Chemistry Commons^™

Corn Stalk Nitrate Interpretation, John E. Sawyer

John E. Sawyer

You’ve gotten results from corn stalk nitrate samples collected this fall. (Corn stalk nitrate analysis form.) Now, what do the results mean? The stalk nitrate test is based on the concentration of nitrate-N in the lower corn stalk (8 inch segment from 6 to 14 inches above the ground) when the plant reaches maturity (See Cornstalk testing to evaluate nitrogen management, PM 1584). In general, a larger amount of plant-available N in the soil during the time period before plant maturity results in a greater concentration of nitrate in the lower stalk. However, the stalk nitrate-N concentration …

Corn Stalk Nitrate Interpretation, John E. Sawyer

John E. Sawyer

You’ve gotten results from corn stalk nitrate samples collected this fall. (Corn stalk nitrate analysis form.) Now, what do the results mean? The stalk nitrate test is based on the concentration of nitrate-N in the lower corn stalk (8 inch segment from 6 to 14 inches above the ground) when the plant reaches maturity (See Cornstalk testing to evaluate nitrogen management, PM 1584). In general, a larger amount of plant-available N in the soil during the time period before plant maturity results in a greater concentration of nitrate in the lower stalk. However, the stalk nitrate-N concentration can be greatly …

C60 And Sc3N@C80(Tmb-Ppo) Derivatives As Constituents Of Singlet Oxygen Generating, Thiol-Ene Polymer Nanocomposites, Emily M. Barker, Ashli R. Toles, Kyle A. Guess, J. Paige Buchanan

Faculty Publications

Numerous functionalization methods have been employed to increase the solubility, and therefore, the processability of fullerenes in composite structures, and of these radical addition reactions continue to be an important methodology. C₆₀ and Sc₃N@C₈₀ derivatives were prepared via radical addition of the photodecomposition products from the commercial photoinitiator TMB-PPO, yielding C₆₀(TMB-PPO)₅ and Sc₃N@C₈₀(TMB-PPO)₃ as preferred soluble derivatives obtained in high yields. Characterization of the mixture of isomers using standard techniques suggests an overall 1PPO:6TMB ratio of addends, reflecting the increased reactivity of the carbon radical. Although, a higher …

Expanding The Versatility Of Nano Assembled Capsules As Platform Of Potential High Payload Mri Contrast Agents, Annah Farashishiko

Dissertations and Theses

Magnetic resonance imaging (MRI) has become a powerful clinical modality in diagnostic medicine. It is non-invasive and offers high spatial and temporal resolution. The goal of molecular imaging is to reveal the pathophysiology underlying the observed anatomy and diagnose diseases. The detection of pathological biomarkers can lead to early recognition of diseases and improved monitoring for recurrence. Clinically available contrast agents are limited in their discrimination of contrast between tissues and they tend to have very high detection limits. Because biomarkers are very low in concentration there is a need for high payload deposition of contrast agent (CA) and targeted …

A New Science, And A New Profession: Sugar Chemistry In Louisiana, 1885-1895, John Alfred Heitmann

John A. Heitmann

Between 1885 and 1895 the Louisiana sugar industry experienced a scientific and technological revolution in methods, process apparatus, and scale of operations. The animal-powered mills and open kettles characteristic of the antebellum period were supplanted by large, technically designed, and scientifically controlled central factories . In 1880 there were approximately 1,000 sugar houses in Louisiana with an average annual production of 110 long tons of sugar per house. By 1900 fewer than 300 factories constituted the state's sugar industry, but yearly production averaged over 980 long tons for each sugar house. One commentator of the period, Mark Twain, described a …

Effects Of Angular Deformation On The Energetics Of The Sn2 Reaction, Vincent De Paul Nzuwah-Nziko, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Quantum calculations are applied to a number of model SN2 reactions. The halides F-, Cl-, and Br- were allowed to attack the central C atom of a set of CH2RI molecules, with R= H, CH3, CH=CH2, C≡CH, and C≡N. For each system the X∙∙C∙∙I angle was distorted in set increments from the optimized value, and the activation energy computed for each angle. The energy of the transition state rose in conjunction with this deformation. However, the distortion energy of the initial X-∙∙CH2RI reaction complex was similar in magnitude. As a result, the activation energy of the reaction was quite insensitive …

Interpretation Of Spectroscopic Markers Of Hydrogen Bonds, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Quantum calculations are used to examine whether a AH∙∙D H-bond is unambiguously verified by a downfield shift of the bridging proton’s NMR signal or a red (or blue) shift of the AH stretching frequency in the IR spectrum. It is found that such IR band shifts will occur even if the two groups experience weak or no attractive force, or if they are drawn in so close together that their interaction is heavily repulsive. The mere presence of a proton-acceptor molecule can affect the chemical shielding of a position occupied by a proton-donor by virtue of its electron density, even …

58th Annual Rocky Mountain Conference On Magnetic Resonance

Rocky Mountain Conference on Magnetic Resonance

Final program, abstracts, and information about the 58th annual meeting of the Rocky Mountain Conference on Magnetic Resonance, co-endorsed by the Colorado Section of the American Chemical Society and the Society for Applied Spectroscopy. Held in Breckenridge, Colorado, July 17-21, 2016.

