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Chemiluminescent Agents For In Vivo Imaging, Jian Cao

Chemistry Theses and Dissertations

Chemiluminescence is the light production directly from a highly exothermic chemical reaction by generating electronically excited species, and the light will be generated upon relaxation to the ground state. We utilize this light as the readout to construct imaging agents for reactive species. Chemiluminescence as an imaging modality has many advantages compared with current widely used imaging modalities, such as fluorescence and bioluminescence. The main advantages are the elimination of extraneous light excitation or genetic modification, which are required for fluorescence and bioluminescence imaging. Therefore, chemiluminescence as a imaging modality holds great potential for in vivo imaging.

In this dissertation, …

Synthesis And Biological Evaluation Of Small Molecular Drug Candidates For The Treatment Of Her2 Overexpressed Breast Cancer, Anran Zhao

ETD Archive

In the US breast cancer is the most common cancer after skin cancer. Currently in the US the average risk of a woman to develop breast cancer in her life is roughly 12%. About 25-30% of breast cancer patients have HER2 overexpressed tumor, and the growth of tumor cell is depend on HER2 pathway. It has been well-documented that patients with over-expressed HER2 are associated with increased disease recurrence, worse prognosis and lower survival. Currently there are two type of HER2 targeting drug. The first group is HER2 monoclonal antibody drugs such as trastuzumab approved by FDA in 1998; the …

The Great Potential Of Redox Active Ligands: Applications In Cancer Research And Redox Active Catalysis, Meredith Miles

Browse all Theses and Dissertations

Metal N-heterocyclic carbene (NHC) complexes have recently gained much popularity due to their tunable, steric, and electronic properties. Applications for such versatile molecules include organocatalysis, olefin metathesis, sundry cyclization reactions, and materials chemistry. Redox active NHCs are of special interest due to their ability to alter the electronic properties of the metal centers they are ligated to. In the first chapter, Au(I)-NHC complexes were synthesized and tested for biological activity in human cancer cell lines. Increasing reactive oxygen species (ROS) in cellular systems has proven to be a successful pathway for treating cancer. The redox active group in this case …

Preparation And Characterization Of A (Viologen) Containing Main Chain Peg-Carbon Nanotubes Phase For Hybrid Supercapacitor Application, Kanishka Rana

Master's Theses

Supercapacitors (SCs) and batteries are recognized as the two most important electrical energy storage devices. SCs have some distinct advantages such as high-power density and long cycle life when compared to batteries. However, they have yet to match the energy densities of batteries. In an effort to improve the energy density of SCs, a hybrid supercapacitor was developed using a pair of single-walled carbon nanotube electrodes and two polyethylene glycol (PEG-400) gel-polymer electrolytes (GPEs) containing redox additives of viologen (V) and ferrocene dicarboxylic acid (Fc), respectively. The introduction of V and Fc, was expected to improve the energy performance of …

Phd, Xiaofei Liang

Stony Brook Theses and Dissertations Collection, 2006-2020 (closed to submissions)

As(III) compounds have high affinity for thiol groups and this affinity has been used in the prior development of FlAsH and related tags for cysteine peptides. We aimed to develop a series of arsenic-based receptors designed to bind to different arrangements of cysteines within native alpha-helical protein structures. Computer modeling was used to define the proper arrangement of arsenic functionality for binding to each targeted sequence. The computer program HostDesigner was then used to discover scaffold structures on which to display the arsenic functionality at the proper distance and relative orientation to bind the targeted sequence. Designed structures were then …

Synthesis Of Structurally Diverse Major Groove Dna Interstrand Crosslinks, Shivam Mukherjee

Stony Brook Theses and Dissertations Collection, 2006-2020 (closed to submissions)

DNA Interstrand Cross-links (ICLs) are extremely cytotoxic lesions caused by a variety of endogenous and exogenous agents. ICLs prevent the separation of two DNA strands and hence block essential cellular functions such as DNA transcription and replication. ICL causing agents are widely used in cancer chemotherapy and the removal of ICLs is associated with the resistance to anticancer agents. Despite the clinical importance of ICLs, the details of the pathways by which these lesions are repaired remain poorly understood. This dissertation focuses on the synthesis of structurally diverse major groove DNA ICLs that induce different degrees of distortion into the …

