Chemistry - Theses, Dissertations, and other Required Graduate Degree Essays

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Structural insights into f-block heterobimetallic dicyanoaurate coordination polymers

Author: 
Date created: 
2021-12-16
Abstract: 

The first series of uranyl ([UO2]2+)-dicyanoaurate coordination polymers has been synthesized and characterized. The diversity of structures generated demonstrates the flexibility of uranyl and dicyanoaurate as building blocks. Small changes in solvent, reactions conditions, dicyanoaurate salt, and ancillary ligands lead to a wide range of structures, ranging from molecular compounds, to a series of one-dimensional chains (including a ladder with alternating aurophilic and peroxo rungs), to a two-dimensional network of aurophilic and hydrogen-bonds, and an unusual three-dimensional lattice of tetranuclear uranyl-oxo-nitrate clusters connected by dicyanoaurate linkers, with the rotation of the clusters providing the increased dimensionality. This final material undergoes a reversible single-crystal to single-crystal transformation on exposure to or removal from water vapour. The luminescence properties of these materials have been found to range from no detectable emission, to only the uranyl-based emission being detected, to both uranyl and either Au(I) or aurophilic emission being detected. Building on this f-block chemistry, a series of lanthanide-dicyanoaurate-2,2′-bipyridine dioxide (OOBipy) coordination polymers has been created with the formula Ln(OOBipy)2(H2O)x(Au(CN2)3)·yEtOH·zH2O, where x and y = 0–2, and z = 0–4. It is possible to convert between these coordination polymers by the addition of heat or water vapour. The coordination polymers containing Sm, Eu, and Tb were found to be emissive, and those with only Eu or Tb were found to have excellent quantum yields. Attempts to create blended materials of Eu and Tb lead to the quenching of Tb’s emission, and blending of Sm and Tb produced lackluster quantum yields. A procedure to export ellipsoidal crystallographic data to 3D printing file formats was documented. This method gives the ability to export structures from the CCDC’s Mercury to 3D printing file formats, allowing 3D ellipsoidal models to be printed quickly and easily. This has been demonstrated using the uranyl-peroxo coordination polymer mentioned above. Additionally, a method of 3D printing complex or challenging structures by breaking them into parts with connectors, printing each part separately, and then assembling the structure post-printing was developed. This has advantages such as multicoloured printing, framework optimization and reduction, print time reduction, and can be used to bypass print size limitations.

Document type: 
Thesis
Supervisor(s): 
Daniel B. Leznoff
Department: 
Science: Department of Chemistry
Thesis type: 
(Thesis) Ph.D.

Structural insights into f-block heterobimetallic dicyanoaurate coordination polymers

Author: 
Date created: 
2021-12-16
Abstract: 

The first series of uranyl ([UO2]2+)-dicyanoaurate coordination polymers has been synthesized and characterized. The diversity of structures generated demonstrates the flexibility of uranyl and dicyanoaurate as building blocks. Small changes in solvent, reactions conditions, dicyanoaurate salt, and ancillary ligands lead to a wide range of structures, ranging from molecular compounds, to a series of one-dimensional chains (including a ladder with alternating aurophilic and peroxo rungs), to a two-dimensional network of aurophilic and hydrogen-bonds, and an unusual three-dimensional lattice of tetranuclear uranyl-oxo-nitrate clusters connected by dicyanoaurate linkers, with the rotation of the clusters providing the increased dimensionality. This final material undergoes a reversible single-crystal to single-crystal transformation on exposure to or removal from water vapour. The luminescence properties of these materials have been found to range from no detectable emission, to only the uranyl-based emission being detected, to both uranyl and either Au(I) or aurophilic emission being detected. Building on this f-block chemistry, a series of lanthanide-dicyanoaurate-2,2′-bipyridine dioxide (OOBipy) coordination polymers has been created with the formula Ln(OOBipy)2(H2O)x(Au(CN2)3)·yEtOH·zH2O, where x and y = 0–2, and z = 0–4. It is possible to convert between these coordination polymers by the addition of heat or water vapour. The coordination polymers containing Sm, Eu, and Tb were found to be emissive, and those with only Eu or Tb were found to have excellent quantum yields. Attempts to create blended materials of Eu and Tb lead to the quenching of Tb’s emission, and blending of Sm and Tb produced lackluster quantum yields. A procedure to export ellipsoidal crystallographic data to 3D printing file formats was documented. This method gives the ability to export structures from the CCDC’s Mercury to 3D printing file formats, allowing 3D ellipsoidal models to be printed quickly and easily. This has been demonstrated using the uranyl-peroxo coordination polymer mentioned above. Additionally, a method of 3D printing complex or challenging structures by breaking them into parts with connectors, printing each part separately, and then assembling the structure post-printing was developed. This has advantages such as multicoloured printing, framework optimization and reduction, print time reduction, and can be used to bypass print size limitations.

