Chemistry Commons^™

Synthesis Of A Dd-Π-Aa Organic Dye For Dye-Sensitized Solar Cells, Hope Lovell

Honors Theses

This project investigates the synthesis of a DD-π-AA (dual donor/dual acceptor) organic dye as a potential sensitizer for dye-sensitized solar cells (DSCs). The design of this dye was based off previous research that found dual donor/dual acceptor dyes exhibited promising results when used in a DSC. The donor groups, acceptor groups, and π-bridge were chosen for their stability, ability to absorb in the near-infrared (NIR) region, and intramolecular charge transfer (ICT) abilities.

While many components of the dye were synthesized, the final stages of the synthetic scheme were not completed due to the loss of time from COVID-19. Had the …

Synthesis Of A Zinc Dipyrrin Complex For Photocatalytic Reduction Of Co2, Sylvia Meredith

Undergraduate Honors Theses

Zinc dipyrrin complexes have the potential to act as cheap, effective photosensitizers. Synthesizing and studying different types could lead to more efficient solar energy harvesting processes, especially the production of solar fuel. Here, two attempts to synthesize 1,3,7,9-tetraphenyl-5-mesityldipyrromethene are reported and discussed. According to ¹H NMR, the first synthesis attempt was not successful. The second synthesis attempt was not purified effectively, so ¹H NMR produced inconclusive results. Further purification strategies or alternate synthesis methods are required.

Visualization And Quantification Of The Laser-Induced Art Of Tio2 By Photoexcitation Of Adsorbed Dyes, Daniela (Labadini) Graf Stillfried Barreto

Graduate Masters Theses

Dye-pretreated anatase TiO2 films, commonly used as photoanodes in dye sensitized solar cells (DSSC), were utilized as a model system to investigate the laser-induced anatase to rutile phase transformation (ART), using N719 dye, N749 dye, D149 dye, and MC540 dye as photo-sensitizers. The visible lasers (532 and 785 nm) used for Raman spectroscopy were able to transform pure anatase into rutile at the laser spot when excitation of the dye sensitizer caused an electron injection from the excited state of the dye molecule into the conduction band of the TiO2. The three dyes with carboxylic acid anchor groups (N719, N749 …

Rare Earth Free Bright And Persistent White Light Emitting Zinc Gallo-Germanate Nanosheets: Technological Advancement To Fibers With Enhanced Quantum Efficiency, Bhupendra B. Srivastava, Santosh K. Gupta, Raul Barbosa, Alexa Villarreal, Karen Lozano, Yuanbing Mao

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

Recent materials science and engineering research focused on defects, dopants, hosts, and morphological structures has resulted in novel cost efficient and sustainable phases with extraordinary properties and performance. Contributing in this direction we have designed dopant and rare earth free white lightemitting zincgallogermanate (ZGG) phosphors in nanosheet (NS) morphology. These ZGG NSs with interlayer and interfacial defects display bright white photoluminescence (PL) with significant quantum yield (QY). Thermal treatment of the as-synthesized ZGG NSs at 750 1C does not degrade their sheet-like morphology while resulting in long persistent luminescence (PerL) with a duration of approximately one hour. Furthermore, to improve …

Photothermal Response Induced By Nanocage-Coated Artificial Extracellular Matrix Promotes Neural Stem Cell Differentiation, Seunghyun Jung, Nathaniel Harris, Isabelle I. Niyonshuti, Samir V. Jenkins, Abdallah M. Hayar, Fumiya Watanabe, Azemat Jamshidi-Parsian, Jingyi Chen, Michael J. Borrelli, Robert J. Griffin

Mechanical Engineering Faculty Publications and Presentations

Strategies to increase the proportion of neural stem cells that differentiate into neurons are vital for therapy of neurodegenerative disorders. In vitro, the extracellular matrix composition and topography have been found to be important factors in stem cell differentiation. We have developed a novel artificial extracellular matrix (aECM) formed by attaching gold nanocages (AuNCs) to glass coverslips. After culturing rat neural stem cells (rNSCs) on these gold nanocage-coated surfaces (AuNC-aECMs), we observed that 44.6% of rNSCs differentiated into neurons compared to only 27.9% for cells grown on laminin-coated glass coverslips. We applied laser irradiation to the AuNC-aECMs to introduce precise …

Synthesis Of Bulky And Polar Galactonoamidines For The Inhibition Of The Human Α-Galactosidase, Ifedi Orizu

