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Mississippi State University
1.
Chakraborty, Amarraj.
The method development for synthesizing chiral CCC-NHC Zr pincer complexes.
Degree: MS, Chemistry, 2015, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-08062015-162047/ 
;
► There are numerous classes of N-heterocyclic carbenes (NHCs) that have been synthesized since the discovery of stable NHCs in 1988. Their application as ligands…
(more)
▼ There are numerous classes of N-heterocyclic carbenes (NHCs) that have been synthesized since the discovery of stable NHCs in 1988. Their application as ligands in metal complexes has received much attention because of their strong sigma-donor and poor pi-acceptor properties. Within these NHC metal complexes, we are interested in studying zirconium metal complexes with pincer NHC ligands. Recently, achiral CCC-NHC pincer zirconium complexes were synthesized and their catalytic activity in intramolecular hydroamination of aminoalkenes were reported.
Herein is reported new reaction conditions which yield pure, chiral CCC-NHC Zr pincer mono(amido) dibromo complex. The enantiopure crystal structure of the same complex is reported. Attempts to synthesize chiral CCC-NHC Zr pincer bis- and tris- amido complexes with the iodo salt of the ligand precursor are summarized. Moreover, syntheses of chiral bis(imidazolinium) ligand precursors with different counter anions are reported with optimized reaction conditions.
Advisors/Committee Members: Keith T. Mead (chair), Andrzej Sygula (committee member), Joseph Emerson (committee member).
Subjects/Keywords: synthesis; Zr chemistry; organometallic chemistry; asymmetric catalysis
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APA (6th Edition):
Chakraborty, A. (2015). The method development for synthesizing chiral CCC-NHC Zr pincer complexes. (Masters Thesis). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-08062015-162047/ ;
Chicago Manual of Style (16th Edition):
Chakraborty, Amarraj. “The method development for synthesizing chiral CCC-NHC Zr pincer complexes.” 2015. Masters Thesis, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-08062015-162047/ ;.
MLA Handbook (7th Edition):
Chakraborty, Amarraj. “The method development for synthesizing chiral CCC-NHC Zr pincer complexes.” 2015. Web. 17 Apr 2021.
Vancouver:
Chakraborty A. The method development for synthesizing chiral CCC-NHC Zr pincer complexes. [Internet] [Masters thesis]. Mississippi State University; 2015. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-08062015-162047/ ;.
Council of Science Editors:
Chakraborty A. The method development for synthesizing chiral CCC-NHC Zr pincer complexes. [Masters Thesis]. Mississippi State University; 2015. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-08062015-162047/ ;
Mississippi State University
2.
DuPont, Jesse Isaac.
The thermodynamics of ligand association and molecular recognition of cationic and metallated porphyrins and ruthenium complexes with model DNA constructs.
Degree: PhD, Chemistry, 2016, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-06282016-191041/
;
► Molecular recognition, particularly as it applies to strong binding interactions between complementary ligand/receptor molecules in solution, is important in such varied areas as molecular…
(more)
▼ Molecular recognition, particularly as it applies to strong binding interactions between complementary ligand/receptor molecules in solution, is important in such varied areas as molecular biology, pharmacology, synthetic chemistry, and chemical detection. Strong binding is the additive result of a number of specific, weak, non-covalent interactions occurring between complementary molecules. This dissertation reports on the energetics of forming complexes between small molecules and model DNA constructs. Ligands included cationic and metallated cationic porphyrins and polyheterocyclic ruthenium compounds. DNA receptors included double stranded B-DNAs (hairpin and short linear sequences) as well G-quadruplex DNAs. Thermodynamic data were collected using isothermal titration calorimetry, circular dichroism spectropolarimetry, ultraviolet-visible spectroscopy, and mass spectrometry. The measured thermodynamic parameters included the changes in free energy, enthalpy and entropy for ligand/receptor complex formation as well as the stoichiometry of the stable complexes.
The first section of this dissertation reports that the binding of cationic porphyrins to model G-quadruplex DNA may proceed through two pathways, end stacking and intercalation. Modulating the number of pyridinium groups on a pyridinium substituted porphyrin yielded differing binding thermodynamics leading to the understanding that a balance of surface area, charge, and geometry affect the ability of a porphyrin to bind to G-quadruplex DNA. Further investigations into the binding of metallated porphyrins developed the understanding that the geometry of the central metal ion affected not only the thermodynamics but could also inhibit the intercalative mode.
It was previously shown that the high affinity binding for binuclear polyheterocyclic ruthenium compounds proceeds through an intercalative mode. To further understand the binding process and the structure-function relationship of the ligand components, the binding of smaller mononuclear complexes that were representative of portions of the binuclear complex was examined in this dissertation. While limiting the intercalative ability lowered the binding affinity, the mononuclear complex with the full intercalating bridge was able bind to DNA with a higher affinity than the binuclear complex.
These studies have been successful in part in determining the contributions of numerous weak interactions including: charge (Coulombic interactions), H-bonding, hydrophobic interactions, and solvent structure (solvation changes), to the overall energetics of this molecular recognition process.
The first section of this dissertation reports that the binding of cationic porphyrins to model G-quadruplex DNA may proceed through two pathways, end stacking and intercalation. Modulating the number of pyridinium groups on a pyridinium substituted porphyrin yielded differing binding thermodynamics leading to the understanding that a balance of surface area, charge, and geometry affect the ability of a porphyrin to bind to…
Advisors/Committee Members: Edwin A. Lewis (chair), Joseph P. Emerson (committee member), Nicholas C. Fitzkee (committee member), Andrzej Sygula (committee member), Keith T. Mead (committee member).