Document type: 
Thesis
Supervisor(s): 
Daniel B. Leznoff
Department: 
Science: Department of Chemistry
Thesis type: 
(Thesis) Ph.D.

Structural insights into f-block heterobimetallic dicyanoaurate coordination polymers

Author: 
Date created: 
2021-12-16
Abstract: 

The first series of uranyl ([UO2]2+)-dicyanoaurate coordination polymers has been synthesized and characterized. The diversity of structures generated demonstrates the flexibility of uranyl and dicyanoaurate as building blocks. Small changes in solvent, reactions conditions, dicyanoaurate salt, and ancillary ligands lead to a wide range of structures, ranging from molecular compounds, to a series of one-dimensional chains (including a ladder with alternating aurophilic and peroxo rungs), to a two-dimensional network of aurophilic and hydrogen-bonds, and an unusual three-dimensional lattice of tetranuclear uranyl-oxo-nitrate clusters connected by dicyanoaurate linkers, with the rotation of the clusters providing the increased dimensionality. This final material undergoes a reversible single-crystal to single-crystal transformation on exposure to or removal from water vapour. The luminescence properties of these materials have been found to range from no detectable emission, to only the uranyl-based emission being detected, to both uranyl and either Au(I) or aurophilic emission being detected. Building on this f-block chemistry, a series of lanthanide-dicyanoaurate-2,2′-bipyridine dioxide (OOBipy) coordination polymers has been created with the formula Ln(OOBipy)2(H2O)x(Au(CN2)3)·yEtOH·zH2O, where x and y = 0–2, and z = 0–4. It is possible to convert between these coordination polymers by the addition of heat or water vapour. The coordination polymers containing Sm, Eu, and Tb were found to be emissive, and those with only Eu or Tb were found to have excellent quantum yields. Attempts to create blended materials of Eu and Tb lead to the quenching of Tb’s emission, and blending of Sm and Tb produced lackluster quantum yields. A procedure to export ellipsoidal crystallographic data to 3D printing file formats was documented. This method gives the ability to export structures from the CCDC’s Mercury to 3D printing file formats, allowing 3D ellipsoidal models to be printed quickly and easily. This has been demonstrated using the uranyl-peroxo coordination polymer mentioned above. Additionally, a method of 3D printing complex or challenging structures by breaking them into parts with connectors, printing each part separately, and then assembling the structure post-printing was developed. This has advantages such as multicoloured printing, framework optimization and reduction, print time reduction, and can be used to bypass print size limitations.

Document type: 
Thesis
Supervisor(s): 
Daniel B. Leznoff
Department: 
Science: Department of Chemistry
Thesis type: 
(Thesis) Ph.D.

Chemical tools for studying O-GlcNAc

Author: 
Date created: 
2021-03-25
Abstract: 

