Chemistry Commons^™

Stabilized, Hybrid Solid-State Photocatalysts For Water Purification: Preparation, Properties And Performance Under Visible Light Irradiation, Karpagavalli Ramji

Seton Hall University Dissertations and Theses (ETDs)

Stabilized heterogeneous photocatalysts that use only solar light and air have been prepared and successfully employed to decontaminate water from organic pollutants. Organic dye pollutants present, for example in textile effluents, are one of the major sources of water pollution owing to their limited biodegradability, toxicity and potential carcinogenic risks. Before certifying water for public consumption, reuse in industries or for discharge in surface water the organic pollutants must be degraded, an effort that is energy intensive and currently requires complex methodologies. We report solid-state photocatalysts that use only visible light and air to treat wastewater. Perfluoroalkyl perfluoro-substituted zinc phthalocyanine …

Combination Therapy: Parp Inhibitor Synergizes The Therapeutic Efficacy Of Doxorubicin In The Treatment Of Prostate Cancer, Momin Ansare

Electronic Theses & Dissertations

Men are most susceptible to prostate cancer in the United States. The general treatment options include surgery, hormone therapy, chemotherapy, and radiation therapy. But in recent days, the nanoformulation have shown promising applications in overcoming the drawbacks of the currently available treatment options. To complement, we tried to enhance the capability of the nanoparticle formulation by loading them with a novel drug combination for the treatment of prostate cancer. Herein, we synthesized folate conjugated iron oxide nanoparticles encapsulated with doxorubicin and olaparib for imaging and targeted treatment of prostate cancer. Both drugs are approved by FDA for clinical cancer treatment. …

Electropolymerization Of Polyaniline In The Presence Of Ferricyanide: Electrochemical, Spectroscopic And Gravimetric Studies, Lucas Marinelli

Master's Theses

In this work, ferricyanide-doped polyaniline (PANI) is electropolymerized by constant current and cyclic voltammetry (CV) measurements with simultaneous monitoring of mass changes using electrochemical quartz crystal microbalance (eQCM). Raman spectroscopy, Fourier transform infrared spectroscopy and CV measurements confirm the incorporation of the ferricyanide into the film and indicate modified electrical conductivity. UV-Vis absorbance spectroscopy and Raman spectroscopy confirm the conducting ‘emeraldine-salt’ state and confirm the presence of polarons, i.e. charge carriers.

The addition of ferricyanide during electropolymerization of the PANI film results in an increase of polymerization rate as confirmed using eQCM. A decrease in counter ion ingress/egress and an …

Synthesis Of Doxorubicin-Based Prodrug And Activatable Mr Nanoprobe For The Imaging And Treatment Of Cancer, Bayan Dous

Electronic Theses & Dissertations

Magnetic Resonance Imaging (MRI) is increasingly being used as a diagnostic tool for cancer. We propose a novel molecular probe, Gadolinium-DTPA disulfide-bonded Doxorubicin (Gd-DTPA-SS-Doxo) encapsulated in iron oxide which could provide a dual modality for detecting malignant growth while simultaneously targeting treatment options. We first synthesized Gd-DTPA-SS-Doxo followed by encapsulation within the poly (acrylic acid) (PAA) coating of iron oxide nanoparticle (IONP), producing a nanoprobe (IO-Gd-DTPA-SS-Doxo) with quenched longitudinal spin lattice magnetic relaxation (T1). After receptor-mediated internalization, Gd-DTPA-SS-Doxo is released from the nanoprobe’s polymeric coating due to the acidic microenvironment of the tumor. When the molecular probe is subjected to …

Synthesis And Integration Of Oligoviologens Into Hydrogel Actuators, Kevin Liles

Arts & Sciences Electronic Theses and Dissertations

Interest in the development of soft-material artificial molecular muscles has inspired scientists to pursue novel stimuli-responsive systems capable of undergoing change in the physical and mechanical properties of a material in response to external stimuli. This interest has been driven primarily by advances, or the desire for advances, in fields such as soft robotics, microfluidics, and bio-compatible drug-delivery systems. In this work, redox-responsive viologens and their ability to form stable radical-cation complexes were evaluated as a method of actuation in stimuli-responsive materials, specifically hydrogels.

