Organic Chemistry Commons^™

Electron Transfer In Electrophilic Aromatic Nitration And Nitrosation, Yirong Mo, Zhenhua Chen

Faculty Research and Creative Activities Award (FRACAA)

No abstract provided.

Facile Synthesis Of Silver Nanoparticles Stabilized By Cationic Polynorbornenes And Their Catalytic Activity In 4-Nitrophenol Reduction, Bharat Baruah, Gregory J. Gabriel, Michelle J. Akbashev, Matthew E. Booher

Faculty Articles

We report the facile one-pot single-phase syntheses of silver nanoparticles stabilized by norbornene type cationic polymers. Silver nanoparticles (AgNPs) stabilized by polyguanidino oxanorbornenes (PG) at 5 and 25 kDa and polyamino oxanorbornenes (PA) at 3 and 15 kDa have been synthesized by the reduction of silver ions with NaBH4 in aqueous solutions at ambient temperature. The four different silver nanoparticles have been characterized by UV-vis spectroscopy, Fourier transform infrared spectroscopy (FTIR), dynamic light scattering (DLS), and transmission electron microscopy (TEM) for their particle size distributions. Interestingly, PG stabilizes the silver nanoparticles better than PA as evident from our spectroscopic data. …

Expulsion Of Leaving Groups From Zwitterionic Intermediates Generated Via Photochemical Electrocyclic Ring Closure Reactions And An Investigation On Tpe Oligomers, Tasnuva Shahrin

Dissertations (1934 -)

Photochemical cleavage reactions have been found widespread use in biological applications that require intracellular photochemical release of biologically active substrates such as peptides, proteins, neurotransmitters, or nucleotide phosphates. The research is to devise photoremovable protecting groups (cage compounds) that can be used to deprotect those biological substrates by irradiation. A number of photocleavage reactions have been developed in recent years which release chlorides, hydroxides, carboxylates, thiolates, and phenolates leaving groups for use in such applications. Nevertheless, photochemical elimination reactions that expel such leaving group anions remain quite uncommon. The cleavage of cage compounds via photolysis requires heterolysis of a bond …

Metal-Organic And Supramolecular Architectures Based On Mechanically Interlocked Molecules, Isurika Rosini Fernando

Dissertations

The focus of this work is on mechanically interlocked molecules (MIMs), which have unusual physicochemical and mechanical properties with potential applications in nano-scale/molecular devices and high strength materials.

Rotaxanes, for example, consist of an axle-like molecule threaded through a wheel-like molecule, with bulky groups at the two ends of the axle preventing the wheel from dissociating. The position of the wheel along the axle can be switched in a controllable and reversible manner by applying external stimuli, a feature that might lead to the next generation of computers. Molecularly woven materials (MWMs), another example of molecules with mechanically interlocked features, …

A Novel Algorithm For Validating Peptide Identification From A Shotgun Proteomics Search Engine, Ling Jian, Xinnan Niu, Zhonghang Xia, Parimal Samir, Chiranthani Sumanasekera, Zheng Mu, Jennifer L. Jennings, Kristen L. Hoek, Tara Allos, Leigh M. Howard, Kathryn M. Edwards, P. Anthony Weil, Andrew J. Link

Chemistry Faculty Research

Liquid chromatography coupled with tandem mass spectrometry (LC–MS/MS) has revolutionized the proteomics analysis of complexes, cells, and tissues. In a typical proteomic analysis, the tandem mass spectra from a LC–MS/MS experiment are assigned to a peptide by a search engine that compares the experimental MS/MS peptide data to theoretical peptide sequences in a protein database. The peptide spectra matches are then used to infer a list of identified proteins in the original sample. However, the search engines often fail to distinguish between correct and incorrect peptides assignments. In this study, we designed and implemented a novel algorithm called De-Noise to …

Spectral Data For "Generation Of Molecular Complexity From Cyclooctatetraene: Preparation Of Optically Active Protected Aminocycloheptitols And Bicyclo[4.4.1]Undecatriene", Mohamed F. El-Mansy, Anobick Sar, Sergey V. Lindeman, William A. Donaldson

Natural Products Synthesis via Organoiron Methodology

Spectral data created in the course of the research project. Supports specific findings in "Generation of Molecular Complexity from Cyclooctatetraene: Preparation of Optically Active Protected Aminocycloheptitols and Bicyclo[4.4.1]undecatriene".

