Analytical Chemistry Commons^™

Application Of Group I Metal Adduction To The Separation Of Steroids By Traveling Wave Ion Mobility Spectrometry, Alana L. Rister, Tiana L. Martin, Eric D. Dodds

Department of Chemistry: Faculty Publications

Steroids represent an interesting class of small biomolecules due to their use as biomarkers and their status as scheduled drugs. Although the analysis of steroids is complicated by the potential for many isomers, ion mobility spectrometry (IMS) has previously shown promise for the rapid separation of steroid isomers. This work is aimed at the further development of IMS separation for the analysis of steroids. Here, traveling wave ion mobility spectrometry (TWIMS) was applied to the study of group I metal adducted steroids and their corresponding multimers for five sets of isomers. Each set of isomers had a minimum of one …

Magnetic Assembly Of Soft Robots With Hard Components, Sen Wai Kwok, Stephen A. Morin, Bobak Mosadegh, Ju-Hee So, Robert F. Shepherd, George M. Whitesides

Department of Chemistry: Faculty Publications

Reconfigurable soft robotic actuators with hard components are described. Magnetic attraction is used to couple flexible molded bodies capable of actuation upon pressurization with other flexible molded bodies and/or with hard components (e.g., frames and connectors) to form a seal for fluidic communication and cooperative actuation. Pneumatic decoupling chambers built into the hard components to decouple the hard components from the magnetically-coupled soft molded bodies are described. The use of magnetic self- alignment coupling and pneumatic de-coupling allows for the remote assembly and disassembly of complex structures involving hard and soft components. The magnetic coupling allows for rapid, reversible reconfiguration …

Flexible Thin Robotic Actuators, Aaron D. Mazzeo, Stephen A. Morin, Robert F. Shepherd, George M. Whitesides, William B. Kalb

Department of Chemistry: Faculty Publications

Some embodiments of the disclosed subject matter includes a laminated robotic actuator. The laminated robotic actuator includes a strain-limiting layer comprising a flexible, non extensible material in the form of a sheet or thin film, a flexible inflatable layer in the form of a thin film or sheet in facing relationship with the strain-limiting layer, wherein the inflatable layer is selectively adhered to the strain-limiting layer, and wherein a portion of an un-adhered region between the strain-limiting layer and the inflatable layer defines a pressurizable channel, and at least one fluid inlet in fluid communication with the pressurizable channel. The …

Mechanistic Studies Of Proton-Coupled Electron Transfer Reactions Involving Antioxidants, Kejie Meng

Theses and Dissertations

The objective of the research was to investigate proton-coupled electron transfer (PCET) reactions involving antioxidants to gain insight into the detailed mechanisms of glutathione (GSH), Trolox, and α-tocopherol (α-TOH). PCET reactions are complex redox reactions that transfer electrons and protons sequentially or in concert. These reactions are ubiquitous in natural or artificial processes that produce electrochemical energy that is extractable as electricity or as chemical fuels of high energy content. Examples of processes based on PCET are photosynthesis, respiration, nitrogen fixation, carbon dioxide reduction, redox fuel cells, and artificial photosynthesis. Antioxidants were selected as a PCET model to understand the …

Synthesis And Kinetic Activity Analysis Of Substituted Pyrazole, Pyrazoline, And Pyrazolidine Alcohol Dehydrogenase Inhibitors, Meagan E. Hackey

Chemistry Theses

Alcohol dehydrogenase inhibitors may be employed for the treatment of parasitic infection in humans. A series of substituted pyrazoline derivatives were synthesized to elucidate the pharmacophore for the inhibition of ADH. Targeted structure modification was used to alter the electronic and steric interactions associated with the enzyme active site. This study identified several effective N-aryl-carboxamide derivatives with horse liver ADH inhibition, comparable to that of 4-methylpyrazole, a known ADH inhibitor. The identification of pharmacophoric regions will allow for the methodological modification of these compounds to improve enzyme affinity and targeted inhibition. Future research may include additional solubility, toxicity and …

Integrating Microscale Enzyme And Lectin Reactions Using Nanogel Assisted Capillary Electrophoresis, Srikanth Gattu

Graduate Theses, Dissertations, and Problem Reports (ETD)