Polyisobutylene-Paclitaxel Conjugates With Pendant Carboxylic Acids And Polystyrene Chains: Towards Multifunctional Stent Coatings With Slow Drug Release, John F. Trant, Mahmoud M. Abd Rabo Moustafa, Inderpreet Sran, Elizabeth R. Gillies

Chemistry and Biochemistry Publications

Drug-eluting stents are used in the treatment of atherosclerosis, where the incorporation of anti-proliferative or anti-inflammatory drugs decreases the rate of restenosis, the recurrence of artery narrowing. However, these stents can suffer from limitations such as drug depletion and delamination of the drug-eluting coating from the stent surface. Described here is an approach aimed at addressing these issues. Starting from a maleic anhydride adduct of polyisobutylene (PIB) prepared from butyl rubber, ring opening using paclitaxel (PTX) or a combination of PTX and polystyrene (PS) afforded covalent conjugates of PTX and PIB or PIB-PS graft copolymers bearing pendant carboxylic acids. When …

Discovery And Characterization Of The Proteins Involved In The Synthesis Of N⁶-Threonylcarbamoyl Adenosine, A Nucleoside Modification Of Trna, Christopher Wayne Deutsch

Dissertations and Theses

N6-threonylcarbamoyl adenosine (t⁶A) is a universally conserved tRNA modification found at position 37 of tRNAs which decode ANN codons. Structural studies have implicated its presence as a requirement for the disruption of a U-turn motif in certain tRNAs, leading to the formation of properly structured anticodon stem loop. This structure is proposed to enhance the base pairing between U₃₆ of tRNA and A₁ of the codon which aids in translational frame maintenance.

Despite significant effort since its discovery in the 1970s the enzymes involved in its biosynthesis remained undiscovered. Bioinformatic analysis identified two proteins as likely …

Synthesis And Structure Activity Relationship Of Novel Small Molecules As Inhibitors Of Plasminogen Activator Inhibitor-1, Karl Michael Upman

Master's Theses and Doctoral Dissertations

Plasminogen activator inhibitor type-1 (PAI-1) is a member of the serine protease inhibitor (serpin) family. PAI-1 is involved in the regulation of fibrinolysis, which is the breakdown of blood clots. PAI-1 inhibits serine proteases tissue-type plasminogen activator (tPA) and urokinase-type plasminogen activator (uPA), which are key factors in fibrinolysis. Excess levels of PAI-1 have also been shown to increase the risk of diabetes, stroke, and atherosclerosis, as well as tumor development. Previous attempts at synthesizing a practical drug for the regulation of PAI-1 have not been successful; therefore, it has been the purpose of this study to further advance progress …

Diastereoselective Aza-Cope Rearrangement-Mannich Cyclizations Of Conformationally Mobile Iminium Cations, Joshua Hunt

Master's Theses and Doctoral Dissertations

We have developed a Lewis-acid catalyzed, diastereoselective aza-Cope rearrangement— Mannich cyclization (ACM) to form acyl pyrrolidines from conformationally mobile substrates. Earlier studies from our lab have shown that substituted acyl pyrrolidines can be synthesized with diastereoselectivity of 50:1 trans to cis, and that unsubstituted pyrrolidines can be synthesized with 13:1 enantioselectivity. This study attempted to observe the stereochemical outcomes of the ACM for disubstituted pyrrolidine systems using oxazolidine starting materials. A proof of concept dimethyl-substituted oxazolidine was subjected to ACM conditions, producing the pyrrolidine with good yields. However, when methyl-phenyl substituted oxazolidine was subjected to ACM conditions, undesired byproduct …

Qualitative Detection Of Selected Designer Drugs And Relevant Metabolites In Environmental Water Samples, Marley Pruyn

FIU Electronic Theses and Dissertations

Designer drugs are compounds which have been synthetically derived from illicit drugs. After consumption, drugs and their metabolites are introduced into the sewage water which is treated and disposed into the environment. A combined target, suspect and non-target workflow was created to detect designer drugs in environmental water samples. Multiple water samples were spiked with an unknown mixture of drugs and metabolites to assess the efficiency of the method. Samples were collected from sewage influent and effluent pipes, downstream from a sewage outfall and reclaimed water. Analysis was conducted with high resolution MS using the QExactive Orbitrap. Screening was performed …

Novel Analytical Methods Combining Non-Denaturing Chromatography And Mass Spectrometry To Study Biopolymer Structure And Interactions, Khaja Muneeruddin

