Chemistry Commons^™

Evaluation And In Vitro Studies Of Folate Peg Biotin And Other Peg Agents, Syed Zahid Hussain

All Capstone Projects

Folate is a member of vitamin B family and plays an essential role in cell survival by participating in the biosynthesis of nucleic and amino acids. Receptors folic acid are frequently over expressed on epithelial cancer cells. These receptors are believed to serve as a receptor-mediated transport system of folic acid into cancer cells and cells associated with inflammation. Interesting, most normal cells in the body have lower frequency of these receptors. Based on these attributes, folate based drug delivery, imaging systems, and diagnostic systems are in several stages of development worldwide.

In this current project, we have characterized the …

Literature Search On Using Dendrimer Nanoparticles As Drug Delivery Vehicles, Sivateja Kasaraneni

All Capstone Projects

The architectural design of dendrimers, multivalency, well-defined molecular weight and higher degree of branching differentiates them as unique and excellent nanocarriers in therapeutic applications such as drug delivery, gene transfection, tumor therapy, imaging and diagnostics. Nanoparticle drug-delivery systems are well known to increase the stability and selectivity of therapeutic agents. However immunogenicity, reticuloendothelial system uptake, drug leakage, cytotoxicity, hemolytic toxicity, poor aqueous solubility restrict the use of these drug delivery systems. These defects are overcame by surface engineering of the dendrimer molecule.

Drug molecule can be efficiently conjugated or encapsulated into the interior of the dendrimer or physically adsorbed onto …

Purification And Analysis Of Folate-Dye Conjugate, Sravya Mothe

All Capstone Projects

Folate receptor has achieved great importance for use in targeted drug delivery and in vitro and in vivo diagnostic assays. Folate receptor (FR) is over expressed on several cancer cell types and activated macrophages, but exists in relatively low abundance on the surface of non-cancerous tissue and non-inflammatory cells. This unique attribute is the hallmark of folate – targeted methodologies allowing the diagnostic agent and/or drug to be ferried to the specific disease sites while preventing “off target” effects in normal tissues. Although several folate-based dyes have been reported, simple and detailed synthetic and purification methods for these conjugates have …

Synthesis, Structure And Attempted Polymerization Of A Diepoxide Macrocycle, Paul Yarincik, Jeffrey H. Glans

Chemistry & Physics Faculty Publications

A novel diepoxide containing paracyclophane was synthesized by peracid oxidation of a known paracyclophane diene. The resulting diepoxide was characterized. It was investigated as a potential monomer for a cyclophane containing polyether by cationic ring opening polymerization. None of the standard catalyst systems for such a polymerization were successful in producing polymer.

Quality Assurance Plan Project For Copper Determination Using Flame Atomic Absorption Spectroscopy, Bharath Raparthi

All Capstone Projects

This study developed a method for determination of Copper by flame atomic absorption spectrometry (FAAS) from the soil samples and mine tailings using Perkin Elmer AAnalyst 800 atomic absorption spectrometer. A detailed procedure has been developed with a detection limit of 0.12 mg/L. In the recent decades, pollution from heavy metals has been increased. Copper is one of the trace metals that has a significant impact and carries risk to the human health. Calibration curve was established with working range 0.1 ppm to 5 ppm with a correlation coefficient of 0.9994. Over 50 environmental samples from the historic Copper mining …

Cox Inhibitors Indomethacin And Sulindac Derivatives As Antiproliferative Agents: Synthesis, Biological Evaluation, And Mechanism Investigation, Snigdha Chennamaneni, Bo Zhong, Rati Lama, Bin Su

Chemistry Faculty Publications

Cyclooxygenase (COX) inhibitors Indomethacin and its structural analogs Sulindac exhibit cell growth inhibition and apoptosis inducing activities in various cancer cell lines via COX independent mechanisms. In this study, the molecular structures of Indomethacin and Sulindac were used as starting scaffolds to design novel analogs and their effects on the proliferation of human cancer cells were evaluated. Compared to Indomethacin and Sulindac inhibiting cancer cell proliferation with IC50s of more than 1 mM, the derivatives displayed significantly increased activities. Especially, one of the Indomethacin analogs inhibited the growth of a series of cancer cell lines with IC50s around 0.5 μM–3 …