Graduate Theses and Dissertations

Glycosidases are amongst the most abundant enzymes in nature. This is due to their role in the degradation of carbohydrates which are the major source of carbon or earth. The absence or malfunction of glycosidases is implicated in numerous diseases such as cancers, diabetes, and lysosomal storage disorders, which make them important drug targets for study in medicinal chemistry. The seminal work by Pauling and Wolfenden showed that enzymes bind to their substrate at the transition state with very strong affinity. Wolfenden estimated the dissociation constant to be around 10-22M. This encouraged the design of glycosidase inhibitors which mimicked one …

Developing Advanced Electrodes And Electrolytes For Energy Storage Beyond Li Ion Batteries, Kevin V. Nielson

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Electric vehicles, smart phones, and portable computers are all powered by lithium-ion batteries. This is because Li-ion batteries can store more energy in less space than other battery technologies. Also, they are rechargeable and last for a long time. The most recent 2019 Nobel prize in chemistry was awarded to John Goodenough, M. Stanley Whittingham and Akira Yoshino “for the development of lithium-ion batteries”. Through their work, they have made possible cars that do not burn fossil fuels and phones that are wireless and portable. Not only can Li-ion power your phone, it is an incredibly efficient way to store …

Whey Protein Powder Analysis By Kjeldahl And Mid-Infrared Spectroscopy, Rose Saxton

Boise State University Theses and Dissertations

There is an ever-expanding number of high protein dietary supplements marketed as beneficial to athletes, body builders, infant formulas, elder care, and animal feed. Consumers will pay more for products with high protein per serving data on their nutritional labels, making the accurate reporting of protein content critical to customer confidence. The Kjeldahl Method (KM) is the industry standard to quantitate dairy proteins, but the result is based on nitrogen content, which is an approximation of nitrogen attributable to protein in milk. Optical spectroscopy is commonly used for quality control measurements and has been identified as having the potential to …

Comparison Of Raman Spectra Of Smokeless Powders For Cartridge Differentiation, Nathan Bartlett

Chemistry

As crimes involving firearms continue to be prevalent, forensic methods processing firearms evidence must keep pace with the changes in said evidence. Scanning Electron Microscopy with Energy Dispersive Spectroscopy, or SEM-EDS, is a method that targets the inorganic portions of gunshot residue (GSR) evidence, namely lead, barium, and antimony, to characterize a cartridge used at a crime scene, and was the most often used analysis method for characterizing ammunition cartridges. The rise of lead-free ammunition has made it so that SEM-EDS alone is not sufficient for the characterization of inorganic gunshot residue (IGSR), and studies have shifted towards being able …

The Business Of Chemistry: The Effect Of Chemical Innovation On The U.S. Cosmetics Market, Tania Gonzalez

Chemistry

This study discusses the relationship between two distinct fields of study: chemistry and economics. Chemistry is a business in itself and has major effects on the US economy. Examining the U.S cosmetics market and the recent development of organic products will show the effect on market growth and the growing importance of organic cosmetics in the United States. The recent awareness and concern for eco-friendly and safer ingredients fueled by millennials is discussed. The average annual expenditure in the U.S. cosmetics market is examined and inflation is taken into account. The purpose is to show the importance of research in …

Remote Performance Modulation Of Ultrafiltration Membranes By Magnetically And Thermally Responsive Polymer Chains, Arijit Sengupta, Anh Vu, Xianghong Qian, Sumith R. Wickramasinghe

Chemical Engineering Faculty Publications and Presentations

Ultrafiltration membranes, that respond to an external magnetic field and local temperature have been developed. Surface-initiated activator-generated electron transfer (AGET) atom transfer radical polymerization (ATRP) has been used to graft poly(N-isopropylacrylamide) (PNIPAm) from the surface of 300 kDa regenerated cellulose membranes. The polymerization initiator was selectively attached to the entire membrane surface, only the outer membrane surface or only the inner pore surface. A superparamagnetic nanoparticle was attached to the end of the polymer chain. The DI water flux as well as the flux and rejection of bovine serum albumin were investigated in the absence and presence of a 20 …

Design And Synthesis Of Polymeric Metastable State Photoacid And Photo Co-Releasing Materials, Adnan Abdallah Muftah Elgattar

Theses and Dissertations

Metastable state photoacids (mPAHs) are molecules that possess a photoinduced metastable state with high acidity and good reversibility. The metastable state lasts long enough to produce a high proton concentration, which can drive various proton transfer processes. MPAHs have been intensively studied in recent years and applied to different chemical, material, biomedical areas. Covalently linking many mPAHs in a polymer allows the generation of a local proton concentration higher than that of the overall system. This dissertation described my PhD work on the synthesis of mPAH polymers using different radical and ring-opening polymerization methods. These polymers can repeatedly produce a …

