Chemistry Commons^™

Myofilament Calcium Sensitivity: Consequences Of The Effective Concentration Of Troponin I, Jalal K. Siddiqui, Svetlana B. Tikunova, Shane D. Walton, Bin Liu, Meredith Meyer, Pieter P. De Tombe, Nathan Neilson, Peter M. Kekenes-Huskey, Hussam E. Salhi, Paul M.L. Janssen, Brandon J. Biesiadecki, Jonathan P. Davis

Chemistry Faculty Publications

Control of calcium binding to and dissociation from cardiac troponin C (TnC) is essential to healthy cardiac muscle contraction/relaxation. There are numerous aberrant post-translational modifications and mutations within a plethora of contractile, and even non-contractile, proteins that appear to imbalance this delicate relationship. The direction and extent of the resulting change in calcium sensitivity is thought to drive the heart toward one type of disease or another. There are a number of molecular mechanisms that may be responsible for the altered calcium binding properties of TnC, potentially the most significant being the ability of the regulatory domain of TnC to …

Vitamin E Circular Dichroism Studies: Insights Into Conformational Changes Induced By The Solvent’S Polarity, Drew Marquardt, Brad J. Van Oosten, Mikel Ghelfi, Jeffrey Atkinson, Thad A. Harroun

Chemistry and Biochemistry Publications

We used circular dichroism (CD) to study differences in CD spectra between α-, δ-, and methylated-α-tocopherol in solvents with different polarities. CD spectra of the different tocopherol structures differ from each other in intensity and peak locations, which can be attributed to chromanol substitution and the ability to form hydrogen bonds. In addition, each structure was examined in different polarity solvents using the Reichardt index—a measure of the solvent’s ionizing ability, and a direct measurement of solvent–solute interactions. Differences across solvents indicate that hydrogen bonding is a key contributor to CD spectra at 200 nm. These results are a first …

Phthalate Plasticizers Covalently Linked To Pvc Via Copper-Free Or Copper Catalyzed Axide-Alkyne Cycloadditions, Aruna Earla, Li Longbo, Philip Costanzo, Rebecca Braslau

Chemistry and Biochemistry

Plasticization of PVC was carried out by covalently linking phthalate derivatives via copper-free (thermal) or copper catalyzed azide-alkyne cycloadditions. Di(2-ethylhexyl) phthalate derivatives (DEHP-ether and DEHP-ester) were synthesized and appended to PVC at two different densities. The glass transition temperatures of the modified PVC decreased with increasing content of plasticizer. PVC-DEHP-ether gave lower glass transition temperatures than PVC-DEHP-ester, reflecting the enhanced flexibility of the ether versus ester linker.

Design And Synthesis Of Novel Azasteroids And Pseudoazulenyl Nitrones, Nagaraju Birudukota

FIU Electronic Theses and Dissertations

Steroids are one of the essential classes of bioactive compounds and are involved in many biological functions which include their role as signaling compounds, the alteration of membrane fluidity and the regulation of a variety of metabolic processes. In order to identify novel compounds with beneficial pharmacological action, the synthesis of modified steroids is gaining much attention in recent years. Among those analogs, azasteroids are one of the most important classes which display a variety of biological activities, often free from undesirable side effects. The challenges in the synthesis of steroids, particularly azasteroids, and the potential of azasteroids as novel …

An Examination Of Student Outcomes In Studio Chemistry, Alan L. Kiste, Gregory E. Scott, Jesse Paul Bukenberger, Miles Markmann, Jennifer Moore

Chemistry and Biochemistry

Twenty years ago, a major curriculum revision at a large, comprehensive university in the Western United States led to the implementation of an integrated lecture/laboratory (studio) experience for our engineering students taking general chemistry. Based on these twenty years of experience, construction of four purpose-built studio classrooms to house the majority of the remaining general chemistry courses was completed in 2013. A detailed study of the effects of the entire ecology of the studio experience on student success was initiated at that time. Data from content knowledge pre- and post-tests, learning attitudes surveys, and student course evaluations show positive effects …