First, a brief overview of hydrogel actuators is covered, with some examples given of the broad …

A New Generation Of Functional Polyisobutylenes For Advanced Applications, Corey M. Parada

Dissertations

Polyisobutylene (PIB) is a fully saturated, aliphatic polymer of high commercial importance due to its superior gas barrier properties and high chemical/oxidative stability. One commercial end-use for PIB is in insulated glass windows (IGU), where it acts as a gas/moisture barrier and sealant. Under certain adverse conditions, catastrophic failure of the PIB sealant may result in aesthetic and functional failure of the IGU, which necessitates replacement of the unit. Thus, there exists a need to improve current generations of thermoplastic PIB sealants to be able to withstand the harsh environments found in current real-world applications.

In the first project, we …

Polyhedral Oligomeric Silsesquioxane-Phosphate Glass Matrix Nanocomposites With Additional Chapter On Phosphate Glass-Poly(Ethylene Terephthalate) Matrix Composites, Kyoungtae Kim

Dissertations

Preparation and characterization of tin fluorophosphate glass (Pglass) matrix nanocomposites incorporating polyhedral oligomeric silsesquioxane (POSS) were investigated on the structural, thermal, morphological, mechanical, and rheological properties. Various processes including synthesis, extrusion and sintering processes were applied to prepare the nanocomposite samples. Another application of POSS with hydrophobic functional groups on the well-structured nanoscale silicate cage with three silanol groups was investigated to present the feasibility to use POSS molecule as a coating material on the surface of the hydrophilic inorganic glass. In addition, Poly(ethylene terephthalate) polymer matrix composites incorporating Pglass was studied to present the benefits of the Pglass with …

Effect Of Network Structure On Free Volume And Gas Transport Properties Of Thiol-Ene And Epoxy-Amine Networks, Ramesh Krishnan Ramakrishnan

Dissertations

Network parameters such as cross-link density or intermolecular interactions were used as effective parameters to control polymer chain packing or free volume and thereby control the mass transport properties of networks.

A series of polyethylene glycol (PEG) based thiol-ene elastomeric networks having a broad range of molecular weight between cross-links, M_c, (inverse of cross-link density) was prepared. The specific volume of the networks was studied as a function of temperature and pressure using high pressure dilatometry, and the obtained PVT data was fit using Simha-Somcynsky equation of state (S-S eos) analysis. Fractional free volume, quantified through S-S eos …

Structure-Property Relationships Of Solvent-Cast Organic Thin Films For Model Corrosion Control Coatings, Austin Maples

Dissertations

This dissertation aimed at answering several fundamental questions, specifically: 1) What is the effect of scribing parameters on visual corrosion assessments? 2) What role do molecular weight, residual solvent, and polymer composition have on morphological changes in organic thin films? 3) What alternatives to visual assessments could be implemented to better understand and detect corrosion before macroscopic failure? This research definitively proved that scribes can vary in type and dimensions, and yet are still comparable if the scribe dimensions before exposure are known. Furthermore, it demonstrated that solvents common to a variety of coating industries could become trapped within the …

Influence Of High Aspect Ratio Nanoparticle Filler Addition On Piezoelectric Nanocomposites, Jeremy A. Armas

Master's Theses

Piezoelectric nanogenerators (PNGs) are a new class of energy harvesting materials that show potential as a direct energy source for low powered electronics. Recently, piezoelectric polymers have been utilized for PNG technology due to low toxicity, high flexibility, and facile solution processing which provide manufacturing opportunities such as screen printing. Throughout the last decade, countless projects have focused on how to enhance the energy harvesting capabilities of these PNGs through the incorporation of nanoparticle fillers, which have been reported to enhance the piezoelectric properties of the film either directly through their intrinsic piezoelectric properties or through acting as surfaces for …