Liposome Encapsulation Of A Photochemical No Precursor For Controlled Nitric Oxide Release And Simultaneous Fluorescence Imaging, Alexis D. Ostrowski, Brian F. Lin, Matthew V. Tirrell, Peter C. Ford

Chemistry Faculty Publications

Described are photochemical studies of the nitric oxide precursors, trans-Cr(L)(ONO)(2)(+) (L = cyclam = 1,4,8,11-tetraazacyclotetradecane, CrONO, or L = mac = 5,7-dimethyl-6-anthracenylcyclam, mac-CrONO) encapsulated in phosphatidylcholine liposomes. The liposomes provide a means to maintain a localized high concentration of NO releasing complexes and are easily modified for in vivo targeting through self-assembly. Steady, controlled release of NO is seen after photolysis of the liposome-encapsulated CrONO as compared to the burst of NO release seen by the unencapsulated complex in oxygenated solutions. The quantum yields for photochemical NO release from liposome-encapsulated CrONO and mac-CrONO were determined in both oxygenated and anoxic …

Probing The Role Of Asn 152 In The Class C Β-Lactamase Ampc, Brianne Docter, Mujahid Anwar, David Leonard, Rachel Powers, Bradley Wallar

Student Summer Scholars Manuscripts

AmpC, a class C β-lactamase, is a main cause of antibiotic resistance to cephalosporins in many species of bacteria. The current proposed mechanism of action involves an acyl-intermediate, where the enzyme becomes covalently attached to the drug at serine-64, before an activated water hydrolyzes the bond and regenerates the enzyme. Although this mechanism is generally accepted, the exact roles that the other active site residues play in recognition and breakdown of the substrate are not fully understood. Here, we investigate the role of the active site residue asparagine-152 (Asn152) in E. coli AmpC by mutating it to a glycine, serine, …

The Influence Of Auxiliary Ligands On The Photophysical Characteristics Of A Series Of Ruthenium (Ii) Polypyridyl Complexes, Luke O'Neill, Laura Perdisatt, Christine O'Connor

Articles

A series of ruthenium polypyridyl complexes were studied using UV/Vis absorption and luminescence spectroscopy as well as luminescence lifetime determination by time correlated single photon counting (TCSPC). The complexes were characterised with regard to the variation in the electronic band-gap as a result of the sequential variation of the auxiliary ligand 2,2’-bipyridine (bpy), 1,10-phenanthroline (phen) and 2,2’-biquinoline (biq) ligands while the main ligand remained constant for three different main ligand types. Luminescence yields were calculated and correlated with structural and electronic variation. It was found that both the absorption and emission characteristics could be tailored through the systematic variation of …

Spectral Characterization Of Cytochromes P450 Active Site And Catalytic Intermediates, Daniel Kaluka

Dissertations (1934 -)

Cytochromes P450 (P450s) have been the subject of intense research for over six decades. Though it is widely accepted that a highly reactive Fe(IV)=O π-cation radical, or the so called compound I, facilitates the oxidation of relatively inert hydrocarbons, spectroscopic characterization of this putative intermediate has eluded detection under turnover conditions, presumably due to its very short lifetime. In this work, chemically inert substrates of P450s have been utilized in a new approach to capture and stabilize this transient intermediate and characterize it with resonance Raman (RR) spectroscopy, which is a well established tool for studying heme proteins. Specifically, perfluorodecanoic …

Real-Time Reaction Monitoring And Flash Separation As A Process Analytical Technology Tool And Hplc Method Development For Melamine In Infant Formula, Gopalakrishnan Venkatasami

Seton Hall University Dissertations and Theses (ETDs)