Subjects/Keywords: ITC; circular dichroism; DNA; G-quadruplex; porphyrin; B-DNA; calorimetry; ESI-MS; NMR
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APA (6th Edition):
DuPont, J. I. (2016). The thermodynamics of ligand association and molecular recognition of cationic and metallated porphyrins and ruthenium complexes with model DNA constructs. (Doctoral Dissertation). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-06282016-191041/ ;
Chicago Manual of Style (16th Edition):
DuPont, Jesse Isaac. “The thermodynamics of ligand association and molecular recognition of cationic and metallated porphyrins and ruthenium complexes with model DNA constructs.” 2016. Doctoral Dissertation, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-06282016-191041/ ;.
MLA Handbook (7th Edition):
DuPont, Jesse Isaac. “The thermodynamics of ligand association and molecular recognition of cationic and metallated porphyrins and ruthenium complexes with model DNA constructs.” 2016. Web. 17 Apr 2021.
Vancouver:
DuPont JI. The thermodynamics of ligand association and molecular recognition of cationic and metallated porphyrins and ruthenium complexes with model DNA constructs. [Internet] [Doctoral dissertation]. Mississippi State University; 2016. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-06282016-191041/ ;.
Council of Science Editors:
DuPont JI. The thermodynamics of ligand association and molecular recognition of cationic and metallated porphyrins and ruthenium complexes with model DNA constructs. [Doctoral Dissertation]. Mississippi State University; 2016. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-06282016-191041/ ;
Mississippi State University
3.
Kumarasinghe, K. G. Upul Ranjan.
Rhodium catalyzed coupling of <I>in situ</I> generated alpha-lactams with indoles and synthesis and surface immobilization of bis-corannulene molecular receptors.
Degree: PhD, Chemistry, 2016, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-06292016-112121/
;
► The first section of this dissertation (Chapter I-III) describes the development of new methodologies for the rhodium catalyzed C-N bond formation between sp3 hybridized…
(more)
▼ The first section of this dissertation (Chapter I-III) describes the development of new methodologies for the rhodium catalyzed C-N bond formation between sp
3 hybridized carbon atom of phenyl substituted alpha-lactams and the nitrogen atom of indole derivatives. Phenyl substituted alpha-lactams generated <I>in situ</I> from the corresponding alpha-bromoamides reacted with indoles in the presence of rhodium catalyst to afford the ring opening products of alpha-lactams. The scope of this methodology was extended to various types of indole derivatives including electron donating and withdrawing substituents. Furthermore, a series of functionalized phenyl substituted alpha-lactams generated <I>in situ</I> reacted with indole to assess the viability of this methodology. The developed method provides an atom-economical approach for the formation of substituted alpha-amino amides in good to excellent yields.
The main goal of the research described in the second section (Chapter IV-VII) is the synthesis of the corannulene-based molecular receptors with polar tethers and their immobilization on silica gel. First, we have considered a preparation of bis-corannulenoanthracene, formally possessing the pentacene core as a potential precursor for a series of barrelene based bis-corannulene receptors with polar groups. Bis-corannulenoanthracene was synthesized by the double Diels-Alder cycloaddition of isocorannulenofuran with bis-benzyne precursor, followed by deoxygenation of the endoxide adducts. While bis-corannulenoanthracene is stable enough to be isolated and stored, its pentacene core undergoes facile cycloaddition with maleic anhydride to afford bis-corannulene molecular receptor with the barrelene tether adorned with the anhydride moiety. The
1H NMR titration experiments carried out in chlorobenzene-<I>d
5</I> proved the high binding affinity of the receptor toward C
60. In addition, the presence of polar anchors on its tether allowed for its deposition on silica gel through the (3-aminopropyl)triethoxysilane linker.
Advisors/Committee Members: Andrzej Sygula (chair), Keith T. Mead (committee member), Todd E. Mlsna (committee member), Dongmao Zhang (committee member), Stephen C. Foster (committee member).
Subjects/Keywords: molecular receptors; corannulene; indole; alpha-lactam; C-N bond formation
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APA (6th Edition):
Kumarasinghe, K. G. U. R. (2016). Rhodium catalyzed coupling of <I>in situ</I> generated alpha-lactams with indoles and synthesis and surface immobilization of bis-corannulene molecular receptors. (Doctoral Dissertation). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-06292016-112121/ ;
Chicago Manual of Style (16th Edition):
Kumarasinghe, K G Upul Ranjan. “Rhodium catalyzed coupling of <I>in situ</I> generated alpha-lactams with indoles and synthesis and surface immobilization of bis-corannulene molecular receptors.” 2016. Doctoral Dissertation, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-06292016-112121/ ;.
MLA Handbook (7th Edition):
Kumarasinghe, K G Upul Ranjan. “Rhodium catalyzed coupling of <I>in situ</I> generated alpha-lactams with indoles and synthesis and surface immobilization of bis-corannulene molecular receptors.” 2016. Web. 17 Apr 2021.
Vancouver:
Kumarasinghe KGUR. Rhodium catalyzed coupling of <I>in situ</I> generated alpha-lactams with indoles and synthesis and surface immobilization of bis-corannulene molecular receptors. [Internet] [Doctoral dissertation]. Mississippi State University; 2016. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-06292016-112121/ ;.
Council of Science Editors:
Kumarasinghe KGUR. Rhodium catalyzed coupling of <I>in situ</I> generated alpha-lactams with indoles and synthesis and surface immobilization of bis-corannulene molecular receptors. [Doctoral Dissertation]. Mississippi State University; 2016. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-06292016-112121/ ;
Mississippi State University
4.
Box, Hannah Killian.
The development of next generation, unsymmetrical CCC-NHC pincer ligand architectures and metalation to form unsymmetrical CCCNHC pincer Ta complexes.
Degree: PhD, Chemistry, 2015, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-04282015-140641/
;
► The impact of <i>N</i>-heterocyclic carbenes (NHC) as ligands for transition metal catalysis has been rigorously investigated since their isolation by Arduengo in 1991. NHCs…
(more)
▼ The impact of <i>N</i>-heterocyclic carbenes (NHC) as ligands for transition metal
catalysis has been rigorously investigated since their isolation by Arduengo in 1991.