The racemic (6-cyclo-heptadienyl)Fe(CO)₃⁺ cation ((±)-7), prepared from cyclooctatetraene, was treated with a variety of carbon and heteroatom nucleophiles. Attack took place at the less hindered C¹ dienyl carbon and decomplexation of the (cycloheptadiene)Fe(CO)₃ complexes gave products rich in functionality for further synthetic manipulation. In particular, a seven-step route was developed from racemic (6-styryl-2,4-cycloheptadien-1-yl)phthalimide ((±)-9 d) to afford the optically active aminocycloheptitols (−)-20 and …

Preparation Of Organofluorine Compounds: Exploring Mono-, Di-, And Tri-Fluorination, Diandra M. Rudzinski

Master's Theses

Organofluorine compounds exhibit biological activity and have advantageous properties for drug design. Natural occurring fluorinated molecules are rare, demanding new synthetic methods for their preparation. A novel route to access trifluoromethyl ketones from Weinreb amide precursors is discussed. This is the first documented method for the use of the Ruppert-Prakash reagent, (trifluoromethyl)trimethylsilane, for the production of trifluoromethyl ketones from amide starting materials. This method is tolerant of aryl and alkyl substrates exhibited by their moderate to excellent yields. A discussion of the unusual reactivity of these amides, their selectivity for mono-trifluoromethylation, and other mono-, and di-fluorination attempts are reported.

Using Stable Isotope Analysis Of Zooplankton To Document Trophic And Biogeochemical Changes In The San Francisco Estuary, Steven C. Westbrook, Julien Moderan

STAR Program Research Presentations

Zooplankton represent a vital link between phytoplankton and fish, like the endangered Delta Smelt. Human interferences (nitrates from waste water, flow alteration, invasive species introduction…) have altered the structure of the San Francisco Estuary (SFE) ecosystem. We use stable isotope analysis to improve our knowledge of the planktonic food web in the SFE and gain insights into its evolution over the past decades. We use the ratios of certain isotopes (Nitrogen, Carbon, Sulfur, etc.) in different species of zooplankton to tell us what it is feeding on as well as the trophic level it feeds in. My research focused on …

Organic Thin-Film Transistors And Tips-Pentacene, Zachary Stewart

Lewis Honors College Capstone Collection

TIPS-Pentacene, an organic semiconductor characterized by its good electronic properties, solubility, and stability, is used primarily in organic thin-film transistors (OTFT). This research seeks to create an OTFT by crafting a stencil, depositing the source and drain onto a substrate’s surface, and processing TIPS-Pentacene onto the channel between them. In addition, if time permits, the electronic properties of several OTFTs will be compared to determine how to optimize their production.

Synthesis And Application Of Atp Analogs For Phosphorylation-Dependent Kinase-Substrate Crosslinking, Satish Kumar Garre Venkata Raghavendra

Wayne State University Dissertations

Phosphorylation is an important post-translational modification that plays a key role in a variety of signaling cascades and cellular functions. Kinases phosphorylate protein substrates in a highly regulated manner and are promiscuous. Understanding kinase-substrate specificity has been challenging and there is a need for new chemical tools. To this end we developed -phosphate modified ATP photocrosslinking analogs ATP-ArN3 and ATP-BP, that crosslink substrate and kinase in a phosphorylation dependent manner. We have successfully demonstrated that ATP-ArN3 and ATP-BP can be used with natural kinase and substrates using cell lysates in vitro. We used our approach to identify novel kinases of …

1. Chromium(0)- Promoted Higher Order Cycloaddition Reactions: Studies Toward The Total Synthesis Of The Cyclocitrinols And Echinopines A And B 2. Total Synthesis Of (±)-Debromoflustramine B Via [4+1] Cyclization Of An Indole Isocyanate And A Bis(Alkylthio)Carbene, Saptarshi De

Wayne State University Dissertations

A facile and short stereoselective synthesis of the functionalized tetracyclic core structure of the cyclocitrinols, a family of unusual C25 steroid isomers, has been accomplished. The key structural unit, the bicyclo[4.4.1]A/B ring system, was constructed by a regioselective Cr(0)-promoted [6π + 4π] photochemical cycloaddition reaction.

A Bronsted acid catalyzed rearrangement of the 11-trimethylsilyl-tetracyclo[8.1.0.03,7.04,11]undeca-5,8-diene ring system to the unusual homotriquinacene ring system. The trimethylsilyl substitution on the cyclopropane moiety was found to be crucial for the rapid transformation which is believed to proceed via carbocation intermediates.

A short concise formal synthesis of Echinopines A and B is reported. The key [5.5.7] …

Adding Gas Chromatography-Mass Spectrometry Data To A Melting Point And Thin-Layer Chromatography Laboratory, Adam M. Azman, Julie A. Barrett, Megan Darragh, John J. Esteb

Scholarship and Professional Work - LAS

The addition of gas chromatography–mass spectrometry (GC–MS) data interpretation to a thin-layer chromatography (TLC) and melting point (mp) laboratory for an introductory organic course is described.