O-GlcNAcylation is a post-translational modification that governs certain cellular pathways essential for eukaryotic cell functioning including transcription, translation, and protein transport. Its activity has been discovered to relate closely with neurodegenerative disorders including Parkinson and Alzheimer disease. O-GlcNAcylation is facilitated by two enzymes: UDP-N-acetyl-D-glucosamine:polypeptidyl-transferase (OGT) transfers O-GlcNAc onto serine and threonine residues; O-GlcNAcase (OGA) cleaves O-GlcNAc off to liberate a free protein substrate. In this dissertation, we focused on developing new chemical tools to better understand the effect of O-GlcNAcylation in a biological context. To monitor the activity of OGT in cell, we demonstrated the use of a fluorophore integrated O-GlcNAc intermediate which can be tolerated by UDP-N-acetylglucosamine pyrophosphorylase and turned over by OGT to monitor O-GlcNAcylation in cells without the need of an engineered cell line. Upon further development, we envision this probe can potentially open the door to directly screen large numbers of OGT ligands in a cellular level. On the other hand, the use of OGA inhibitor has proven to decrease tau accumulation in tau-overexpression mice; aggregation of hyperphosphorylated tau is a pathological hallmark of Alzheimer disease. Current inhibitors have been hindered by the challenge of high total polar surface area hence lowering their permeability across blood brain barrier. We further investigated the effect of the side chain with the use of click chemistry approach to increase its versatility which allow quick tethering towards improving the pharmacokinetic of the inhibitors. To better access these iminocyclitol inhibitors, we also further developed new chemistries along with the incorporation of α-chlorohydrin aldol-ring annulation approach to generate the polyhydroxy-pyrrolidine core structure. We also demonstrated effort towards synthesis of a non-saccharide OGA inhibitor which incorporate structural key elements of 1,2,-dideoxy-2’-ethylamino-α-D-glucopyranoso-[2,1-d-Δ2’-thiazoline] (Thiamet-G), 6-acetamido-6-deoxy-castanospermine (6-Ac-Cas) and O-(2-acetamido-2-deoxy-D-glucopyranosylidene)-amino-N-phenylcarbamate (PUGNAc). These inhibitors should prove useful, following further refinement, for the wider community.

Document type: 
Thesis
File(s): 
Supervisor(s): 
David Vocadlo
Department: 
Science: Department of Chemistry
Thesis type: 
(Thesis) Ph.D.

Structural insights into f-block heterobimetallic dicyanoaurate coordination polymers

Author: 
Date created: 
2021-12-16
Abstract: 

The first series of uranyl ([UO2]2+)-dicyanoaurate coordination polymers has been synthesized and characterized. The diversity of structures generated demonstrates the flexibility of uranyl and dicyanoaurate as building blocks. Small changes in solvent, reactions conditions, dicyanoaurate salt, and ancillary ligands lead to a wide range of structures, ranging from molecular compounds, to a series of one-dimensional chains (including a ladder with alternating aurophilic and peroxo rungs), to a two-dimensional network of aurophilic and hydrogen-bonds, and an unusual three-dimensional lattice of tetranuclear uranyl-oxo-nitrate clusters connected by dicyanoaurate linkers, with the rotation of the clusters providing the increased dimensionality. This final material undergoes a reversible single-crystal to single-crystal transformation on exposure to or removal from water vapour. The luminescence properties of these materials have been found to range from no detectable emission, to only the uranyl-based emission being detected, to both uranyl and either Au(I) or aurophilic emission being detected. Building on this f-block chemistry, a series of lanthanide-dicyanoaurate-2,2′-bipyridine dioxide (OOBipy) coordination polymers has been created with the formula Ln(OOBipy)2(H2O)x(Au(CN2)3)·yEtOH·zH2O, where x and y = 0–2, and z = 0–4. It is possible to convert between these coordination polymers by the addition of heat or water vapour. The coordination polymers containing Sm, Eu, and Tb were found to be emissive, and those with only Eu or Tb were found to have excellent quantum yields. Attempts to create blended materials of Eu and Tb lead to the quenching of Tb’s emission, and blending of Sm and Tb produced lackluster quantum yields. A procedure to export ellipsoidal crystallographic data to 3D printing file formats was documented. This method gives the ability to export structures from the CCDC’s Mercury to 3D printing file formats, allowing 3D ellipsoidal models to be printed quickly and easily. This has been demonstrated using the uranyl-peroxo coordination polymer mentioned above. Additionally, a method of 3D printing complex or challenging structures by breaking them into parts with connectors, printing each part separately, and then assembling the structure post-printing was developed. This has advantages such as multicoloured printing, framework optimization and reduction, print time reduction, and can be used to bypass print size limitations.

Document type: 
Thesis
Supervisor(s): 
Daniel B. Leznoff
Department: 
Science: Department of Chemistry
Thesis type: 
(Thesis) Ph.D.