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Rat Brain Pro-Oxidant Effects Of Peripherally Administered 5 Nm Ceria 30 Days After Exposure, Sarita S. Hardas, Rukhsana Sultana, Govind Warrier, Mo Dan, Rebecca L. Florence, Peng Wu, Eric A. Grulke, Michael T. Tseng, Jason M. Unrine, Uschi M. Graham, Robert A. Yokel, D. Allan Butterfield

Chemistry Faculty Publications

The objective of this study was to determine the residual pro-or anti-oxidant effects in rat brain 30 days after systemic administration of a 5 nm citrate-stabilized ceria dispersion. A ∼4% aqueous ceria dispersion was iv-infused (0 or 85 mg/kg) into rats which were terminated 30 days later. Ceria concentration, localization, and chemical speciation in the brain was assessed by inductively coupled plasma mass spectrometry (ICP-MS), light and electron microscopy (EM), and electron energy loss spectroscopy (EELS), respectively. Pro- or anti-oxidant effects were evaluated by measuring levels of protein carbonyls (PC), 3-nitrotyrosine (3NT), and protein-bound-4-hydroxy-2-trans-nonenal (HNE) in the hippocampus, cortex, and …

Fast Melt Cooled Superconducting Alloys: (Bi1.97pb0.03sr2can‐1cuno2n+4+Δ)2 N/N’ N<24 Intergrowth, J. Kmiec, Juana Acrivos, D. Gulamova, J. Chigvinadze

Faculty Publications, Chemistry

High temperature layer superconducting cuprate (HTLSC) alloys: (Bi1.97Pb0.03Sr2Can-1CunO2n+4+δ)2 called (2s:2:n-1:n) have been grown from n-oxide stoichiometric melts in concentrated sun flux, followed by rapid cooling SFQA technology that preserves the melt tiling after annealing at 845±5oC**. Synchrotron XRD at the DOE SLAC-SSRL near the Cu K-edge has identified the mixing of n ≠ n’ alloys as observed by many in thin films last century. An ideal D17 4h Space Group structure obtains {an, bn, cn} = {3.815 Å, an+ubn, 2dP(n+3)+ucn} where dP is a perovskite sandwich, (CuO2)1/2|_Ca|(CuO2)1/2, thickness, and un are the amplitudes of periodic lattice distortions, PLD also observed …

An Expeditious Iodine-Catalyzed Synthesis Of 3-Pyrrole-Substituted 2-Azetidinones, Debasish Bandyopadhyay, Jessica Cruz, Ram N. Yadav, Bimal K. Banik

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

2-Azetidinones and pyrroles are two highly important classes of molecules in organic and medicinal chemistry. A green and practical method for the synthesis of 3-pyrrole-substituted 2-azetidinones using catalytic amounts of molecular iodine under microwave irradiation has been developed. Following this method, a series of 3-pyrrole-substituted 2-azetidinones have been synthesized with a variety of substituents at N-1 and at C-4. The procedure is equally effective for mono-as well as polyaromatic groups at the N-1 position of the 2-azetidinone ring. The C-4 substituent has no influence either on the yield or the rate of the reaction. Optically pure 3-pyrrole-substituted 2-azetidinones have also …

Project Synthesis Of N Acetyl L Histidine Ethyl Amide And Standard Operating Procedure For Fractional Collector, Maneesha Jakkampudi

All Student Theses and Dissertations

Photo oxidation of proteins leads to the formation of cross links of the amino acids in the proteins and leads to induction of cataracts, photo aging of the skin and in the Photodynamic therapy of tumors.

