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Full-Text Articles in Physical Sciences and Mathematics
Synthesis And Reactivity Of Heteroatom Embedded Cycloalkynes In Spaac, Nickel Catalyzed Alkylarylation Of Alkenes, And Carbofluorination Of Alkynes, Namrata Khanal
Chemistry and Chemical Biology ETDs
Part I covers Chapters 1, 2, and 3
cycloaddition reactions, that is utilized in biorthogonal chemistry. This metal free version The strain promoted azide-alkyne cycloaddition (SPAAC) reaction is one of the popular 1,3-dipolar of click reaction offers advantage over copper catalyzed click reaction. Since it eliminates the use of copper that is toxic to cells, it is considered favorable for biocompatible reaction. Due to the increased reactivity with dipoles without the use of metal catalyst, cycloalkynes, in particular cyclooctynes, have been employed as the biorthogonal reagent in biorthogonal chemical reaction for the study of a biological processes in vivo. The …
Synthesis And Surface Modification Of Azide Decorated Silver Nanoclusters, Alexander H. Stöckli
Synthesis And Surface Modification Of Azide Decorated Silver Nanoclusters, Alexander H. Stöckli
Electronic Thesis and Dissertation Repository
In nanocluster research, easy modification of the cluster surface while maintaining the cluster core remains a key challenge. Herein we report the synthesis, structure, and properties of four targeted Ag20 nanoclusters (NCs) with surface azide moieties, two of which have 8 azide moieties, [CO3@Ag20(StBu)10(m-N3-C6H4COO)8(DMF)4] and [CO3@Ag20(StBu)10(p-N3-C6H4COO)8(DMF)4], and two of which have 6 azide moieties, [CO3@Ag20(S …
Synthesis And Characterization Of Sustainable And Biobased Copolymers From Lignocellulosic, Guery Saenz
Synthesis And Characterization Of Sustainable And Biobased Copolymers From Lignocellulosic, Guery Saenz
Theses and Dissertations
Natural compounds have been the primary resource used to produce polymeric materials by humankind since the mid-1900s. Yet, progress in bio-based polymers from renewable feedstock has encountered some obstacles, mainly due to the low prices of petroleum-based monomers, compared to natural and sustainable materials. However, most commodity plastics are non-degradable materials, and solid plastic waste accumulation adversely affects the environment. As the world population is growing and demanding chemicals, energy, and plastics materials, polymer research is focusing on synthesizing bio-based and degradable polymers. Thus, biomass, a sustainable and inexpensive feedstock, is highly appropriate for designing alternative thermoplastics that are degradable …
Chemical Reactions At Metal Surfaces: Functionalization Strategies And Spectroscopic Characterization, Sydney Legge
Chemical Reactions At Metal Surfaces: Functionalization Strategies And Spectroscopic Characterization, Sydney Legge
Electronic Thesis and Dissertation Repository
Tremendous interest in increasing the control over surface properties has led to high demand for new efficient methods for chemical surface modifications. In this work, several approaches toward surface functionalization are explored, and modified surfaces are subsequently characterized using uniquely suited spectroscopic techniques. In the first part of this thesis, strain-promoted alkyne-azide cycloaddition (SPAAC) reactions are investigated for their potential to precisely tune the surface properties of gold substrates at the monolayer level. The utility of SPAAC reactions in preparing biorecognition interfaces for cell adhesion is then examined. Polarization modulation infrared reflection-absorption spectroscopy is used to characterize adsorbed monolayers and …
Leveraging Antibodies For Positron Emission Tomography And Near-Infrared Fluorescence Imaging Of Cancer, Kimberly C. Fung
Leveraging Antibodies For Positron Emission Tomography And Near-Infrared Fluorescence Imaging Of Cancer, Kimberly C. Fung
Dissertations, Theses, and Capstone Projects
The high specificity and affinity of antibodies make them attractive for developing drugs to diagnose and treat cancer. The overarching goal of this work is to explore the synthesis and use of antibody-based imaging agents in preclinical models of cancer. This work can be described as two-fold. In the first part, we investigated how the use of a glycans-specific bioconjugation strategy affects Fc gamma RI binding and why it results in improved in vivo performance of immunoconjugates. To do so, we used the clinically relevant positron emission tomography (PET) imaging agent, 89Zr-DFO-pertuzumab, in mouse models of human breast cancer. …
Strategies For The Preparation Of Functional Pendant Group Polymer Materials Via Click Chemistry, Rajeshwar Vasdev
Strategies For The Preparation Of Functional Pendant Group Polymer Materials Via Click Chemistry, Rajeshwar Vasdev
Electronic Thesis and Dissertation Repository
