subject:(Department of Chemistry)

Addis Ababa University

1. Gebremedhn, Elias. Computational and Experimental Study on the Dual Fluorescence Phenomenon of 4-(N, N-dimethylamino)- benzonitrile and Related Compounds .

Degree: 2012, Addis Ababa University

URL: http://etd.aau.edu.et/dspace/handle/123456789/712

► Abstract: The behavior of the ground and the first two excited states of the compound 4-(N,N-dimethylamino)-benzonitrile (4DMABN) have been studied using both experimental and theoretical… (more)

Subjects/Keywords: Department of Chemistry

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APA (6^th Edition):

Gebremedhn, E. (2012). Computational and Experimental Study on the Dual Fluorescence Phenomenon of 4-(N, N-dimethylamino)- benzonitrile and Related Compounds . (Thesis). Addis Ababa University. Retrieved from http://etd.aau.edu.et/dspace/handle/123456789/712

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Gebremedhn, Elias. “Computational and Experimental Study on the Dual Fluorescence Phenomenon of 4-(N, N-dimethylamino)- benzonitrile and Related Compounds .” 2012. Thesis, Addis Ababa University. Accessed January 18, 2020. http://etd.aau.edu.et/dspace/handle/123456789/712.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Gebremedhn, Elias. “Computational and Experimental Study on the Dual Fluorescence Phenomenon of 4-(N, N-dimethylamino)- benzonitrile and Related Compounds .” 2012. Web. 18 Jan 2020.

Vancouver:

Gebremedhn E. Computational and Experimental Study on the Dual Fluorescence Phenomenon of 4-(N, N-dimethylamino)- benzonitrile and Related Compounds . [Internet] [Thesis]. Addis Ababa University; 2012. [cited 2020 Jan 18]. Available from: http://etd.aau.edu.et/dspace/handle/123456789/712.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Gebremedhn E. Computational and Experimental Study on the Dual Fluorescence Phenomenon of 4-(N, N-dimethylamino)- benzonitrile and Related Compounds . [Thesis]. Addis Ababa University; 2012. Available from: http://etd.aau.edu.et/dspace/handle/123456789/712

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Zurich

2. Huber, S M. Hemiporphyrazines: Synthesis, Photophysical Properties and Reactivity.

Degree: 2012, University of Zurich

URL: https://www.zora.uzh.ch/id/eprint/71542/1/Master_Thesis_Sabrina_Huber_May_2012.pdf

► DNA quadruplex structures are attracting great scientific interest because of increasing evidence that these structures play important roles in biological processes ranging from replication, transcription,… (more)

▼ DNA quadruplex structures are attracting great scientific interest because of increasing evidence that these structures play important roles in biological processes ranging from replication, transcription, and recombination to telomere integrity. The use of small molecules to selectively target these structures in vivo is emerging as a promising way to interfere with telomere replication in tumor cells and provides potential anticancer agents. A large number of quadruplex binding ligands have already been reported. In general, they selectively interact with terminal GGGG-tetrads via π-π stacking interactions. However, in addition to GGGG-tetrads, GCGC-tetrads are known to be involved in quadruplex formation in vitro. Even though these so-called “mixed tetrads” might also have biological relevance, selective GCGC-tetrad binding probes have not yet been reported. Hemiporphyrazines (Hps) are non-aromatic, 20 π-electron phthalocyanine (Pc) derivatives that consist of two co-facial pyridine rings and two co-facial isoindole units linked through four aza bridges. Due to their planarity, extended π-conjugation, and C2-type symmetry, they are good candidates for selectively targeting GCGC-tetrads. Unsubstituted Hps are, however, notoriously insoluble materials and therefore little is known about their chemical and photophysical properties. As a consequence, this Master thesis is focused on the synthesis, structure, photophysical and reactivity properties of Hps to assess their potential as future GCGC-tetrad binding ligands. Free-base hemiporphyrazine (HpH2) was synthesized and its structure was analyzed by single crystal X-ray diffraction. HpH2 adopts a nearly planar structure and its macrocyclic core contains alternating double and single bonds. This is consistent with the non-aromatic character of these compounds. Furthermore, HpH2 has a very high water affinity and readily absorbs water from the atmosphere to form a yellow monohydrate (HpH2·H2O). This compound has a saddle-shaped conformation and distinct photophysical properties. The use of bulky metal triflates (M(OTf)2) as sources of metal ions during macrocyclization furnished metallo Hps (MHps) with enhanced solubility properties. Octahedral zinc and nickel trans-ditriflate hemiporphyrazine complexes “HpH2Zn(OTf)2” and “HpH2Ni(OTf)2” provide two such examples.

Subjects/Keywords: Department of Chemistry; 540 Chemistry

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APA (6^th Edition):

Huber, S. M. (2012). Hemiporphyrazines: Synthesis, Photophysical Properties and Reactivity. (Thesis). University of Zurich. Retrieved from https://www.zora.uzh.ch/id/eprint/71542/1/Master_Thesis_Sabrina_Huber_May_2012.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Huber, S M. “Hemiporphyrazines: Synthesis, Photophysical Properties and Reactivity.” 2012. Thesis, University of Zurich. Accessed January 18, 2020. https://www.zora.uzh.ch/id/eprint/71542/1/Master_Thesis_Sabrina_Huber_May_2012.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Huber, S M. “Hemiporphyrazines: Synthesis, Photophysical Properties and Reactivity.” 2012. Web. 18 Jan 2020.

Vancouver:

Huber SM. Hemiporphyrazines: Synthesis, Photophysical Properties and Reactivity. [Internet] [Thesis]. University of Zurich; 2012. [cited 2020 Jan 18]. Available from: https://www.zora.uzh.ch/id/eprint/71542/1/Master_Thesis_Sabrina_Huber_May_2012.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Huber SM. Hemiporphyrazines: Synthesis, Photophysical Properties and Reactivity. [Thesis]. University of Zurich; 2012. Available from: https://www.zora.uzh.ch/id/eprint/71542/1/Master_Thesis_Sabrina_Huber_May_2012.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Zurich

3. Can, Daniel. An Approach Towards Theragnostic Receptor Targeting with 5-Cyclopentadienyl Derivatives of the fac-{99mTc(CO)3}- and fac-{Re(CO)3}-Core.

Degree: 2012, University of Zurich

URL: https://www.zora.uzh.ch/id/eprint/74763/1/20131778.pdf

► The chemical and biological evaluation of organometallic probes for nuclear medical applications in comparison to their purely organic analogs, or the study of the metal-mediated… (more)

Subjects/Keywords: Department of Chemistry; 540 Chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Can, D. (2012). An Approach Towards Theragnostic Receptor Targeting with 5-Cyclopentadienyl Derivatives of the fac-{99mTc(CO)3}- and fac-{Re(CO)3}-Core. (Thesis). University of Zurich. Retrieved from https://www.zora.uzh.ch/id/eprint/74763/1/20131778.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Can, Daniel. “An Approach Towards Theragnostic Receptor Targeting with 5-Cyclopentadienyl Derivatives of the fac-{99mTc(CO)3}- and fac-{Re(CO)3}-Core.” 2012. Thesis, University of Zurich. Accessed January 18, 2020. https://www.zora.uzh.ch/id/eprint/74763/1/20131778.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Can, Daniel. “An Approach Towards Theragnostic Receptor Targeting with 5-Cyclopentadienyl Derivatives of the fac-{99mTc(CO)3}- and fac-{Re(CO)3}-Core.” 2012. Web. 18 Jan 2020.

Vancouver:

Can D. An Approach Towards Theragnostic Receptor Targeting with 5-Cyclopentadienyl Derivatives of the fac-{99mTc(CO)3}- and fac-{Re(CO)3}-Core. [Internet] [Thesis]. University of Zurich; 2012. [cited 2020 Jan 18]. Available from: https://www.zora.uzh.ch/id/eprint/74763/1/20131778.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Can D. An Approach Towards Theragnostic Receptor Targeting with 5-Cyclopentadienyl Derivatives of the fac-{99mTc(CO)3}- and fac-{Re(CO)3}-Core. [Thesis]. University of Zurich; 2012. Available from: https://www.zora.uzh.ch/id/eprint/74763/1/20131778.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Zurich

4. Barman, Samir. Design, synthesis and postsynthetic modification of metal-organic materials for hydrogenstorage and chemosensing.

Degree: 2012, University of Zurich

URL: https://www.zora.uzh.ch/id/eprint/75114/1/20131675.pdf

► Poröse metallorganische Gerüste (engl. metal-organic frameworks, MOFs) wurden in den letzten Dekaden, auf Grund ihrer hohen spezifischen Oberfläche, abstimmbarer Porengrösse, funktionalisierbarer Porenwände und definierter Wasserstoffbindungstellen,… (more)

▼ Poröse metallorganische Gerüste (engl. metal-organic frameworks, MOFs) wurden in den letzten Dekaden, auf Grund ihrer hohen spezifischen Oberfläche, abstimmbarer Porengrösse, funktionalisierbarer Porenwände und definierter Wasserstoffbindungstellen, intensiv als vielversprechendes Wasserstoffspeichermaterial untersucht. Neuere Ergebnisse belegen, dass MOFs mit grosser Oberfläche und hoher Porosität bis zu 10-15 Gew.-% Wasserstoff bei Flüssig- Stickstoff-Temperatur und 40-80 bar Wasserstoffdruck liefern können. Die Speicherkapazität bei Raumtemperatur, die wahrscheinlich bedeutend für praktische Anwendung wäre, sinkt dazu im Gegensatz dramatisch unter ein Zehntel der Kapazität bei tiefem Temperaturen. Der Hauptgrund hierfür ist, dass die Wasserstoffadsorption in MOFs durch Physisorptionsprozesse geschieht und daher nur schwache van-der-Waals-Kräfte die primäre Bindungskraft bilden. Verschiedene Ansätze haben kürzlich gezeigt wie Bindungskräfte zwischen MOFs und Wasserstoff verstärkt werden können, um so signifikante Mengen Wasserstoff bei relativ höheren Temperaturen zu liefern. Basierend auf neueren bekannten Ergebnissen, entwickelten wir chemisch abstimmbare, poröse MOFs durch rationelles Design der organischen Bausteine der Materialien oder durch Anbringung geeigneter chemischer Bausteine an die Oberflächer der funktionelle Gruppen tragenden MOFs. Die chemische Abstimmung scheint bedeutend, um fortgeschrittene polare Bindungen durch Dipol-Dipol- oder Dipol-induzierter Dipol-Wechselwirkungen oder Wasserstoffbindungen in Verbindung mit kinetischem Einfangen der Wasserstoffmoleküle zu sein. Im Besonderen hat die hier präsentierte Forschungsarbeit das systematische Design, Synthese und postsynthetische Modifikation von MOFs für Wasserstoffspeicherung und den sensitiven Nachweis von nitroaromatischen Sprengstoffen untersucht. Um den Effekt der Polarisierung auf die Stabilisierung von Wasserstoff in MOFs zu untersuchen, wurde eine Reihe neuer MOFs, basierend auf polarisierten Azulenliganden, entwickelt und ihre Wasserstoffspeichereigenschaften wurden intensiv untersucht. Zusätzlich konnte eine neue Methode für die postsynthetische Modifikation amin-funktionalisierter MOFs zur Einführung polarisierter Gruppen durch Gasphasen-Festphasen-Reaktionen aufgezeigt werden. Des Weiteren wurde eine innovative Strategie zu Einführung hoher Konzentrationen von vakanten Metallbindungstellen untersucht. Die Anwesenheit die Metallbindungsstellen wurde als förderlich für die Unterstützung von Wasserstoffmolekülen nachgewiesen. In einer weiteren Studie haben wir 3D-formbeständige organische Rezeptoren basierend auf Triptycentetracarboxylat für den hochselektiven und hochsensitiven Nachweis von Sprengstoffen duch lichtinduzierten Elektronentransfer-Quenching-Mechanismus angewendet. Zusammenfassend betrachtet, hat diese Doktorarbeit zum Feld der Wasserstoffspeicherung und der Nutzung von MOFs als Chemosensoren beigetragen.

Subjects/Keywords: Department of Chemistry; 540 Chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Barman, S. (2012). Design, synthesis and postsynthetic modification of metal-organic materials for hydrogenstorage and chemosensing. (Thesis). University of Zurich. Retrieved from https://www.zora.uzh.ch/id/eprint/75114/1/20131675.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Barman, Samir. “Design, synthesis and postsynthetic modification of metal-organic materials for hydrogenstorage and chemosensing.” 2012. Thesis, University of Zurich. Accessed January 18, 2020. https://www.zora.uzh.ch/id/eprint/75114/1/20131675.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Barman, Samir. “Design, synthesis and postsynthetic modification of metal-organic materials for hydrogenstorage and chemosensing.” 2012. Web. 18 Jan 2020.

Vancouver:

Barman S. Design, synthesis and postsynthetic modification of metal-organic materials for hydrogenstorage and chemosensing. [Internet] [Thesis]. University of Zurich; 2012. [cited 2020 Jan 18]. Available from: https://www.zora.uzh.ch/id/eprint/75114/1/20131675.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Barman S. Design, synthesis and postsynthetic modification of metal-organic materials for hydrogenstorage and chemosensing. [Thesis]. University of Zurich; 2012. Available from: https://www.zora.uzh.ch/id/eprint/75114/1/20131675.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Zurich

5. Shen, Yunjun. Synthesis of metal-containing biomolecule conjugates for potential use in 99mTc molecular imaging.

Degree: 2014, University of Zurich

URL: https://www.zora.uzh.ch/id/eprint/90842/1/20142053.pdf

► Im Rahmen dieser Arbeit wurde eine Reihe von kleinen, tripodalen Liganden mit verschiedenen funktionellen Gruppen konzipiert und synthetisiert. Die resultierenden Komplexe mit der [99mTc(CO)3]+ Einheit… (more)

Subjects/Keywords: Department of Chemistry; 540 Chemistry

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APA (6^th Edition):

Shen, Y. (2014). Synthesis of metal-containing biomolecule conjugates for potential use in 99mTc molecular imaging. (Thesis). University of Zurich. Retrieved from https://www.zora.uzh.ch/id/eprint/90842/1/20142053.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Shen, Yunjun. “Synthesis of metal-containing biomolecule conjugates for potential use in 99mTc molecular imaging.” 2014. Thesis, University of Zurich. Accessed January 18, 2020. https://www.zora.uzh.ch/id/eprint/90842/1/20142053.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Shen, Yunjun. “Synthesis of metal-containing biomolecule conjugates for potential use in 99mTc molecular imaging.” 2014. Web. 18 Jan 2020.