Synthesis And Performance Of Novel Supramolecular Tools For Single-Particle Cryogenic Electron Microscopy And Drug And Gene Delivery, Kyle J. Wright

Open Access Dissertations

High-resolution biomacromolecular structure elucidation is fundamentally important to structure-based drug design and basic research into complex biochemical processes. Cryo-EM is an emerging alternative to XRD and NMR that is complementary in many ways relative to XRD and NMR. Materials approaches to cryo-EM are anticipated to greatly facilitate the cryo-EM process, allowing progress toward a more high-throughput application of cryo-EM to address challenges in structural biology. ^ Various affinity-based approaches inspired by approaches previously introduced for 2D crystallization were developed for facilitation of cryo-EM. A library of affinity lipopolymer constructs were synthesized consisting of lipopolymers of various PEG molecular weights conjugated …

A Pes Study Of Factors Influencing Metal Partitioning In Aquatic Systems: “Design Of Experiment As, Cd, Co, Cr, Cu, Pb, Ni, And Zn”, Eid A. Alkhatib, John Rapaglia, Leon Theim

Chemistry & Physics Faculty Publications

Mobility and bioavailability of heavy metals are related to their partitioning amongst suspended sediment and water. A Particle Entrainment Simulator (PES) is used to simulate sediment resuspention in natural surface water systems. The simulations were carried out under various conditions of water/suspended solids conditions. Five factors, each at various levels, are tested collectively: the pH of water at two levels (4 and 8), shear stress on bottom sediment at three levels (0.1, 0.3, and 0.5 N/m2 ) salinity of water at two levels (0.01 and 14.0 ppt), organic matter in sediment at three levels (0.50, 1.93, and 3.80%) and temperature …

Interactions In The Cpsrp Dependent Targeting Of Light Harvesting Chlorophyll Binding Protein To The Thylakoid Membrane, Rory Henderson

Graduate Theses and Dissertations

Targeting of proteins is a critical component of cellular function. A universally conserved targeting system of the cytosol utilizes a signal recognition particle (SRP) to target many proteins contranslationally to the endoplasmic reticulum in eukaryotes or the inner membrane in prokaryotes. A homologous SRP system exists in the chloroplast that delivers light harvesting chlorophyll binding proteins (LHCP) to they thylakoid membrane. The chloroplast SRP (cpSRP) is a heterodimer composed of a novel 43 kDa subunit and a 54 kDa subunit homologous to a component of the SRP system, SRP54. Many details regarding the interactions between the proteins of the cpSRP …

Characterization Of Wy 14,643 And Its Complex With Aldose Reductase, Michael Sawaya, Malkhey Verma, Vaishnavi Balendiran, Nigam Rath, Duilio Cascio, Ganesaratnam Balendiran

Chemistry & Biochemistry Faculty Works

The peroxisome proliferator, WY 14,643 exhibits a pure non-competitive inhibition pattern in the aldehyde reduction and in alcohol oxidation activities of human Aldose reductase (hAR). Fluorescence emission measurements of the equilibrium dissociation constants, Kd, of oxidized (hAR•NADP+) and reduced (hAR•NADPH) holoenzyme complexes display a 2-fold difference between them. Kd values for the dissociation of WY 14,643 from the oxidized (hAR•NADP+•WY 14,643) and reduced (hAR•NADPH•WY 14,643) ternary complexes are comparable to each other. The ternary complex structure of hAR•NADP+•WY 14,643 reveals the first structural evidence of a fibrate class drug binding to hAR. These observations demonstrate how fibrate molecules such as …

Bioorthogonal Reactions: Synthesis And Evaluation Of Different Ligands In Copper Catalyzed Azide-Alkyne1,3-Dipolar Cycloaddition (Cuaac), Zainab Abdullah Almansaf

Graduate Theses and Dissertations

The Copper CatalyzedAzide-Alkyne1,3-Dipolar Cycloaddition (CuAAC) reaction has unique features that qualify it to be one of the best click reactions. Its applications have been shown in different aspects and for multiple purposes. The oxidative degradation of biological systems (labile proteins and live cells) is, however, generally recognized as the major problem when using this reaction in living systems. Reactive oxidation species can be easily produced in the presence of copper(II), ascorbate and air, and this is the main cause of toxicity. However, the uses of ligands have shown a major impact on reducing copper toxicity, protecting Cu(I) from the redox …