Oxidation of proteins involves significant modification of particular amino acids residues with consequent photodynamic damage. Studies show that tryptophan, tyrosine and histidine side chains gives rise to semi stable peroxides on exposure to singlet oxygen these oxidized structures are studied with low temperature NMR. These peroxides or species derived from them have been postulated as key intermediates in subsequent reactions such as cross linking …

Quantitative Determination Of Acetylsalicyclic Acid And Acetaminophen By Q-Nmr (Quantitative Nuclear Magnetic Resonance) Technique, Gouthami Kanduri

All Student Theses and Dissertations

The pharmaceutical industry mainly uses chromatographic techniques such as High Performance Liquid Chromatography (HPLC) and Gas Chromatography (GC), to determine the quantity of the active ingredient and other material in the drugs. A large effort goes into developing methods using chromatography techniques. The method development and running HPLC and GC are time consuming. Methods need to be updated as the chromatographic columns and the instruments wear out. On the other hand, Nuclear Magnetic Resonance (NMR) technique is mainly used for qualitative analysis to determine the identity of compounds. However, Proton-NMR technique does provide quantitative information of compounds but to develop …

Syntheses And Electronic Properties Of Rhodium(Iii) Complexes Bearing A Redox-Active Ligand, Sarath Wanniarachchi, Brendan J Liddle, Brandon Kizer, Jeewantha S. Hewage, Sergey V. Lindeman, James R. Gardinier

Chemistry Faculty Research and Publications

A series of rhodium(III) complexes of the redox-active ligand, H(L = bis(4-methyl-2-(1H-pyrazol-1-yl)phenyl)amido), was prepared, and the electronic properties were studied. Thus, heating an ethanol solution of commercial RhCl3·3H2O with H(L) results in the precipitation of insoluble [H(L)]RhCl3, 1. The reaction of a methanol suspension of [H(L)]RhCl3 with NEt4OH causes ligand deprotonation and affords nearly quantitative yields of the soluble, deep-green, title compound (NEt4)[(L)RhCl3]·H2O, 2·H2O. Complex 2·H2O reacts readily with excess pyridine, triethylphosphine, or pyrazine (pyz) to eliminate NEt4Cl and give charge-neutral complexes trans-(L)RhCl2(py), trans-3, trans-(L)RhCl2(PEt3), trans- 4, or trans-(L)RhCl2(pyz), trans-5, where the incoming Lewis base is trans- to the amido …

Chemical Proteomics-Based Analysis Of Off-Target Binding Profiles For Rosiglitazone And Pioglitazone: Clues For Assessing Potential For Cardiotoxicity, Brian R. Hoffmann, Mohamed F. El-Mansy, Daniel S. Sem, Andrew S. Greene

Chemistry Faculty Research and Publications

Drugs exert desired and undesired effects based on their binding interactions with protein target(s) and off-target(s), providing evidence for drug efficacy and toxicity. Pioglitazone and rosiglitazone possess a common functional core, glitazone, which is considered a privileged scaffold upon which to build a drug selective for a given target—in this case, PPARγ. Herein, we report a retrospective analysis of two variants of the glitazone scaffold, pioglitazone and rosiglitazone, in an effort to identify off-target binding events in the rat heart to explain recently reported cardiovascular risk associated with these drugs. Our results suggest that glitazone has affinity for dehydrogenases, consistent …

Structural, Spectroscopic, And Electrochemical Properties Of Nonheme Fe(Ii)-Hydroquinonate Complexes: Synthetic Models Of Hydroquinone Dioxygenases, Amanda E. Baum, Heaweon Park, Denan Wang, Sergey V. Lindeman, Adam T. Fiedler

Chemistry Faculty Research and Publications

Using the tris(3,5-diphenylpyrazol-1-yl)borate (^Ph2Tp) supporting ligand, a series of mono- and dinuclear ferrous complexes containing hydroquinonate (HQate) ligands have been prepared and structurally characterized with X-ray crystallography. The monoiron(II) complexes serve as faithful mimics of the substrate-bound form of hydroquinone dioxygenases (HQDOs) – a family of nonheme Fe enzymes that catalyze the oxidative cleavage of 1,4-dihydroxybenzene units. Reflecting the variety of HQDO substrates, the synthetic complexes feature both mono- and bidentate HQate ligands. The bidentate HQates cleanly provide five-coordinate, high-spin Fe(II) complexes with the general formula [Fe(^Ph2Tp)(HL^X)] (1X), where HL^X is …