High-Throughput Assessment Of A Novel, Thiol-Acrylate Hydrogel For Tumor Spheroid Synthesis In A Microfluidic Device, Nathan Daniel Kersker

LSU Master's Theses

The extracellular environment plays an important role in regulating cell behavior. The mechanical, structural, and compositional properties of the extracellular matrix can determine the fate of the growing cells. Standard two-dimensional culturing in a flask fails to represent a native cellular environment. To create the native environment suitable for cells, hydrogels were previously studied. One of the most extensively studied synthetic hydrogels was a poly(ethylene glycol diacrylate) (PEGDA) hydrogel. However, the need for UV polymerization may introduce unwanted changes in cell morphology and viability. The hydrogel being proposed was a form of a thiol-acrylate hydrogel that can eliminate this problem …

Film Stabilizaiton And Photophysics Of Unconventional Conjugated Polymers, Kara Martin

Doctoral Dissertations

Conjugated polymers offer a unique opportunity to develop high performing, flexible, lightweight, and large area electronic devices. With advances in conjugated polymer understanding and synthesis, the use of polymers as active layer materials in electronic applications, rather than just substrate materials, has become more promising. However, defects in morphological stability, as well as imperfect electronic understanding, are still present, limiting the use of these materials in commercializable electronics. Fundamental understanding of structure-property relationships can allow for facile synthetic solutions to major drawbacks of conjugated polymer integration in standard device architectures. Chapter 1 presents background research on the history of conjugated …

Investigating The Role Of Topological Frustration On Morphology Of Novel Multiblock Copolymers, Rohit Gupta

Doctoral Dissertations

Multiblock copolymers have gained considerable attention due to their ability to offer immense potential for designing soft materials with complex architectures for diverse applications. The enlarged parameter space offered by these multiblock copolymers gives access to a wide variety of multiply continuous morphologies which can be used to produce highly ordered nanostructures. The investigation on multiblock copolymers has been subjected to two critical limitations: (i) A suitable synthetic strategy for accessing these structures and (ii) computational tools which can help in application driven design of these molecules. In this dissertation, the goal was to develop methodologies for the synthesis of …

Impact Of Chemical Doping On The Thermoelectric Charge Transport Of Organic Semiconductors, Connor J. Boyle

Doctoral Dissertations

The thermoelectric properties of organic semiconductors allow them to directly convert heat into electricity without the use of moving parts and to directly convert electricity into heat without the use of working fluids. These properties offer opportunities for the generation of electricity from non-conventional or renewable sources of heat and for refrigeration without the risk of leaking harmful working fluids at any length scale down to the nanoscale. Since organic materials are lightweight, flexible, and made from abundant resources, these opportunities could one day become affordable for widespread use and could be expanded to include specialized and otherwise difficult to …

The Balance Between Dipole-Dipole Interactions And Steric Exclusion On Ordering In Cationic Polymers, Chinomso Nwosu

Doctoral Dissertations

Structure-property correlations in charged polymers is an interesting facet of polymer science. Understanding the effects of intermolecular forces on the morphologies of polymers can lead to the design of membranes with desired structures to improve properties, for example ion conductivity. In random, comb-shaped polycations, competing intermolecular forces result in two different short-range orderings. Side-chain steric repulsion results in backbone-backbone morphology characterized by periodic spacing between polymer backbones. However, dipole - dipole attraction in these polycations can facilitate the formation of ionomer cluster morphology characterized by a spacing between clustered dipoles. Although both of these short-range orderings have disparate origins, their …

Surface Functionalization Of Fabrics And Threads For Smart Textiles, Morgan Baima