Electrogenerated Chemiluminescence Study Of Semiconductor Nanoparticles Towards Sensitive Detection Of Biomolecules, Yiliyasi Wusimanjiang

Dissertations

The main focus of this dissertation is to unfold the fundamental aspects of electrogenerated chemiluminescence (ECL) generation from semiconductor nanoparticles (also known as quantum dots or QDs) within different ECL systems. The ECL and photo-physical interactions between the CdTe QDs (λ_emission= ~760 nm) and the CdSe QDs (λ_emission= ~550 nm), as well as the effects of carbon nanotubes on ECL of QDs were separately investigated. Optimum experimental conditions for peptide bond formation on an electrode surface through EDC (1-ethyl-3-(-3-dimethylaminopropyl) carbodiimide hydrochloride)/NHS (N-Hydroxysulfosuccinimide) coupling were also revealed using cyclic voltammetry technique. Based on the information …

Characterization Of Wy 14,643 And Its Complex With Aldose Reductase, Michael R. Sawaya, Malkhey Verma, Vaishnavi Balendiran, Nigam P. Rath, Duilio Cascio, Ganesaratnam K. Balendiran

Nigam Rath

Conformationally Superarmed S-Ethyl Glycosyl Donors As Effective Building Blocks For Chemoselective Oligosaccharide Synthesis In One Pot, Mithila Bandara, Jagodige Yasomanee, Nigam Rath, Christian Pedersen, Mikael Bols, Alexei Demchenko

Chemistry & Biochemistry Faculty Works

A new series of superarmed glycosyl donors has been investigated. It was demonstrated that the S-ethyl leaving group allows for high reactivity, which is much higher than that of equally equipped S-phenyl glycosyl donors that were previously investigated by our groups. The superarmed S-ethyl glycosyl donors equipped with a 2-O-benzoyl group gave complete β-stereoselectivity. Utility of the new glycosyl donors has been demonstrated in a one-pot one-addition oligosaccharide synthesis with all of the reaction components present from the beginning.

Development Of In Vivo Systems For Detecting And Studying Ribosome Inhibition By Small Molecules, Shijie Huang

Chemistry and Chemical Biology ETDs

The ribosome is the quintessential antibacterial drug target, with many structurally and mechanistically distinct classes of antibacterial agents acting by inhibiting ribosome function. Detecting and quantifying ribosome inhibition by small molecules and investigating their binding modes and mechanisms of action are critical to antibacterial drug discovery and development efforts. To develop a ribosome inhibition assay that is operationally simple, yet provides direct information on the drug target and the mechanism of action, we have developed engineered E. coli strains harboring an orthogonal ribosome controlled green fluorescent protein reporter that produce fluorescent signal when the O-ribosome is inhibited. As a proof …

Engineering Small Molecule Based Dimerization To Induce Translation And Provide Optogenetic Control, Catherine Wright

Chemistry and Chemical Biology ETDs

We wanted to develop a system that combines the spatial control of photoactivation and control of translation to build a tool to spatially control translation in neurons. This kind of tool could be used to investigate the role of spatially controlled translation of any protein in neural behavior. In this way the development and growth of neural processes could be studied to elucidate the mechanisms for spatially sensitive events such as pathfinding, repair, or long-term potentiation.