Vancouver:

Shen Y. Synthesis of metal-containing biomolecule conjugates for potential use in 99mTc molecular imaging. [Internet] [Thesis]. University of Zurich; 2014. [cited 2020 Jan 18]. Available from: https://www.zora.uzh.ch/id/eprint/90842/1/20142053.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Shen Y. Synthesis of metal-containing biomolecule conjugates for potential use in 99mTc molecular imaging. [Thesis]. University of Zurich; 2014. Available from: https://www.zora.uzh.ch/id/eprint/90842/1/20142053.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Zurich

6. Schnabl, Joachim Anton. Studies on the stabilization of RNA structures through metal ions, ion-π interactions and metallo-supramolecular helicates.

Degree: 2013, University of Zurich

URL: https://www.zora.uzh.ch/id/eprint/91034/1/20152366.pdf

► Teil I Supramolekulare zweikernige Eisen(II)-Komplexe [Fe 2 L3 ]4+ sind helikale Zylinder die dank ihren ausserordentlichen DNS Bindungseigenschaften potentielle Antikrebsmittel sind. Die Zylinder können einerseits… (more)

▼ Teil I Supramolekulare zweikernige Eisen(II)-Komplexe [Fe 2 L3 ]4+ sind helikale Zylinder die dank ihren ausserordentlichen DNS Bindungseigenschaften potentielle Antikrebsmittel sind. Die Zylinder können einerseits spezifisch an Y-förmige dreiarmige DNS Kreuzungen binden. Es wurde aber auch eine Anlagerung an die grosse Furche doppelsträngiger DNS gezeigt. Die geeignete Grösse und Form der Helikate sowie ihre hohe elektrostatische Ladung sind verantwortlich für diese nichtkovalenten Wechselwirkungen. Behandlung von Krebszelllinien mit den zylinderförmigen Komplexen resultierten in erhöhten Zellsterblichkeitsraten ohne das Erbgut der Zellen zu schädigen. Dieser alternative Mechanismus des Eisen(II) Supramoleküls könnte ein vielversprechender Schritt in Richtung Behandlung von Krebs sein, welcher schon Resitenzen gegen andere Chemotherapeutika aufweist. Die nichtkovalente Art der Erkennung von dreiarmigen Kreuzungen könnte somit die Entwicklung neuartiger Medikamente ermöglichen. RNS erfüllt verschiedene regulatorische Funktionen in einer Zelle. Da DNS und RNS eine sehr ähnliche Struktur aufweisen, stellte sich die Frage ob der Zylinder auch an RNS binden würde. RNS kommt meist als einzelsträngiges Molekül vor welches ein hohes natürliches Vorkommen an dreiarmigen Kreuzungen als potentielle Zielbindungsstellen enthält Die Beeinflussung der RNS in lebenden Zellen könnte ein Schlüsselelement in der Antitumoraktivität des Zylinders sein. In der ersten Studie dieser Dissertation wurden deshalb verschiedene RNS Konstrukte künstlichem oder natürlichem Ursprungs als Ziel für die Eisen(II) Zylinder verwendet. Das RNS Analogon der kürzlich entdeckten dreiarmigen DNS Kreuzung konnten erfolgreich kristallisiert und die Struktur mittels Röntgenkristallografie charakterisiert werden. Ferner wurden zwei weitere Kristallstrukturen der dreiarmigen RNS Kreuzung mit Kobalt(II) und Nickel(II) Zylindern gelöst. Diese drei Kristallstrukturen haben eine identische Topologie. Der Metallzylinder befindet sich im Zentrum der dreiarmigen RNS Kreuzung. Die inneren Ringe der aromatischen Liganden des Zylinders sind in π-Stapelwechselwirkung mit den zentralen Basenpaaren der RNS, die als drei Doppelhelices vom Inneren der dreiarmigen Kreuzung wegführt. Ein Vergleich der bekannten Kristallstruktur der dreiarmige DNS Kreuzung mit der dreiarmige RNS Kreuzung zeigt einen strukturellen Unteschied: Die enge Öffnung an der einen Seite der dreiarmigen DNS Kreuzung beschränkt die innere Platzierung des Zylinders auf eine gewisse Tiefe. Der Zylinder kann aber mit der dreiarmigen RNS Kreuzung eine maximale π-Stapeloberfläche einnehmen: beide Öffnungen der Kreuzung sind weit genug für eine freie Beweglichkeit des Zylinders und ermöglichen somit eine energetisch optimale Geometrie. Dies ist die erste Charakterisierung einer induzierten dreiarmigen RNS Kreuzung, die spezifisch durch einen supramolekularen Zylinder erkannt wurde. Teil II Tertiärstrukturen grosser Polyanionen wie DNS oder gerade RNS (z.B. Ribozyme) schliessen eine hochkomplexe dreidimensionale…

Subjects/Keywords: Department of Chemistry; 540 Chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Schnabl, J. A. (2013). Studies on the stabilization of RNA structures through metal ions, ion-π interactions and metallo-supramolecular helicates. (Thesis). University of Zurich. Retrieved from https://www.zora.uzh.ch/id/eprint/91034/1/20152366.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Schnabl, Joachim Anton. “Studies on the stabilization of RNA structures through metal ions, ion-π interactions and metallo-supramolecular helicates.” 2013. Thesis, University of Zurich. Accessed January 18, 2020. https://www.zora.uzh.ch/id/eprint/91034/1/20152366.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Schnabl, Joachim Anton. “Studies on the stabilization of RNA structures through metal ions, ion-π interactions and metallo-supramolecular helicates.” 2013. Web. 18 Jan 2020.

Vancouver:

Schnabl JA. Studies on the stabilization of RNA structures through metal ions, ion-π interactions and metallo-supramolecular helicates. [Internet] [Thesis]. University of Zurich; 2013. [cited 2020 Jan 18]. Available from: https://www.zora.uzh.ch/id/eprint/91034/1/20152366.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Schnabl JA. Studies on the stabilization of RNA structures through metal ions, ion-π interactions and metallo-supramolecular helicates. [Thesis]. University of Zurich; 2013. Available from: https://www.zora.uzh.ch/id/eprint/91034/1/20152366.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Zurich

7. Capolicchio, Samanta. Synthesis of Diphosphoinositol Polyphosphates.

Degree: 2015, University of Zurich

URL: https://www.zora.uzh.ch/id/eprint/106364/1/20152470.pdf

► Diphosphoinositol polyphosphates (PP-InsPy) represent a novel group of secondary messengers that regulate diverse important cellular processes, including signal transduction, vesicle trafficking and apoptosis. Recently, it… (more)

▼ Diphosphoinositol polyphosphates (PP-InsPy) represent a novel group of secondary messengers that regulate diverse important cellular processes, including signal transduction, vesicle trafficking and apoptosis. Recently, it has been reported that PP-InsPy phosphorylate proteins in a process known as protein pyrophosphorylation. This new type of posttranslational modification occurs in vitro, but it is still unclear if it occurs also in vivo. The concentration of PP-InsPy in cells is very low which makes their isolation from biological sources difficult. PP-InsPy have been prepared enzymatically. However, this method does not permit to obtain large amount of material necessary for biological studies. Additionally, it is not suitable for the preparation of non-natural isomers and the stereochemistry of the synthesized molecules cannot be assigned. Therefore, an efficient method to prepare a scalable amount of PP-InsPy is essential to study the structure and functions of PP-InsPy. The preparation of PP-InsPy by chemical synthesis offers the best opportunities to prepare a scalable amount of material with known stereochemistry. Additionally, this method can provide the access to several non-natural derivatives that can be used as chemical tools to study the metabolism of PP-InsPy. Different syntheses of enantiomerically pure inositol polyphosphates have been reported, but PP-InsPy are not commercially available and the quality of earlier preparations has been called into question. Asymmetric phosphorylation is an outstanding way to introduce a phosphate group in a specific position in the structure of myo-inositol. We will report a novel total synthesis of unsymmetric diphosphoinositol polyphosphates using a C2-symmetric phosphoramidite to desymmetrize different inositol derivatives. This novel phosphorylating reagent enabled us to target all four possible unsymmetric X-PP-InsP5 (1-PP-InsP5, 3-PP-InsP5, 4-PP-InsP5 and 6-PP-InsP5). Additionally, 1,5-(PP)2-InsP4 and 3,5-(PP)2-InsP4 were prepared for the first time with the same methodology. A novel synthesis of the symmetric 5-PP-InsP5 and the first total synthesis of meso 5-PPP-InsP5 will be also reported. These results represent a new approach in the envisaged total syntheses of PP-InsPy as well as the starting point for the development of efficient reagents for asymmetric phosphorylation and pyrophosphorylation. Additionally, it provided us with tools that can be used to decipher inositol related cellular signalling pathways.

Subjects/Keywords: Department of Chemistry; 540 Chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Capolicchio, S. (2015). Synthesis of Diphosphoinositol Polyphosphates. (Thesis). University of Zurich. Retrieved from https://www.zora.uzh.ch/id/eprint/106364/1/20152470.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Capolicchio, Samanta. “Synthesis of Diphosphoinositol Polyphosphates.” 2015. Thesis, University of Zurich. Accessed January 18, 2020. https://www.zora.uzh.ch/id/eprint/106364/1/20152470.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Capolicchio, Samanta. “Synthesis of Diphosphoinositol Polyphosphates.” 2015. Web. 18 Jan 2020.

Vancouver:

Capolicchio S. Synthesis of Diphosphoinositol Polyphosphates. [Internet] [Thesis]. University of Zurich; 2015. [cited 2020 Jan 18]. Available from: https://www.zora.uzh.ch/id/eprint/106364/1/20152470.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Capolicchio S. Synthesis of Diphosphoinositol Polyphosphates. [Thesis]. University of Zurich; 2015. Available from: https://www.zora.uzh.ch/id/eprint/106364/1/20152470.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Zurich

8. Unzue Lopez, Andrea. Small Organic Molecules as Tunable Tools for Biology.

Degree: 2015, University of Zurich

URL: https://www.zora.uzh.ch/id/eprint/106367/1/20162588.pdf

► Drug discovery and development is a very challenging interdisciplinary endeavor that needs the contribution of medical doctors, biologists, chemists, X-ray crystallographers, and computer scientists, among… (more)

▼ Drug discovery and development is a very challenging interdisciplinary endeavor that needs the contribution of medical doctors, biologists, chemists, X-ray crystallographers, and computer scientists, among many others, in order to be successful. The first part of this Ph. D. thesis focuses on the development of EphB4 receptor tyrosine kinase inhibitors. EphB4 has been linked to angiogenesis, which involves the formation of new blood vessels supplying tumor cells with the necessary nutrients. Protein kinases play a key role in cell signaling by phosphorylating specific proteins and thus, the inhibition of their enzymatic activity by small organic molecules has been widely explored in drug design. In this work, the biological properties of an EphB4 inhibitor identified by computer simulations were improved by the synthesis of several analogues. Their binding affinities were characterized by an array of biochemical and cell based assays, concluding with the validation of one of the most promising derivatives in an in vivo cancer xenograft model. The second part of the thesis deals with the development of novel bromodomain ligands starting from a micromolar potent in silico discovered hit. Bromodomain proteins are epigenetic readers that constitute an emerging topic in the field of drug discovery and are thus considered as very attractive targets for the development of novel therapeutic drugs. A careful, structure-based design of analogues resulted in the discovery of nanomolar potent CREBBP ligands with an unprecedented selectivity profile among the bromodomain protein family. Moreover, the screening of the synthesized analogues against several cancer cell lines revealed leukemia as a possible therapeutical application for the developed compounds. The third aspect of this work deals with actin: a very attractive, but yet unexplored target in medicinal chemistry. Actin is a cytoskeletal protein that participates in many important cellular functions and has been linked to key pathogenic cellular processes such as angiogenesis, cell adhesion, cytokinesis and metastasis. A new computational approach to discover novel actin leads targeting the ATP binding site of actin resulted in the selection of promising compounds, which were synthesized and tested. The developed small organic molecules constitute valuable tools for the study of actin dynamics as they are able to modify the actin cytoskeleton in cells and moderately inhibit actin polymerization in vitro; thus becoming promising starting hits for the development of more potent actin binders. The last part of this Ph.D. thesis describes the synthesis of neuroprotective compounds by the development of fumaric acid and hydroxytyrosol conjugates, for which the corresponding receptor is unknown. The biological effects of the synthesized analogues are currently under investigation, but the synergistic effect of fumaric acid and hydroxytyrosol is expected to be beneficial in the context of neuroprotection.

Subjects/Keywords: Department of Chemistry; 540 Chemistry

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APA (6^th Edition):

Unzue Lopez, A. (2015). Small Organic Molecules as Tunable Tools for Biology. (Thesis). University of Zurich. Retrieved from https://www.zora.uzh.ch/id/eprint/106367/1/20162588.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Unzue Lopez, Andrea. “Small Organic Molecules as Tunable Tools for Biology.” 2015. Thesis, University of Zurich. Accessed January 18, 2020. https://www.zora.uzh.ch/id/eprint/106367/1/20162588.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Unzue Lopez, Andrea. “Small Organic Molecules as Tunable Tools for Biology.” 2015. Web. 18 Jan 2020.