Doctoral Dissertations

Biotherapeutics, an emerging class of medicines containing biopolymers (e.g., proteins, peptide, and polysaccharides) have been developed for a variety of indications including cancer, autoimmune, genetic, and blood diseases. Among these biopolymers protein therapeutics have been the rapidly growing segment in the pharmaceutical industry. This trend combined with the complexity of proteins has necessitated the development of powerful and robust analytical methods to study their structure and interactions with physiological partners. Mass spectrometry (MS) has become an indispensable tool to analyze various attributes of protein drugs such as profiling of intact mass, amino acid sequencing, and post translational modifications (PTMs). In …

Synthesis And Characterization Of Polymeric Anion Exchange Membranes, Wenxu Zhang

Doctoral Dissertations

As alkaline anion exchange membrane fuel cells (AAEMFC) are regarded as promising and important energy devices, the development of high performance anion exchange membranes are in urgent need, as well as fundamental investigation on the structure-property relationship, which are the motivation of this dissertation. Three different polymer systems are presented and focused on polymer synthesis, material morphology, and ion transport phenomena. Crosslinked membranes are promising as practical materials, however, the understanding and further improvement of its performance is hindered by the lack of an ordered morphology or well-defined chemical structure. In Chapter 2, a series of crosslinked membranes were design …

Photolysis Of Triazenylbenzoic Acids For Click Chemistry, Adam Gann

Doctoral Dissertations

Copper catalyzed cycloaddition of terminal alkynes and azides has revolutionized the field of bioconjugate chemistry. Unfortunately, typical copper catalysts are known to disrupt relevant biological systems, so it has become necessary to develop new, copper-free methods that are less cytotoxic. particular interest are "click" probes which can be activated with an outside light source, giving the user spatial and temporal control over the system being investigated. We have developed a method in which an aryl diazonium salt is rapidly generated using photolysis of the triazene functional group, and subsequently coupled with an electron rich aromatic nucleophile to yield an azobenzene. …

Magnetic Doping Of Semiconductor Molecular Models And Colloidal Nanocrystals, Swamy Pittala

Doctoral Dissertations

Spin-based electronics use the spins of electrons in addition to their charges and have potential applications to create a next generation of quantum computers, capable of storing vast amounts of data in an energy-efficient way. Diluted magnetic semiconductor quantum dots (DMS-QDs) have shown great promise as ideal materials for application in spin-based electronics. However, doping impurities into quantum confined colloidal nanocrystals (NCs) has been a great challenge due to the lack of control over the dopant reactivity during the specific stages of nucleation and growth. The mechanism of dopant incorporation into nanocrystals is complex and well-defined and atomically precise molecular …

Kinetic And Dynamic Insights Into The Substrate Interactions And Catalysis Of Factor Inhibiting Hif-1 (Fih-1), Cristina B. Martin

Doctoral Dissertations

inhibiting HIF-1 (FIH-1) modulates the master regulator of hypoxia sensing, hypoxia inducible factor-1 (HIF-1), by transcriptional repression making it an attractive potential target for treatment of hypoxia-related diseases. Given that similar enzymes are present within the cell and that they have other important physiological roles, defining the therapeutic window by which it can be selectively targeted becomes an issue. Consequently, it’s necessary to have a deeper understanding of the substrate interactions in FIH-1 that contributes to catalysis as this is one avenue that can be explored for future therapeutic investigations. The overall goal of this dissertation is to gain kinetic …

Nanomaterials At Liquid/Liquid Interfaces: Assembly And Rheology, Tao Feng

Doctoral Dissertations

This dissertation concentrated on the behavior of nanomaterials at liquid/liquid interfaces. A strategy of segregating acid-treated SWCNTs at oil/water interfaces was developed by adding amine-terminated polystyrene (PS-NH₂) in the oil phase. Electrostatic binding between carboxylic acid of SWCNTs and amine drives the assembly of SWCNTs, monitored by pendant drop tensiometry and confocal microscopy. A sharp transition of interfacial segregation against SWCNT solution pH was revealed, with the transition point at the pKa of carboxyl. The reduced SWCNT surface charge density at low pH was found to be beneficial for segregation due to the attenuated repulsions between adsorbed …

Design, Synthesis, And Applications Of Nano-Assemblies Based On Amphiphilic Macromolecules, Hui Wang

Doctoral Dissertations

Recent progress in nanotechnology has been significantly impacting a variety of areas such as utilization in microelectronics, multiphase catalysis, sensing and therapeutics. Our interests are to develop new nanomaterials to understand their structure-property relationships and to utilize them for various applications. In this thesis, we discuss our findings on the design, synthesis and applications of nanomaterials formed by self-assembly of amphiphilic molecules. Micelles are self-assembled nanostructures formed by amphiphilic molecules. They are capable of sequestering hydrophobic guest molecules in an aqueous environment. Other than surfactants, micelles can also be formed by amphiphilic polymers or dendrimers, which are macromolecular surfactants in …