This thesis describes the development of a polymer via a unique masking-unmasking strategy allowing for physical and chemical modification as desired. Modifiable polymers may lead to improved applications in drug delivery, photo-patterning and emissive materials design. In recent years, these potential traits have motivated the search for efficient protocols for the synthetic modification of polymers. Accordingly, click chemistry, characterized by fast, clean and high yielding reactions represents an effective tool for the modification of polymers. To achieve this goal, an efficient methodology is created to incorporate a highly reactive strained alkyne functional group as a modification site to expand the …
Pretargeted Radioimmunotherapy Utilizing The Inverse Electron Demand Diels-Alder Reaction, Rosemery Membreno
Pretargeted Radioimmunotherapy Utilizing The Inverse Electron Demand Diels-Alder Reaction, Rosemery Membreno
Dissertations, Theses, and Capstone Projects
Radioimmunotherapy capitalizes on the specificity and affinity of antibodies for their antigens to localize radioactivity at the tumor site. One limitation in using antibodies is their long circulation time, which can take days to weeks to fully clear from blood circulation. When a radioisotope is directly conjugated to this immunoglobulin vector, the red marrow and other healthy organs are receiving a constant radiation dose while it is in blood circulation. This not only harms healthy organs, but limits the dose of radioactivity that can be administered thus prolonging treatment. A promising alternative to limit the radiation dose to non-tumor tissue …
Design, Synthesis And Biological Evaluation Of Novel Estradiol-Triazole Analogs Targeting Epidermal Growth Factor Receptors In Colorectal Cancer, Faez Alotaibi
Electronic Theses and Dissertations
Colorectal cancer is a life threatening and second cause of death from cancer in the United States. Several proteins (molecular targets) are highly expressed in Colorectal cancer (CRC). Among these molecular targets is Epidermal Growth Factor Receptors (EGFRs) which are overexpressed in cancer cells. Targeting and blocking the downstream signaling could lead to cease cell proliferation and division and hence control the spread of the disease. Molecular modeling is a powerful tool in drug discovery, which has been utilized to design many drug candidates that exhibit biological effect in many disease including cancer. Additionally, pharmacophores such as 1,2,3-triazole showed potency …
Synthesis And Characterization Of "Click Inspired" Thiol-Ene-Fullerene Nanocomposites, Amber Danielle Windham
Synthesis And Characterization Of "Click Inspired" Thiol-Ene-Fullerene Nanocomposites, Amber Danielle Windham
Dissertations
This work explores the covalent incorporation of C60 and Sc3N@C80 fullerenes into thiol-ene networks by a facile, one-pot photochemical reaction with multifunctional thiol and alkene monomers. Synthesis of disulfide bonds within the tri-functional thiol monomer served to photochemically initiate the reaction when cleaved. This was followed by thermal curing of the pre-polymer for preparation of fullerene-containing thiol-ene films. Films were characterized by standard techniques including infrared spectroscopy, gel percent, and thermogravimetric analysis. The role of C60 and Sc3N@C80 as suitable alkenes for free-radical reaction with multifunctional thiols was investigated by preparing a …
Targeted Delivery Of Nrf2 Sirna Using Modular Polymeric Micellar Nanodelivery System For Efficient Target Gene Knockdown In Hepatocellular Carcinoma, Shaimaa Mohamed Ibrahim Yousef
Targeted Delivery Of Nrf2 Sirna Using Modular Polymeric Micellar Nanodelivery System For Efficient Target Gene Knockdown In Hepatocellular Carcinoma, Shaimaa Mohamed Ibrahim Yousef
Wayne State University Theses
Tumor selective drug delivery as well as chemotherapy associated multi drug resistance (MDR) pose tremendous hurdles for effective cancer therapy. In this regard, designing multifunctional nanocarriers loaded with drug/gene payloads and engineered with tumor targeting ligands can serve as a modular platform for targeted drug/gene delivery. In this study we undertook the synthesis of a self-assembling block copolymer constructed using poly(styrene-co-maleic anhydride, partial iso-octyl ester) (SMAPIE) and branched polyethylenimine (PEI) as building blocks and evaluated its micelle forming ability, siRNA complexation and siRNA delivery potentials. In addition, we engineered galactosamine decorated nanomicelles using modular “click” chemistry based approaches for evaluating …
The Development Of Metal-Organic Compounds For Use As Molecular Imaging Agents, Emily J. Simpson
The Development Of Metal-Organic Compounds For Use As Molecular Imaging Agents, Emily J. Simpson
Electronic Thesis and Dissertation Repository
Molecular imaging probes allow for the non-invasive diagnosis of many diseases through the use of a targeting entity for site specific delivery, as well as a signal for external visualization of probe accumulation in the body. This thesis will focus on the development of new approaches to synthesize targeting peptides and chelators for radionuclide incorporation towards the design of novel molecular imaging probes.