Protein glycosylation is one of the most prevalent post-translational modifications which plays an important role in determining the structure, stability, and function of proteins. Changes in glycosylation patterns are a hallmark of cancer and other diseases. Characterizing glycosylation is difficult because these structures vary in their linkage and monomer sequence, which gives rise to vast microheterogenity that could affect the function of the molecule. A novel method using capillary gel electrophoresis by integrating microscale enzymes and lectin reactions in the capillary was developed to verify glycan structure by analyzing monosaccharides. Capillary electrophoresis (CE) improves upon conventional methods of glycan structure …

Development And Characterization Of A Paper Based Analytical Device For Heparin Quantification, Carolanne Norris

Undergraduate Honors Thesis Projects

Paper-based analytical devices (PAD) have gained popularity in the past ten to fifteen years due to many favorable mechanical properties.1 They have largely been used to analyze small ionic species, such as Na+ and Li+, but little research has been done on their capability of to analyze large polyionic species, for instance the highly sulfonated polysaccharide heparin.2,3 This study explores adaptation of a traditional optode design to a low cost PAD that employs a smartphone as a detector. Throughout the study variables, such as membrane composition, pH, volume of solution, time, addition of a polymer, use of different cell phone …

Characterization Of Fragrant Chemical Components Of Essential Oils Of Lavender, Violet, And Bergamot By Gas Chromatography-Mass Spectrometry, Akeem Babalola Opakunle

Chemistry Theses

The characterization of fragrant chemical composition of commercial samples of lavender, violet and bergamot essential oil were analyzed using gas chromatography-mass spectrometry (GC-MS) techniques. The analysis led to the characterization of a total of 28 compounds for lavender oil, 17 compounds for violet oil, and 11 compounds for bergamot oil. The commercial sample of lavender essential oil has shown to be abundant in linalool, (21.40%), linalyl acetate (18.96%), trans-β- ocimene (7.41%), endo-borneol (6.53%), β-ocimene (6.43%), geranyl acetate (6.15%), β-myrcene (5.88%), terpinen-4-ol (5.70%) and cis-β-farnesene (4.40%). For commercial sample of violet essential oil, the major components in abundant were α-longipinene (37.35%), …

Determination Of The Oxidative Capacity Of Soot Toward Gsh And Characterization Of Soot Physicochemical Properties, Kaylee Troth

All Master's Theses

Fine atmospheric particulate matter (PM_2.5) emitted during the combustion of fossil and biomass fuels is known to adversely affect human health. While the underlying mechanisms are thought to be driven by the generation of reactive oxygen species (ROS), specific particle characteristics responsible for this detrimental effect are not well understood. In this research, the quantitative determination of the biologically relevant antioxidant, glutathione (GSH), was optimized for use as an indicator of oxidative stress to shed light on relevant particle characteristics. This was accomplished via fluorescent spectroscopy for GSH determination by way of reaction with o-phthalaldehyde (OPA), a …

Stability Of Bimetallic Clusters In Protein Model Systems, Sean Hartnett

Master’s Theses

Heterobimetallic cofactors are commonly found in proteins and allow them to perform unique chemical processes that would otherwise not be possible. The interactions between these metals allow the protein to accomplish difficult chemical transformations. Previously, the thermodynamic stability of a Fe^II /Mn^II cluster in the dinucleating ligand F-HXTA (5-fluoro-2-hydroxy-1,3-xylene-α,α′-diamine-N,N,N′,N′-tetraacetic acid) has been investigated in our lab as a model of cluster assembly in the proteins ribonucleotide reductase (RNR) and R2-like ligand binding oxidases (R2lox). By measuring equilibrium concentrations of F-HXTA complexes via ¹⁹F-NMR, it was found that the equilibrium for metal exchange between the homobimetallic …

Integrated Immunoassays On Paper/Polymer Hybrid Microfluidic Devices For Low-Cost Detection Of Disease Biomarkers, Sanjay Sharma Timilsina

Open Access Theses & Dissertations

Infectious diseases and cancers have been the major cause of global death and disability causing a significant impact on global health and economies. Enzyme-linked immunosorbent assay (ELISA) is one of the most widely used laboratory diagnostic methods for infectious diseases and cancer. ELISA detects proteins based on their binding to immobilized antibodies or antigen. Even though most ELISAs performed today in 96-well plates are well suited for high throughput assays, performing ELISA in low-resource settings is limited by several factors, such as long incubation time, large volumes of precious reagents, and well-equipped laboratories. Herein, we have developed multiple simple, miniaturized …