Chemically induced dimerization was used to install a switch into the activation of translation for specific genes. An abscisic acid (ABA) dependent dimerization of …

The Optimization Of Pressure Cycling Technology (Pct) For Differential Extraction Of Sexual Assault Casework, Vanessa Martinez

FIU Electronic Theses and Dissertations

A two-step protocol has been devised as a rapid and selective alternative to conventional differential extraction techniques with an increased recovery of DNA. The protocol involves pressure cycling with the Barocycler^® NEP 2320 from Pressure Biosciences. Inc. in alkaline conditions for epithelial cell lysis and removal. This step is followed by alkaline lysis at 95^º C for extraction of sperm cell DNA. At 1:1 or 2:1 female to male cell ratios, high selectivity and complete separation can be achieved. But at higher ratios, male allelic dropout is observed. This protocol has been modified to generate a clean male …

Interspecies Comparison Of Peptide Substrate Reporter Metabolism Using Compartment-Based Modeling [Post-Print], Allison Tierney, Nhat Pham, Kunwei Yang, Brooks Emerick, Michelle Kovarik

Faculty Scholarship

Peptide substrate reporters are fluorescently labeled peptides that can be acted upon by one or more enzymes of interest. Peptide substrates are readily synthesized and more easily separated than full-length protein substrates; however, they are often more rapidly degraded by peptidases. As a result, peptide reporters must be made resistant to proteolysis in order to study enzymes in intact cells and lysates. This is typically achieved by optimizing the reporter sequence in a single cell type or model organism, but studies of reporter stability in a variety of organisms are needed to establish the robustness and broader utility of these …

Use Of A Uav For Water Sampling To Assist Remote Sensing Of Bacterial Flora In Freshwater Environments, Dylan Cornell, Maryann Herman, Fernando Ontiveros

Undergraduate External Publications

Ground truth data collection in bodies of water traditionally relies on the use of watercraft and manual sampling. The transport and cost associated with the use of this type of equipment, as well as the time required to reach the site of collection, may all be significantly reduced by the use of small unmanned aerial vehicles (UAV) or drones. In this project we evaluate the implementation of a modified UAV with the ability to collect a small volume of surface water up to 400m offshore. The bacterial flora found in the water of several locations in the Lake Ontario-Rochester Embayment …

Infrared Spectroscopy Of The Nitrogenase Mofe Protein Under Electrochemical Control: Potential-Triggered Co Binding, P. Paengnakorn, Philip A. Ash, Sudipta K. Shaw, Karamatullah Danyal, T. Chen, Dennis R. Dean, Lance C. Seefeldt, Kylie A. Vincent

Chemistry and Biochemistry Faculty Publications

We demonstrate electrochemical control of the nitrogenase MoFe protein, in the absence of Fe protein or ATP, using europium(III/II) polyaminocarboxylate complexes as electron transfer mediators. This allows the potential dependence of proton reduction and inhibitor (CO) binding to the active site FeMo-cofactor to be established. Reduction of protons to H2 is catalyzed by the wild type MoFe protein and Β-98^Tyr→His and Β-^99Phe→His variants of the MoFe protein at potentials more negative than -800 mV (vs. SHE), with greater electrocatalytic proton reduction rates observed for the variants compared to the wild type protein. Electrocatalytic proton reduction is strongly …

Pharmacological Validation Of An Inward-Rectifier Potassium (Kir) Channel As An Insecticide Target In The Yellow Fever Mosquito Aedes Aegypti, Matthew F. Rouhier, Rene Raphemot, Jerod S. Denton, Peter M. Piermarini

Matthew F Rouhier

Mosquitoes are important disease vectors that transmit a wide variety of pathogens to humans, including those that cause malaria and dengue fever. Insecticides have traditionally been deployed to control populations of disease-causing mosquitoes, but the emergence of insecticide resistance has severely limited the number of active compounds that are used against mosquitoes. Thus, to improve the control of resistant mosquitoes there is a need to identify new insecticide targets and active compounds for insecticide development. Recently we demonstrated that inward rectifier potassium (Kir) channels and small molecule inhibitors of Kir channels offer promising new molecular targets and active compounds, respectively, …

Discovery And Characterization Of A Potent And Selective Inhibitory Of Aedes Aegypti Inward Rectifier Potassium Channels, Matthew F. Rouhier, Rene Raphemot, Daniel R. Swale, Emily Days, C. David Weaver, Kimberly M. Lovell, Leah C. Konkel, Darren W. Engers, Sean F. Bollinger, Corey Hopkins, Peter M. Piermarini, Jerod S. Denton