NHCs have become abundant in late-transition metal chemistry. This is attributed to
NHCs being stronger sigma-donors than even the strongest phosphine analogues, thus
constructing a transition metal-NHC complex with improved stability, catalytic
reactivity, and selectivity. Additionally, pincer ligands have become recognized as an
important class of ligands for transition metal complexes. The unique steric and
electronic tunability of pincer ligands has resulted in pincer-transition metal complexes
being exploited as catalysts for a multitude of transformations. Both ligand classes, NHC
and pincer, have been reported as stable organometallic catalysts that demonstrate high
catalytic activity. The combination of these two ligand systems by incorporation of NHCs
into pincer ligands has attracted considerable attention. NHC pincer systems have been
reported as stable organometallic catalysts that demonstrate high catalytic activity.
The expansion of CCC-NHC ligand precursor methodologies and application of
the newly reported methodologies in order to diversify CCC-NHC ligand architectures is
reported. Extension of the amine elimination methodology yielded unsymmetrical CCCNHC
Ta pincer complexes.
Studies on the manipulation of the previously reported symmetrical CCC-NHC
pincer Ta complexs coordination sphere to synthesize a rare Ta diimido complex with
unique reactivity towards advantageous proton sources and oxidative amination of
aminoalkenes are also expanded upon. These next generation catalysts developed from
these architectures may prove useful in catalyzing a broad array of transformations not
previously accessible through the four standard NHC containing pincer ligand
architectures.
Advisors/Committee Members: Keith T. Mead (chair), Andrzej Sygula (committee member), Joseph P. Emerson (committee member), Todd E. Mlsna (committee member), Debbie J. Beard (committee member).
Subjects/Keywords: Unsymmetrical CCCNHC; Ta complexes; Oxidative Amination
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APA (6th Edition):
Box, H. K. (2015). The development of next generation, unsymmetrical CCC-NHC pincer ligand architectures and metalation to form unsymmetrical CCCNHC pincer Ta complexes. (Doctoral Dissertation). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-04282015-140641/ ;
Chicago Manual of Style (16th Edition):
Box, Hannah Killian. “The development of next generation, unsymmetrical CCC-NHC pincer ligand architectures and metalation to form unsymmetrical CCCNHC pincer Ta complexes.” 2015. Doctoral Dissertation, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-04282015-140641/ ;.
MLA Handbook (7th Edition):
Box, Hannah Killian. “The development of next generation, unsymmetrical CCC-NHC pincer ligand architectures and metalation to form unsymmetrical CCCNHC pincer Ta complexes.” 2015. Web. 17 Apr 2021.
Vancouver:
Box HK. The development of next generation, unsymmetrical CCC-NHC pincer ligand architectures and metalation to form unsymmetrical CCCNHC pincer Ta complexes. [Internet] [Doctoral dissertation]. Mississippi State University; 2015. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-04282015-140641/ ;.
Council of Science Editors:
Box HK. The development of next generation, unsymmetrical CCC-NHC pincer ligand architectures and metalation to form unsymmetrical CCCNHC pincer Ta complexes. [Doctoral Dissertation]. Mississippi State University; 2015. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-04282015-140641/ ;
Mississippi State University
5.
Karunarathna, A A Sasith Nadeesha.
Computational study of pi-pi stacking interactionsin large curved and planar polycyclicaromatic hydrocarbons.
Degree: PhD, Chemistry, 2013, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10252013-164325/
;
► Theoretical studies of pi-pi interactions on several dimers of curved polycyclic aromatic systems have been carried out. In the first part, dispersion corrected density…
(more)
▼ Theoretical studies of pi-pi interactions on several dimers of curved polycyclic
aromatic systems have been carried out. In the first part, dispersion corrected density
functional theory methods (DC-DFT) were used to evaluate the basis set superposition
errors (BSSE) in dispersion interactions of the corannulene dimer, and the accuracy of the
calculations using DC-DFT methods was compared with high level benchmark
calculations. In these calculations, Grimmes B97D DC-DFT method provided
reasonably accurate results with the benchmark calculations. In addition, BSSE obtained
with the B97D method along with cc-pVQZ basis set was negligible.
Furthermore, a series of calculations were carried out to obtain the pi-pi
interaction energy and most stable conformation for the sumanene dimer system. In these
calculations, Grimmes B97D method was used. The potential energy minimum of the
sumanene dimer was determined as the concave-convex stacked arrangement with one
monomer unit rotated to 60°. The binding energy of the dimer was found to be 19.34
kcal/mol with a 3.72 angstrom distance between two monomer units.
Dimers of three different heterosumanenes along with the parent sumanene were
also studied. In this set of calculations, two different concave-convex dimer motifs were
chosen, eclipsed and staggered (60° rotated). For all the heterosumanenes, as well as the
parent sumanene, the staggered conformation is the most stable geometry. The parent
sumanene had the highest binding energy. The NH substituted sumanene produced the
second highest binding energy, while the O analog was the weakest bonded dimer.
Finally, dispersion calculations were carried out for the planar aromatic
compound of triphenylene. The pi-system of the dimer was distorted by rotating one
monomer unit around the principle axis and parallel displacing one monomer unit relative
to the other one. Among the rotational dimers, the 39° rotated dimer was the minimum
energy conformation. Interaction energy of that dimer was 14.42 kcal/mol with 3.40
angstrom separation between monomers at the B97D/cc-pVQZ level. The parallel
displaced minimum energy dimer has a binding energy about 1.0 kcal/mol smaller than
the rotational minimum energy geometry.