Doctoral Dissertations

The future of electronics is moving toward wearable devices and therefore requires a shift away from hard, inflexible materials towards fibers, threads, and fabrics that conform to the shape of the body. Therefore new methods for incorporating textiles as electronic components are needed to replace conventional processing techniques used with smooth, flat substrates like glass, silicon, and many polymers. Toward this end, this work investigates different methods that can be used to tune textile surfaces for electronic functionality, including weaving, solution grafting, and initiated chemical vapor deposition (iCVD). While all of these methods were used to make triboelectrically-active textiles, iCVD …

Unexpected Effects Of Inorganic Phosphate Glass On Crystallization And Thermo-Rheological Behavior Of Polyethylene Terephthalate, Kyoungtae Kim, Shahab Kashani Rahimi, Todd M. Alam, Eric G. Sorte, Joshua U. Otaigbe

Faculty Publications

The effects of ultra-low glass transition temperature (T_g) phosphate glass (Pglass) on the thermal, morphological, rheological, mechanical, and crystallization properties of hybrid Pglass/poly(eththylene terephthalate)(PET) were investigated. Nano- and micro-scale distribution of the Pglass in the PET polymer matrix was observed. The polydispersed Pglass in the PET matrix functioned as a nucleation agent, resulting in increasing crystallization temperature. The Pglass in the PET matrix decreased the T_g, indicating a plasticizing effect of the Pglass in the hybrids that was confirmed by the significantly decreased complex viscosity of the PET matrix. In addition, with increasing temperature, a non-terminal …

Isolation Of Rna From A Mixture And Its Detection By Utilizing A Microgel-Based Optical Device, Molla R. Islam, Shakiba Azimi, Faranak Teimoory, Glen Loppnow, Michael J. Serpe

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

In this investigation, we show that RNA can be separated from a solution containing DNA and RNA and the isolated RNA can be detected using poly (N-isopropylacrylamide-co-N-(3-aminopropyl) methacrylamide hydrochloride) microgel-based optical devices (etalons). The isolation of RNA was accomplished by using hairpin-functionalized magnetic beads (MMPDNA) and differential melting, based on the fact that the DNA–RNA hybrid duplex is stronger (i.e., high melting temperature) than the DNA–DNA duplex (i.e., low melting temperature). By performing concurrent etalon sensing and fluorescent studies, we found that the MMPDNA combined with differential melting was capable of selectively separating RNA from DNA. This selective separation and …

Iron Oxide Nanomagnets In Polymer Matrices – Synthesis And Characterization, Shenjie Qiu

Dissertations, Theses, and Capstone Projects

Magneto-responsive polymer-iron oxide materials have been fabricated by coating various polymers on iron oxide nanoparticles (NPs). The stability of magneto-responsive polymer-iron oxide materials relies on the selection of appropriate coating anchors, such as catechols and silanes. This dissertation describes two robust polymer coating systems on iron oxide NPs. One system focuses on thermo-responsive nitrated catechol-N-isopropylacrylamide polymers with binding enhancement factors (EnF) of ~40 and ~20 towards iron oxide NPs and a boronic acid compared to the polymers without the nitro group. The second system involves coating of poly(vinyl alcohol) (PVA) on iron oxide NPs via a silane anchor …

Flexible And Versatile Soft Templates For Mesoporous Silicas And Organosilicas Based On Pluronic Block Copolymer Surfactants And Their Mixtures, George Farid

Dissertations, Theses, and Capstone Projects

In this dissertation, the work will be discussed that was focused on the synthesis of consolidated periodic mesoporous materials such as 2-D hexgonal ordered mesoporous silicas (SBA-15) as well as single-micelle-templated silica and organosilica nanotubes and nanospheres using triblock copolymer surfactants and their mixtures in the presence of a swelling agent. The introductory section, Chapter 1, will address the current state of the tunability of single-micelle-templated silica and organosilica nanotubes and will compare it with the work presented in this dissertation on the use of a dual-surfactant templating systems. Chapter 2 of the dissertation discusses transmission electron microscopy characterization of …

Sintering-Induced Nucleation And Growth Of Noble Metal Nanoparticles For Plasmonic Resonance Ceramic Color, Nathan Dinh, Michael C. Leopold, Ryan Coppage