Vancouver:

Unzue Lopez A. Small Organic Molecules as Tunable Tools for Biology. [Internet] [Thesis]. University of Zurich; 2015. [cited 2020 Jan 18]. Available from: https://www.zora.uzh.ch/id/eprint/106367/1/20162588.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Unzue Lopez A. Small Organic Molecules as Tunable Tools for Biology. [Thesis]. University of Zurich; 2015. Available from: https://www.zora.uzh.ch/id/eprint/106367/1/20162588.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Zurich

9. Felber, Michael. Bifunctional Ligand Systems for the Radiolabeling of Nanoparticles and Biomolecules with the fac-[99mTc(CO)3]+-Core.

Degree: 2015, University of Zurich

URL: https://www.zora.uzh.ch/id/eprint/118686/1/20152444.pdf

► The application of nanoparticles (NPs) in the medical field is increasingly growing in importance. NPs such as mesoporous silica NPs, polymeric NPs, magnetic NPs, gold… (more)

▼ The application of nanoparticles (NPs) in the medical field is increasingly growing in importance. NPs such as mesoporous silica NPs, polymeric NPs, magnetic NPs, gold NPs (AuNPs), and quantum dots (QDs) are promising candidates for the design of novel imaging, drug delivery or theranostic agents. A major challenge after administration of NPs to living organisms is the exact localization. Among the various techniques to assess the biodistribution of functional nanostructures, radiolabeling and subsequent detection of the emitted γ-photons allows for noninvasive imaging by single photon emission computed tomography (SPECT) or positron emission tomography (PET). Moreover, radiolabeling provides an accurate quantification of nanostructure localization in different organs or tissues by performing an ex vivo biodistribution. For the 99mTc labeling of AuNPs and QDs a novel coating ligand was synthesized, containing a thiol group as an anchor for the NP surface, a spacer (e.g. polyethylene glycol PEG) and the 2,3-diaminopropionic acid (DAP) chelator for the [99mTc(CO)3]+ fragment. This ligand is multi-functional; it combines the metal chelate with conjugating functions to biological vectors in one single molecule. The concept allows coupling of any targeting function to the chelator. An example with a small molecule target for the prostate specific membrane antigen (PSMA) is given. Derivatized AuNPs and QDs can directly be labeled in one step with [99mTc(OH2)3(CO)3]+. The AuNPs in particular are highly stable in buffer and serum, a prerequisite for in vivo studies excluding misinterpretation of the biodistribution data. AuNPs with differing sizes (7 nm and 14 nm core diameter) were administered intravenously into nude NMRI mice bearing LNCaP xenografts. MicroSPECT images show for both probes rapid clearance from the blood pool via the hepatobiliary pathway. The 7 nm AuNPs revealed a significantly higher bone uptake than the 14 nm AuNPs. The high affinity towards bone mineral is further confirmed in vitro with hydroxyapatite. In case NPs have an intrinsic property for contrast, radiolabeling automatically leads to multi-modal imaging agents. Particularly the development of NP-based dual-modality probes for magnetic resonance imaging (MRI)/PET or MRI/SPECT is intensively investigated. One of the most commonly used radionuclide for clinical SPECT imaging is 99m Tc and the labeling of Fe3O4 NPs with 99mTc was shown to be a successful strategy to obtain dual-modality imaging agents. The focus in this thesis is on the 99mTc labeling of gold containing magnetic nanomaterials (Fe3O4-Au core-shell and heterostructured Fe3O4-Au Dumbbell-like NPs). The key elements for the labeling are novel coating ligands, consisting of mono- or dithiol anchors for the gold surface, a PEG linker and various chelators for the [99mTc(CO)3]+ fragment. In a variety of labeling experiments, favorable coatings were examined and their stability tested. The findings presented herein can form the basis for the development of potential, NP-based…

Subjects/Keywords: Department of Chemistry; 540 Chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Felber, M. (2015). Bifunctional Ligand Systems for the Radiolabeling of Nanoparticles and Biomolecules with the fac-[99mTc(CO)3]+-Core. (Thesis). University of Zurich. Retrieved from https://www.zora.uzh.ch/id/eprint/118686/1/20152444.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Felber, Michael. “Bifunctional Ligand Systems for the Radiolabeling of Nanoparticles and Biomolecules with the fac-[99mTc(CO)3]+-Core.” 2015. Thesis, University of Zurich. Accessed January 18, 2020. https://www.zora.uzh.ch/id/eprint/118686/1/20152444.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Felber, Michael. “Bifunctional Ligand Systems for the Radiolabeling of Nanoparticles and Biomolecules with the fac-[99mTc(CO)3]+-Core.” 2015. Web. 18 Jan 2020.

Vancouver:

Felber M. Bifunctional Ligand Systems for the Radiolabeling of Nanoparticles and Biomolecules with the fac-[99mTc(CO)3]+-Core. [Internet] [Thesis]. University of Zurich; 2015. [cited 2020 Jan 18]. Available from: https://www.zora.uzh.ch/id/eprint/118686/1/20152444.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Felber M. Bifunctional Ligand Systems for the Radiolabeling of Nanoparticles and Biomolecules with the fac-[99mTc(CO)3]+-Core. [Thesis]. University of Zurich; 2015. Available from: https://www.zora.uzh.ch/id/eprint/118686/1/20152444.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Zurich

10. Bonmarin, M. Development of Ultrafast Time-Resolved Chiral Infrared Spectroscopy.

Degree: 2010, University of Zurich

URL: https://www.zora.uzh.ch/id/eprint/38323/1/diss-Bonmarin10.pdf

► Among the different techniques available to study the molecular structure, chiral spectroscopy is a fast, reliable method, where molecules can be investigated in the liquid… (more)

▼ Among the different techniques available to study the molecular structure, chiral spectroscopy is a fast, reliable method, where molecules can be investigated in the liquid phase. Chiral spectroscopy is based on optical activity. A molecule is said to be optically active if it interacts differently with left- and right-circular polarised light. The difference of absorption between the two circular states is referred to as circular dichroism (CD), whereas the difference of refraction is known as optical rotatory dispersion (ORD). Because the optical activity finds its origin in asymmetry, it is directly dependent of the molecular geometry. Probing optically active vibrational transitions allows to retrieve even more structural information as infrared spectra are usually more resolved than electronics ones. Extension of this technique to the recording of time-resolved chiral vibrational signals may enable the dynamics of conformation changes in biomolecules such as peptides and proteins to be followed with unprecedented details. Toward this goal, we report the first pulsed laser set-up capable of recording both static infrared CD and ORD spectra and photo-induced changes in vibrational circular dichroism (VCD) with picosecond time resolution. A femtosecond laser system is synchronized to a photo elastic modulator to produce alternating left- and right-circular polarised mid-IR pulses. Transient changes in vibrational circular dichroism of the CH-stretch vibrations of the cobalt-sparteine complex Co(sp)Cl2 are presented in a first proof-of-principle experiment. Both static and transient vibrational chiral spectroscopy suffer two important drawbacks: Chiral signals are usually small and sensitive to polarisation-based artefacts, which mainly originate from the interaction between an imperfect probe beam polarisation and a non isotropic sample. We report on a new scheme for synchronizing the laser system and the photo elastic modulator which generates almost perfect probe polarisation states. The technique reduces possible polarisation-based artefacts and allows multichannel detection of the chiral signals normally obscured by polarisation sensitive optics of the monochromator. To increase signal size, a self-heterodyning configuration is implemented where a part of the probe pulse acts as a phase-locked local oscillator heterodyning the chiral signal. The technical improvements presented in this thesis should open the door to measurements of transient vibrational chiral spectra of biomolecules.

Subjects/Keywords: Department of Chemistry; 540 Chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Bonmarin, M. (2010). Development of Ultrafast Time-Resolved Chiral Infrared Spectroscopy. (Thesis). University of Zurich. Retrieved from https://www.zora.uzh.ch/id/eprint/38323/1/diss-Bonmarin10.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Bonmarin, M. “Development of Ultrafast Time-Resolved Chiral Infrared Spectroscopy.” 2010. Thesis, University of Zurich. Accessed January 18, 2020. https://www.zora.uzh.ch/id/eprint/38323/1/diss-Bonmarin10.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Bonmarin, M. “Development of Ultrafast Time-Resolved Chiral Infrared Spectroscopy.” 2010. Web. 18 Jan 2020.

Vancouver:

Bonmarin M. Development of Ultrafast Time-Resolved Chiral Infrared Spectroscopy. [Internet] [Thesis]. University of Zurich; 2010. [cited 2020 Jan 18]. Available from: https://www.zora.uzh.ch/id/eprint/38323/1/diss-Bonmarin10.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Bonmarin M. Development of Ultrafast Time-Resolved Chiral Infrared Spectroscopy. [Thesis]. University of Zurich; 2010. Available from: https://www.zora.uzh.ch/id/eprint/38323/1/diss-Bonmarin10.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Stellenbosch University

11. Geswindt, Theodor Earl. Chemical speciation of RhIII complexes in acidic, halide-rich media by means of 103Rh NMR spectroscopy : the importance of speciation in the selective separation and recovery of rhodium.

Degree: PhD, Chemistry and Polymer Science, 2013, Stellenbosch University

URL: http://hdl.handle.net/10019.1/85647

► ENGLISH ABSTRACT: In this thesis, the recovery of RhIII from both synthetically prepared and authentic industrial PGM-containing solutions was systematically investigated via organic precipitation methods… (more)

▼ ENGLISH ABSTRACT: In this thesis, the recovery of RhIII from both synthetically prepared and authentic industrial PGM-containing solutions was systematically investigated via organic precipitation methods using several commercially available, N-containing organic receptors including (amongst others) diethylenetriamine (Deta), triethylenetetramine (Teta), tetraethylenepentamine (Tepa) and tris(2-aminoethyl)amine (Tren). These organic receptors act as precipitating agents in the presence of an appropriate protonating agent (HCl) by lowering the solubility of the PGM chlorido-anions through an ion-pairing mechanism. The recovery of RhIII from synthetically prepared PGM (RhIII and PtIV) containing solutions using these precipitants was excellent, while poor Rh recovery from authentic industrial process solutions was achieved. The poor Rh recovery from these process solutions was ascribed to the species distribution of the [RhCln(H2O)6-n]3-n complexes. In order to validate the proposition that RhIII speciation effects are responsible for the poor Rh recovery observed during the precipitation studies, attempt were made to describe the species distribution of the [RhCln(H2O)6-n]3-n (n=3-6) by means of high-resolution 103Rh NMR spectroscopy. A detailed high-resolution 103Rh NMR spectroscopic study of the series of [RhCln(H2O)6-n]3-n (n=3-6) complexes was conducted. During this study, all six RhIII aqua chlorido-complexes have unambiguously been characterized by means of high-resolution 103Rh NMR spectroscopy, proving the powerful analytical capability of this technique. Characterization of these complexes is based on the detailed analysis of the 35Cl/37Cl isotope effects which is observed in the 19.11 MHz 103Rh NMR resonances of the [RhCln(H2O)6-n]3-n (n=3-6) complexes in aqueous HCl solutions at 292 K. These resonances show that the “finestructure” of each of the 103Rh resonances may be understood in terms of its unique isotopologue, and in certain cases, the isotopomer distribution of each complex, which manifests as a result of its statistically expected 35Cl/37Cl isotopologue and isotopomer distributions. As a result, the 103Rh NMR resonance structure serves as a unique “NMRfingerprint”, which allows for the unambiguous assignment of [RhCln(H2O)6-n]3-n (n=3-6) complexes, without the reliance on accurate δ(103Rh) chemical shifts. Furthermore, this study reports the first direct species distribution diagram for the [RhCln(H2O)6-n]3-n (n=3-6) series of complexes (in aqueous HCl solutions at 292 K) as a function of the “free” (unbound) chloride concentration, constructed from 103Rh NMR measurements. The need for a revised speciation diagram of [RhCln(H2O)6-n]3-n (n=3-6) complexes is clearly reflected by the vast differences observed in the literature reported species distribution diagrams, which makes it difficult to decide which set of experimental conditions (if any) is required for the quantitative and “selective” recovery of RhIII from aqueous HCl solutions containing associated PGMs (Pt,… Advisors/Committee Members: Koch, Klaus Robert, Stellenbosch University. Faculty of Science. Dept. of Chemistry and Polymer Science..

Subjects/Keywords: Chemistry; Department of Chemistry and Polymer Science

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APA (6^th Edition):

Geswindt, T. E. (2013). Chemical speciation of RhIII complexes in acidic, halide-rich media by means of 103Rh NMR spectroscopy : the importance of speciation in the selective separation and recovery of rhodium. (Doctoral Dissertation). Stellenbosch University. Retrieved from http://hdl.handle.net/10019.1/85647

Chicago Manual of Style (16^th Edition):

Geswindt, Theodor Earl. “Chemical speciation of RhIII complexes in acidic, halide-rich media by means of 103Rh NMR spectroscopy : the importance of speciation in the selective separation and recovery of rhodium.” 2013. Doctoral Dissertation, Stellenbosch University. Accessed January 18, 2020. http://hdl.handle.net/10019.1/85647.

MLA Handbook (7^th Edition):

Geswindt, Theodor Earl. “Chemical speciation of RhIII complexes in acidic, halide-rich media by means of 103Rh NMR spectroscopy : the importance of speciation in the selective separation and recovery of rhodium.” 2013. Web. 18 Jan 2020.

Vancouver:

Geswindt TE. Chemical speciation of RhIII complexes in acidic, halide-rich media by means of 103Rh NMR spectroscopy : the importance of speciation in the selective separation and recovery of rhodium. [Internet] [Doctoral dissertation]. Stellenbosch University; 2013. [cited 2020 Jan 18]. Available from: http://hdl.handle.net/10019.1/85647.

Council of Science Editors:

Geswindt TE. Chemical speciation of RhIII complexes in acidic, halide-rich media by means of 103Rh NMR spectroscopy : the importance of speciation in the selective separation and recovery of rhodium. [Doctoral Dissertation]. Stellenbosch University; 2013. Available from: http://hdl.handle.net/10019.1/85647

University of North Carolina

12. Peacor, Brendan. Application of Small Molecule Receptors to the Analysis of Post-translational Modifications Using Fluorescent Indicator Displacement Assays.