The Rich Chemistry Of Cyclotriveratrylene (Ctv) And Ct-Inspired Reactions: Anthracenes With Organic Light-Emitting Diode (Oled) Applications And The Discovery Of Cascade Reactions, Samuel Sarsah

Dissertations

Cyclotriveratrylene (CTV) is a supramolecular scaffold with applications in host-guest chemistry, analytical detection, drug delivery and liquid crystals. We have discovered that CTV rearranges to a highly functionalized anthracene derivative that is ideal for the synthesis of 9,10-disubstituted anthracene derivatives that are useful for the construction of organic light-emitting diodes (OLEDs). Several diaryl anthracene derivatives have been synthesized and analyzed, and were found to have excellent electroluminescent properties, including one analog that exhibits an exceptionally high quantum yield. Red, green and blue are the primary colors needed for full color display, but blue fluorescence emitting organic compounds used in OLEDs …

Diffusion Of Vitamin B12 Across A Mesoporous Metal Organic Framework, Veronica Valencia

Undergraduate Journal of Mathematical Modeling: One + Two

We measure the rate of uptake and the rate of release of a Vitamin B12 solution (dissolved in water) at 2 different temperatures (room temperature and 37°C) by the mesoporous metal organic framework TbMOF-100 at 1-hour intervals using a spectrophotometer. Using the Beer-Lambert law, we calculate the concentration of the stock solution based on the absorbance values obtained with the spectrophotometer. These values allow for the quantification of the initial rate of uptake and the rate of uptake at a random incubation time of the Vitamin B12 by the TbMOF-100. We also calculate the value of the coefficient of diffusion …

Preparation Of Phosphonoterephthalic Acids Via Palladium-Catalyzed Coupling Of Aromatic Iodoesters, Nathaniel Ivan, Vladimir Benin, Alexander Morgan

Chemistry Faculty Publications

The current article reports in detail the preparation of two phosphonoterephthalic acids: 2-phosphonoterephthalic acid (1) and 2,5-diphosphonoterephthalic acid (2). Efficient, scalable syntheses have been developed for both compounds based on Pd-catalyzed coupling reactions of iodinated terephthalate esters. Phosphonoterephthalic acids are potentially useful as flame-retardant additives or as monomers for the construction of acid-pendant polymer chains.

Synthesis Of Orthogonally Protected Azalanthionines (Lanazanines) By Sequential Ring-Opening Of N-Substituted Aziridine 2-Carboxylates, Keith O'Brien, Keith Ó Proinsias, Fintan Kelleher

Articles

Orthogonally protected azalanthionines (lanazanines, 4-azadiaminopimelic acids or b-aminoalaninoalanines) have been synthesised in good yields by the ring-opening of N-protected aziridine 2-carboxylates with suitably protected diaminopropanoic acids (DAPs). The required DAPs were also synthesised by ring-opening of N-protected aziridine 2-carboxylates with para-methoxybenzylamine.

Study On Polydimethylsiloxane (Pdms) Surface Over The Time, Saeed A. Bigdeli

Summer Community of Scholars Posters (RCEU and HCR Combined Programs)

No abstract provided.

Synthetic Approaches To Thiacorannulene, Rama Yaghi

Legacy Theses & Dissertations (2009 - 2024)

Thiacorannulene is an unknown, open geodesic heteropolyarene comprised of a central five-membered ring surrounded by four benzene rings and one thiophene ring. This heterobuckybowl is expected to have unique physical, chemical and biological properties. The curvature in thiacorannulene should provide two distinct surfaces, convex and concave, and should affect properties such as dipole moment, ionization potential, metal binding, etc. Having a thiophene ring embedded in its structure is expected to influence the reactivity of this compound. We sought to devise syntheses of the unknown heterobuckybowl based on earlier, optimized syntheses of buckybowls, heterobuckybowls, and heterocirculenes. Details of our attempted syntheses …

(S)-Trifluoroselenomethionine : A New Non-Natural Amino Acid With Enhanced Methioninase-Induced Cytotoxicity Toward Human Colon Cancer Cells, Stephene Nathele Lodge

Legacy Theses & Dissertations (2009 - 2024)

Abstract

Iron (Iii) Tosylate Catalyzed Synthesis Of 3,4-Dihydropyrimidin-2(1h)-Ones/Thiones, Ram Mohan, Jacob Starcevich, Thomas Laughlin

Scholarship

No abstract provided.