Advisors/Committee Members: Dr. Dongmao Zhang (committee member), Dr. William P. Henry (committee member), Dr. Svein Saebo (chair), Dr. Steven R. Gwaltney (committee member), Dr. ANdrzej Sygula (committee member).
Subjects/Keywords: Curved PAHs; dispersion interactions; pi-pi stacking; DFT-D methods
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APA (6th Edition):
Karunarathna, A. A. S. N. (2013). Computational study of pi-pi stacking interactionsin large curved and planar polycyclicaromatic hydrocarbons. (Doctoral Dissertation). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-10252013-164325/ ;
Chicago Manual of Style (16th Edition):
Karunarathna, A A Sasith Nadeesha. “Computational study of pi-pi stacking interactionsin large curved and planar polycyclicaromatic hydrocarbons.” 2013. Doctoral Dissertation, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-10252013-164325/ ;.
MLA Handbook (7th Edition):
Karunarathna, A A Sasith Nadeesha. “Computational study of pi-pi stacking interactionsin large curved and planar polycyclicaromatic hydrocarbons.” 2013. Web. 17 Apr 2021.
Vancouver:
Karunarathna AASN. Computational study of pi-pi stacking interactionsin large curved and planar polycyclicaromatic hydrocarbons. [Internet] [Doctoral dissertation]. Mississippi State University; 2013. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10252013-164325/ ;.
Council of Science Editors:
Karunarathna AASN. Computational study of pi-pi stacking interactionsin large curved and planar polycyclicaromatic hydrocarbons. [Doctoral Dissertation]. Mississippi State University; 2013. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10252013-164325/ ;
Mississippi State University
6.
Peiris, Prangige Kumudu Vilasini.
B ring substituted flavonols: hydrogen bonding, Ru(II) complexes and Al(III) chelation.
Degree: PhD, Chemistry, 2013, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10302013-131458/
;
► Flavonols are hydroxyl-substituted flavonoids and naturally occur as secondary metabolites in plants. Several studies have discovered extensive medicinal properties of flavonols. The present work…
(more)
▼ Flavonols are hydroxyl-substituted flavonoids and naturally occur as secondary metabolites in plants. Several studies have discovered extensive medicinal properties of flavonols. The present work reports on structural and functional investigation of the B ring substituted flavonols based on spectroscopic and electrochemical techniques. The purpose of this study is to determine the influence of the B ring substitutions on the hydrogen bonding interactions, the electronic effects in ruthenium complexes and the Al
3+ chelation of B ring substituted flavonols.
The electronic effects of the B rings were changed by introducing methyl, methoxy and nitro groups at position 4ʹ on the B ring. The 3ʹ-methyl substitution was performed in order to increase the electronic density of the B ring via inductive effects. The 2ʹ-methyl and 2ʹ, 6ʹ-dimethyl substitutions increased the steric effects around the inter-ring bond between the B and the C rings, and the B ring was highly deconjugated from the AC rings. The intramolecular hydrogen bonding distances at 3-hydroxy-4-carbonyl units of the B ring substituted flavonols were elongated while the dihedral angles between the B and AC increased. Strong intermolecular hydrogen bonding interactions were also observed in the crystal structures of 4ʹ-methylflavonol, 4ʹ-methoxyflavonol, 4ʹ-nitroflavonol and 2ʹ,6ʹ-dimethylflavonol. Furthermore, several crystal packing patterns were observed, and it is postulated that dihedral angles and intramolecular hydrogen bonding distances are both affected by the intermolecular hydrogen bonding interactions and the crystal packing forces.
In addition, the ruthenium complexes of B ring substituted flavonols were synthesized and characterized by spectroscopic and electrochemical techniques. B ring substitution effects were minimal in IR spectroscopy and X-ray crystallography. The levels of the conjugation of the ruthenium-flavonolate complexes were demonstrated by electronic absorption spectra recorded in methanol at room temperature. The most positive oxidation potential was obtained with the electron withdrawing nitro group substitution, and the electron donating substitutions resulted in more negative oxidation potentials.
The spectroscopic investigation of the complex formation of Al(III) with flavonols and 3-hydroxychromone is described. The stoichiometric composition and stability constants are also given. The comparison of the results obtained from Al(III) chelation shows significant effects of the B ring substitutions.
Advisors/Committee Members: Steven R. Gwaltney (committee member), Andrzej Sygula (committee member), William P. Henry (chair), Joseph P. Emerson (committee member), Todd E. Mlsna (committee member).
Subjects/Keywords: substituent effects; flavonols; ruthenium complexes; aluminum ion chelation; hydrogen bonding; x-ray crystallography; electrochemistry; synthesis
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APA (6th Edition):
Peiris, P. K. V. (2013). B ring substituted flavonols: hydrogen bonding, Ru(II) complexes and Al(III) chelation. (Doctoral Dissertation). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-10302013-131458/ ;
Chicago Manual of Style (16th Edition):
Peiris, Prangige Kumudu Vilasini. “B ring substituted flavonols: hydrogen bonding, Ru(II) complexes and Al(III) chelation.” 2013. Doctoral Dissertation, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-10302013-131458/ ;.
MLA Handbook (7th Edition):
Peiris, Prangige Kumudu Vilasini. “B ring substituted flavonols: hydrogen bonding, Ru(II) complexes and Al(III) chelation.” 2013. Web. 17 Apr 2021.
Vancouver:
Peiris PKV. B ring substituted flavonols: hydrogen bonding, Ru(II) complexes and Al(III) chelation. [Internet] [Doctoral dissertation]. Mississippi State University; 2013. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10302013-131458/ ;.
Council of Science Editors:
Peiris PKV. B ring substituted flavonols: hydrogen bonding, Ru(II) complexes and Al(III) chelation. [Doctoral Dissertation]. Mississippi State University; 2013. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10302013-131458/ ;
Mississippi State University
7.
Rajapaksha, R.M. Suranga Mahesh.