Chemistry Faculty Publications

This study demonstrates the formation of nanoparticles (NPs) from metal salts within ceramic glazes, such that the use of this colorant technology is more accessible to artisans, employs less metal content, is less environmentally harmful, and allows for the use of traditional kilns. Gold NPs have been demonstrated to possess a specific, low material loading use as a ceramic glaze colorant via plasmon resonance. Pre-synthesized gold NPs that are added to ceramic glazes have been found to significantly change in size after firing in both reductive and oxidative atmospheres, but still maintain some size relationships and color properties. Unfortunately, it …

Plant Stimuli-Responsive Biodegradable Polymers For The Use In Timed Release Fertilizer Coatings, Spencer Heuchan

Electronic Thesis and Dissertation Repository

The use of nitrogen-based fertilizers continues to accelerate with human population growth and increases in global food requirements. Enhanced efficiency fertilizers (EEFs) have been developed to improve the synchronization between nutrient supply and crop nutrient demand. However, many of the current controlled release fertilizers are coated with non-degradable polymers that contribute to accumulation of microplastics within ecosystems. This thesis describes research towards the development of a new class of fertilizer coatings using a self-immolative polymer known as poly (ethyl glyoxylate) (PEtG). PEtG itself does not have suitable properties to produce a viable coating but once blended with another degradable polyester …

Biomass Based Monomers For Synthesis Of Renewably Sourced Polymers, Anushka E. Vithanage

Electronic Theses and Dissertations

Limited fossil resources have raised research focus on synthesizing novel, sustainable polymers and renewably sourcing existing petroleum based polymers. This work presents the synthesis and ring opening polymerization (ROP) of a new functionalized lactone monomer, methoxy-δ-hexalactone (MDHL), to yield a functionalized polyester (polyMDHL). MDHL can be renewably sourced from hydroxymethylfurfural, a renewable platform chemical. MDHL was synthesized from methyl cyclopentanone-2-carboxylate by a five-step synthesis with a global yield of 23%. ROP of MDHL was conducted with benzyl alcohol initiator, catalyzed by diphenyl phosphate. 1H Nuclear Magnetic Resonance spectroscopy verified polyMDHL chemical structure. Targeting higher molecular weights for polyMDHL by increasing …

Chemically Cross-Linked Polysaccharide-Based Hydrogels Via Thiol-Norbornene Reaction As Sustainable Biomaterials, Nayereh Dadoo

Electronic Theses and Dissertations

Hydrogels are 3D polymeric networks with high water content and are widely being investigated for biomedical applications such as tissue engineering. Polysaccharides have been used to fabricate hydrogels due to their natural abundance, biocompatibility, and immunogeniety. Additionally, polysaccharide-based hydrogels can provide mechanical and biological cues similar to those of the natural environments. In this work, thiol-norbornene chemistry was used to fabricate polysaccharide-based hydrogels including hyaluronic acid (HA), carboxymethyl cellulose (CMC), and cellulose nanofibrils (CNFs). Hydrogels with tunable physical and mechanical properties were achieved. The properties of these hydrogels were spatiotemporally modified by photopatterning. Also, high stem cell viability was achieved …

Thienoisatin Oligomers As N-Type Molecular Semiconductors, Natalie M. Kadlubowski, Xuyi Luo, Jianguo Mei

The Summer Undergraduate Research Fellowship (SURF) Symposium

Organic field effect transistors (OFETs) offer many advantages compared to traditional inorganic transistors, such as flexibility and solution processability. In this study we design and synthesize two thienoisatin-based organic semiconducting small molecules, then investigate their electronic properties in n-type OFETs. To introduce n-type charge transport, electron-withdrawing dicarbonitrile moieties were installed on thienoisoindigo and bis-thienoisatin molecules, which led to a quinoidal conjugation on thienoisoindigo, while maintaining an aromatic conjugation on the bis-thienoisatin. Following the syntheses, the molecules were characterized to determine highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels via cyclic voltammetry, as well as any potential …