The Aqueous Stability Of N-Acyl-L-Homoserine Lactones, Their Affinity For Cyclodextrin Inclusion, And The Investigation Of A Catalyst For Their Hydrolysis, Eric William Ziegler

Theses and Dissertations

Many bacteria demonstrate population-density dependent gene expression, a phenomenon known as quorum sensing, to regulate phenotypes that, if expressed by an individual bacterium, would be ineffective. While some of these phenotypes are innocuous (e.g., exhibiting bioluminescence), certain bacteria employ quorum sensing regulated phenotypes in their pathogenesis. Traditionally, infections by these pathogens have been treated with antibiotic therapies. However, with the emergence of multidrug resistant strains, alternative strategies are being considered for attenuation of quorum sensing regulated traits that do not apply selective pressures. Macrocycles — in particular the cyclodextrins — that are capable of forming inclusion complexes with Gram-negative quorum …

Crystal Structure Of Tris, Colin T. Hartgerink, Richard J. Staples, Carolyn E. Anderson

University Faculty Publications and Creative Works

The title ketenyl­idene, [Au3(C2O)(C26H35O2P)3](C2F6NO4S2), was obtained upon exposure of [2-(di­cyclo­hexyl­phosphino)-2′,6′-dimeth­oxy-1,1′-biphen­yl]gold(I) bis­(tri­fluoro­methane­sulfon­yl)imide to acetic anhydride at elevated temperature. The ketenyl­idene bridge caps the tri-gold cluster. The title compound has provided crystals that upon analysis represent the first tri-gold ketenyl­idene with atomic distances indicative of bonding inter­action between the gold atoms.

Electrochemical Oxidation Of Individual Silver Nanoparticles: Exploring The Effect Of Particle Shape, Capping Ligand, Electrolyte, And Potential On The Signal, Jazlynn Sikes

Graduate Theses and Dissertations

Nanomaterials have revolutionized science and technology. Their unique properties can be exploited, and nanoparticles are being used as catalysts, antimicrobials, drug delivery vehicles, sensors, and more. However, the fundamental properties of nanomaterials and their interactions with their surrounding environments are still poorly understood. In this work, a single-particle approach was used to observe the effects of capping ligand, surrounding solution, and particle shape on the oxidative process to gain deeper understanding of silver nanoparticle properties. When allowed the opportunity, the particles will adsorb to the electrode surface then oxidize in rapid succession upon electrode activation, regardless of capping ligand as …

Metastable State Photoacids And Ultrasound Responsive Carbon Monoxide Releasing Polymer Micelle, Osamah Zaid Saleh Alghazwat

Theses and Dissertations

This dissertation described my Ph.D. work on the development of a novel metastable state photoacids (mPAH), which can be activated by near infrared light and a reversible mPAH switched by different wavelengths of light. Also, it described the development of a micelle that responded to ultrasound to localized carbon monoxide CO delivery. An introduction of metastable state photoacid is given in Chapter 1. In Chapter 2, described my work on the development of a novel mPAH, which can be activated by near infrared light is an important factor for various biological functions. mPAH was designed and synthesized with a donor-acceptor-donor …

Stereochemical Control In Suzuki Cross Coupling Reactions Of Acyclic (Z)-Beta-Haloacroleins, William Carrick

Honors Theses

Beta-chloroenals are readily accessible substances and are efficient precursors for a variety of heterocyclic compounds. Suzuki type cross-coupling reactions of such compounds with arylboronic acids yield ��,��-diarylacroleins with control of stereochemistry. The oxidation of these enals to the corresponding acids and subsequent oxidative lactonization leads to formation of the respective coumarins. The chemistry involved in these transformations with special attention to stereochemistry of the Suzuki coupling reaction will be discussed. A full NMR analysis involving 1H, 13C, COSY, NOESY, HSQC, and HMBC was performed to unambiguously confirm the structure and show that the reaction proceeds with retention of stereochemistry.