Novel one-pot syntheses of uracils and arylidenehydantoins, and analysis of xylitol in chewing gum by GC-MS.
Degree: PhD, Chemistry, 2017, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-03202017-111123/
;
► The first section of this dissertation (Chapter I-III) describes the development of new methodologies to prepare uracil and arylidenehydantoin derivatives. A regioselective synthesis of…
(more)
▼ The first section of this dissertation (Chapter I-III) describes the development of
new methodologies to prepare uracil and arylidenehydantoin derivatives. A regioselective
synthesis of 6-alkyl- and 6-aryluracils was developed by the dimerization of 3-alkyl- and
3-aryl-2-propynamides promoted by either Cs
2CO
3 or K
3PO
4. A range of 3-aryl-2-
propynamides, with both electron-deficient and electron-rich 3-aryl substituents, were
successfully reacted in high yields. A synthetic route to prepare arylidenehydantoins was
developed using the Pd-catalyzed dimerization of 3-aryl-2-propynamides. Both electron
rich and electron deficient 3-aryl-2-propynamides were dimerized successfully to
produce the desired arylidenehydantoins in moderate to excellent yields. The second section of this dissertation (Chapter IV and V) describes the
development of a reliable low-cost method to determine amounts of xylitol in sugar free
gum samples to predict dangerous exposure levels for dogs. Xylitol is generally
considered safe for human consumption and is frequently used in sugar free gum,
however, it is extremely toxic to dogs. It is unknown if partially consumed chewing gum
is also dangerous. A method to determine xylitol content of these sugar free gum samples
employing GC-MS with direct aqueous injection (DAI) is presented. This method was
successfully applied to over 120 samples including, fresh gum, 5 min, 15 min, and 30
min chewed gum samples. Further extension of this work resulted in the development of
an undergraduate laboratory experiment for upper-level undergraduate chemistry students
which teaches calibration methods, xylitol extraction, sample preparation for GC-MS
analysis, and data analysis.
Advisors/Committee Members: Todd E. Mlsna (chair), Charles U. Pittman, Jr (chair), Andrzej Sygula (committee member), David O. Wipf (committee member), Colleen N. Scott (committee member).
Subjects/Keywords: GC-MS; xylitol; arylidenehydantoins; uracils; one-pot
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APA (6th Edition):
Rajapaksha, R. M. S. M. (2017). Novel one-pot syntheses of uracils and arylidenehydantoins, and analysis of xylitol in chewing gum by GC-MS. (Doctoral Dissertation). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-03202017-111123/ ;
Chicago Manual of Style (16th Edition):
Rajapaksha, R M Suranga Mahesh. “Novel one-pot syntheses of uracils and arylidenehydantoins, and analysis of xylitol in chewing gum by GC-MS.” 2017. Doctoral Dissertation, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-03202017-111123/ ;.
MLA Handbook (7th Edition):
Rajapaksha, R M Suranga Mahesh. “Novel one-pot syntheses of uracils and arylidenehydantoins, and analysis of xylitol in chewing gum by GC-MS.” 2017. Web. 17 Apr 2021.
Vancouver:
Rajapaksha RMSM. Novel one-pot syntheses of uracils and arylidenehydantoins, and analysis of xylitol in chewing gum by GC-MS. [Internet] [Doctoral dissertation]. Mississippi State University; 2017. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-03202017-111123/ ;.
Council of Science Editors:
Rajapaksha RMSM. Novel one-pot syntheses of uracils and arylidenehydantoins, and analysis of xylitol in chewing gum by GC-MS. [Doctoral Dissertation]. Mississippi State University; 2017. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-03202017-111123/ ;
Mississippi State University
8.
Clark, Wesley.
<i>N</i>-heterocyclic carbene complexes of Ag(I) and Zr(IV): Ag(I)-halide cubane type clusters and the mechanism of hydroamination with CCC-NHC pincer complexes.
Degree: PhD, Chemistry, 2015, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10222015-140450/
;
► The synthesis and characterization of the first series of tetra-NHC-Ag(I)-X cubane clusters are reported. The clusters were characterized with 1H and 13C NMR spectroscopy,…
(more)
▼ The synthesis and characterization of the first series of tetra-NHC-Ag(I)-X cubane clusters are reported. The clusters were characterized with
1H and
13C NMR spectroscopy, ESI-TOF MS, and single crystal X-ray diffraction. Crossover experimental data were consistent with intramolecular exchange, which can be visualized by a molecular rotating type mechanism.
Additionally, CCC-NHC Zr(IV) pincer type complexes were synthesized and characterized with
1H and
13C NMR spectroscopy, CHN combustion analysis, and X-ray crystallography. A large rate effect was observed based on the halogen and metal center for the hydroamination/cyclization of unactivated aminoalkenes. Zirconium based pincers provided faster reaction rates than their hafnium counterparts (Zr>Hf). Precatalysts with iodide ligands provided faster reaction rates than their bromide and chloride counterparts (I>Br>Cl). The mechanism of hydroamination for Zr(IV) CCC-NHC complexes was also investigated for bis(iodide) and bis(amido) ligand classes. A full kinetic analysis of substrate and precatalyst have been identified along with the formation of small amounts
of an oxidized product. The proposed mechanism contains an imido-type intermediate whose formation depends greatly on which set of ligand class is used.
Advisors/Committee Members: Keith T. Mead (chair), Stephen C. Foster (committee member), Joseph Emerson (committee member), Edwin Lewis (committee member), Andrzej Sygula (committee member).
Subjects/Keywords: catalysis; organometallic
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APA (6th Edition):
Clark, W. (2015). <i>N</i>-heterocyclic carbene complexes of Ag(I) and Zr(IV): Ag(I)-halide cubane type clusters and the mechanism of hydroamination with CCC-NHC pincer complexes. (Doctoral Dissertation). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-10222015-140450/ ;
Chicago Manual of Style (16th Edition):
Clark, Wesley. “<i>N</i>-heterocyclic carbene complexes of Ag(I) and Zr(IV): Ag(I)-halide cubane type clusters and the mechanism of hydroamination with CCC-NHC pincer complexes.” 2015. Doctoral Dissertation, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-10222015-140450/ ;.