Interfacial Corrosion Of Copper And The Formation Of Copper Hydroxychloride, Mary Teague, Shengxi Li, Hongbo Cong

Williams Honors College, Honors Research Projects

Electrical circuitry is an industry, among many others, heavily using the element of copper. Ensuring the mechanical integrity of Cu is crucial, especially in salt environments, for the multifaceted composition of circuits. 4N NaCl solution (equilibrium concentration in ~84% RH) simulated this three-phase system. Rectangular Cu samples were partially immersed in both ambient and continuous lab air sparging atmospheres to understand waterline corrosion of the metal. Open circuit potentials (OCP) were continuously taken during the immersion testing for a maximum of 5 days. A scanning electron microscopy (SEM) equipped with an energy dispersive X-ray spectrometer (EDS), Raman spectroscopy, and 3-D …

Tandem Mass Spectrometry (Ms/Ms) For Determination Of Architecture Of Synthetic Polymers, Shoumik Saha

Williams Honors College, Honors Research Projects

Tandem Mass Spectrometry (MS/MS) was used to determine the architecture of synthetic polymers and they are difluorene-N₃, 3-difluorene-N₃ and VPOSS-3-difluorene. VPOSS materials usually exhibit electrochemical properties and the research was performed to determine their accurate structure and to provide evidence of their proper synthesis. The compounds were mixed with a matrix solution, DCTB, and a silver salt to enable proper protonation. The solvent mixture was on a MALDI plate and then put into the mass spectrometer. The mass spectrum generated was analyzed and each fragment was identified to structures with the synthetic polymers via ChemDraw. Thus, trial …

Abnormal Phase Transition Between Two-Dimensional High-Density Liquid Crystal And Low-Density Crystalline Solid Phases, Wenbin Li, Longjuan Kong, Baojie Feng, Huixia Fu, Hui Li, Xiao Cheng Zeng, Kehui Wu, Lan Chen

Xiao Cheng Zeng Publications

Some two-dimensional liquid systems are theoretically predicted to have an anomalous phase transition due to unique intermolecular interactions, for example the first-order transition between two-dimensional high-density water and low-density amorphous ice. However, it has never been experimentally observed, to the best of our knowledge. Here we report an entropy-driven phase transition between a high-density liquid crystal and low-density crystalline solid, directly observed by scanning tunneling microscope in carbon monoxide adsorbed on Cu(111). Combined with first principle calculations, we find that repulsive dipole–dipole interactions between carbon monoxide molecules lead to unconventional thermodynamics. This finding of unconventional thermodynamics in two-dimensional carbon monoxide …

Toward The Detection Of The Triatomic Negative Ion Spn−: Spectroscopy And Potential Energy Surfaces, Tarek Trabelsi, Majdi Hochlaf, Joseph S. Francisco

Department of Chemistry: Faculty Publications

High level theoretical calculations using coupled-cluster theory were performed to provide an accurate description of the electronic structure, spectroscopic properties, and stability of the triatomic negative ion comprising S, N, and P. The adiabatic electron affinities (AEAs) and vertical detachment energies

(VDEs) of PNS, SPN, PSN, and cyc-PSN were calculated. The predicted AEA and VDE of the linear SPN isomer are large: 2.24 and 3.04 eV, respectively. The potential energy surfaces (PESs) of the lowest-lying electronic states of the SPN isomer along the PN and SP bond lengths and bond angle were mapped. A set of spectroscopic parameters for …

Characterization Of Solution-Phase Drug-Protein Interactions By Ultrafast Affinity Extraction, Sandya Beeram, Xiwei Zheng, Kyungah Suh, David S. Hage

Department of Chemistry: Faculty Publications

A number of tools based on high-performance affinity separations have been developed for studying drug-protein interactions. An example of one recent approach is ultrafast affinity extraction. This method has been employed to examine the free (or non-bound) fractions of drugs and other solutes in simple or complex samples that contain soluble binding agents. These free fractions have also been used to determine the binding constants and rate constants for the interactions of drugs with these soluble agents. This report describes the general principles of ultrafast affinity extraction and the experimental conditions under which it can be used to characterize such …