Synthesis Of Hybrid Inositol Glycan Analogues, Sudi Sabet

Master's Theses

A 2010 study by Centers for Disease Control and Prevention has projected that one of three US adults could have diabetes by the year 2050. More than 90% of the diagnosed cases are Type II diabetes, a condition characterized by insulin resistance. In search of new antidiabetic drugs, a class of natural, phosphorylated, inositol-containing pseudosaccharides called inositol glycans (IGs) has been studied for years. These compounds have insulin-mimetic activity in insulin-sensitive cells and can stimulate processes such as lipogenesis and glucose transport. Due to the heterogeneity of IGs, it is very difficult to isolate them from their natural sources, and …

Ambidentate Salicylaldimines N-(3-Aminopropyl) Morpholine: Coordination Behaviour Towards Copper, Nickel And Zinc Divalent Ions And Biological Applications / Nurul Azimah Binti Ikmal Hisham, Nurul Azimah Ikmal Hisham

Student Works (2010-2019)

Two flexidentate Schiff-base ligands condensed from salicylaldehyde or 5-chlorosalicylaldehyde with N-(3-aminopropyl)morpholine were prepared in situ and reacted with zinc(II), copper(II) and nickel(II) salts. These compounds were characterised by elemental analyses and various physico-chemical techniques. Single crystal X-ray analyses were carried out on nine different complexes. Upon complexation, the Schiff bases underwent deprotonation at the hydroxyl to act as mono-anionic ligands. When a ligand:metal ratio of 2:1 was applied, the deprotonated Schiff bases coordinated metal ions through phenolate and imine groups in a square-planar or tetrahedral geometry. In contrast, 5-chlorosalicylaldimine reacted with the metal ions in a 1:1 ratio to form …

Surface Studies Of Organic Thin Films Using Scanning Probe Microscopy And Nanofabrication, Venetia Denae Lyles

LSU Doctoral Dissertations

Porphyrins and metalloporphyrins have unique chemical and electronic properties and thus provide useful model structures for nanoscale studies of the role of chemical structure for electronic properties. Porphyrins have been proposed as viable materials for molecular-based information-storage devices, gas sensors, photovoltaic cells, organic light-emitting diodes and molecular wires. The function and efficiency of porphyrins in devices is largely attributable to molecular architecture and how the molecules are self-organized. Modifications of the porphyrin macrocycle, peripheral groups or bound metal ions can generate a range of electrical, photoelectrical or magnetic properties. The conductive properties are greatly influenced at the molecular level by …

Chemical Defense Of An Asian Snake Reflects Local Availability Of Toxic Prey And Hatchling Diet, D. A. Hutchinson, A. H. Savitzky, G. M. Burghardt, C. Nguyen, J. Meinwald, F. C. Schroeder, A. Mori

Biological Sciences Faculty Publications

Species that sequester toxins from prey for their own defense against predators may exhibit population-level variation in their chemical arsenal that reflects the availability of chemically defended prey in their habitat. Rhabdophis tigrinus is an Asian snake that possesses defensive glands in the skin of its neck (nuchal glands'), which typically contain toxic bufadienolide steroids that the snakes sequester from consumed toads. In this study, we compared the chemistry of the nuchal gland fluid of R.tigrinus from toad-rich and toad-free islands in Japan and determined the effect of diet on the nuchal gland constituents. Our findings demonstrate that captive-hatched juveniles …

The Development Of An Effective Water-Soluble Receptor For Pyrene Derivative Dyes, Ashley Longstreet

Undergraduate Theses and Capstone Projects

A receptor with enhanced water solubility was synthesized from an existing receptor to be used as a pyranine fluorescence quencher in endovesiculation detection assays. The existing receptor consisted of a cyclen core with four protruding arms containing an aryl nitro group at each end. Its poor water solubility limited the accuracy and precision of the endovesiculation assay because the low concentration of receptor did not match the concentration of pyranine. To increase the water solubility, ethoxy groups were attached to the ends of each arm by first selectively reducing the nitro group to an amine with NaBHU4, H2, and a …

Synthesis, Characterization And Biological Activity Of Copper (Ii) And Zinc (Ii) Complexes Of Thiosemicarbazones And Their N(4)-Substituted Derivatives Derived From 2,4-Dihydroxybenzaldehyde., Tan Kong Wai

Student Works (2010-2019)