Experimental Documentation Of The Structural Consequences Of Hydrogen-Bonding Interactions To The Proximal Cysteine Of A Cytochrome P450, Piotr J. Mak, Yuting Yang, Sangchoul Im, Lucy A. Waskell, James R. Kincaid

Chemistry Faculty Research and Publications

Resonance Raman spectroscopy is used to document, for the first time, a 6 cm−1 decrease of the Fe-S stretch by introducing an H-bond donor into the proximal pocket of a cytochrome P450, which interacts with the key cysteine thiolate axial ligand. The anticipated trans-effect on bound exogenous ligands is also confirmed and evidence is obtained supporting intimate interaction of the new histidyl-imidazole fragment with the heme periphery.

Cop1 Mediates The Coordination Of Root And Shoot Growth By Light Through Modulation Of Pin1- And Pin2-Dependent Auxin Transport In Arabidopsis, Massimiliano Sassi, Yanfen Lu, Yonghong Zhang, Juan Wang, Pankaj Dhonukshe, Ikram Blilou, Minqiu Dai, Juan Li, Ximing Gong, Yvon Jaillais, Xuhong Yu, Jan Traas, Ida Ruberti, Haiyang Wang, Ben Scheres, Teva Vernoux, Jian Xu

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

When a plant germinates in the soil, elongation of stem-like organs is enhanced whereas leaf and root growth is inhibited. How these differential growth responses are orchestrated by light and integrated at the organismal level to shape the plant remains to be elucidated. Here, we show that light signals through the master photomorphogenesis repressor COP1 to coordinate root and shoot growth in Arabidopsis. In the shoot, COP1 regulates shoot-to-root auxin transport by controlling the transcription of the auxin efflux carrier gene PIN-FORMED1 (PIN1), thus appropriately tuning shoot-derived auxin levels in the root. This in turn directly influences root elongation and …

Exploring The Role Of A Conserved Class A Residue In The Ω-Loop Of Kpc-2 Β-Lactamase: A Mechanism For Ceftazidime Hydrolysis

Chemistry Faculty Publications

Gram-negative bacteria harboring KPC-2, a class A β-lactamase, are resistant to all β-lactam antibiotics and pose a major public health threat. Arg-164 is a conserved residue in all class A β-lactamases and is located in the solvent-exposed Ω-loop of KPC-2. To probe the role of this amino acid in KPC-2, we performed site-saturation mutagenesis. When compared with wild type, 11 of 19 variants at position Arg-164 in KPC-2 conferred increased resistance to the oxyimino-cephalosporin, ceftazidime (minimum inhibitory concentration; 32→128 mg/liter) when expressed in Escherichia coli. Using the R164S variant of KPC-2 as a representative β-lactamase for more detailed analysis, we …

Characterization Of The Libs Plasma Of An Explosive Stimulant, 3-Nitrobenzoic Acid, Nathan Andrew Bullock

Student Theses and Dissertations

An organic nitro compound representative of nitro based explosives is examined using Laser Induced Breakdown Spectroscopy (LIBS). This technique shows promise in the field of analytical chemistry and is a candidate for the standoff detection of explosives. In this thesis we examined the formation of diatomic molecules produced in the plasma. The trends observed are discussed, including the possibility of non-LTE conditions as well as optical thickness. We discuss the various formation pathways of these molecules and temperature effects on their formation. Matrix effects are examined in the context of the measurement of excitation temperatures and implications for the real …

Fe(Ii) Complexes That Mimic The Active Site Structure Of Acetylacetone Dioxygenase: O2 And No Reactivity, Heoweon Park, Michael M. Bittner, Jacob Baus, Sergey V. Lindeman, Adam T. Fiedler