Histidine is a tridentate chelator that can be attached in a pendant fashion to a biomolecule in order to coordinate technetium-99m. Once coordinated, it forms a neutral complex that is capable of forming diastereomers with inverted stereochemistry …
Synthesis Of Carbohydrate Functionalized Dendrons For Use As Multivalent Scaffold And In Self-Assembled Structures, Namrata Jain
Synthesis Of Carbohydrate Functionalized Dendrons For Use As Multivalent Scaffold And In Self-Assembled Structures, Namrata Jain
Electronic Thesis and Dissertation Repository
Carbohydrates are implicated in a large number of biological processes ranging from cell-cell interactions to bacterial and viral infection. Lectins are carbohydrate-binding proteins that are generally specific for certain sugars. However, typical carbohydrate–lectin interactions tend to have very low monomeric binding affinities. In many cases, the binding of saccharide ligands by protein receptors can be improved significantly through the attachment of multiple saccharide residues to a common support. Dendronized polymers constitute a class of macromolecules whose nanoscale size, rigidity, and functionality can be controlled with precision by tuning their molecular architecture. It is hypothesized that due to their large size …
The Application Of Novel Donor Acceptor Cyclopropanes In The Synthesis Of Linearly Fused Tricyclic Triazoles, Michelle E. Flisar
The Application Of Novel Donor Acceptor Cyclopropanes In The Synthesis Of Linearly Fused Tricyclic Triazoles, Michelle E. Flisar
Electronic Thesis and Dissertation Repository
Previous work in the Kerr group has shown the success of donor-acceptor cyclopropanes as substrates in a variety of synthetic reactions; this document will apply the use of donor acceptor cyclopropanes in various synthetic reactions. This was done using a 2-substituted 1,1-cyclopropanediester, in the Overman Rearrangement, which has yet to be explored using DA cyclopropanes. Another useful DA cyclopropane is the novel acetylene-bearing donor acceptor diester cyclopropanes which would be synthetically useful in a wide variety of reactions. In particular, the Conia-ene cyclization occurred intramolecularly with this alkyne DA cyclopropane with a large library of nucleophiles. Finally, taking this acetylene-bearing …
Photocleavable Junctions In Complex Polymer Architectures And Photoetchable Thermoplastics, Elizabeth Surles Sterner
Photocleavable Junctions In Complex Polymer Architectures And Photoetchable Thermoplastics, Elizabeth Surles Sterner
Doctoral Dissertations
Polymer materials have become important tools in nanomanufacturing due to their facile processing and ready attainment of the necessary feature sizes. The development of cleavable junctions has led to advances in the production of polymer nanotemplates. Photocleavage strategies have come to the forefront of the field because photons, as a cleavage stimulus, do not have the mass-transport limitations of chemical methods, and provide for targeted two- and three-dimensional feature control. This dissertation presents a method for producing photocleavable materials by one-pot copper-catalyzed azide-alkyne “click” chemistry (CuAAC), activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) and activated ester …
Detection Of Heavy Transition Metal Cations Using Novel Chemosensors, Shannon Rhodes
Detection Of Heavy Transition Metal Cations Using Novel Chemosensors, Shannon Rhodes
Honors College Theses
Transition metals (TM) are found in the environment and living systems. When present in excess, these metals can trigger health problems, which include memory loss and cognitive functions. In this project, commercially-available compounds were used to aid in the making of novel mono- and di-triazole molecular sensors with a well-known reaction called “click chemistry”. These sensors were used efficiently and selectively to attract a specific metal like iron III, copper, and zinc. Six sensors were tested via UV-spectroscopy, NMR, and fluorescence with the cations and selectivity increased as the sensors were altered.