Four thiosemicarbazones ligands (1-4) have been prepared with good yield by refluxing 2,4-dihydroxybenzaldehyde with thiosemicarbazide or N(4)-substituted thiosemicarbazide in ethanol or methanol. From these four ligands, 16 new ternary metal complexes (5-20) with the general formulation of M(B)L have been prepared from the reactions of metal acetates with 2,4-dihydroxybenzaldehyde N(4)-substituted thiosemicarbazone in the presence of N,N-heterocyclic base (M2+ = Zn2+ or Cu2+; B = 2,2'-bipyridine, (bpy); 1,10-phenanthroline, (phen); L2- = doubly deprotonated thiosemicarbazones = 2,4-dihydroxybenzaldehyde thiosemicarbazonato, (HT); 2,4-dihydroxybenzaldehyde 4-methylthiosemicarbazonato, (HM); 2,4-dihydroxybenzaldehyde 4-ethylthiosemicarbazonato, (HE) and 2,4-dihydroxybenzaldehyde 4-phenylthiosemicarbazonato, (HP)) These compounds have been characterized by elemental analyses, IR, UV-Vis, NMR and magnetic …

Gonadotropin Releasing Hormone In Agnathans, Scott Ira Kavanaugh

Doctoral Dissertations

Hagfish and lampreys are the only two representatives of Agnathans among extant vertebrates. The regulatory hypothalamic neurohormone, gonadotropin-releasing hormone (GnRH), regulates reproduction in all vertebrates through the hypothalamic-pituitary-gonadal axis. Most vertebrates have at least two forms of GnRH in the brain. In hagfish the primary amino acid structure of GnRH has not been identified as yet, however, indirect methods have shown an immunoreactive GnRH or a GnRH-like peptide in the brain of hagfish. In addition concentrations of brain immunoreactive-GnRH have been correlated with reproductive stages in the Atlantic hagfish ( Myxine glutinosa). Therefore the objective of the first study was …

A Hybrid First Year Science Course For Engineering Students – Integrating Biology With Chemistry, David Harding, Pauline Schwartz, Jean Nocito-Gobel, Agamemnon Koutsospyros

Civil Engineering Faculty Publications

Biology is playing an increasingly important role in many engineering fields. With the typical engineering program already having a high credit hour requirement, the question becomes, how to best integrate biology concepts into a packed engineering curriculum. A typical biology course is not likely to introduce the important concepts of biology to engineering students. The solution here is to develop a hybrid course that integrates chemistry and biology. In the course, Chemistry with Applications to Biosystems, the concept is to develop a course that integrally links important concepts of chemistry and biology. The course focuses on the areas of biology …

I Complexation Of Iron(Ii), Cobalt(Ii), Nickel(Ii) And Copper(Ii) By Hexadentate Tripodal Aminopyridyl Chelators Ii Binding Preferences For Zinc(Ii) Relative To Nickel(Ii) And Copper(Ii) In Novel Tetradentate Aminopyridyl Chelators, Matthew Lloyd Childers

Master's Theses and Capstones

Chapter I. Effects of pyridyl-ring alkylation on complexation of Fe(II), Co(II), Ni(II) and Cu(II) by chelators based on cis,cis -1,3,5-triaminocyclohexane (tach) have been studied. The chelators studied are derivatives of tachpyr, where the ring substituents are 3-Me, 4-Me, 5-Me, 6-Me or 6-MeO (tach-x-Rpyr). Divalent complexes were synthesized for most combinations of the 4 metals and 5 chelators. Their bonding and structure were analyzed by UV/Vis/NIR spectroscopy, magnetic moment determination and single crystal X-ray crystallography. Steric repulsions between the 6-substituents result in substantially weakened metal-ligand interaction. Effects of these repulsions include bond angle and length distortions, decrease of coordination number to …

Revisiting The Legal Link Between Genetics And Crime, Deborah W. Denno

Law and Contemporary Problems

In 1994, convicted murderer Stephen Mobley became a cause celebre when he appealed his death sentence before the Georgia Supreme Court in the case of Mobley v. State. Denno describes the potential implications arising from the high-profile case of Stephen Mobley. He sought to introduce a then-cutting-edge theory that violence could be based on a genetic or neurochemical abnormality as mitigating evidence during capital sentencing.