Structural insights into f-block heterobimetallic dicyanoaurate coordination polymers

Author: 
Date created: 
2021-12-16
Abstract: 

The first series of uranyl ([UO2]2+)-dicyanoaurate coordination polymers has been synthesized and characterized. The diversity of structures generated demonstrates the flexibility of uranyl and dicyanoaurate as building blocks. Small changes in solvent, reactions conditions, dicyanoaurate salt, and ancillary ligands lead to a wide range of structures, ranging from molecular compounds, to a series of one-dimensional chains (including a ladder with alternating aurophilic and peroxo rungs), to a two-dimensional network of aurophilic and hydrogen-bonds, and an unusual three-dimensional lattice of tetranuclear uranyl-oxo-nitrate clusters connected by dicyanoaurate linkers, with the rotation of the clusters providing the increased dimensionality. This final material undergoes a reversible single-crystal to single-crystal transformation on exposure to or removal from water vapour. The luminescence properties of these materials have been found to range from no detectable emission, to only the uranyl-based emission being detected, to both uranyl and either Au(I) or aurophilic emission being detected. Building on this f-block chemistry, a series of lanthanide-dicyanoaurate-2,2′-bipyridine dioxide (OOBipy) coordination polymers has been created with the formula Ln(OOBipy)2(H2O)x(Au(CN2)3)·yEtOH·zH2O, where x and y = 0–2, and z = 0–4. It is possible to convert between these coordination polymers by the addition of heat or water vapour. The coordination polymers containing Sm, Eu, and Tb were found to be emissive, and those with only Eu or Tb were found to have excellent quantum yields. Attempts to create blended materials of Eu and Tb lead to the quenching of Tb’s emission, and blending of Sm and Tb produced lackluster quantum yields. A procedure to export ellipsoidal crystallographic data to 3D printing file formats was documented. This method gives the ability to export structures from the CCDC’s Mercury to 3D printing file formats, allowing 3D ellipsoidal models to be printed quickly and easily. This has been demonstrated using the uranyl-peroxo coordination polymer mentioned above. Additionally, a method of 3D printing complex or challenging structures by breaking them into parts with connectors, printing each part separately, and then assembling the structure post-printing was developed. This has advantages such as multicoloured printing, framework optimization and reduction, print time reduction, and can be used to bypass print size limitations.

Document type: 
Thesis
Supervisor(s): 
Daniel B. Leznoff
Department: 
Science: Department of Chemistry
Thesis type: 
(Thesis) Ph.D.

Structural insights into f-block heterobimetallic dicyanoaurate coordination polymers

Author: 
Date created: 
2021-12-16
Abstract: 

The first series of uranyl ([UO2]2+)-dicyanoaurate coordination polymers has been synthesized and characterized. The diversity of structures generated demonstrates the flexibility of uranyl and dicyanoaurate as building blocks. Small changes in solvent, reactions conditions, dicyanoaurate salt, and ancillary ligands lead to a wide range of structures, ranging from molecular compounds, to a series of one-dimensional chains (including a ladder with alternating aurophilic and peroxo rungs), to a two-dimensional network of aurophilic and hydrogen-bonds, and an unusual three-dimensional lattice of tetranuclear uranyl-oxo-nitrate clusters connected by dicyanoaurate linkers, with the rotation of the clusters providing the increased dimensionality. This final material undergoes a reversible single-crystal to single-crystal transformation on exposure to or removal from water vapour. The luminescence properties of these materials have been found to range from no detectable emission, to only the uranyl-based emission being detected, to both uranyl and either Au(I) or aurophilic emission being detected. Building on this f-block chemistry, a series of lanthanide-dicyanoaurate-2,2′-bipyridine dioxide (OOBipy) coordination polymers has been created with the formula Ln(OOBipy)2(H2O)x(Au(CN2)3)·yEtOH·zH2O, where x and y = 0–2, and z = 0–4. It is possible to convert between these coordination polymers by the addition of heat or water vapour. The coordination polymers containing Sm, Eu, and Tb were found to be emissive, and those with only Eu or Tb were found to have excellent quantum yields. Attempts to create blended materials of Eu and Tb lead to the quenching of Tb’s emission, and blending of Sm and Tb produced lackluster quantum yields. A procedure to export ellipsoidal crystallographic data to 3D printing file formats was documented. This method gives the ability to export structures from the CCDC’s Mercury to 3D printing file formats, allowing 3D ellipsoidal models to be printed quickly and easily. This has been demonstrated using the uranyl-peroxo coordination polymer mentioned above. Additionally, a method of 3D printing complex or challenging structures by breaking them into parts with connectors, printing each part separately, and then assembling the structure post-printing was developed. This has advantages such as multicoloured printing, framework optimization and reduction, print time reduction, and can be used to bypass print size limitations.