Applications Of Diels-Alder Chemistry In Polymer Synthesis, Joshua C. Stambaugh, Philip J. Costanzo, Sierra E. Gosting

STAR Program Research Presentations

Diels-Alder chemistry is utilized for a myriad of commercial applications during polymer synthesis, ranging from self-healing materials to heat responsive materials to emulsion coatings. In particular, the ability to regulate and control the amount and type of functional group linkages is key component for polymer applications. A common strategy that is employed is the use of phenolic maleimide as a dienophile during Diels-Alder synthesis to control the linkages on a polymer, which determines its properties and functionality. This summer was the beginning of a project to prepare a commercial scale, water-based emulsion floor coating/polish. The first step in this project …

Synthesis And Characterization Of Block Copolymers For Shear Force Responsive Materials And Sugar Conjugated Fluorescent Probes, Jacob Ryan Blankenship

MSU Graduate Theses

Herein, I present my work towards two goals: shear force-responsive materials and sugarconjugated fluorescent probes for bacterial identification applications. The first work is on the development of stimuli-responsive polymers that allow for precise control over the release of encapsulated material. Stimuli-responsive polymers are becoming increasingly important in drug delivery and other applications. However there have been few reports on shear force-responsive micellar systems. I show the synthesis, and characterization by ¹H and ¹³C NMR of four macro-chain transfer agents (macro-CTAs), one of which has not been previously reported. The resulting macro-CTAs were used in polymerization of vinyl acetate …

New Insights Into The Design Of Conjugated Polymers For Intramolecular Singlet Fission, Jiahua Hu, Ke Xu, Lei Shen, Qin Wu, Guiying He, Jie-Yu Wang, Jian Pei, Jianlong Xia, Matthew Y. Sfeir

Publications and Research

Singlet fission (SF), a multiple exciton generation process that generates two triplet excitons after the absorption of one photon, can potentially enable more efficient solar cell designs by harvesting energy normally lost as heat. While low-bandgap conjugated polymers are highly promising candidates for efficient SF-based solar cells, few polymer materials capable of SF have been reported because the SF process in polymer chains is poorly understood. Using transient spectroscopy, we demonstrate a new, highly efficient (triplet yield of 160-200%) isoindigo-based donor–acceptor polymer and show that the triplet pairs are directly emissive and exhibit a time-dependent energy evolution. Importantly, aggregation in …

Effects Of High Pressure On Photochemical Reactivity Of Organic Molecular Materials Probed By Vibrational Spectroscopy, Jiwen Guan

Electronic Thesis and Dissertation Repository

Chemical transformations of molecular materials induced by high pressure and light radiation exhibit novel and intriguing aspects that have attracted much attention in recent years. Particularly, under the two stimuli, entire transformations of molecular species can be realized in condensed phases without employing additional chemical constraints, e.g., the need of solvents, catalysts or radical initiators. This new synthetic approach in chemistry therefore satisfies increasing need for production methods with reduced environmental impacts. Motivated by these promises, my Ph. D thesis focuses on this state-of-the-art branch of high-pressure photochemistry. Specifically, high pressure is employed to create the necessary reaction conditions to …

Polymeric Peptide Mimics For Protein Delivery, Coralie Backlund

Doctoral Dissertations

The plasma membrane is a major obstacle in the development and use of biomacromolecules for intracellular applications. Consequently, proteins with intracellular targets represent an enormous, yet under studied avenue for therapeutics. Extended research has aimed at facilitating intracellular delivery of exogenous proteins using protein transduction domains (PTDs), which allow transport of bioactive molecules into cells. Synthetic polymers, inspired by PTDs, provide a well-controlled platform to vary molecular architecture for structure activity relationship studies. Specifically, this thesis focuses on the use of ring-opening metathesis, a facile and efficient polymerization technique, through which we can vary structural parameters to optimize delivery of …