Materials Chemistry Commons^™

Probing The Structure And Photophysics Of Porphyrinoid Systems For Functional Materials, Christopher D. Farley

Dissertations, Theses, and Capstone Projects

Porphyrins (Pors) and their many cousins, including phthalocyanines (Pcs), corroles (Cors), subphthalocyanines (SubPcs), porphyrazines (Pzs), and naphthalocyanines (NPcs), play amazingly diverse roles in biological and non-biological systems because of their unique and tunable physical and chemical properties. These compounds, collectively known as porphyrinoids, can be employed in any number of functional devices that have the potential to address the challenges of modern society. Their incorporation into such devices, however, depends on many structural factors that must be well understood and carefully controlled in order to achieve the desired behavior. Self-assembly and self-organization are key processes for developing these new technologies, …

Sustainable Molecular Gelators: Beta-D-Glucoside Derived Structuring Agents And Their Material Application, Julian R. Silverman

Dissertations, Theses, and Capstone Projects

Though molecular gelators may by synthesized and formulated into gels following a variety of methods, it should serve that the most valued methods may utilize renewable and waste resources and follow sustainable procedures. Molecular gelators are systems capable of structuring liquids into solid-like materials and they represent a class of surfactant and amphiphilic materials which posses the capability to be not only useful in their ability to form gels, but multifunctional in the ability to respond smartly to a variety of stimuli. Thus there is an interest in the development of sustainable molecular gelators capable of being applied to applications, …

Development Of New Radiolabeling Methods And Insights On Ionizing Radiation Interactions With Nanoparticles, Travis Shaffer

Dissertations, Theses, and Capstone Projects

Nanoparticles are often combined with radionuclides for various applications, ranging from waste remediation to imaging and therapy in the medical field. The overarching aim of this body of work is two-fold. The first aim is development of new radiolabeling methods for various nanoparticles that allow stable attachment of a variety of imaging and therapeutic radionuclides. The second portion more fully describes mechanisms of interaction between ionizing radiation and nanoparticles.

The following advancements will be presented in this dissertation: i) a new radiolabeling method for silica and silica-based nanoparticles that does not require the use of specific chelators, with both radiochemical …

Electrochemical Properties Of Melting Gel Coatings, Lisa C. Klein, Ahmad Dengah, Kutaiba Al-Marzoki, Gabriela Rodriguez, Andrei Jitianu, Jadra Mosa, Mario Amapricio

Publications and Research

Organic-inorganic melting gel coatings were applied to titanium alloy substrates to decrease their corrosion and extend their lifetime in an electrochemical application. Melting gels containing phenyl substitutions were coated onto the substrates. The ratio of diphenyl dimethoxysilane (DPhDMS) to methanol was varied to change the thickness of the coatings. The coatings were inspected visually to see that there is good adhesion between the coating and the substrate. Nanoindenter tests were performed to determine hardness

Design Rules For The Nucleation, Growth, And Encapsulation Of Gold Nanoparticles With Applications To Cancer Imaging, Matthew A. Wall

Dissertations, Theses, and Capstone Projects

Surface-enhanced Raman scattering (SERS) nanoparticles are exciting candidates for high-precision cancer imaging due to their highly specific spectral signature (Raman “fingerprint”) and propensity for passive targeting of cancerous tissues. However, the signal intensity of currently available SERS nanoparticles is insufficient for cancer imaging via passive targeting in most solid tumors. The overarching aim of this body of work is to develop a new generation of SERS nanoparticles with sufficiently low limits of detection to enable robust detection of various solid tumors in vivo.

The complexity of SERS nanoparticles requires significant advances to the theoretical and experimental understanding of metal …

Ultrafast Spectroscopy And Energy Transfer In An Organic/Inorganic Composite Of Zinc Oxide And Graphite Oxide, Jeff A. Secor

Dissertations, Theses, and Capstone Projects

The energy transfers and nature of defect levels of an organic/inorganic composite of Zinc Oxide and Graphite are studied with multidimensional spectroscopy. The edge and surface states of each composite are uncovered using excitation emission experiments showing which defect states are mediating the energy transfer from the metal oxide to the graphite oxide. Multidimensional time resolved spectroscopy further describes the effect of the carbon phase on the energy transfer pathways in the material.

Hybrid Sol–Gel Glasses With Glass-Transition Temperatures Below Room Temperature, Andrei Jitianu, Guadalupe Gonzalez, Lisa C. Klein

Publications and Research

Melting gels are hybrid gels that have the ability to soften and flow at around 100 ° C for some combinations of mono- and di-substituted alkoxysiloxanes, where substitutions are either all aromatic or all aliphatic. In this study, melting gels were prepared using phenyltriethoxysilane (PhTES) and dimethyldiethoxysilane (DMDES), meaning both an aromatic and aliphatic substitution. Differential scanning calorimetry was performed to identify glass-transition temperatures, and thermal gravimetric analysis coupled with differential thermal analysis (TGA-DTA) was performed to measure weight loss. The glass-transition temperatures ( T g ) ranged from – 61 ° C to + 5.6 ° C, which are …