Synthesis Of Phosphonopeptides And Alpha, Alpha-Dialkylated Amino Acid-Rich Peptides., Sheila Denise Rushing

LSU Historical Dissertations and Theses

Peptides and peptide analogs are central to the understanding of biological and biochemical phenomena as well as in the development of new pharmaceutical agents. This research encompasses two classes of peptide mimetics: phosphonopeptides and short, amphipathic peptides rich in alpha,alpha-disubstituted amino acids (alphaalphaAA). The focus of the first part of the peptide analog project was on the preparation of sterically-hindered phosphonamide and thiophosphonamide dipeptides. Conditions were developed, based on our P(III) synthetic approach, for the preparation of the phosphonamide dipeptides, Cbz-CyhGly psi [P (O) (OpNb) NH] Trp-NH2 and Cbz-CyhGly psi [P (O) (OpNb) NH] Trp-OMe, which were previously unattainable by …

Transition Metal Complexes Of Novel Ligands Derived From The Cis,Cis-1,3,5-Triaminocyclohexane (Tach) Framework: Structural And Biological Studies, Gyungse Park

Doctoral Dissertations

Transition and Group IIB metal complexes of novel ligands derived from cis,cis-1,3,5-triaminocyclohexane (tach) were prepared for structural and biological activity study. Copper(II) complexes of N,N ',N″-trialkylated derivatives of tach [Cu(tach-R3)Cl2] (R = Me, Et, Pr, furanyl, and thiophenyl) were prepared from CuCl2 in MeOH or MeOH/Et2O solvent. The structures of [Cu(tach-R3)Cl2] in the solid and solution (aqueous and methanolic) states were extensively studied by UV-vis and EPR spectroscopies and were consistent to X-ray structure of [Cu(tach-Et 3)Br0.8Cl1.2] which reveals a slightly distorted square-based pyramidal geometry. Displacement of halide ions with water molecules in aqueous media was observed by the band …

Structure And Function Studies Of De Novo Peptides Containing Novel Amino Acids., Ted Joseph Gauthier

LSU Historical Dissertations and Theses

A series of amphipathic peptides rich in alpha,alpha-disubstituted amino acids (alphaalphaAA's) was synthesized and studied for antimicrobial activity and helix preferences in various solvent systems. In addition, a constrained lactam dipeptide amino acid was synthesized and incorporated into a peptide to examine beta-sheet dimer formation. Several short, amphipathic, 310- and alpha-helical peptides containing 80% alphaalphaAA's were synthesized using various combinations of 1-aminocyclohexane-1-carboxylic acid, alpha-aminoisobutyric acid, and 4-aminopiperidine-4-carboxylic acid. The peptides showed direct antimicrobial activity against E. coli and S. aureus. In addition, several of the peptides showed in vivo and in vitro activity against Brucella abortus and Mycobacterium chelonei. Studies …

The Interface And Characterization Of An Lfesr Spectrometer And Preliminary Study To Detect Ultrasound Induced Radicals By Lfesr Spectroscopy, William Ryan

Theses

A modular low frequency electron spin resonance (LFESR) spectrometer has been interfaced, characterized, and applied in a test to detect ultrasound-induced free radicals with low frequency ESR spectroscopy The modular system, which operates at -250 MHz, was interfaced with a 486DX2 66 MHz PC, using a multifunction PC compatible interface board to facilitate integrated software control of the modular components. The operating software was programmed in Microsoft Visual C++ to execute in the Windows operating environment. Computer control of the magnet was calibrated, using the 2,5-di-tert-butyl parabenzosemiquinone anion radical as a gfactor and hyperfine splitting standard. Preparation of the semiquinone …

Isolation, Structural Elucidation And Structure-Activity Studies Of Natural Products From Regional Plants Of The Asteraceae., Tiansheng Lu

LSU Historical Dissertations and Theses

In a biochemical systematic study of the plant family Asteraceae combined with a search for bioactive natural products, the isolation and structural elucidation of secondary metabolites from seven plant species is reported. Investigation of the roots of Solidago canadensis provided six known and one new clerodane diterpenes related to kolavenic acid and five known matricaria ester-type polyacetylenes. The roots and aerial parts of Solidago rugosa afforded the known diterpenes kolavenol, hardwickiic acid, ($-$)-kaur-16-en-19-oic acid, (+)-manool, (+)-3$\beta$-hydroxymanool, manoyl oxide and ent-abietic acid and the new labdane diterpene, (+)-18-tigloyloxymanool, plus four new ent-abietane diterpenes. The isolation of two new and eight known …

Methyl Oleate Ozonides In Aqueous Micelles: Formation, Stability, And Initiation Of Lipid Peroxidation, And, Relative Antioxidant Efficiencies In Aqueous Micelles Of Anionic And Cationic Surfactants., Mingdan Wu

