description: While many investigations have been performed to establish a better understanding of the effects that magnetic fields and nanoparticles have on cells, the fundamental mechanisms behind the interactions are still yet unknown, and investigations on concurrent exposure are quite limited in scope. This study was therefore established to investigate the biological impact of concurrent exposure to magnetic nanoparticles and extremely-low frequency magnetic fields using an in-vitro CHO-K1 cell line model, in an easily reproducible manner to establish grounds for further in-depth mechanistic, proteomic, and genomic studies. Cells were cultured and exposed to 10nm Fe3O4 nanoparticles, and DC or low frequency (0Hz, 50Hz, and 100Hz) 2.0mT magnetic fields produced by a Helmholtz coil pair. The cells were then observed under confocal fluorescence microscopy, and subject to MTT biological assay to determine the synergistic effects of these concurrent exposures. No effects were observed on cell morphology or microtubule network; however, cell viability was observed to decrease more drastically under the combined effects of magnetic field and nanoparticle exposures, as compared to independent exposures alone. It was concluded that no significant difference was observed between the types of magnetic fields, and their effects on the nanoparticle exposed cells, but quite clearly there are deleterious synergistic effects of these concurrent magnetic field and nanoparticle exposure conditions.
Date: May 2015
Creator: Coker, Zachary
Partner: UNT Libraries

Interfacial Electrochemistry of Metal Nanoparticles Formation on Diamond and Copper Electroplating on Ruthenium Surface

Description: An extremely facile and novel method called spontaneous deposition, to deposit noble metal nanoparticles on a most stable form of carbon (C) i.e. diamond is presented. Nanometer sized particles of such metals as platinum (Pt), palladium (Pd), gold (Au), copper (Cu) and silver (Ag) could be deposited on boron-doped (B-doped) polycrystalline diamond films grown on silicon (Si) substrates, by simply immersing the diamond/Si sample in hydrofluoric acid (HF) solution containing ions of the corresponding metal. The electrons for the reduction of metal ions came from the Si back substrate. The diamond/Si interfacial ohmic contact was of paramount importance to the observation of the spontaneous deposition process. The metal/diamond (M/C) surfaces were investigated using Raman spectroscopy, scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS) and x-ray diffractometry (XRD). The morphology (i.e. size and distribution) of metal nanoparticles deposits could be controlled by adjusting the metal ion concentration, HF concentration and deposition time. XRD data indicate the presence of textured and strained crystal lattices of Pd for different Pd/C morphologies, which seem to influence the electrocatalytic oxidation of formaldehyde (HCHO). The sensitivity of electrocatalytic reactions to surface crystal structure implies that M/C could be fabricated for specific electrocatalytic applications. The research also presents electroplating of Cu on ruthenium (Ru), which a priori is a promising barrier material for Cu interconnects in the sub 0.13 μm generation integrated circuits (ICs). Cu plates on Ru with over 90% efficiency. The electrochemical nucleation and growth studies using the potentiostatic current transient method showed a predominantly progressive nucleation of Cu on Ru. This was also supported by SEM imaging, which showed that continuous thin films of Cu (ca. 400 Å) with excellent conformity could be plated over Ru without dendrite formation. Scotch tape peel tests and SEM on Cu/Ru samples both at room temperature (RT) and ...
Access: This item is restricted to the UNT Community Members at a UNT Libraries Location.
Date: May 2003
Creator: Arunagiri, Tiruchirapalli Natarajan
Partner: UNT Libraries