Molecular Helices As Electron Acceptors In High-Performance Bulk Heterojunction Solar Cells, Yu Zhong, M. Tuan Trinh, Rongsheng Chen, Geoffrey E. Purdum, Petr P. Khlyabich, Melda Sezen, Seokjoon Oh, Haiming Zhu, Brandon Fowler, Boyuan Zhang, Wei Wang, Chang-Yong Nam, Matthew Y. Sfeir, Charles T. Black, Michael L. Steigerwald, Yueh-Lin Loo, Fay Ng, X.-Y. Zhu, Colin Nuckolls

Publications and Research

Despite numerous organic semiconducting materials synthesized for organic photovoltaics in the past decade, fullerenes are widely used as electron acceptors in highly efficient bulk-heterojunction solar cells. None of the non-fullerene bulk heterojunction solar cells have achieved efficiencies as high as fullerene-based solar cells. Design principles for fullerene-free acceptors remain unclear in the field. Here we report examples of helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealed …

Kinetic Study Of The Oxygen Reduction Reaction On Α-Ni(Oh)2 And Α-Ni(Oh)2 Supported On Graphene Oxide, Elaheh Farjami, L. Jay Deiner

Publications and Research

The kinetics of the oxygen reduction reaction on α-Ni(OH)2 and α-Ni(OH)2 supported on graphene oxide (α-Ni(OH)2/GO) were investigated using rotating disk linear sweep voltammetry in alkaline solutions of varying oxygen and hydroxyl concentrations. Over the full hydroxyl concentration range (0.05 M to 0.5M), α-Ni(OH)2/GO displayed higher activity than unsupported α-Ni(OH)2. The electron transfer numbers were 2.9 ± 0.2 for α-Ni(OH)2, 3.4 ± 0.1 for α-Ni(OH)2/GO at low [OH−], and 3.8–3.9 for α-Ni(OH)2/GO at high [OH−]. Compared to α-Ni(OH)2, α-Ni(OH)2/GO displayed higher chemical reaction rate constants and higher electron transfer rate constants. These differences suggest that the synergy between the α-Ni(OH)2 …

Corrosion Protection Of 304 Stainless Steel With Melting Gels Coatings, Mario Aparicio, Andrei Jitianu, Gabriela Rodriguez, Ahmad Dengah, Kutaiba Marzoki, Jadra Mosa, Lisa C. Klein

Publications and Research

Methyl-substituted melting gels were used to coat AISI 304 stainless steel substrates. Crack-free coatings up to 1 mm in thickness were obtained. SEM micrographs of cross-sections con fi rm good adhesion to the surface. Samples were subjected to structural characterization using FT-IR, and Raman spectroscopy. Mechanical properties were investigated by micro-scratch tests. Electrochemical analyses (anodic polarization and electrochemical impedance spectroscopy) were performed in 3.5% NaCl solutions. Electrochemical tests show excellent performance of the coatings against corrosion with no sign of degradation after several months of immersion.

Structural Patterns At All Scales In A Nonmetallic Chiral Au_133(Sr)_52 Nanoparticle, Chenjie Zeng, Yuxiang Chen, Kristin Kirschbaum, Kannatassen Appavoo, Matthew Y. Sfeir, Rongchao Jin

Publications and Research

Structural ordering is widely present in molecules and materials. However, the organization of molecules on the curved surface of nanoparticles is still the least understood owing to the major limitations of the current surface characterization tools. By the merits of x-ray crystallography, we reveal the structural ordering at all scales in a super robust 133–gold atom nanoparticle protected by 52 thiolate ligands, which is manifested in self-assembled hierarchical patterns starting from the metal core to the interfacial –S–Au–S– ladder-like helical “stripes” and further to the “swirls” of carbon tails. These complex surface patterns have not been observed in the smaller …

Supercharging: An Investigation Into The Effects Of External Amino Acid Residue Charge On The Solubility And Internal Electric Character Of Bound Ligands In A Heme-Binding De Novo-Designed Protein, Cooper French

Dissertations and Theses

De novo protein design offers many interesting prospects both as a means to better understand natural protein dynamics and as a potential resource in biomedical and industrial applications. In this work I describe the modification of a simple, well-characterized heme-binding protein by altering side chain residue identities on the hydrophilic surface of the protein to produce variants with a range of net external charges. These charge modifications had a significant impact on nearly every measurable character of the protein. This work establishes the hard limits of supercharging within our experimental protein scaffold system, demonstrating that excessive positive charge increased the …

Horizontally-Aligned Carbon Nanotubes Arrays And Their Interactions With Liquid Crystal Molecules: Physical Characteristics And Display Applications, Frederick Roussel, Jean-Francois Brun, Alexandre Allart, Limin Huang, Stephen O'Brien

Publications and Research

We report on the physical characteristics of horizonthally-grown Single-Walled Carbon Nanotubes (h-al-SWNT) arrays and their potential use as transparent and conducting alignment layer for liquid crystals display devices. Microscopy (SEM and AFM), spectroscopic (Raman) and electrical investigations demonstrate the strong anisotropy of h-al-SWNT arrays. Optical measurements show that h-al-SWNTs are efficient alignment layers for Liquid Crystal (LC) molecules allowing the fabrication of optical wave plates. Interactions between h-al-SWNT arrays and LC molecules are also investigated evidencing the weak azimuthal anchoring energy at the interface, which, in turn, leads to LC devices with a high pretilt angle. The electro-optical reponses of …