Matthew F Rouhier

Vector-borne diseases such as dengue fever and malaria, which are transmitted by infected female mosquitoes, affect nearly half of the world's population. The emergence of insecticide-resistant mosquito populations is reducing the effectiveness of conventional insecticides and threatening current vector control strategies, which has created an urgent need to identify new molecular targets against which novel classes of insecticides can be developed. We previously demonstrated that small molecule inhibitors of mammalian Kir channels represent promising chemicals for new mosquitocide development. In this study, high-throughput screening of approximately 30,000 chemically diverse small-molecules was employed to discover potent and selective inhibitors of Aedes …

Eliciting Renal Failure In Mosquitoes With A Small-Molecule Inhibitor Of Inward-Rectifying Potassium Channels, Matthew F. Rouhier, Rene Raphemot, Corey R. Hopkins, Rocco D. Gogliotti, Kimberly M. Lovel, Rebecca M. Hine, Dhairyasheel Ghosalkar, Anthony Longo, Klaus W. Beyenbach, Jerod S. Denton, Peter M. Piermarini

Matthew F Rouhier

Mosquito-borne diseases such as malaria and dengue fever take a large toll on global health. The primary chemical agents used for controlling mosquitoes are insecticides that target the nervous system. However, the emergence of resistance in mosquito populations is reducing the efficacy of available insecticides. The development of new insecticides is therefore urgent. Here we show that VU573, a small-molecule inhibitor of mammalian inward-rectifying potassium (Kir) channels, inhibits a Kir channel cloned from the renal (Malpighian) tubules of Aedes aegypti (AeKir1). Injection of VU573 into the hemolymph of adult female mosquitoes (Ae. aegypti) disrupts the production and excretion of urine …

Atomic Tiles: Manipulative Resources For Exploring Bonding And Molecular Structure, Alan L. Kiste, Rebecca G. Hooper, Gregory E. Scott, Seth Bush

Chemistry and Biochemistry

A simple manipulative resource, Atomic Tiles, is described for scaffolding the learning of Lewis structures without using algorithmic, rule-based methods of drawing. Students use Atomic Tiles to (1) create models of bonding that lead to drawing Lewis structures, (2) use the structures they create to infer patterns required for rational structures and common organic functional groups, (3) translate between Lewis structures and molecular models, and (4) use molecular models to identify isomers.

The Coastal Monitor: Vol. 1, No. 3, John Tanacredi Ph.D.

The Coastal Monitor

Each fall I teach a course in “Ecology” and in the spring, “Marine Biology”; two seminal courses absolutely necessary and required to complete a BS Degree in Earth and Environmental Studies at Molloy College. To a large extent I draw on my 48 years of life experiences; flight meteorologist, “Hurricane Hunter” in the US Navy (1968-1970), environmental impact analyst with the US Coast Guard’s Bridge Administration on Governors Island (1974-1978); Coastal Barrier Parks Coordinator and Research Ecologist with the National Park Service (1978-2001); Research Associate in the Invertebrate Zoology Department at the American Museum of Natural History(1982-2000); Chairman Department of …

Development Of Dihydrochalcone Functionalized Gold Nanoparticles For Augmented Antineoplastic Activity, Jason N. Payne

Masters Theses & Specialist Projects

Phloridzin, an antidiabetic and antineoplastic agent usually found in fruit trees, is a dihydrochalcone constituent that has a clinical/pharmaceutical significance as a sodiumglucose linked transport 2 (SGLT2) inhibitor. Phloridzin never experienced widespread clinical usage in the pharmaceutical market due to its side effects and poor bioavailability when compared to other antidiabetic therapeutics. The poor bioavailability is primarily attributed to the degradation of the glycosidic bond of the phloridzin, resulting in the formation of phloretin, the aglycone of phloridzin and glucose. While phloretin displays a reduced capacity of SGLT2 inhibition, this nutraceutical shows enhanced antineoplastic activity in comparison to phloridzin. Gold …

Visible-Light Generation Of High-Valent Metal-Oxo Intermediates And A Biomimetic Oxidation Catalyzed By Manganese Porphyrins With Iodobenzene Diacetate, Ka Wai Kwong

Masters Theses & Specialist Projects

High-valent iron-oxo intermediates play central roles as active oxidants in enzymatic and synthetic catalytic oxidations. Many transition metal catalysts are designed for biomimetic studies of the predominant oxidation catalysts in Nature, the cytochrome P450 enzymes.