Synthesis And Conductivity Analysis Of A Methyl (Polyethylene Glycol) Comb Polymer, Olivia Fox

Honors Theses

The overall goal of work in this field is to improve materials for use in a variety of applications in fuel cell and battery production. This thesis specifically investigates the synthesis of two variations of a methyl (polyethylene glycol) comb polymer electrolyte (MePEG_nwhere n=7) to understand how the molecular structure of an ion-conducting polymer affects its electrochemical properties. The MePEG used in this synthesis contains seven ethylene glycol groups and was added to a poly (methylhydrosiloxane) comb polymer backbone. In the first sample, the polymer contained only the MePEG sidechain, and in the second sample, the polymer contained …

Chemical Shift Assignments Of The N-Terminal Domain Of Psd95 (Psd95-Nt), Yonghong Zhang, Johannes W. Hell, James B. Ames

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

Postsynaptic density protein-95 (PSD95) contributes to the postsynaptic architecture of neuronal synapses and plays an important role in controlling synaptic plasticity. The N-terminal domain of PSD95 (residues 1–71, called PSD95-NT) interacts with target proteins (calmodulin, α-actinin-1 and CDKL5), which regulate the Ca2+-dependent degradation of glutamate receptors. We report complete backbone NMR chemical shift assignments of PSD95-NT (BMRB No. 50752).

Biomedical Applications And Syntheses Of Selected Anthraquinone Dyes, Richard Sirard

Senior Honors Theses

Anthraquinones are aromatic organic compounds that have multiple applications in the biomedical field. Some anthraquinone-based compounds are used as fluorophores to contrast cell nuclei while others act as chemotherapeutic agents. However, there are not many fluorescent anthraquinone cell stains currently available. In this study, commercially available anthraquinone dyes, in addition to other dye families and compounds, were reviewed for their unique properties, advantages, and drawbacks. The development and characterization of three novel anthraquinone fluorophores revealed promising photophysical characteristics, like large Stokes shifts. One of the compounds, RBS3, was chosen for fixed and live cell staining and exhibited desirable biomedical properties. …

Modeling The Problem Of Integral Geometry On A Family Of Hyperbolic And Spherical Curves, Azamat Pirimbetov, N. Uteuliev, G. Djaykov

Karakalpak Scientific Journal

The problems of integral geometry in a strip on a family of curves of hyperbolic and spherical type are considered which have numerous applications in problems of geophysics, thermoacoustic and photoacoustic tomography. Explicit formulas are obtained for the Fourier image of the solution of integral geometry problems in the class of smooth compactly supported functions. Further, the obtained formulas are investigated for stability using numerical methods. To solve the problems, algorithms are constructed. Numerical and graphical results of applying these algorithms to solving the problems are presented.

Water Splitting By Mixed Chalcogenide Catalysts, Isabella Feltenstein

Undergraduate Research Conference at Missouri S&T

The depleting supply of fossil fuels has led to deeper investigation of water-splitting as a sustainable energy source. Specifically, using transition metal chalcogenides to catalyze the water-splitting reaction through oxygen and hydrogen evolution reactions. While the decreasing electronegativity of the chalcogenide group increases their activity, it also decreases their stability, leading to the investigation of mixed anion chalcogenides in order to keep both the stability and activity high. This research will further the understanding and efficiency of water-splitting for energy storage and inspire more research in the future. In these experiments, cobalt telluroselenide (Cox-Tey-Sez) and nickel telluroselenide (Nix-Tey-Sez) catalysts were …

Thermal, Mechanical, And Rehealing Properties Of Cross-Linked Ionene Networks, Katelyn Lindenmeyer

Honors College Theses

Polymers which contain ionic liquid groups have numerous applications in a wide variety of fields. Past research from our group has shown that IL-containing polymers which exist in covalently crosslinked networks can exhibit good ionic conductivities despite the hindrance in polymer chain mobility and relaxation. In part one of this thesis, efforts to create ionic networks which have the capability of being rehealed after exposure to an external stimulus are discussed. Thermoreversible maleimide-furan chemistry was incorporated into an imidazolium-containing ionene network. Maleimide-terminated, imidazolium-containing monomers were coupled with furan-functionalized monomers, prepared from commercially available multifunctional acrylates. Thermal, mechanical and rheological characterization …

Effect Of Precise Control Of Crosslink Density On The Thermal, Mechanical, And Conductive Properties Of Covalently Crosslinked Ionene Networks, Alexander Thome

Honors College Theses

Ionic liquids (ILs), besides being well known as environmentally friendly solvents, have attracted attention for a wide variety of other applications, including gas separation, 3D-printing and electrochemical actuators. However, for many such applications, incorporation of the IL moiety into a polymeric material eliminates the use of mechanically unstable free ILs while maintaining many of their electrochemical benefits. Such polymers can take two basic forms: poly(ionic liquid)s are ion-containing polymers in which the IL group is attached pendant to the polymeric backbone, while ionenes are ion-containing polymers in which the IL group is anchored directly into the backbone of the repeating …

Application Of Atomically Precise Metal Nanoclusters In Electrocatalysis, Zhi-Hua Zhuang, Wei Chen