Degree: Chemistry, 2015, University of North Carolina

URL: https://cdr.lib.unc.edu/record/uuid:c1bcbe9f-1815-4625-8690-0143e1d4d2fa

► This dissertation focuses on the application of small molecule receptors to a fluorescent assay for the study of histone post-translational modifications, both in real-time enzyme… (more)

▼ This dissertation focuses on the application of small molecule receptors to a fluorescent assay for the study of histone post-translational modifications, both in real-time enzyme reactions and endpoint characterization of analytes. In the first section, dynamic combinatorial chemistry was used to generate a series of A2X receptors that varied the functionality of the X monomer. This allowed us to systematically study the contribution of pocket depth and electrostatic interactions on binding methylated lysine. We discovered that changing the location of a carboxylate increased affinity to K(Me)2, presumably through a salt bridge, while an additional carboxylate increased affinity across the entire lysine series. Additionally, formation of a deeper binding pocket saw a selectivity increase for K(Me)3 over the lower methylation states. The remaining sections describe the application of the Waters lab suite of receptors to fluorescence indicator displacement assays (IDAs). In these assays, fluorescence signal is directly proportional to the competitive binding of a histone analyte. We applied a sensor system using the receptor A2N and the fluorophore Lucigenin (LCG) to study the enzymatic dimethylation of histone H3 lysine 9 by the methyltransferase G9a. Optimization of the enzymatic buffer system established an effective methyltransferase reaction to short histone 3 peptide substrates. Applying these conditions to the fluorescent assay we are able to monitor enzymatic activity, allowing future experiments to test enzyme response to neighboring modifications in the ‘histone code’. This assay was also applied to the preliminary examination of the arginine methyltransferases, demonstrating the general applicability of the assay to the full range of enzymatic methylation reactions. With the large number of receptors previously established, we sought to develop a general discriminatory assay capable of recognizing histone modifications beyond the designed scope of the sensor. By combining the fluorescent IDA signal for four different receptors, A2B, A2D, A2N, and A2G, we were able to accurately classify thirteen different histone peptides in a single output. Each peptide had multiple modifications, including arginine methylation and lysine methylation, as well as lysine methylation and threonine phosphorylation. The classification assay was able to distinguish both the degree of modification as well as the site of the specific modifications, all based on the slight perturbations neighboring residues make on binding affinity. This assay was also preliminarily applied to the sensing of complex enzymatic reactions by performing a mock kinase experiment, in which we were able to classify distinct ‘time-point’ of enzymatic phosphorylation on two separate substrates. The final section focuses on the expansion of the target class of analytes for the combinatorial sensor array. While the previous study focused on modification-neighboring methylation events, here we describe the classification of the neutral modifications of… Advisors/Committee Members: Peacor, Brendan, Waters, Marcey, Johnson, Jeffrey, Lawrence, David, Weeks, Kevin, Frye, Stephen.

Subjects/Keywords: Chemistry; Chemistry, Organic; College of Arts and Sciences; Department of Chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Peacor, B. (2015). Application of Small Molecule Receptors to the Analysis of Post-translational Modifications Using Fluorescent Indicator Displacement Assays. (Thesis). University of North Carolina. Retrieved from https://cdr.lib.unc.edu/record/uuid:c1bcbe9f-1815-4625-8690-0143e1d4d2fa

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Peacor, Brendan. “Application of Small Molecule Receptors to the Analysis of Post-translational Modifications Using Fluorescent Indicator Displacement Assays.” 2015. Thesis, University of North Carolina. Accessed January 18, 2020. https://cdr.lib.unc.edu/record/uuid:c1bcbe9f-1815-4625-8690-0143e1d4d2fa.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Peacor, Brendan. “Application of Small Molecule Receptors to the Analysis of Post-translational Modifications Using Fluorescent Indicator Displacement Assays.” 2015. Web. 18 Jan 2020.

Vancouver:

Peacor B. Application of Small Molecule Receptors to the Analysis of Post-translational Modifications Using Fluorescent Indicator Displacement Assays. [Internet] [Thesis]. University of North Carolina; 2015. [cited 2020 Jan 18]. Available from: https://cdr.lib.unc.edu/record/uuid:c1bcbe9f-1815-4625-8690-0143e1d4d2fa.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Peacor B. Application of Small Molecule Receptors to the Analysis of Post-translational Modifications Using Fluorescent Indicator Displacement Assays. [Thesis]. University of North Carolina; 2015. Available from: https://cdr.lib.unc.edu/record/uuid:c1bcbe9f-1815-4625-8690-0143e1d4d2fa

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of North Carolina

13. Blakeman, Kenion. Development of High Pressure Mass Spectrometry for Handheld Instruments.

Degree: Chemistry, 2015, University of North Carolina

URL: https://cdr.lib.unc.edu/record/uuid:820f3ab8-4f2d-419a-b07e-391cc3f141a7

► This work describes the development of microscale ion traps intended for high pressure mass spectrometry in handheld mass spectrometers. By operating at pressures approaching 1… (more)

▼ This work describes the development of microscale ion traps intended for high pressure mass spectrometry in handheld mass spectrometers. By operating at pressures approaching 1 Torr, the major size, weight and power (SWaP) contributor, the turbopump can be eliminated. Unlike other mass analyzers, ion traps can successfully operate at higher pressures by reducing the trap size and operating at higher RF drive frequencies. HPMS was first demonstrated with helium buffer gas with volatile organic compounds (VOCs) and a ro = 500 µm cylindrical ion trap (CIT). RF frequencies up to 10 MHz minimized mass resolution loss with pressure. HPMS with nitrogen and air were then explored as field available buffer gases to eliminate helium tanks in the field, reducing instrument size and weight. Peak widths at 1.0 Torr were 0.7 Da for helium and 5 Da for nitrogen and air were observed at RF drive frequencies of 10 MHz. As peak widths widen at high pressures due to more frequent collisions, the RF frequency was increased along with a reduction in trap size to regain mass resolution. Five CITs were operated at 1 Torr in air with RF drive frequencies between 6.14 MHz to 59.44 MHz resulting in peak widths improving from 5.5 Da to 0.8 Da. Stretched length ion traps (SLITs) and 7-element CIT arrays improved sensitivity over the single element traps by factors of 6 and 7. Operating at ambient air pressures between 250 mTorr and 1.0 Torr with RF frequencies between 30 MHz and 60 MHz reduced peak widths to sub-0.6 Da. Finally, printed circuit board (PCB) and silicon ion traps were developed as alternative materials to metal ion traps. Both PCB and Si traps lower trap capacitance reducing RF power needs and improving instrument SWaP. PCB traps had a factor of two lower sensitivity and peak widths within 10% of metal traps while silicon ion traps had twice the signal intensity of metal traps and better peak widths by up to 30 %. In terms of fabrication, PCB traps can be mass produced while Si traps can be produced with higher dimensional fidelity than metal ion traps. Advisors/Committee Members: Blakeman, Kenion, Ramsey, J. Michael, Jorgenson, James, Lockett, Matthew, Cahoon, James, Brustad, Eric.

Subjects/Keywords: Chemistry; Chemistry, Analytic; College of Arts and Sciences; Department of Chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Blakeman, K. (2015). Development of High Pressure Mass Spectrometry for Handheld Instruments. (Thesis). University of North Carolina. Retrieved from https://cdr.lib.unc.edu/record/uuid:820f3ab8-4f2d-419a-b07e-391cc3f141a7

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Blakeman, Kenion. “Development of High Pressure Mass Spectrometry for Handheld Instruments.” 2015. Thesis, University of North Carolina. Accessed January 18, 2020. https://cdr.lib.unc.edu/record/uuid:820f3ab8-4f2d-419a-b07e-391cc3f141a7.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Blakeman, Kenion. “Development of High Pressure Mass Spectrometry for Handheld Instruments.” 2015. Web. 18 Jan 2020.

Vancouver:

Blakeman K. Development of High Pressure Mass Spectrometry for Handheld Instruments. [Internet] [Thesis]. University of North Carolina; 2015. [cited 2020 Jan 18]. Available from: https://cdr.lib.unc.edu/record/uuid:820f3ab8-4f2d-419a-b07e-391cc3f141a7.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Blakeman K. Development of High Pressure Mass Spectrometry for Handheld Instruments. [Thesis]. University of North Carolina; 2015. Available from: https://cdr.lib.unc.edu/record/uuid:820f3ab8-4f2d-419a-b07e-391cc3f141a7

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of North Carolina

14. Sharpe, Robert. ON THE MERITS OF STEREOSELECTIVE DESYMMETRIZATION REACTIONS IN THE ASSEMBLY OF COMPLEX NATURAL MOLECULES: THE TOTAL SYNTHESIS OF PACTAMYCIN AND PASPALINE.

Degree: Chemistry, 2015, University of North Carolina

URL: https://cdr.lib.unc.edu/record/uuid:79c97a39-bad6-48cd-9a6f-75bb32b6448d

► I. Asymmetric Synthesis of the Aminocyclitol Pactamycin, a Universal Translocation Inhibitor A concise, enantioselective synthesis of the aminocyclopentitol natural product pactamycin is presented. The critical… (more)

▼ I. Asymmetric Synthesis of the Aminocyclitol Pactamycin, a Universal Translocation Inhibitor A concise, enantioselective synthesis of the aminocyclopentitol natural product pactamycin is presented. The critical feature of this approach was the execution of an asymmetric Mannich reaction and symmetry-breaking diketone monoreduction to assemble the C1, C2, and C7 relative stereochemistries early in the route, enabling facile construction of the remaining core functionalities. A remarkable series of serendipitous stereochemical outcomes ensued in the sequence that followed, ultimately providing the title compound in fifteen steps from the commercially available 2,4-pentanedione, constituting the shortest reported synthesis to date. The development and evolution of this synthetic strategy is thoroughly detailed, and an analysis of observed outcomes is presented. This synthesis was designed to immediately enable the facile preparation of structural analogs for the purposes of structure-activity relationship investigations. II. Preparation and Biological Evaluation of Synthetic and Polymer-Encapsulated Congeners of the Antitumor Agent Pactamycin: Insight into Functional Group Effects and Biological Activity Using the previously described total synthesis of pactamycin as a platform for synthetic diversity, twenty-five unique synthetic congeners of the natural product have been prepared to provide greater understanding into the source of pactamycin’s biological profile. Specific attention was given to the production of synthetic derivatives at the branch points of pactamycin’s unique functional groups (i.e. aniline, salicylate, and dimethylurea). In addition, the encapsulation of pactamycin and its derivatives into the PRINT© technology was demonstrated. This work has provided unprecedented access to a large number of pactamycin synthetic congeners, and subsequent in vitro analysis of the prepared compounds revealed a number of insights into the source of pactamycin’s activity. III. Inception and Development of a Global and Local Desymmetrization Approach to the Synthesis of Steroidal Alkaloids: Stereocontrolled Total Synthesis of Paspaline. An enantioselective synthesis of the indole diterpene alkaloid paspaline is described. Key features of this synthesis included the execution of both “global” and “local” desymmetrization reactions to enable expedient assembly of challenging quaternary centers in the core structure. A complete account of the conception and development of this approach is described, and an analysis of desired (and undesired) outcomes is provided. The described route affords a new conceptual blueprint for installing challenging stereocenters in this family of molecules, and the steps contained therein provide the synthetic community with complimentary disconnections in the arena of steroid natural product synthesis. Advisors/Committee Members: Sharpe, Robert, Johnson, Jeffrey, Meek, Simon, Crimmins, Michael T., Gagne, Michel, Brookhart, Maurice.

Subjects/Keywords: Chemistry, Organic; Chemistry; College of Arts and Sciences; Department of Chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Sharpe, R. (2015). ON THE MERITS OF STEREOSELECTIVE DESYMMETRIZATION REACTIONS IN THE ASSEMBLY OF COMPLEX NATURAL MOLECULES: THE TOTAL SYNTHESIS OF PACTAMYCIN AND PASPALINE. (Thesis). University of North Carolina. Retrieved from https://cdr.lib.unc.edu/record/uuid:79c97a39-bad6-48cd-9a6f-75bb32b6448d

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Sharpe, Robert. “ON THE MERITS OF STEREOSELECTIVE DESYMMETRIZATION REACTIONS IN THE ASSEMBLY OF COMPLEX NATURAL MOLECULES: THE TOTAL SYNTHESIS OF PACTAMYCIN AND PASPALINE.” 2015. Thesis, University of North Carolina. Accessed January 18, 2020. https://cdr.lib.unc.edu/record/uuid:79c97a39-bad6-48cd-9a6f-75bb32b6448d.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Sharpe, Robert. “ON THE MERITS OF STEREOSELECTIVE DESYMMETRIZATION REACTIONS IN THE ASSEMBLY OF COMPLEX NATURAL MOLECULES: THE TOTAL SYNTHESIS OF PACTAMYCIN AND PASPALINE.” 2015. Web. 18 Jan 2020.

Vancouver:

Sharpe R. ON THE MERITS OF STEREOSELECTIVE DESYMMETRIZATION REACTIONS IN THE ASSEMBLY OF COMPLEX NATURAL MOLECULES: THE TOTAL SYNTHESIS OF PACTAMYCIN AND PASPALINE. [Internet] [Thesis]. University of North Carolina; 2015. [cited 2020 Jan 18]. Available from: https://cdr.lib.unc.edu/record/uuid:79c97a39-bad6-48cd-9a6f-75bb32b6448d.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Sharpe R. ON THE MERITS OF STEREOSELECTIVE DESYMMETRIZATION REACTIONS IN THE ASSEMBLY OF COMPLEX NATURAL MOLECULES: THE TOTAL SYNTHESIS OF PACTAMYCIN AND PASPALINE. [Thesis]. University of North Carolina; 2015. Available from: https://cdr.lib.unc.edu/record/uuid:79c97a39-bad6-48cd-9a6f-75bb32b6448d

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of North Carolina

15. Treadway, James. Synthesis and Chromatographic Evaluation of Superficially Porous Particles for Ultrahigh Pressure Liquid Chromatography.