In this work, a new photochemical method to generate high-valent iron-oxo porphyrin models was discovered. As controlled by the electronic nature of porphyrin ligands, iron(IV)-oxo porphyrin radical cations (Compound I model) and iron(IV)-oxo porphyrin derivatives (Compound II model) were produced. These observations indicate that the photochemical reactions involve a heterolytic cleavage of O-Br in precursors to give a putative iron(V)-oxo intermediate, which might relax to …

Bioenergetics: Experimental Demonstration Of Excess Protons And Related Features, Haitham A. Saeed

Chemistry & Biochemistry Theses & Dissertations

Over the last 50 years, ever since the Nobel-prize work of Peter Mitchell’s Chemiosmotic theory, the question whether bioenergetics energy transduction occurs through localized or delocalized protons has been a controversial issue among scientists. Recently, a proton-electrostatics localization hypothesis was formulated which may provide a new and clear understanding of localized and delocalized proton-coupling energy transduction in many biological systems. The aim of this dissertation was to test this new hypothesis.

To demonstrate the fundamental behavior of localized protons in a pure water-membrane-water system in relation to the newly derived pmf equation, excess protons and excess hydroxyl anions were generated …

Specific Binding Affinity Of The Non-Catalytic Domain Of Eukaryotic Like Type Ib Topoisomerase Of Vaccinia Virus, Benjamin R. Reed

Dissertations, Theses, and Capstone Projects

Topoisomerases are ubiquitous proteins that alter supercoiling in double stranded DNA (dsDNA) during transcription and replication and. vaccinia and the closely related poxvirus variola virus, at 314 amino acids in length, encode the smallest of the type I topoisomerases(TopIB). TopIB is a two domain protein that recognizes the sequence 5’-T/CCCTT, cleaves at the 3’-end and relaxes supercoiling through rotation. The C-terminal domain (CTD) alone contains the catalytic activity and specificity. Deletion of the N-terminal domain results in a greatly reduced rate of relaxation and rapid dissociation. Biochemical data suggests that the N-terminal domain (NTD) is important for pre-cleavage binding and …

Metabolic Profiling Of Genetically Modified Potato Periderm Tissues, Liqing Jin

Dissertations, Theses, and Capstone Projects

Potato tubers are protected from dehydration and pathogens by a covering peel (periderm) impregnated with suberin, a complex cross-linked biopolymer that contains both polyaliphatic and lignin-like aromatic domains. Current models describing the macromolecular structure of suberin assume that ferulic acid cross-links both domains as it may form carboxyl ester bonds with aliphatic monomers and non-ester radical-coupled bonds with phenolics. Ferulic acid also links by ester bonds to glycans and acts in cross-linking polysaccharides and lignin. Fatty alcohol/ω-hydroxyacid hydroxycinnamoyl transferase (FHT) is a BADH acyltransferase responsible for the synthesis of akyl-ferulates that is necessary for suberin biosynthesis. Periderm from FHT-RNAi …

Metabolic Profiling And Polymer Formation Of Gene Silenced Potato Periderms, Qing Cai

Dissertations, Theses, and Capstone Projects

Suberin is a biopolyester constituent of specialized plant periderm tissues formed within the phellem cell walls. Suberin and waxes of the periderm layer act to prevent water diffusion, mechanical breakdown and pathogenic invasion in plants. Ferulic esters, ω-hydroxyacids and α,ω-fatty diacids are considered to be the most important linkage between aliphatic and aromatic suberin domains and also linked with cell-wall polysaccharides. The potato gene FHT (fatty ω- hydroxyacid/fatty alcohol hydroxycinnamoyl transferase) esterifies ferulic acid to suberin. Diminished levels of feruloyl transferase activity have been associated with lowered amounts of feruloyl esters of fatty acids in both suberin-associated waxes and suberin …