Ph Responsive Hydrogen Bonding Motif To Improve The Sensitivity Of Tumor Imaging, Fatimah Mohammed Algarni
Ph Responsive Hydrogen Bonding Motif To Improve The Sensitivity Of Tumor Imaging, Fatimah Mohammed Algarni
Electronic Thesis and Dissertation Repository
Magnetic resonance imaging (MRI) is a powerful non-invasive medical diagnostic technique. Superparamagnetic iron oxide nanoparticles (SPIO) are effective contrast agents and provide high sensitivity contrast in MRI. Recent research has demonstrated that nanoparticle clusters exhibit significantly higher relaxivity than individual nanoparticles.
In order to increase the sensitivity of tumor imaging, supramolecular chemistry was introduced to this field and a novel conjugation method was developed using click chemistry between azide functionalized nanoparticles and pH-sensitive hydrogen bonding building blocks. This pH-sensitive hydrogen bonded complex was synthesized to cluster nanoparticles under mildly acidic biological conditions.
Due to the unexpected X-ray crystal structure of …
Homogeneous And Heterogeneous Approaches To 1,2,4-Triazine-Accelerated Copper-Catalyzed Azide-Alkyne Cycloadditions, Ashleigh Lauren Prince
Homogeneous And Heterogeneous Approaches To 1,2,4-Triazine-Accelerated Copper-Catalyzed Azide-Alkyne Cycloadditions, Ashleigh Lauren Prince
Doctoral Dissertations
Over the last decade, the domain of click chemistry has grown exponentially and has significantly impacted the fields of organic synthesis, medicinal chemistry, molecular biology, and materials science. The ideal model of a click reaction has become the copper-catalyzed azide-alkyne cycloaddition (CuAAC). Inherent limitations of CuAAC, including high temperatures, long reaction times, and difficult purifications, have been minimized by the development of nitrogen-based ligands. Herein, we present a novel application of 1,2,4-triazines by investigating their use as accelerants for CuAAC.
A diverse library of 1,2,4-triazines were synthesized in order to examine the molecular determinants of their catalytic activity. These ligands …
Precision Synthesis Of Functional Materials Via Raft Polymerization And Click-Type Chemical Reactions, Joel Diez Flores
Precision Synthesis Of Functional Materials Via Raft Polymerization And Click-Type Chemical Reactions, Joel Diez Flores
Dissertations
The need to tailor polymeric architectures with specific physico-chemical properties via the simplest, cleanest, and most efficient synthetic route possible has become the ultimate goal in polymer synthesis. Recent progress in macromolecular science, such as the discoveries of controlled/“living” free radical polymerization (CRP) methods, has brought about synthetic capabilities to prepare (co)polymers with advanced topologies, predetermined molecular weights, narrow molecular weight distributions, and precisely located functional groups. In addition, the establishment of click chemistry has redefined the selected few highly efficient chemical reactions that become highly useful in post-polymerization modification strategies. Hence, the ability to make well-defined topologies afforded by …
Characterization Of Metastasis-Associated Cell Surface Glycoproteins In Prostate Cancer, Lifang Yang
Characterization Of Metastasis-Associated Cell Surface Glycoproteins In Prostate Cancer, Lifang Yang
Theses and Dissertations in Biomedical Sciences
Prostate cancer (PCa) is a major health problem in males in the United States. Its lethality is mostly attributed to the primary tumor metastasizing to distant sites that are highly resistant to conventional therapies. Serum Prostate Specific Antigen (PSA) is the only protein biomarker used in clinic for prediction of prostate cancer recurrence following local therapies. Nonetheless, PSA lacks the ability to predict the behavior of an individual tumor in an individual patient. Therefore, development of reliable biomarkers for detection of metastatic potential in primary tumors, as well as discovery of new therapeutic targets, is in a great need for …
The First Attachment And Post-Functionalization Of Polybutadiene And Thio-Click Functionalized Polybutadiene On H-Terminated Si(111), Todd Devere Wickard
The First Attachment And Post-Functionalization Of Polybutadiene And Thio-Click Functionalized Polybutadiene On H-Terminated Si(111), Todd Devere Wickard
Theses and Dissertations
I report the attachment of polymers with pendant vinyl groups to hydrogen-terminated silicon(111) (Si(111)-H) under mild conditions. 1,2-addition polybutadiene (Mw 3200-3500) was attached to Si(111)-H at room temperature with visible light. I also report the partial functionalization, in solution, of 1,2-addition polybutadiene with various thiols using thiol-click chemistry. These compounds bind to Si(111)-H via visible light activation. The partially functionalized polybutadienes allow further functionalization at the surface through unreacted carbon-carbon double bonds. Surfaces were characterized with contact angle goniometry, spectroscopic ellipsometry, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and atomic force microscopy (AFM).