Degree: Chemistry, 2015, University of North Carolina

URL: https://cdr.lib.unc.edu/record/uuid:f7bdff89-494d-4a01-8c40-ccac5f087af5

► Chromatographic separations play a vital role in the separation and analysis of biological samples. Superficially porous particle have emerged as a useful particle architecture for… (more)

▼ Chromatographic separations play a vital role in the separation and analysis of biological samples. Superficially porous particle have emerged as a useful particle architecture for liquid chromatography. These particles have received significant attention recently for the chromatographic efficiency gains that they display. Ultrahigh pressure liquid chromatography employs small particles and high pressures to also yield highly efficient separations. Increasingly, the field of chromatography had employed a combination of these two methods for creating highly efficient columns. One portion of this work details the work with micron-sized superficially porous particles for the separation of intact proteins and other large molecules. Superficially porous particles specifically tailored for the separation of large molecules are not currently commercially available in the single micron size range. One aspect of this work describes the synthetic route that was utilized to create these particles in such a small overall particle size. Another aspect of this work details an evaluation of the separation capabilities of these particles when packed into capillary columns. These columns were utilized for the separation of small molecules, peptides and proteins. Another portion of this work concerns the utilization of commercially manufactured superficially porous particles. One chapter focuses on the creation of highly efficient capillary columns packed with commercial prototype superficially porous particles. The capillary columns created in that chapter exhibit isocratic efficiencies for the separation of small molecules rivaling those seen for capillary columns packed with fully porous particles. This is the first time that such efficient separations have been demonstrated using superficially porous particles packed into capillary columns. A final section of the dissertation focuses on the comparison between commercially available fully and superficially porous particles packed into capillary columns. These particles were bonded with either conventional or charged-surface reversed-phase bondings. The separation characteristics for these columns were evaluated in terms of separating small molecules, peptides, and proteins. It was seen that both the bonded phase and the particle morphology contributed to separation differences between the columns. This work provides insight into which particle and bonding type should be pursued for future investigations. Advisors/Committee Members: Treadway, James, Jorgenson, James, Schoenfisch, Mark H., Ramsey, J. Michael, Pielak, Gary J., Erie, Dorothy.

Subjects/Keywords: Chemistry, Analytic; Chemistry; College of Arts and Sciences; Department of Chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Treadway, J. (2015). Synthesis and Chromatographic Evaluation of Superficially Porous Particles for Ultrahigh Pressure Liquid Chromatography. (Thesis). University of North Carolina. Retrieved from https://cdr.lib.unc.edu/record/uuid:f7bdff89-494d-4a01-8c40-ccac5f087af5

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Treadway, James. “Synthesis and Chromatographic Evaluation of Superficially Porous Particles for Ultrahigh Pressure Liquid Chromatography.” 2015. Thesis, University of North Carolina. Accessed January 18, 2020. https://cdr.lib.unc.edu/record/uuid:f7bdff89-494d-4a01-8c40-ccac5f087af5.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Treadway, James. “Synthesis and Chromatographic Evaluation of Superficially Porous Particles for Ultrahigh Pressure Liquid Chromatography.” 2015. Web. 18 Jan 2020.

Vancouver:

Treadway J. Synthesis and Chromatographic Evaluation of Superficially Porous Particles for Ultrahigh Pressure Liquid Chromatography. [Internet] [Thesis]. University of North Carolina; 2015. [cited 2020 Jan 18]. Available from: https://cdr.lib.unc.edu/record/uuid:f7bdff89-494d-4a01-8c40-ccac5f087af5.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Treadway J. Synthesis and Chromatographic Evaluation of Superficially Porous Particles for Ultrahigh Pressure Liquid Chromatography. [Thesis]. University of North Carolina; 2015. Available from: https://cdr.lib.unc.edu/record/uuid:f7bdff89-494d-4a01-8c40-ccac5f087af5

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of North Carolina

16. Grinias, James. Characterization and Control of Band Broadening in Ultra-High Pressure Liquid Chromatography Columns.

Degree: Chemistry, 2014, University of North Carolina

URL: https://cdr.lib.unc.edu/record/uuid:bbe9f8e7-f865-470d-85ba-ddcf19f54243

► Improving column performance remains paramount to advancing liquid chromatography (LC) technology. To that end, a series of experiments was designed to both measure and reduce… (more)

▼ Improving column performance remains paramount to advancing liquid chromatography (LC) technology. To that end, a series of experiments was designed to both measure and reduce band broadening in LC columns. The main broadening mechanisms (multiple flow path dispersion, longitudinal molecular diffusion, and resistance to mass transfer) were investigated. Dispersion due to multiple flow paths within a packed bed were studied with a series of columns prepared using different packing conditions. Packed column microstructure was analyzed by confocal laser scanning microscopy (CLSM) to determine bed morphology. Column efficiency was correlated to the bed morphology and the radial particle size distribution. Research on longitudinal molecular diffusion focused on the validity of different stationary phase diffusion models. Evidence was found supporting the recently proposed surface-restricted model of surface diffusion. This result has implications affecting both gradient separations and the calculation of the van Deemter B-term. An attempt to reduce the resistance to mass transfer term in the stagnant mobile phase focused on the implementation of a novel sub-2 μm macroporous silica stationary phase support. Unfortunately, the raw packing material contained a significant number of small mesoporous fines that limited the theoretical benefits of these particles, so a hydrodynamic chromatography (HDC) method was developed to remove the fines and reduce the particle size distribution (PSD). In addition to the classical on-column broadening mechanisms described above, broadening effects due to LC operation were studied, including frictional heating and extracolumn band broadening. When mobile phase flows over particles, frictional heating occurs. This heating can decrease column efficiency in sub-2 μm particle-packed columns larger than 1.0 mm in diameter. Studies of frictional heating effects on columns with different dimensions, particle types, and thermal environments were conducted to determine the impact these effects on performance. The LC instrument can diminish efficiency due to extra-column volumes that increase the measured peak variance. The variance contributions of the injector and connecting tubing on a capillary UHPLC system were measured. A possible coupling effect between the components was found that increases the tau-type (exponential decay) broadening contributions from the injector more than theory predicts. Advisors/Committee Members: Grinias, James, Jorgenson, James, Schoenfisch, Mark H., Ramsey, J. Michael, Lockett, Matthew, Dempsey, Jillian.

Subjects/Keywords: Chemistry, Analytic; Chemistry; College of Arts and Sciences; Department of Chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Grinias, J. (2014). Characterization and Control of Band Broadening in Ultra-High Pressure Liquid Chromatography Columns. (Thesis). University of North Carolina. Retrieved from https://cdr.lib.unc.edu/record/uuid:bbe9f8e7-f865-470d-85ba-ddcf19f54243

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Grinias, James. “Characterization and Control of Band Broadening in Ultra-High Pressure Liquid Chromatography Columns.” 2014. Thesis, University of North Carolina. Accessed January 18, 2020. https://cdr.lib.unc.edu/record/uuid:bbe9f8e7-f865-470d-85ba-ddcf19f54243.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Grinias, James. “Characterization and Control of Band Broadening in Ultra-High Pressure Liquid Chromatography Columns.” 2014. Web. 18 Jan 2020.

Vancouver:

Grinias J. Characterization and Control of Band Broadening in Ultra-High Pressure Liquid Chromatography Columns. [Internet] [Thesis]. University of North Carolina; 2014. [cited 2020 Jan 18]. Available from: https://cdr.lib.unc.edu/record/uuid:bbe9f8e7-f865-470d-85ba-ddcf19f54243.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Grinias J. Characterization and Control of Band Broadening in Ultra-High Pressure Liquid Chromatography Columns. [Thesis]. University of North Carolina; 2014. Available from: https://cdr.lib.unc.edu/record/uuid:bbe9f8e7-f865-470d-85ba-ddcf19f54243

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of North Carolina

17. Bertucci, Michael. Synthetic Agents for the Derivatization of N-Acyl Homoserine Lactones.

Degree: Chemistry, 2014, University of North Carolina

URL: https://cdr.lib.unc.edu/record/uuid:af7e4f51-ad3f-4584-a217-3a9671bf915e

► Quorum sensing is a process of chemical communication in bacteria that enables bacteria to coordinate group function, including unified gene expression. As the quorum sensing… (more)

▼ Quorum sensing is a process of chemical communication in bacteria that enables bacteria to coordinate group function, including unified gene expression. As the quorum sensing mechanism is in part responsible for the virulent activity of many bacteria, inhibiting the communication pathway has the potential to lead to the development of novel antibiotics. The central focus of this dissertation is the investigation of strategies for chemically activating and modifying N-acyl homoserine lactones (AHLs), the agent of chemical communication in gram-negative bacteria. Probing the inherent reactivity of the AHLs is critical to understanding their evolved function while uncovering novel modes of inhibition and tools for chemical biology. Initial studies began by utilizing small molecule thiourea and guanidine-based catalysts for accelerating ring-opening reactions of the AHL by amines. The supramolecular catalysts achieved ten and sixty-five fold increases in reaction rate, respectively, for the addition of piperidine to the characteristic α-amino-γ-butyrolactone moiety. This demonstrated the susceptibility of the chemical messengers to be activated for nucleophilic attack through appropriate arrangement of hydrogen bond donors and acceptors. Further studies on the derivatization of the AHLs continued with the development of a hydrazine-mediated transamidation reaction under aqueous conditions. Experimental evidence supports the progression of the reaction via a condensation at the α-carbon of the chemical messenger, followed by an intramolecular cyclization to cleave the AHL at the amide bond. The reaction is operable at physiological pH and is specific for the 3-oxo-AHL in the presence of other AHLs. To rapidly identify a scaffold of non-covalent interactions to increase rate of the transamidation reaction, a reactive tagging assay was developed for high-throughput screening of hydrazine-containing peptide libraries. Combinatorial libraries were synthesized with designer Boc-protected hydrazines and screened against the AHL. Colorimetric hit development was achieved through a strained-cyclooctyne functionalized dye selecting peptides that react most readily with the chemical messenger. First generation library hits were resynthesized and screened for biofilm and quorum sensing inhibition. Further library development and screening holds the potential to identify peptides sequences and structures with the greatest propensity for rapidly functionalizing the 3-oxo-AHL. Advisors/Committee Members: Bertucci, Michael, Gagne, Michel, Waters, Marcey, Brustad, Eric, Lawrence, David, Templeton, Joseph.

Subjects/Keywords: Chemistry; Chemistry, Organic; College of Arts and Sciences; Department of Chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Bertucci, M. (2014). Synthetic Agents for the Derivatization of N-Acyl Homoserine Lactones. (Thesis). University of North Carolina. Retrieved from https://cdr.lib.unc.edu/record/uuid:af7e4f51-ad3f-4584-a217-3a9671bf915e

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Bertucci, Michael. “Synthetic Agents for the Derivatization of N-Acyl Homoserine Lactones.” 2014. Thesis, University of North Carolina. Accessed January 18, 2020. https://cdr.lib.unc.edu/record/uuid:af7e4f51-ad3f-4584-a217-3a9671bf915e.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Bertucci, Michael. “Synthetic Agents for the Derivatization of N-Acyl Homoserine Lactones.” 2014. Web. 18 Jan 2020.

Vancouver:

Bertucci M. Synthetic Agents for the Derivatization of N-Acyl Homoserine Lactones. [Internet] [Thesis]. University of North Carolina; 2014. [cited 2020 Jan 18]. Available from: https://cdr.lib.unc.edu/record/uuid:af7e4f51-ad3f-4584-a217-3a9671bf915e.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Bertucci M. Synthetic Agents for the Derivatization of N-Acyl Homoserine Lactones. [Thesis]. University of North Carolina; 2014. Available from: https://cdr.lib.unc.edu/record/uuid:af7e4f51-ad3f-4584-a217-3a9671bf915e

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of North Carolina

18. Uba, Franklin. Development of Nanofluidic Devices for Single-Molecule DNA Diagnostics.

Degree: Chemistry, 2014, University of North Carolina

URL: https://cdr.lib.unc.edu/record/uuid:da41c21d-a148-4906-81fe-c4b4461f8afd

► Fluidic devices that possess structures less than 150 nm in one or two dimensions are generating great interest due to the unique properties afforded by… (more)

▼ Fluidic devices that possess structures less than 150 nm in one or two dimensions are generating great interest due to the unique properties afforded by this size domain not accessible at the microscale. As molecules travel through nanochannels, they undergo hydrophobic and van der Waals interactions with the channel walls at a degree that depends on the size of the channel, the surface chemistry of the wall and the debye length (governed by the ionic strength of the electrolyte solution). In this work, we report the fabrication of nanometer sized structures (nanoslits, nanochannels and nanoelectrodes) in thermoplastic and fused silica substrates for the analysis of dsNA. In the case of thermoplastics, mixed-scale micro- and nanofluidic networks were fabricated using a simple, high resolution, single-step thermal embossing process and the fluidic structures were enclosed via low temperature fusion bonding to a cover plate. Nanochannels were chemically modified and the associated electrokinetic parameters - surface charge density, zeta potential and electroosmotic flow - were evaluated. In the fused silica substrate, we developed an integrated nanosensing device comprising of a single nanochannel and two pairs of transverse electron-conducting (~50 × 50 nm) nanoelectrodes separated by a nanometer gap (nanogap) and poised at the input and output ends of the nanochannel. This device serves a foundation for a novel technique we developing for the sequencing of DNA molecule by measuring the transit time of the monomer units entering and exiting a nanochannel (5 to 50 nanochannels) after being clipped from a single polymer digested with an enzyme. Further experiments on single molecule electrophoresis will provide information on possible routes that can be adopted to engineer proper nanochannel wall chemistry for the enhancement or reduction of solute/wall interactions. Advisors/Committee Members: Uba, Franklin, Soper, Steven, Jorgenson, James, Murray, Royce W., Ashby, Valerie, Taylor, Anne, Lockett, Matthew.