LSU Historical Dissertations and Theses

Ozonation of methyl oleate has been shown for the first time to form ozonides in aqueous micelles of sodium dodecyl sulfate (SDS) and in L-$\alpha$-distearoyl-phosphatidylcholine (DSPC) liposomes. The total yield of ozonides in 0.02 M SDS micelles exposed to 26 ppm ozone at pH 7.4 and 22$\sp\circ$C is 11.1%. This 11.1% consists of 7.5% of the normal ozonide (MOO2), ca. 4.2% of trans-isomer and ca. 3.3% of cis-isomer, and the rest 3.6% is accounted for by the cross ozonides (MOO1 and MOO3). Regarding the hydrolytic stability of the ozonides under physiologically relevant conditions (e.g., pH 7.4 and 37$\sp\circ$C), the half-lives …

In Vitro Studies On Cigarette Smoke-Mediated Damage To Human Alpha-1-Proteinase Inhibitor., Mark Dennis Evans

LSU Historical Dissertations and Theses

The effect, in vitro, of water soluble components of the particulate phase of cigarette smoke on the elastase inhibitory capacity (EIC) of human alpha-1-proteinase inhibitor ($\alpha\sb1$PI) is studied. Basic features of aqueous cigarette tar extract-mediated damage to $\alpha\sb1$PI are presented, as are mechanistic studies addressing the identities of damaging species and the nature of damage to $\alpha\sb1$PI. Aqueous cigarette tar extract (ACT) causes a slow loss of EIC, and retains this $\alpha\sb1$ PI damaging ability for hours. The damage to $\alpha\sb1$PI by ACT is dependent on its hydrogen peroxide content. Hydroxyl radicals or hypervalent metal species in the homogeneous phase …

Free Radical Production From Criegee Ozonides., James Conrad Ewing

LSU Historical Dissertations and Theses

Allylbenzene ozonide (ABO), a model for poly-unsaturated fatty acid (PUFA) ozonides, is shown to initiate the autoxidation of methyl linoleate (18:2ME) at 37$\sp\circ$C under 760 torr of oxygen. This process is inhibited by d-alpha-tocopherol ($\alpha$-T) and 2,6-di-tert-butyl-4-methylphenol (BHT). Rates of initiated autoxidation were measured by appearance of conjugated diene (C.D.) and oxygen-uptake experiments; rates are proportional to the square root of ABO concentration, implying that the usual free radical autoxidation rate law is obeyed. Activation parameters for the thermal decomposition of ABO were determined under N$\sb2$ in the presence of radical scavengers and found to be E$\sb{\rm a}$ = 28.2 …

Nitrone Spin Traps For Biological Studies. (Volumes I And Ii)., William Reeves Huie

LSU Historical Dissertations and Theses

A variety of aldonitrones for spin-trapping investigations have been synthesized, purified, and characterized. The alicyclic 5-member ring nitrones 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and 3,3,5,5-tetramethyl-1-pyrroline-N-oxide (TMPO) and its long-chain derivatives were prepared in 3 or 4 steps. The reaction steps involved a Michael addition to yield the $\gamma$-nitrocarbonyl compound, subsequent mild reduction with zinc and aqueous ammonium chloride to yield the cyclic intermediate nitrone, a Grignard addition reaction to give the hydroxylamine, and finally copper-catalyzed aerial oxidation of the hydroxylamine to provide the aldonitrone. Poor overall yields were obtained. In contrast, the acyclic aromatic nitrone $\alpha$-phenyl-N-tert-butyl nitrone (PBN) and its derivatives were prepared …

A Comparative Analysis Of Dna Molecular Crosslinking By Dichloro-N-Substituted Azaadamantane Isomers, Harry Robbins

Theses

A series of anti, anti-dichloro-N-substituted azaadamantanes have been synthesized (Henkel et al, 1981, J. Org. Chem. , 46, 3483) representing conformationally rigid nitrogen mustards incorporated into an adamantyl framework with well defined stereochemistry and fixed separation distances between alkylating centers of 3.6 A (1) and 2.5 X (2,3) (Henkel et al, 1981, J. Org. Chem., 46, 3483) to be used as structurally rigid probes of DNA alkylation and intermolecular crosslink formation leading to cytotoxicity. The aqueous solution stability and the extent of intermolecular DNA crosslink formation for both the N-methyl and N-piperdinoethyl series of isomers have been measured using novel …