Document type: 
Thesis
Supervisor(s): 
Daniel B. Leznoff
Department: 
Science: Department of Chemistry
Thesis type: 
(Thesis) Ph.D.

Structural insights into f-block heterobimetallic dicyanoaurate coordination polymers

Author: 
Date created: 
2021-12-16
Abstract: 

The first series of uranyl ([UO2]2+)-dicyanoaurate coordination polymers has been synthesized and characterized. The diversity of structures generated demonstrates the flexibility of uranyl and dicyanoaurate as building blocks. Small changes in solvent, reactions conditions, dicyanoaurate salt, and ancillary ligands lead to a wide range of structures, ranging from molecular compounds, to a series of one-dimensional chains (including a ladder with alternating aurophilic and peroxo rungs), to a two-dimensional network of aurophilic and hydrogen-bonds, and an unusual three-dimensional lattice of tetranuclear uranyl-oxo-nitrate clusters connected by dicyanoaurate linkers, with the rotation of the clusters providing the increased dimensionality. This final material undergoes a reversible single-crystal to single-crystal transformation on exposure to or removal from water vapour. The luminescence properties of these materials have been found to range from no detectable emission, to only the uranyl-based emission being detected, to both uranyl and either Au(I) or aurophilic emission being detected. Building on this f-block chemistry, a series of lanthanide-dicyanoaurate-2,2′-bipyridine dioxide (OOBipy) coordination polymers has been created with the formula Ln(OOBipy)2(H2O)x(Au(CN2)3)·yEtOH·zH2O, where x and y = 0–2, and z = 0–4. It is possible to convert between these coordination polymers by the addition of heat or water vapour. The coordination polymers containing Sm, Eu, and Tb were found to be emissive, and those with only Eu or Tb were found to have excellent quantum yields. Attempts to create blended materials of Eu and Tb lead to the quenching of Tb’s emission, and blending of Sm and Tb produced lackluster quantum yields. A procedure to export ellipsoidal crystallographic data to 3D printing file formats was documented. This method gives the ability to export structures from the CCDC’s Mercury to 3D printing file formats, allowing 3D ellipsoidal models to be printed quickly and easily. This has been demonstrated using the uranyl-peroxo coordination polymer mentioned above. Additionally, a method of 3D printing complex or challenging structures by breaking them into parts with connectors, printing each part separately, and then assembling the structure post-printing was developed. This has advantages such as multicoloured printing, framework optimization and reduction, print time reduction, and can be used to bypass print size limitations.

Document type: 
Thesis
Supervisor(s): 
Daniel B. Leznoff
Department: 
Science: Department of Chemistry
Thesis type: 
(Thesis) Ph.D.

Structural insights into f-block heterobimetallic dicyanoaurate coordination polymers

Author: 
Date created: 
2021-12-16
Abstract: 