MLA Handbook (7th Edition):
Clark, Wesley. “<i>N</i>-heterocyclic carbene complexes of Ag(I) and Zr(IV): Ag(I)-halide cubane type clusters and the mechanism of hydroamination with CCC-NHC pincer complexes.” 2015. Web. 17 Apr 2021.
Vancouver:
Clark W. <i>N</i>-heterocyclic carbene complexes of Ag(I) and Zr(IV): Ag(I)-halide cubane type clusters and the mechanism of hydroamination with CCC-NHC pincer complexes. [Internet] [Doctoral dissertation]. Mississippi State University; 2015. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10222015-140450/ ;.
Council of Science Editors:
Clark W. <i>N</i>-heterocyclic carbene complexes of Ag(I) and Zr(IV): Ag(I)-halide cubane type clusters and the mechanism of hydroamination with CCC-NHC pincer complexes. [Doctoral Dissertation]. Mississippi State University; 2015. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10222015-140450/ ;
Mississippi State University
9.
Reilly, Sean William.
Synthesis and catalytic activity of CCC-NHC group 9 metal pincer complexes.
Degree: PhD, Chemistry, 2015, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10222015-145433/
;
► <I>N</I>-Heterocyclic carbenes (NHCs) are one of the few ligand systems that can finely tune transition metal catalysts via sterics and electronics. The strong sigma-donating…
(more)
▼ <I>N</I>-Heterocyclic carbenes (NHCs) are one of the few ligand systems that can finely tune transition metal catalysts via sterics and electronics. The strong sigma-donating properties of these ancillary ligands allow the development of robust tridentate NHC pincer framework, which has emerged as an alternative to the phosphine pincer ligands. The combination of NHC and pincer systems has resulted in a new generation of catalytically active organometallic complexes reported throughout the literature.
CCC-NHC Rh pincer complexes were found to be catalytically active in C-C and C-B bond formation via 1,4-addition reactions. In addition, the <I>in-situ</I> generated CCC-NHC Ir(H) pincer complex demonstrated catalytic activity in borylation of arene C-H bonds. Preliminary results are comparable to the C-H borylation results published by Hartwig and co-workers. The CCC-NHC Ir(H) pincer complex may also prove to be a suitable catalyst for alkane dehydrogenation, due to framework similarities of the highly active and durable PCP and POCOP pincer hydride systems.
Expansion of group 9 metal sources for transmetalation of the CCC-NHC Zr pincer complex afforded the development of CCC-NHC Rh(CO) and CCC-NHC Co complexes. Group 9 metal carbonyl complexes have been reported as active catalysts in photocatalytic C-H activation of small molecules. Testing of Co sources for transmetalation afforded three rare Co pincer complexes, and the first examples of CCC-NHC Co pincer complexes to date. Development of CCC-NHC pincer complexes with base metals provide cost-effect alternatives to pincer systems with precious metal centers, and is reported herein.
Advisors/Committee Members: Keith T. Mead (chair), Andrzej Sygula (committee member), Joesph P. Emerson (committee member), Edwin A. Lewis (committee member), Stephen C. Foster (committee member).
Subjects/Keywords: C-H activation; pincer; NHC; carbene
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APA ·
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APA (6th Edition):
Reilly, S. W. (2015). Synthesis and catalytic activity of CCC-NHC group 9 metal pincer complexes. (Doctoral Dissertation). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-10222015-145433/ ;
Chicago Manual of Style (16th Edition):
Reilly, Sean William. “Synthesis and catalytic activity of CCC-NHC group 9 metal pincer complexes.” 2015. Doctoral Dissertation, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-10222015-145433/ ;.
MLA Handbook (7th Edition):
Reilly, Sean William. “Synthesis and catalytic activity of CCC-NHC group 9 metal pincer complexes.” 2015. Web. 17 Apr 2021.
Vancouver:
Reilly SW. Synthesis and catalytic activity of CCC-NHC group 9 metal pincer complexes. [Internet] [Doctoral dissertation]. Mississippi State University; 2015. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10222015-145433/ ;.
Council of Science Editors:
Reilly SW. Synthesis and catalytic activity of CCC-NHC group 9 metal pincer complexes. [Doctoral Dissertation]. Mississippi State University; 2015. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10222015-145433/ ;
Mississippi State University
10.
Akurathi, Gopalakrishna.
Design, synthesis and characterization of chiral CCC-NHC transition metal complexes and catalytic activity.
Degree: PhD, Chemistry, 2016, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-06202016-112340/
;
► The first stable free N-heterocyclic carbene (NHC) was isolated in 1991, since then many classes of NHCs were synthesized and isolated. N-heterocyclic carbene ligands…
(more)
▼ The first stable free N-heterocyclic carbene (NHC) was isolated in 1991, since then many classes of NHCs were synthesized and isolated. N-heterocyclic carbene ligands have become a common ligand in the synthesis of metal complexes, due to their strong σ-donation with poor π-acceptor ability. Among all the NHC metal complexes, Hollis group was interested in exploring CCC-NHC pincer complexes. In 2005, Hollis and co-workers synthesized and isolated first achiral CCC-NHC zirconium pincer amido complex and studied its catalytic ability to perform intramolecular hydroamination of aminoalkenes. Later, Hollis group designed and developed new NHCs with a saturated chiral backbone, and used these new ligands to generate a new series of metal complexes.