Chemistry Faculty Research and Publications

Acetylacetone dioxygenase (Dke1) is a bacterial enzyme that catalyzes the dioxygen-dependent degradation of β-dicarbonyl compounds. The Dke1 active site contains a nonheme monoiron(II) center facially ligated by three histidine residues (the 3His triad); coordination of the substrate in a bidentate manner provides a five-coordinate site for O₂ binding. Recently, we published the synthesis and characterization of a series of ferrous β-diketonato complexes that faithfully mimic the enzyme–substrate intermediate of Dke1 (Park, H.; Baus, J.S.; Lindeman, S.V.; Fiedler, A.T. Inorg. Chem.2011, 50, 11978–11989). The 3His triad was modeled with three different facially coordinating N3 supporting ligands, and …

Restricted Access Media And Methods For Making Restricted Access Media, David S. Hage, Chunling Wa, Abby Jackson, Hai Xuan

David Hage Publications

The present invention is directed to restricted access media (RAM), methods for preparing restricted access media, and kits for preparing restricted access media that contain protected ligand binding agents or protected enzymes. Certain RAM provided contain a plurality of protected regions of the Support that contain ligand binding agents that are protected by blocking agents. Certain RAM provided contain a plurality of protected regions of the support that contain unbound ligand binding agents or enzymes that are retained in the protected regions by a capping agent. Methods of making the RAM of the invention and associated kits are also provided.

Structural Insight Into The Mechanism Of Oxygen Activation And Substrate Selectivity Of Flavin-Dependent N-Hydroxylating Monooxygenases, Stefano Franceschini, Michael Fedkenheuer, Nancy J. Vogelaar, Howard H. Robinson, Pablo Sobrado, Andrea Mattevi

Chemistry Faculty Research & Creative Works

SidA from the human pathogen Aspergillus fumigatus catalyzes the generation of N5-hydroxyornithine in the biosynthesis of siderophores, a reaction essential for virulence. The crystal structures of SidA in complex with ornithine and lysine reveal the geometry of the interactions among flavin, NADP+, and the substrate amine group that underlie the hydroxylation reaction. The structural elucidation of the enzyme in complex with arginine provides insight into the role of electrostatics and hydrogen bonding in the mechanism of oxygen activation in this family of enzymes. © 2012 American Chemical Society.

Synthesis And Characterization Of Chain-End Functionalization Of Glycosaminoglycans, Nikola Paulic, Jacob J. Weingart

Undergraduate Research Posters 2012

This presentation reports the CSU Summer Undergraduate Research project, which is the synthesis and characterization of chain-end functionalized CS derivatives, which will be used to investigate various bio-orthogonal conjugation reactions in attempt to create a novel CS-rTM conjugate.

Differential Protein Expression In Polystichum Acrostichoides Due To Metal Exposure, Paul Alexander Ilkanich, Pratheek C. Koneru

Undergraduate Research Posters 2012

Plants are considered the most cost effective and environmentally sound way to clean up the soils and water contaminated with toxic metals. We focused our studies on the fern species Polystichum acrostichoides. A total of 17 protein spots were up regulated and 3 proteins were down regulated upon various metal exposures, and are arranged to be subjected to liquid chromatography-tandem mass spectrometry for further identification.

Derivatization Of Free Glycans For Glycan Sensor And Glyco-Functionalization Applications, Rhonda D. Jones

Undergraduate Research Posters 2012

Glycans, especially, cell surface glycans acting as receptors, are involved in a wide range of biological processes. Analysis of the cell surface glycans provides a basis for understanding the molecular mechanism of glycan-mediated biological process. The present method can be applied in derivatizing sugars from natural sources for glycan sensor and glyco-functionalization applications.

Method And Apparatus For Jet-Assisted Drilling Or Cutting, David A. Summers, Klaus Woelk, Kenneth Doyle Oglesby, Greg Galecki

Mining Engineering Faculty Research & Creative Works

An abrasive cutting or drilling system, apparatus and method, which includes an upstream supercritical fluid and/or liquid carrier fluid, abrasive particles, a nozzle and a gaseous or low-density supercritical fluid exhaust abrasive stream. The nozzle includes a throat section and, optionally, a converging inlet section, a divergent discharge section, and a feed section.