Subjects/Keywords: Chemistry; Chemistry, Analytic; College of Arts and Sciences; Department of Chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Uba, F. (2014). Development of Nanofluidic Devices for Single-Molecule DNA Diagnostics. (Thesis). University of North Carolina. Retrieved from https://cdr.lib.unc.edu/record/uuid:da41c21d-a148-4906-81fe-c4b4461f8afd

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Uba, Franklin. “Development of Nanofluidic Devices for Single-Molecule DNA Diagnostics.” 2014. Thesis, University of North Carolina. Accessed January 18, 2020. https://cdr.lib.unc.edu/record/uuid:da41c21d-a148-4906-81fe-c4b4461f8afd.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Uba, Franklin. “Development of Nanofluidic Devices for Single-Molecule DNA Diagnostics.” 2014. Web. 18 Jan 2020.

Vancouver:

Uba F. Development of Nanofluidic Devices for Single-Molecule DNA Diagnostics. [Internet] [Thesis]. University of North Carolina; 2014. [cited 2020 Jan 18]. Available from: https://cdr.lib.unc.edu/record/uuid:da41c21d-a148-4906-81fe-c4b4461f8afd.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Uba F. Development of Nanofluidic Devices for Single-Molecule DNA Diagnostics. [Thesis]. University of North Carolina; 2014. Available from: https://cdr.lib.unc.edu/record/uuid:da41c21d-a148-4906-81fe-c4b4461f8afd

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of North Carolina

19. Do, Dung. STEREOSELECTIVE FUNCTIONALIZATION OF MELDRUM'S ACIDS AND THE EFFORTS TOWARD TOTAL SYNTHESIS OF ECHINOSPORIN.

Degree: Chemistry, 2014, University of North Carolina

URL: https://cdr.lib.unc.edu/record/uuid:4fce5301-7cb1-4cfc-8b0a-8d5d6615a1c8

► I. Cu(II)-Catalyzed Aerobic Hydroperoxidation of Meldrum's Acid Derivatives and Application in Intramolecular Functionalization to Access Complex Building Blocks Aerobic hydroperoxidation of Meldrum's acid derivatives via… (more)

▼ I. Cu(II)-Catalyzed Aerobic Hydroperoxidation of Meldrum's Acid Derivatives and Application in Intramolecular Functionalization to Access Complex Building Blocks Aerobic hydroperoxidation of Meldrum's acid derivatives via a Cu(II)-catalyzed process is presented. The mild reaction conditions are tolerant to variety of vulnerable functional groups. Au(I)-catalyzed endoperoxidations of hydroperoxyalkynes have been reported for the first time. Cleavage of the OO bond provides 1,n-diols with differentiation of the hydroxy groups. A novel research plan centered on the hydroperoxidation of designed Meldrum's acids to generally access fully substituted hemiketal-viable substrates for preparation of complex building blocks is also discussed. II. Conceptual Blueprint for a Stereoselective Heterofunctionalization of Carbonyl Compounds The glamour of a general stereoselective heterofunctionalization of carbonyl compounds encourage us to develop a novel a-heterofunctionalization of lactone. The strategy based on a highly diastereoselective Michael addition of variety of nucleophiles to readily accessible chiral alkylidene Meldrum's acid and a feasible heterofunctionalization of Meldrum's acids to access difunctionalization adducts. Those compounds have been carried on a symmetry-breaking intramolecular lactonization to reveal a new stereocenter with excellent chirality induction at carbon bearing heterofunctional group. Limited efforts provided a proof of concept for a stereoselective fluorination of lactone. III. Efforts Toward The Total Synthesis of Echinosoirin Two approaches for the construction of the echinosporin core are presented. A key strategy includes the rapid formation of the fully substituted-dihydropyran substructure via intermolecular inverse electron demand hetero Diels-Alder reaction of a chiral heterodiene. Highly diastereoselective cyclizations realized by the use of copper(II) triflate and tBu-box ligand, provided access to the dihydropyran core. The stereochemical features of this cycloaddition were previously well established and produced the dihydropyran with high diastereocontrol. An advanced intermediates diazoketone 3.54 was prepared as a single diastereomer in mulltigram-scale and will provide requisite material for further manipulations. Advisors/Committee Members: Do, Dung, Johnson, Jeffrey, Nicewicz, David, Brookhart, Maurice, Alexanian, Erik, Templeton, Joseph.

Subjects/Keywords: Chemistry; Chemistry, Organic; College of Arts and Sciences; Department of Chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Do, D. (2014). STEREOSELECTIVE FUNCTIONALIZATION OF MELDRUM'S ACIDS AND THE EFFORTS TOWARD TOTAL SYNTHESIS OF ECHINOSPORIN. (Thesis). University of North Carolina. Retrieved from https://cdr.lib.unc.edu/record/uuid:4fce5301-7cb1-4cfc-8b0a-8d5d6615a1c8

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Do, Dung. “STEREOSELECTIVE FUNCTIONALIZATION OF MELDRUM'S ACIDS AND THE EFFORTS TOWARD TOTAL SYNTHESIS OF ECHINOSPORIN.” 2014. Thesis, University of North Carolina. Accessed January 18, 2020. https://cdr.lib.unc.edu/record/uuid:4fce5301-7cb1-4cfc-8b0a-8d5d6615a1c8.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Do, Dung. “STEREOSELECTIVE FUNCTIONALIZATION OF MELDRUM'S ACIDS AND THE EFFORTS TOWARD TOTAL SYNTHESIS OF ECHINOSPORIN.” 2014. Web. 18 Jan 2020.

Vancouver:

Do D. STEREOSELECTIVE FUNCTIONALIZATION OF MELDRUM'S ACIDS AND THE EFFORTS TOWARD TOTAL SYNTHESIS OF ECHINOSPORIN. [Internet] [Thesis]. University of North Carolina; 2014. [cited 2020 Jan 18]. Available from: https://cdr.lib.unc.edu/record/uuid:4fce5301-7cb1-4cfc-8b0a-8d5d6615a1c8.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Do D. STEREOSELECTIVE FUNCTIONALIZATION OF MELDRUM'S ACIDS AND THE EFFORTS TOWARD TOTAL SYNTHESIS OF ECHINOSPORIN. [Thesis]. University of North Carolina; 2014. Available from: https://cdr.lib.unc.edu/record/uuid:4fce5301-7cb1-4cfc-8b0a-8d5d6615a1c8

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of North Carolina

20. Batz, Nicholas. Development and Application of Surface Coatings for Microchip Capillary Electrophoresis-Electrospray Ionization-Mass Spectrometry Analysis of Biological Analytes.

Degree: Chemistry, 2014, University of North Carolina

URL: https://cdr.lib.unc.edu/record/uuid:e98451f7-4e17-4bea-bf32-f548ff861d9d

► This work describes the development of improved surface coating methods for microchip capillary electrophoresis-electrospray ionization-mass spectrometry (CE-ESI-MS) and their application for the analysis of biological… (more)

▼ This work describes the development of improved surface coating methods for microchip capillary electrophoresis-electrospray ionization-mass spectrometry (CE-ESI-MS) and their application for the analysis of biological analytes. A new coating method based on chemical vapor deposition (CVD) of aminopropyl silane (APS) reagents is demonstrated. The method improved the efficiency of separations over previously used surface coatings while also promoting batch processing of multiple devices at once. The separation performance was quantified using a new efficiency metric based on CE theory. Microchips coated via CVD produced the most efficient liquid phase separations coupled to MS reported to date. The CVD method was found to produce a base layer well suited for subsequent modification. APS surfaces administered via CVD were modified with n-hydroxy succinimide (NHS) esters of polyethylene glycol (PEG) with varying PEG chain lengths. These coatings were found to produce highly efficient separations while offering a range of electroosmotic flow (EOF) values. PEGylation resulted in increased peak capacity and resolution as compared to APS coatings for the separation of intact proteins and digested proteins using CE-ESI microchips coupled with MS. Microfluidic CE-ESI devices with separation channels of 1 cm and 3 cm in length were coated with APS via CVD and used for high speed (HS) CE-ESI-MS of peptides and proteins. These devices were capable of CE separation times ranging from 10 s to < 1 s. To adequately sample the temporally narrow peaks generated by these devices a new MS data collection with increased data acquisition rates was developed. Both MS and tandem MS analyses were demonstrated using this high speed MS data acquisition method. The HSCE-ESI-MS separations performed on the 1 cm microchip are the fastest liquid phase separations coupled to MS reported to date. Finally, the performance limits of both the APS and PEG surface coatings were investigated. APS was applied to a CE-ESI device with a 1 m separation channel to test the ability of the CVD method to coat long channels. This device achieved > 1.4 million theoretical plates for the separation of peptide standards. A PEG surface coating was used to analyze an intact monoclonal antibody to determine structural charge variants as well as variants arising from glycosylation differences. Additionally, this PEG surface was used to inhibit the effects of sample matrix components that were deleterious to CE-ESI-MS through on-chip mobility-based sample clean-up. This approach facilitated the analysis of biological samples in matrices that would otherwise be incompatible with microchip CE-ESI-MS. Advisors/Committee Members: Batz, Nicholas, Ramsey, J. Michael, Ramsey, J. Michael, Jorgenson, James, Allbritton, Nancy, Wightman, R. Mark, Taylor, Anne.

Subjects/Keywords: Chemistry; Chemistry, Analytic; College of Arts and Sciences; Department of Chemistry

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APA (6^th Edition):

Batz, N. (2014). Development and Application of Surface Coatings for Microchip Capillary Electrophoresis-Electrospray Ionization-Mass Spectrometry Analysis of Biological Analytes. (Thesis). University of North Carolina. Retrieved from https://cdr.lib.unc.edu/record/uuid:e98451f7-4e17-4bea-bf32-f548ff861d9d

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Batz, Nicholas. “Development and Application of Surface Coatings for Microchip Capillary Electrophoresis-Electrospray Ionization-Mass Spectrometry Analysis of Biological Analytes.” 2014. Thesis, University of North Carolina. Accessed January 18, 2020. https://cdr.lib.unc.edu/record/uuid:e98451f7-4e17-4bea-bf32-f548ff861d9d.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Batz, Nicholas. “Development and Application of Surface Coatings for Microchip Capillary Electrophoresis-Electrospray Ionization-Mass Spectrometry Analysis of Biological Analytes.” 2014. Web. 18 Jan 2020.

Vancouver:

Batz N. Development and Application of Surface Coatings for Microchip Capillary Electrophoresis-Electrospray Ionization-Mass Spectrometry Analysis of Biological Analytes. [Internet] [Thesis]. University of North Carolina; 2014. [cited 2020 Jan 18]. Available from: https://cdr.lib.unc.edu/record/uuid:e98451f7-4e17-4bea-bf32-f548ff861d9d.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Batz N. Development and Application of Surface Coatings for Microchip Capillary Electrophoresis-Electrospray Ionization-Mass Spectrometry Analysis of Biological Analytes. [Thesis]. University of North Carolina; 2014. Available from: https://cdr.lib.unc.edu/record/uuid:e98451f7-4e17-4bea-bf32-f548ff861d9d

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

National University of Ireland – Galway

21. Kellehan, David. Synthesis and Application of Chiral AraBOX ligands for Asymmetric Catalysis .

Degree: 2012, National University of Ireland – Galway

URL: http://hdl.handle.net/10379/3405

► This thesis deals with the design, synthesis and reactivity of novel 4,4'-bisoxazoline ligands and their metal complexes; (S,S)-MePrAraBOX, (S,S)-PhPrAraBOX, (S,R)-MePrAraBOX, (S,R)-PhPrAraBOX, (S,R)-BnOAcAraBOX and (S,R)-BnOHAraBOX. Metal… (more)

▼ This thesis deals with the design, synthesis and reactivity of novel 4,4'-bisoxazoline ligands and their metal complexes; (S,S)-MePrAraBOX, (S,S)-PhPrAraBOX, (S,R)-MePrAraBOX, (S,R)-PhPrAraBOX, (S,R)-BnOAcAraBOX and (S,R)-BnOHAraBOX. Metal complexes of these ligands have been applied to transition metal catalysed asymmetric reactions, in particular asymmetric Diels Alder, cyclopropanation and allylic alkylation reactions. A copper(II) complex of (S,R)-PhPrAraBOX catalysed a benchmark Diels Alder reaction in up to 57% ee, the highest enantioselectivity yet achieved for a 4,4'-BOX ligand in a Diels Alder reaction. An ee of 70% was achieved with a copper(I) complex of (S,S)-MePrAraBOX in a benchmark asymmetric cyclopropanation reaction, which is also the highest enantioselectivity yet achieved for a 4,4'-BOX ligand in these reactions. The ligands were also applied to the asymmetric allylic alkylation reaction. They were the first 4,4'-BOX ligands to generate enantiocontrol in the reaction, with a palladium complex of (S,S)-MePrAraBOX producing an ee of 72%. The rationalisation of these results, in particular the results relating to the cyclopropanation reaction, are supported by computational studies carried out by colleagues in Zaragoza. The 4,4'-bisoxazoline ligands (S,R)-BnOAcAraBOX and (S,R)-BnOHAraBOX, which contain secondary binding sites, were applied to the Diels Alder and asymmetric allylic alkylation reactions with low activity and selectivity. Ligand (S,R)-BnOHAraBOX was also applied to an asymmetric alkylation of benzaldehyde, showing low conversion and no selectivity. Chapter One deals with the introduction of the general concepts of asymmetric synthesis and asymmetric catalysis. Chapter Two discusses the synthesis of the 4,4'-bisoxazoline ligands and the application of the metal complexes of these ligands to the asymmetric reactions. Chapter Three contains the full experimental details for the project, including spectral and analytical data. Advisors/Committee Members: O'Leary, Patrick (advisor).

Subjects/Keywords: Bisoxazoline ligands; Asymmetric catalysis; Department of Chemistry

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APA (6^th Edition):

Kellehan, D. (2012). Synthesis and Application of Chiral AraBOX ligands for Asymmetric Catalysis . (Thesis). National University of Ireland – Galway. Retrieved from http://hdl.handle.net/10379/3405

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Kellehan, David. “Synthesis and Application of Chiral AraBOX ligands for Asymmetric Catalysis .” 2012. Thesis, National University of Ireland – Galway. Accessed January 18, 2020. http://hdl.handle.net/10379/3405.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Kellehan, David. “Synthesis and Application of Chiral AraBOX ligands for Asymmetric Catalysis .” 2012. Web. 18 Jan 2020.