Systems And Methods For Actuating Soft Robotic Actuators, Robert F. Shepherd, Adam Stokes, Stephen A. Morin, Ludovico Cademartiri, Jacob Freake, Rui Nunes, Xin Chen, George M. Whitesides

Department of Chemistry: Faculty Publications

Systems and methods for providing a soft robot is provided. In one system , a robotic device includes a flexible body having a fluid chamber, where a portion of the flexible body includes an elastically extensible material and a portion of the flexible body is strain limiting relative to the elastically extensible material. The robotic device can further include a pressurizing inlet in fluid communication with the fluid chamber, and a pressurizing device in fluid communication with the pressurizing inlet, the pressurizing device including a reaction chamber configured to accommodate a gas producing chemical reaction for providing pressurized gas to …

Tin Nanoparticles Encapsulated Carbon Nanoboxes As High-Performance Anode For Lithium-Ion Batteries, Ziming Yang, Hong-Hui Wu, Zhiming Zheng, Yong Cheng, Pei Li, Qiaobao Zhang, Ming-Sheng Wang

Department of Chemistry: Faculty Publications

One of the crucial challenges for applying Sn as an anode of lithium-ion batteries (LIBs) is the dramatic volume change during lithiation/delithiation process, which causes a rapid capacity fading and then deteriorated battery performance. To address this issue, herein, we report the design and fabrication of Sn encapsulated carbon nanoboxes (denoted as Sn@C) with yolk@shell architectures. In this design, the carbon shell can facilitate the good transport kinetics whereas the hollow space between Sn and carbon shell can accommodate the volume variation during repeated charge/discharge process. Accordingly, this composite electrode exhibits a high reversible capacity of 675 mAh g^{−1 …}

Anatomy Of Stem Teaching In American Universities: A Snapshot From A Large-Scale Observation Study, Marilyne Stains, Jordan Harshman, Megan K. Barker, Stephanie V. Chasteen, Renee Cole, Sue Ellen Dechenne-Peters, M. Kevin Eagan Jr., Joan M. Esson, Jennifer K. Knight, Frank A. Laski, Marc Levis-Fitzgerald, Christopher J. Lee, Stanley M. Lo, Lisa M. Mcdonnell, Timothy A. Mckay, Nicole Michelotti, Michael S. Palmer, Kathryn M. Plank, Tamara M. Rodela, Erin R. Sanders, Natalie G. Schimpf, Patricia M. Schulte, Michelle Smith, Mackenzie Stetzer, Jackie Stewart, Blaire Van Valkenburgh, Erin Vinson, Laura K. Weir, Paul J. Wendel, Lindsay B. Wheeler, Anna M. Young

Department of Chemistry: Faculty Publications

National and local initiatives focused on the transformation of STEM teaching in higher education have multiplied over the last decade. These initiatives often focus on measuring change in instructional practices, but it is difficult to monitor such change without a national picture of STEM educational practices, especially as characterized by common observational instruments. We characterized a snapshot of this landscape by conducting the first large scale observation-based study. We found that lecturing was prominent throughout the undergraduate STEM curriculum, even in classrooms with infrastructure designed to support active learning, indicating that further work is required to reform STEM education. Additionally, …

Reductive Cleavage Of Organic Peroxides By Iron Salts And Thiols, Anderw Olson, Abigail J. Jameson, Shiva K. Kyasa, Boone W. Evans, Patrick H. Dussault

Department of Chemistry: Faculty Publications

Despite the low bond strength of the oxygen− oxygen bond, organic peroxides are often surprisingly resistant to cleavage by nucleophiles and reductants. As a result, achieving decomposition under mild conditions can be challenging. Herein, we explore the reactivity of a selection of peroxides toward thiolates, phenyl selenide, Fe(II) salts, and iron thiolates. Peroxides activated by conjugation, strain, or stereoelectronics are rapidly cleaved at room temperature by thiolate anions, phenylselenide, or Fe(II) salts. Under the same conditions, unhindered dialkyl peroxides are only marginally reactive; hindered peroxides, including triacetone triperoxide and diacetone diperoxide (DADP), are inert. In contrast, all but the most …