Journal of Electrochemistry

Metal nanoclusters (M NCs) consist of only several to a few hundred of metal atoms and possess core sizes less than 2 nm. Owing to the quantum size effect, the electronic states of M NCs evolve to discrete levels similar to the molecule energy gaps, other than a continuous density of states to produce plasmon characteristic of bulk metal nanoparticles (M NPs). In comparison with the conventional M NPs, M NCs exhibit dramatically unique electronic and optical properties, such as molecule-like energy gaps, strong photoluminescence and high catalytic properties, which make them promising for potential application in numerous fields, such …

Preface To The Special Issue Of The Journal Of Electrochemistry Celebrating 100 Years Of Chemistry At Xiamen University, Chang-Jian Lin, Shi-Gang Sun

Journal of Electrochemistry

No abstract provided.

Luminol/Sulfamic Acid Electrochemiluminescence And Its Application For Dopamine Detection, Tesfaye Hailemariam Barkae, Mohamed Ibrahim Halawa, Tadesse Haile Fereja, Shimeles Addisu Kitte, Xian-Gui Ma, Ye-Quan Chen, Guo-Bao Xu

Journal of Electrochemistry

Herein, sulfamic acid (SA) was utilized, for the first time, to enhance significantly the luminol electrochemiluminescence (ECL). With the SA concentration increased from 0.1 μmol·L^-1 to 500 μmol·L^-1 the ECL intensity increased proportionally. The developed luminol/SA ECL system was employed to detect dopamine (DA) based on its prominent quenching effect. The Stern-Volmer equation of I_o/I= 1+K_sv[DA] could be applied to express well the quenching mechanism of DA in the luminol/SA ECL system. The calibration plot showed that the increase in the DA concentration from 0.5 to 20 μmol·L^-1 decreased linearly the ECL intensity …

Electrochemiluminescence Imaging Hydrogen Evolution Reaction On Single Platinum Nanoparticles Using A Bipolar Nanoelectrode Array, Xiang Qin, Zhong-Qiu Li, Jian-Bin Pan, Jian Li, Kang Wang, Xing-Hua Xia

Journal of Electrochemistry

A high-density (5.7 × 10⁸ cm^-2) nanoelectrode array with the electrode diameter of 200 nm and the interelectrode distance of 450 nm were fabricated. The nanoelectrode array consisted of gold nanowires embedded in a porous anodic aluminum oxide (AAO) matrix, having regular nanoelectrode distribution and highly uniform nanoelectrode size. The gold nanoelectrode array was used as a closed bipolar nanoelectrode array combined with electrochemiluminescence (ECL) method to map the electrocatalytic activity of platinum nanoparticles toward hydrogen evolution reaction (HER) by modifying the catalysts on single nanoelectrodes. Results show that HER on single bipolar nanoelectrodes could be imaged …

Oxygen-Exposure Induced Rapid Oxidation Of Spiro-Ometad In Cspbibr2 Perovskite Solar Cells, Wei-Guo Wang, Tian Bai, Gao-Fei Xue, Mei-Dan Ye

Journal of Electrochemistry

2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenyl-amine)-9,9′-spirobifluorene (Spiro-OMeTAD) is the most widely used hole transport material in perovskite solar cells (PSCs). However, its oxidation in the air takes a long time and results in the attack of perovskite by water. In this regard, we performed the oxidation process of Spiro-OMeTAD in oxygen, where perovskite can be protected from water, guaranteeing the integrity of perovskite. It was demonstrated that the champion Spiro-OMeTAD based CsPbIBr₂ PSCs after oxygen oxidation achieved a 7.19% power conversion efficiency (PCE), showing a higher PCE than 6.29% of the champion device oxidized in air. A series of electrochemical characterization methods were applied …

Theoretical Studies Of Metal-N-C For Oxygen Reduction And Hydrogen Evolution Reactions In Acid And Alkaline Solutions, Xue-Ping Qin, Shang-Qian Zhu, Lu-Lu Zhang, Shu-Hui Sun, Min-Hua Shao

Journal of Electrochemistry

Single atom catalysts (SAC) have been regarded as the promising alternatives to platinum group metals due to their low costs and potentially high catalytic activities in various electrocatalytic reactions. The atomic mechanism understanding of activity discrepancy among different metal and nitrogen co-doped carbon-based catalysts is still lacking. Here, non-precious metal and nitrogen co-doped carbons (Me-N-C, Me = Fe and Co) as the model catalysts are investigated by combining experimental and theoretical studies to explore the catalytic activities and corresponding reaction mechanisms toward oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) at universal pHs. Atomic theoretical simulations suggest that Fe-N-C …