Vancouver:

Kellehan D. Synthesis and Application of Chiral AraBOX ligands for Asymmetric Catalysis . [Internet] [Thesis]. National University of Ireland – Galway; 2012. [cited 2020 Jan 18]. Available from: http://hdl.handle.net/10379/3405.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Kellehan D. Synthesis and Application of Chiral AraBOX ligands for Asymmetric Catalysis . [Thesis]. National University of Ireland – Galway; 2012. Available from: http://hdl.handle.net/10379/3405

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of North Carolina

22. Gabriel, Michelle. Imaging Ultrafast Dynamics in Nanomaterials Using Spatially-Separated Pump-Probe Microscopy.

Degree: Chemistry, 2015, University of North Carolina

URL: https://cdr.lib.unc.edu/record/uuid:57d3f9ac-a11a-4f7a-9ba2-e96f3833a342

► Understanding the fundamental physics of nanomaterials is critical for the advancement and rational design of new nanotechnologies. On the nanoscale, differences between individual structures, and… (more)

Subjects/Keywords: Chemistry; Chemistry, Analytic; Chemistry, Physical and theoretical; College of Arts and Sciences; Department of Chemistry

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APA (6^th Edition):

Gabriel, M. (2015). Imaging Ultrafast Dynamics in Nanomaterials Using Spatially-Separated Pump-Probe Microscopy. (Thesis). University of North Carolina. Retrieved from https://cdr.lib.unc.edu/record/uuid:57d3f9ac-a11a-4f7a-9ba2-e96f3833a342

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Gabriel, Michelle. “Imaging Ultrafast Dynamics in Nanomaterials Using Spatially-Separated Pump-Probe Microscopy.” 2015. Thesis, University of North Carolina. Accessed January 18, 2020. https://cdr.lib.unc.edu/record/uuid:57d3f9ac-a11a-4f7a-9ba2-e96f3833a342.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Gabriel, Michelle. “Imaging Ultrafast Dynamics in Nanomaterials Using Spatially-Separated Pump-Probe Microscopy.” 2015. Web. 18 Jan 2020.

Vancouver:

Gabriel M. Imaging Ultrafast Dynamics in Nanomaterials Using Spatially-Separated Pump-Probe Microscopy. [Internet] [Thesis]. University of North Carolina; 2015. [cited 2020 Jan 18]. Available from: https://cdr.lib.unc.edu/record/uuid:57d3f9ac-a11a-4f7a-9ba2-e96f3833a342.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Gabriel M. Imaging Ultrafast Dynamics in Nanomaterials Using Spatially-Separated Pump-Probe Microscopy. [Thesis]. University of North Carolina; 2015. Available from: https://cdr.lib.unc.edu/record/uuid:57d3f9ac-a11a-4f7a-9ba2-e96f3833a342

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of North Carolina

23. Turner, Abigail. Epidermal Growth Factor Receptor Tyrosine Kinase Assays in Single Intact Cells Using Capillary Electrophoresis.

Degree: Chemistry, 2015, University of North Carolina

URL: https://cdr.lib.unc.edu/record/uuid:524c1556-dc54-49ee-9403-39d0fbb45663

► Quantification of abnormal Epidermal Growth Factor Receptor (EGFR) tyrosine kinase activity is critical to the clinical success of targeted inhibitors used to treat EGFR-dependent cancers.… (more)

Subjects/Keywords: Chemistry; College of Arts and Sciences; Department of Chemistry

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APA (6^th Edition):

Turner, A. (2015). Epidermal Growth Factor Receptor Tyrosine Kinase Assays in Single Intact Cells Using Capillary Electrophoresis. (Thesis). University of North Carolina. Retrieved from https://cdr.lib.unc.edu/record/uuid:524c1556-dc54-49ee-9403-39d0fbb45663

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Turner, Abigail. “Epidermal Growth Factor Receptor Tyrosine Kinase Assays in Single Intact Cells Using Capillary Electrophoresis.” 2015. Thesis, University of North Carolina. Accessed January 18, 2020. https://cdr.lib.unc.edu/record/uuid:524c1556-dc54-49ee-9403-39d0fbb45663.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Turner, Abigail. “Epidermal Growth Factor Receptor Tyrosine Kinase Assays in Single Intact Cells Using Capillary Electrophoresis.” 2015. Web. 18 Jan 2020.

Vancouver:

Turner A. Epidermal Growth Factor Receptor Tyrosine Kinase Assays in Single Intact Cells Using Capillary Electrophoresis. [Internet] [Thesis]. University of North Carolina; 2015. [cited 2020 Jan 18]. Available from: https://cdr.lib.unc.edu/record/uuid:524c1556-dc54-49ee-9403-39d0fbb45663.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Turner A. Epidermal Growth Factor Receptor Tyrosine Kinase Assays in Single Intact Cells Using Capillary Electrophoresis. [Thesis]. University of North Carolina; 2015. Available from: https://cdr.lib.unc.edu/record/uuid:524c1556-dc54-49ee-9403-39d0fbb45663

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of North Carolina

24. Turlington, Christopher. Oxygen Atom Transfer to Half-Sandwich Complexes of Iridium and Rhodium.

Degree: Chemistry, 2015, University of North Carolina

URL: https://cdr.lib.unc.edu/record/uuid:57f2ae3c-469e-44bd-864d-735ee8991ad7

► The oxidation chemistry of half-sandwich iridium and rhodium complexes was explored. Iridium(Cp*) and rhodium(Cp*) complexes were prepared with various bidentate ligands and then reacted with… (more)

Subjects/Keywords: Chemistry; College of Arts and Sciences; Department of Chemistry

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APA (6^th Edition):

Turlington, C. (2015). Oxygen Atom Transfer to Half-Sandwich Complexes of Iridium and Rhodium. (Thesis). University of North Carolina. Retrieved from https://cdr.lib.unc.edu/record/uuid:57f2ae3c-469e-44bd-864d-735ee8991ad7

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Turlington, Christopher. “Oxygen Atom Transfer to Half-Sandwich Complexes of Iridium and Rhodium.” 2015. Thesis, University of North Carolina. Accessed January 18, 2020. https://cdr.lib.unc.edu/record/uuid:57f2ae3c-469e-44bd-864d-735ee8991ad7.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Turlington, Christopher. “Oxygen Atom Transfer to Half-Sandwich Complexes of Iridium and Rhodium.” 2015. Web. 18 Jan 2020.

Vancouver:

Turlington C. Oxygen Atom Transfer to Half-Sandwich Complexes of Iridium and Rhodium. [Internet] [Thesis]. University of North Carolina; 2015. [cited 2020 Jan 18]. Available from: https://cdr.lib.unc.edu/record/uuid:57f2ae3c-469e-44bd-864d-735ee8991ad7.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Turlington C. Oxygen Atom Transfer to Half-Sandwich Complexes of Iridium and Rhodium. [Thesis]. University of North Carolina; 2015. Available from: https://cdr.lib.unc.edu/record/uuid:57f2ae3c-469e-44bd-864d-735ee8991ad7

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of North Carolina

25. Busan, Steven. Frameworks for large-scale RNA structure profiling in transcriptomes and disease.

Degree: Chemistry, 2015, University of North Carolina

URL: https://cdr.lib.unc.edu/record/uuid:fa2d2fe1-0129-4227-a872-ce956896a54e

► In addition to their role as intermediaries on the route to protein synthesis, RNA molecules have long been known to base-pair into complex structures that… (more)

Subjects/Keywords: Chemistry; College of Arts and Sciences; Department of Chemistry

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APA (6^th Edition):

Busan, S. (2015). Frameworks for large-scale RNA structure profiling in transcriptomes and disease. (Thesis). University of North Carolina. Retrieved from https://cdr.lib.unc.edu/record/uuid:fa2d2fe1-0129-4227-a872-ce956896a54e

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Busan, Steven. “Frameworks for large-scale RNA structure profiling in transcriptomes and disease.” 2015. Thesis, University of North Carolina. Accessed January 18, 2020. https://cdr.lib.unc.edu/record/uuid:fa2d2fe1-0129-4227-a872-ce956896a54e.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Busan, Steven. “Frameworks for large-scale RNA structure profiling in transcriptomes and disease.” 2015. Web. 18 Jan 2020.

Vancouver:

Busan S. Frameworks for large-scale RNA structure profiling in transcriptomes and disease. [Internet] [Thesis]. University of North Carolina; 2015. [cited 2020 Jan 18]. Available from: https://cdr.lib.unc.edu/record/uuid:fa2d2fe1-0129-4227-a872-ce956896a54e.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Busan S. Frameworks for large-scale RNA structure profiling in transcriptomes and disease. [Thesis]. University of North Carolina; 2015. Available from: https://cdr.lib.unc.edu/record/uuid:fa2d2fe1-0129-4227-a872-ce956896a54e

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of North Carolina

26. Rice, Greggory. High-throughput Experiment Driven Modeling of RNA Interactions and Structures.

Degree: Chemistry, 2015, University of North Carolina

URL: https://cdr.lib.unc.edu/record/uuid:cbeb11b0-d2f3-4f68-8945-5a924e10bd59

► The higher order structure of an RNA is often essential to its biological function, modulating its interactions with ligands, protein partners, and other RNAs. Modeling… (more)

▼ The higher order structure of an RNA is often essential to its biological function, modulating its interactions with ligands, protein partners, and other RNAs. Modeling RNA secondary structure, assessing the accuracy of RNA structural models, and discovering new functional motifs are challenging problems that are confounded by the length and complexity of the studied RNA. Improvements in structure modeling accuracy can be made by incorporating SHAPE (selective 2'-hydroxyl acylation analyzed by primer extension) and DMS (dimethyl sulfate) chemical probing data, however these models remain imperfect. In this work I apply principals of molecular modeling in interpret chemical probing experiments and create analytical and experimental tools that enable large-scale experiment-driven modeling of RNA interactions and structures. First, I use electronic structure modeling to propose a mechanism to explain the preferential reactivity of the SHAPE reagent 1M6 at nucleotides exhibiting an available open stack in folded RNAs. I also use molecular modeling at the nucleotide level to develop a model that accurately predicts the disruptive effects of SHAPE adducts on RNA tertiary structure. Second, I create a new energy potential for RNA structure prediction using information from a three-reagent SHAPE experiment that increases the accuracy of modeling accuracy from 85% to above 90% for some of the most difficult-to-predict RNA structures. Third, working collaboratively with others in the lab, I validate a new approach for melding SHAPE chemical probing with deep sequencing in a new technique termed SHAPE mutational profiling (SHAPE-MaP). The ability to quickly generate structural data for RNAs of unprecedented size using SHAPE-MaP presents a new challenge: accurately modeling large RNA secondary structures. To solve this problem I develop software, called SuperFold, which uses a windowed modeling algorithm to enable rapid secondary structure prediction and discovery of the most stable structural motifs in long RNAs. Fourth, I extend the RING-MaP experiment and analysis to enable use with random primers and applied it to the bacterial ribosome. With the improved RING-MaP experiment I am able to detect structural interaction networks within the small ribosomal subunit. Additionally, I am able to perturb those structural networks by adding the antibiotic spectinomycin. Coupled together, the work presented here will provide valuable tools that democratize RNA structure analysis and help others in the RNA community understand the role of RNA structure at new and exciting scales. Advisors/Committee Members: Rice, Greggory, Weeks, Kevin, Pielak, Gary J., Laederach, Alain, Dokholyan, Nikolay, Lawrence, David.

Subjects/Keywords: Biochemistry; Bioinformatics; Chemistry; College of Arts and Sciences; Department of Chemistry

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APA (6^th Edition):

Rice, G. (2015). High-throughput Experiment Driven Modeling of RNA Interactions and Structures. (Thesis). University of North Carolina. Retrieved from https://cdr.lib.unc.edu/record/uuid:cbeb11b0-d2f3-4f68-8945-5a924e10bd59

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Rice, Greggory. “High-throughput Experiment Driven Modeling of RNA Interactions and Structures.” 2015. Thesis, University of North Carolina. Accessed January 18, 2020. https://cdr.lib.unc.edu/record/uuid:cbeb11b0-d2f3-4f68-8945-5a924e10bd59.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Rice, Greggory. “High-throughput Experiment Driven Modeling of RNA Interactions and Structures.” 2015. Web. 18 Jan 2020.

Vancouver:

Rice G. High-throughput Experiment Driven Modeling of RNA Interactions and Structures. [Internet] [Thesis]. University of North Carolina; 2015. [cited 2020 Jan 18]. Available from: https://cdr.lib.unc.edu/record/uuid:cbeb11b0-d2f3-4f68-8945-5a924e10bd59.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Rice G. High-throughput Experiment Driven Modeling of RNA Interactions and Structures. [Thesis]. University of North Carolina; 2015. Available from: https://cdr.lib.unc.edu/record/uuid:cbeb11b0-d2f3-4f68-8945-5a924e10bd59

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of North Carolina

27. Noucti, Njamkou. NICKEL-CATALYZED CYCLOADDITIONS OF ENE-ALLENES.

Degree: Chemistry, 2015, University of North Carolina

URL: https://cdr.lib.unc.edu/record/uuid:23872fdd-a25f-4d79-b4ee-c8f5dc6d3826

► Nickel–catalyzed reactions of alkene and allene π–components are reported. Through ligand–controlled selectivity, a common intermediate can be diverted to four distinct reaction pathways: (1) [2+2+2]… (more)

Subjects/Keywords: Chemistry, Organic; College of Arts and Sciences; Department of Chemistry

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APA (6^th Edition):

Noucti, N. (2015). NICKEL-CATALYZED CYCLOADDITIONS OF ENE-ALLENES. (Thesis). University of North Carolina. Retrieved from https://cdr.lib.unc.edu/record/uuid:23872fdd-a25f-4d79-b4ee-c8f5dc6d3826

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Noucti, Njamkou. “NICKEL-CATALYZED CYCLOADDITIONS OF ENE-ALLENES.” 2015. Thesis, University of North Carolina. Accessed January 18, 2020. https://cdr.lib.unc.edu/record/uuid:23872fdd-a25f-4d79-b4ee-c8f5dc6d3826.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Noucti, Njamkou. “NICKEL-CATALYZED CYCLOADDITIONS OF ENE-ALLENES.” 2015. Web. 18 Jan 2020.