This dissertation is focused on the design, synthesis and characterization of several chiral bi-dentate NHC ligands with varying substituents on the backbone. These NHC ligands were used to synthesize several chiral mono, bis and tris amido CCC-NHC zirconium pincer complexes. Further, transmetallation to cobalt complexes were achieved.
Intramolecular hydroamination was measured for several chiral bis and tris amido CCC-NHC pincer zirconium catalysts. Variants of these catalytic systems were generated with
differing steric hinderance and electronic structure. The enantioselectivity of these novel new molecules were studied.
Advisors/Committee Members: Keith T. Mead (chair), Todd E. Mlsna (committee member), David O. Wipf (committee member), Joseph P. Emerson (committee member), Andrzej Sygula (committee member).
Subjects/Keywords: CCC-NHC; chiral zirconium metal complexes; pincer complexes
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APA (6th Edition):
Akurathi, G. (2016). Design, synthesis and characterization of chiral CCC-NHC transition metal complexes and catalytic activity. (Doctoral Dissertation). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-06202016-112340/ ;
Chicago Manual of Style (16th Edition):
Akurathi, Gopalakrishna. “Design, synthesis and characterization of chiral CCC-NHC transition metal complexes and catalytic activity.” 2016. Doctoral Dissertation, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-06202016-112340/ ;.
MLA Handbook (7th Edition):
Akurathi, Gopalakrishna. “Design, synthesis and characterization of chiral CCC-NHC transition metal complexes and catalytic activity.” 2016. Web. 17 Apr 2021.
Vancouver:
Akurathi G. Design, synthesis and characterization of chiral CCC-NHC transition metal complexes and catalytic activity. [Internet] [Doctoral dissertation]. Mississippi State University; 2016. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-06202016-112340/ ;.
Council of Science Editors:
Akurathi G. Design, synthesis and characterization of chiral CCC-NHC transition metal complexes and catalytic activity. [Doctoral Dissertation]. Mississippi State University; 2016. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-06202016-112340/ ;
Mississippi State University
11.
De Silva, Nuwan Dileepa.
Synthesis, characterization, and catalytic activity of silica supported bimetallic copper catalysts for organic oxidation reactions and the study of benzylation of triketones.
Degree: PhD, Chemistry, 2013, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-07292013-010516/
;
► The dissertation describes research work on development of bimetallic heterogeneous catalysts for oxidation of organic compounds. Binuclear metal complexes are an interesting class of…
(more)
▼ The dissertation describes research work on development of bimetallic heterogeneous catalysts for oxidation of organic compounds. Binuclear metal complexes are an interesting class of compounds due to their catalytic activity. The approach involves anchoring a triketone ligand to Cab-O-Sil via a linker. Specifically, silica gel was allowed to react with <i>p</i>-chloromethylphenyltrimethoxysilane followed by coupling with deprotonated triketone compounds. The viability of this approach was verified by performing the benzylation reaction of triketones with benzyl halides under basic conditions. The benzylation of 2,4,6-heptanetrione and 1,5-diphenyl-1,3,5-pentanetrione is achieved with benzyl bromide using <i>n</i>-tetrabutylammonium fluoride as base. These benzylation reaction conditions were used to attach the triketones to the surface-attached linker. Once the ligand is attached to the silica gel, the catalyst is formed by coordinating two copper(II) ions from solution to the deprotonated triketone. The coordination of copper(II) ions to the triketone was monitored using UV-vis spectroscopy. The modified silica gel is characterized by diffuse reflectance infrared Fourier spectroscopy (DRIFTS), and thermal gravimetric analysis (TGA) at the different stages of catalyst formation. All techniques indicated significant attachment of linker and triketone to the support. The oxidation of 3,5-di-<i>tert</i>-butyl catechol (DTBC) and benzyl alcohol was carried out under aerobic conditions using these catalysts. The kinetics of the DTBC oxidation and benzyl alcohol oxidation was studied using bimetallic and monometallic catalytic systems. The copper complexes of the triketone ligands were also evaluated as catalysts for the oxidation of DTBC. New bimetallic metal complexes with triketone ligands having a benzyl group were synthesized and characterized by high resolution mass spectroscopy and IR spectroscopy. In addition to a detailed description of the synthesis and characterization of new triketone compounds, and the heterogeneous catalyst systems, a comparison of the kinetics of the oxidation of DTBC using these catalysts will be discussed.
Advisors/Committee Members: William P. Henry (chair), David O. Wipf (committee member), Andrzej Sygula (committee member), Joseph Emerson (committee member), Dongmao Zhang (committee member).
Subjects/Keywords: benzylation; catechol; bimetallic
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APA ·
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MLA ·
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CSE |
Export
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APA (6th Edition):
De Silva, N. D. (2013). Synthesis, characterization, and catalytic activity of silica supported bimetallic copper catalysts for organic oxidation reactions and the study of benzylation of triketones. (Doctoral Dissertation). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-07292013-010516/ ;
Chicago Manual of Style (16th Edition):
De Silva, Nuwan Dileepa. “Synthesis, characterization, and catalytic activity of silica supported bimetallic copper catalysts for organic oxidation reactions and the study of benzylation of triketones.” 2013. Doctoral Dissertation, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-07292013-010516/ ;.
MLA Handbook (7th Edition):
De Silva, Nuwan Dileepa. “Synthesis, characterization, and catalytic activity of silica supported bimetallic copper catalysts for organic oxidation reactions and the study of benzylation of triketones.” 2013. Web. 17 Apr 2021.
Vancouver:
De Silva ND. Synthesis, characterization, and catalytic activity of silica supported bimetallic copper catalysts for organic oxidation reactions and the study of benzylation of triketones. [Internet] [Doctoral dissertation]. Mississippi State University; 2013. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-07292013-010516/ ;.
Council of Science Editors:
De Silva ND. Synthesis, characterization, and catalytic activity of silica supported bimetallic copper catalysts for organic oxidation reactions and the study of benzylation of triketones. [Doctoral Dissertation]. Mississippi State University; 2013. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-07292013-010516/ ;
Mississippi State University
12.