The first series of uranyl ([UO2]2+)-dicyanoaurate coordination polymers has been synthesized and characterized. The diversity of structures generated demonstrates the flexibility of uranyl and dicyanoaurate as building blocks. Small changes in solvent, reactions conditions, dicyanoaurate salt, and ancillary ligands lead to a wide range of structures, ranging from molecular compounds, to a series of one-dimensional chains (including a ladder with alternating aurophilic and peroxo rungs), to a two-dimensional network of aurophilic and hydrogen-bonds, and an unusual three-dimensional lattice of tetranuclear uranyl-oxo-nitrate clusters connected by dicyanoaurate linkers, with the rotation of the clusters providing the increased dimensionality. This final material undergoes a reversible single-crystal to single-crystal transformation on exposure to or removal from water vapour. The luminescence properties of these materials have been found to range from no detectable emission, to only the uranyl-based emission being detected, to both uranyl and either Au(I) or aurophilic emission being detected. Building on this f-block chemistry, a series of lanthanide-dicyanoaurate-2,2′-bipyridine dioxide (OOBipy) coordination polymers has been created with the formula Ln(OOBipy)2(H2O)x(Au(CN2)3)·yEtOH·zH2O, where x and y = 0–2, and z = 0–4. It is possible to convert between these coordination polymers by the addition of heat or water vapour. The coordination polymers containing Sm, Eu, and Tb were found to be emissive, and those with only Eu or Tb were found to have excellent quantum yields. Attempts to create blended materials of Eu and Tb lead to the quenching of Tb’s emission, and blending of Sm and Tb produced lackluster quantum yields. A procedure to export ellipsoidal crystallographic data to 3D printing file formats was documented. This method gives the ability to export structures from the CCDC’s Mercury to 3D printing file formats, allowing 3D ellipsoidal models to be printed quickly and easily. This has been demonstrated using the uranyl-peroxo coordination polymer mentioned above. Additionally, a method of 3D printing complex or challenging structures by breaking them into parts with connectors, printing each part separately, and then assembling the structure post-printing was developed. This has advantages such as multicoloured printing, framework optimization and reduction, print time reduction, and can be used to bypass print size limitations.

Document type: 
Thesis
Supervisor(s): 
Daniel B. Leznoff
Department: 
Science: Department of Chemistry
Thesis type: 
(Thesis) Ph.D.

Structural insights into f-block heterobimetallic dicyanoaurate coordination polymers

Author: 
Date created: 
2021-12-16
Abstract: 

The first series of uranyl ([UO2]2+)-dicyanoaurate coordination polymers has been synthesized and characterized. The diversity of structures generated demonstrates the flexibility of uranyl and dicyanoaurate as building blocks. Small changes in solvent, reactions conditions, dicyanoaurate salt, and ancillary ligands lead to a wide range of structures, ranging from molecular compounds, to a series of one-dimensional chains (including a ladder with alternating aurophilic and peroxo rungs), to a two-dimensional network of aurophilic and hydrogen-bonds, and an unusual three-dimensional lattice of tetranuclear uranyl-oxo-nitrate clusters connected by dicyanoaurate linkers, with the rotation of the clusters providing the increased dimensionality. This final material undergoes a reversible single-crystal to single-crystal transformation on exposure to or removal from water vapour. The luminescence properties of these materials have been found to range from no detectable emission, to only the uranyl-based emission being detected, to both uranyl and either Au(I) or aurophilic emission being detected. Building on this f-block chemistry, a series of lanthanide-dicyanoaurate-2,2′-bipyridine dioxide (OOBipy) coordination polymers has been created with the formula Ln(OOBipy)2(H2O)x(Au(CN2)3)·yEtOH·zH2O, where x and y = 0–2, and z = 0–4. It is possible to convert between these coordination polymers by the addition of heat or water vapour. The coordination polymers containing Sm, Eu, and Tb were found to be emissive, and those with only Eu or Tb were found to have excellent quantum yields. Attempts to create blended materials of Eu and Tb lead to the quenching of Tb’s emission, and blending of Sm and Tb produced lackluster quantum yields. A procedure to export ellipsoidal crystallographic data to 3D printing file formats was documented. This method gives the ability to export structures from the CCDC’s Mercury to 3D printing file formats, allowing 3D ellipsoidal models to be printed quickly and easily. This has been demonstrated using the uranyl-peroxo coordination polymer mentioned above. Additionally, a method of 3D printing complex or challenging structures by breaking them into parts with connectors, printing each part separately, and then assembling the structure post-printing was developed. This has advantages such as multicoloured printing, framework optimization and reduction, print time reduction, and can be used to bypass print size limitations.

Document type: 
Thesis
Supervisor(s): 
Daniel B. Leznoff
Department: 
Science: Department of Chemistry
Thesis type: 
(Thesis) Ph.D.