Vancouver:

Noucti N. NICKEL-CATALYZED CYCLOADDITIONS OF ENE-ALLENES. [Internet] [Thesis]. University of North Carolina; 2015. [cited 2020 Jan 18]. Available from: https://cdr.lib.unc.edu/record/uuid:23872fdd-a25f-4d79-b4ee-c8f5dc6d3826.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Noucti N. NICKEL-CATALYZED CYCLOADDITIONS OF ENE-ALLENES. [Thesis]. University of North Carolina; 2015. Available from: https://cdr.lib.unc.edu/record/uuid:23872fdd-a25f-4d79-b4ee-c8f5dc6d3826

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of North Carolina

28. Wong, Hiu Ching. Perfluoropolyether-based Electrolytes for Lithium Battary Applications.

Degree: Chemistry, 2015, University of North Carolina

URL: https://cdr.lib.unc.edu/record/uuid:f593f758-94b3-4a6e-83d0-226d0be9a1e0

► Large-scale rechargeable batteries are expected to play a key role in today's emerging sustainable energy landscape. State-of-the-art lithium-ion batteries are not only widely used in… (more)

▼ Large-scale rechargeable batteries are expected to play a key role in today's emerging sustainable energy landscape. State-of-the-art lithium-ion batteries are not only widely used in electric vehicles, but they are currently gaining traction as backup power in aircraft and smart grid applications. In all of these cases, safety surrounding the electrolyte, an essential component of a lithium-ion battery, is a challenging limitation: the low flash points of currently used small molecule organic alkyl carbonates impose a high risk of ignition under most operating conditions. For this reason, extensive efforts are being made to develop viable nonflammable electrolytes to replace these organic solvents. Herein, we describe new classes of nonflammable liquid and solid electrolytes composed of oligomeric perfluoropolyethers. These materials are promising electrolyte alternatives due to their low glass transition temperatures, high chemical stability, capacity to dissolve lithium salts such as lithium bis(trifluoromethane)sulfonimide lithium salt, and compatibility with various common polymers such as poly(ethylene glycol). Synthetic modifications used to introduce a wide range of functional groups has created a platform of intrinsically fireproof materials that can be chemically tailored to achieve the desired physical, thermal, mechanical, and electrochemical properties for specific battery applications. Using this approach carbonate-, thiol-, allyl-, and propargyl- functionalized perfluoropolyethers were prepared from the commercially available hydroxyl-terminated PFPEs. The terminal group and molecular weight effects on the bulk properties of these materials were systematically characterized and their viability as electrolytes was evaluated. The described work ultimately paves the way towards further optimization of perfluoropolyether materials towards the development of high performance lithium- ion batteries. The interesting properties of these materials invite an extensive study into the fundamental mesoscale ion transport and the relationship between perfluoropolyether chemical structure and electrolyte electrochemical property, as well as a closer analysis into the perfluoropolyether and electrode interface. Investigation in these areas using techniques such as advanced nuclear magnetic resonance spectroscopy and transmission electron microscopy is proposed. Advisors/Committee Members: Wong, Hiu Ching, DeSimone, Joseph M., Sheiko, Sergei, Ashby, Valerie, Murray, Royce W., Gagne, Michel.

Subjects/Keywords: Chemistry; College of Arts and Sciences; Department of Chemistry

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APA (6^th Edition):

Wong, H. C. (2015). Perfluoropolyether-based Electrolytes for Lithium Battary Applications. (Thesis). University of North Carolina. Retrieved from https://cdr.lib.unc.edu/record/uuid:f593f758-94b3-4a6e-83d0-226d0be9a1e0

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Wong, Hiu Ching. “Perfluoropolyether-based Electrolytes for Lithium Battary Applications.” 2015. Thesis, University of North Carolina. Accessed January 18, 2020. https://cdr.lib.unc.edu/record/uuid:f593f758-94b3-4a6e-83d0-226d0be9a1e0.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Wong, Hiu Ching. “Perfluoropolyether-based Electrolytes for Lithium Battary Applications.” 2015. Web. 18 Jan 2020.

Vancouver:

Wong HC. Perfluoropolyether-based Electrolytes for Lithium Battary Applications. [Internet] [Thesis]. University of North Carolina; 2015. [cited 2020 Jan 18]. Available from: https://cdr.lib.unc.edu/record/uuid:f593f758-94b3-4a6e-83d0-226d0be9a1e0.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Wong HC. Perfluoropolyether-based Electrolytes for Lithium Battary Applications. [Thesis]. University of North Carolina; 2015. Available from: https://cdr.lib.unc.edu/record/uuid:f593f758-94b3-4a6e-83d0-226d0be9a1e0

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of North Carolina

29. Gesmundo, Nathan. The Development of Complexity Generating Organic Photoredox Transformations and the Application of These Transformations in Complex Molecule Synthesis.

Degree: Chemistry, 2015, University of North Carolina

URL: https://cdr.lib.unc.edu/record/uuid:3eb42de0-b8bc-449f-a83e-b9a07eb3ea78

► Described herein are three methods for the direct functionalization of alkenes, enabled by organic photoredox catalysis. Additionally, a model system studying the application of a… (more)

▼ Described herein are three methods for the direct functionalization of alkenes, enabled by organic photoredox catalysis. Additionally, a model system studying the application of a photoredox cyclization method in natural product synthesis is described. I. Introduction to Visible Light Photoredox Catalysis An overview of visible light photoredox catalysis is presented. The principles of photoredox catalysis and single electron transfer are discussed and excited state photooxidants are introduced. II. Cyclization-Endoperoxidation Cascade of Unconjugated Dienes Mediated by a Pyrylium Photoredox Catalyst A method for the direct synthesis of bicyclic endoperoxides from unconjugated dienes using a pyrylium photoredox catalyst is presented. The reaction proceeds through the intermediacy of a distonic cation radical, with molecular oxygen serving as the peroxide source. Emphasis of this chapter is on the complimentary nature of our endoperoxidation strategy. III. Development of a Method to Directly Access γ-Lactam and Pyrrolidine Heterocycles via Polar Radical Crossover Cyclizations A method for the direct synthesis of γ-lactam and pyrrolidine heterocycles from alkenes and unsaturated N-nucleophiles is described. The reaction proceeds via a cation radical intermediate and utilizes a dual catalytic system comprised of an acridinium photooxidant and a redox active hydrogen atom donor to produce the heterocyclic products. The boundaries of this mode of reactivity are explored and the complimentary nature of this method is emphasized. IV. Application of a Cation Radical Mediated Polar Radical Crossover Cycylization in a Rubriflordilactone B Model System A model system to explore the possibility of rubriflordilactone B synthesis utilizing a polar radical crossover cyclization as the key step is designed. Work on a key Mukaiyama vinylogous aldol reaction is presented as well as exploratory work on the central tetrahydrofuran-forming cyclization. Discussions of related syntheses, retrosynthetic analysis, and future work are also presented. V. Hydrotrifluoromethylation of Aliphatic Alkenes and Styrenes A method for the catalytic hydrotrifluoromethylation of alkenes using an organic photoredox system is disclosed. The strategy operates by single electron oxidation of sodium trifluoromethane sulfinate and is tolerant of aliphatic and styrenyl alkene substrates. A dual catalytic system of an acridinium photoredox catalyst and a redox-active hydrogen atom donor is used to generate the observed products. Advisors/Committee Members: Gesmundo, Nathan, Nicewicz, David, Johnson, Jeffrey, Alexanian, Erik, Templeton, Joseph, You, Wei.

Subjects/Keywords: Chemistry, Organic; College of Arts and Sciences; Department of Chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Gesmundo, N. (2015). The Development of Complexity Generating Organic Photoredox Transformations and the Application of These Transformations in Complex Molecule Synthesis. (Thesis). University of North Carolina. Retrieved from https://cdr.lib.unc.edu/record/uuid:3eb42de0-b8bc-449f-a83e-b9a07eb3ea78

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Gesmundo, Nathan. “The Development of Complexity Generating Organic Photoredox Transformations and the Application of These Transformations in Complex Molecule Synthesis.” 2015. Thesis, University of North Carolina. Accessed January 18, 2020. https://cdr.lib.unc.edu/record/uuid:3eb42de0-b8bc-449f-a83e-b9a07eb3ea78.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Gesmundo, Nathan. “The Development of Complexity Generating Organic Photoredox Transformations and the Application of These Transformations in Complex Molecule Synthesis.” 2015. Web. 18 Jan 2020.

Vancouver:

Gesmundo N. The Development of Complexity Generating Organic Photoredox Transformations and the Application of These Transformations in Complex Molecule Synthesis. [Internet] [Thesis]. University of North Carolina; 2015. [cited 2020 Jan 18]. Available from: https://cdr.lib.unc.edu/record/uuid:3eb42de0-b8bc-449f-a83e-b9a07eb3ea78.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Gesmundo N. The Development of Complexity Generating Organic Photoredox Transformations and the Application of These Transformations in Complex Molecule Synthesis. [Thesis]. University of North Carolina; 2015. Available from: https://cdr.lib.unc.edu/record/uuid:3eb42de0-b8bc-449f-a83e-b9a07eb3ea78

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of North Carolina

30. Pinkin, Nicholas. Discovery and Application of Small Molecule Receptors for the Recognition of Trimethyllysine in Water.

Degree: Chemistry, 2015, University of North Carolina

URL: https://cdr.lib.unc.edu/record/uuid:0cbbde68-e1f4-45ab-87fe-4f94c8807ce6

► This dissertation broadly focuses on the discovery of novel small molecule receptors for trimethyllysine (Kme3) and the detailed characterization of the mechanisms through which they… (more)

▼ This dissertation broadly focuses on the discovery of novel small molecule receptors for trimethyllysine (Kme3) and the detailed characterization of the mechanisms through which they achieve their selectivity. In the first section, an iterative redesign approach was employed to improve the known receptor A2B, resulting in the novel receptor A2N, which is a nanomolar binder for Kme¬3. A2N binds Kme3 with 10-fold improved affinity and 5-fold improved selectivity over Kme2 compared to A2B. This is a testament to the power of using iterative redesign for improving receptors, and it suggests that further enhancements in affinity and selectivity are possible through additional rounds of redesign. In the context of different histone peptide sequences, we found the binding properties of A2N to be sensitive to the presence of Lys and Arg residues neighboring a site of Kme3 recognition. To gain a better understanding of how these residues alter the binding interaction, we used a poly-Gly model peptide to specifically investigate the strength and distance dependence of the neighboring secondary interactions. We determined that both residues are capable of binding to the outside of the receptor, producing a multivalent interaction that improves the affinity of A2N for both Kme0 and Kme3, while weakening the selectivity for Kme3 over Kme0. Our results emphasize the challenge inherent in designing non-sequence specific receptors, but lend insight into design principles that will aid the future development of such pan-selective receptors In the final section, synthetic methods were developed for the fine-tuned modification of the carboxylic acids on all Waters group receptors. These methods enabled us to synthesize a series of A2B and A2N derivatives whose outer carboxylic acids were systematically distanced from the receptors, allowing us to study their contributions to the primary interaction with Kme3 and the secondary interaction with Arg or Lys. We discovered that spacing the carboxylates has a direct effect on the affinity and selectivity of each receptor for Kme3 within the binding pocket. Further, our results using A2N indicated that increased spacing weakens the secondary interaction with Arg more dramatically than the primary interaction with KmeX, suggesting that with enough spacing, a completely non-sequence specific variant of A2N could be designed. The techniques developed for functionalizing the receptors also allowed us to generate a series of biotinylated derivatives of A2B, A2N, A2D and A2G that were directly applicable to peptide microarrays (in collaboration with Brian Strahl). Our results indicated that the receptors bind to the arrays, albeit in a non-selective fashion based upon the PTMs present on the bound peptides. We are currently working to optimize these biotinylated receptors, as well as the buffer conditions used for the microarray experiments, to increase the sensitivity of Kme3 detection. In the final section, we report the coupling of an environmentally sensitive dye to A2B to enable an… Advisors/Committee Members: Pinkin, Nicholas, Waters, Marcey, Johnson, Jeffrey, Gagne, Michel, Weeks, Kevin, Brustad, Eric.

Subjects/Keywords: Chemistry; College of Arts and Sciences; Department of Chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Pinkin, N. (2015). Discovery and Application of Small Molecule Receptors for the Recognition of Trimethyllysine in Water. (Thesis). University of North Carolina. Retrieved from https://cdr.lib.unc.edu/record/uuid:0cbbde68-e1f4-45ab-87fe-4f94c8807ce6

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Pinkin, Nicholas. “Discovery and Application of Small Molecule Receptors for the Recognition of Trimethyllysine in Water.” 2015. Thesis, University of North Carolina. Accessed January 18, 2020. https://cdr.lib.unc.edu/record/uuid:0cbbde68-e1f4-45ab-87fe-4f94c8807ce6.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Pinkin, Nicholas. “Discovery and Application of Small Molecule Receptors for the Recognition of Trimethyllysine in Water.” 2015. Web. 18 Jan 2020.

Vancouver:

Pinkin N. Discovery and Application of Small Molecule Receptors for the Recognition of Trimethyllysine in Water. [Internet] [Thesis]. University of North Carolina; 2015. [cited 2020 Jan 18]. Available from: https://cdr.lib.unc.edu/record/uuid:0cbbde68-e1f4-45ab-87fe-4f94c8807ce6.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Pinkin N. Discovery and Application of Small Molecule Receptors for the Recognition of Trimethyllysine in Water. [Thesis]. University of North Carolina; 2015. Available from: https://cdr.lib.unc.edu/record/uuid:0cbbde68-e1f4-45ab-87fe-4f94c8807ce6

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

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