Bandara, Nilantha.
STUDIES ON HEXAHAPTO-DIBENZO[<i>a</i>,<i>e</i>]CYCLOOCTATETRAENE COMPLEXES OF CHROMIUMTRICARBONYL AND CATIONIC MANGANESETRICARBONYL.
Degree: PhD, Chemistry, 2011, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-11022011-114211/
;
► Mono- and dinuclear chromiumtricarbonyl and manganesetricarbonyl complexes of dibenzo[<i>a</i>,<i>e</i>]cyclooctatetraene (DBCOT) were synthesized and characterized. In the bis(chromiumtricarbonyl)DBCOT synthesis, the main product was the <i>syn</i>,<i>anti</i>…
(more)
▼ Mono- and dinuclear chromiumtricarbonyl and manganesetricarbonyl complexes of dibenzo[<i>a</i>,<i>e</i>]cyclooctatetraene (DBCOT) were synthesized and characterized. In the bis(chromiumtricarbonyl)DBCOT synthesis, the main product was the <i>syn</i>,<i>anti</i> isomer where the two Cr(CO)
3 moieties coordinate to opposite faces of the DBCOT backbone. This complex exhibits three dynamic processes in solution. A ring inversion of the organic skeleton occurs while the two chromiumtricarbonyl moieties undergo tripod rotation.
This is the first study where eight-membered ring inversion is studied for a pi-coordinated metallic system. The rate of inversion at various temperatures was determined by
1H NMR line shape analysis at two different field strengths (300 and 600 MHz). Compared with other cyclooctatetraene compounds reported, there is a large positive entropy of activation and a relatively high enthalpy of activation in this system. DFT calculations, using the B3LYP/6-31G** basis set, were performed to gain a better understanding of the experimental results. It is proposed that free rotation of both Cr(CO)
3 groups in the planar transition
state are responsible for the large entropy of activation for ring inversion in hexahapto,hexahapto-dibenzo[<i>a</i>,<i>e</i>]cyclooctatetraene-<i>syn</i>,<i>anti</i>-bis(tricarbonylchromium). The relatively large enthalpy of activation is due to a stabilizing interaction between the <i>endo</i> carbonyl groups on the <i>syn</i>-Cr(CO)
3 and the remote arene.
In the monometallic DBCOT complexes, the metal can either be inside or outside the tub conformation. Interestingly, the crystal structures show opposite orientations for the isoelectronic chromium and manganese systems. The Cr(CO)
3 group is positioned <i>anti</i> relative to the DBCOT backbone while the Mn(CO)
3+ is <i>syn</i>. It should be noted that the optimized gas phase geometries obtained through DFT calculations agree with the crystallographic results. Electrochemical studies were performed to investigate the change in redox behavior associated with coordination of mono and bis-chromium units to the DBCOT backbone.
Four new organometallic crystal structures are reported in this dissertation. Different tripod orientations, DBCOT backbone angles, and metal orientation relative to the interior of the organic skeleton are found. C-H...O, C-H...pi, and charge assisted C-H...F hydrogen bonding interactions were observed in the solid
state packing. The structural motifs found suggest these complexes could serve as organometallic synthons in supramolecular chemistry.
Advisors/Committee Members: Dr. Stephen C. Foster (committee member), Dr. Andrzej Sygula (committee member), Dr. David O. Wipf (committee member), Dr. Steven R. Gwaltney (committee member), Dr. William P. Henry (chair).
Subjects/Keywords: Dibenzocyclooctatetraene; Ring Inversion; Arenechromiumtricarbonyl; Dynamic NMR; Arenemanganesetricarbonyl; Theoretical Calculations; DFT; Crystal Structure; Organometallic Synthesis
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APA ·
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CSE |
Export
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APA (6th Edition):
Bandara, N. (2011). STUDIES ON HEXAHAPTO-DIBENZO[<i>a</i>,<i>e</i>]CYCLOOCTATETRAENE COMPLEXES OF CHROMIUMTRICARBONYL AND CATIONIC MANGANESETRICARBONYL. (Doctoral Dissertation). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-11022011-114211/ ;
Chicago Manual of Style (16th Edition):
Bandara, Nilantha. “STUDIES ON HEXAHAPTO-DIBENZO[<i>a</i>,<i>e</i>]CYCLOOCTATETRAENE COMPLEXES OF CHROMIUMTRICARBONYL AND CATIONIC MANGANESETRICARBONYL.” 2011. Doctoral Dissertation, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-11022011-114211/ ;.
MLA Handbook (7th Edition):
Bandara, Nilantha. “STUDIES ON HEXAHAPTO-DIBENZO[<i>a</i>,<i>e</i>]CYCLOOCTATETRAENE COMPLEXES OF CHROMIUMTRICARBONYL AND CATIONIC MANGANESETRICARBONYL.” 2011. Web. 17 Apr 2021.
Vancouver:
Bandara N. STUDIES ON HEXAHAPTO-DIBENZO[<i>a</i>,<i>e</i>]CYCLOOCTATETRAENE COMPLEXES OF CHROMIUMTRICARBONYL AND CATIONIC MANGANESETRICARBONYL. [Internet] [Doctoral dissertation]. Mississippi State University; 2011. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-11022011-114211/ ;.
Council of Science Editors:
Bandara N. STUDIES ON HEXAHAPTO-DIBENZO[<i>a</i>,<i>e</i>]CYCLOOCTATETRAENE COMPLEXES OF CHROMIUMTRICARBONYL AND CATIONIC MANGANESETRICARBONYL. [Doctoral Dissertation]. Mississippi State University; 2011. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-11022011-114211/ ;
13.
Mathews, Martin.
ADVANCING Li/CFx BATTERY CHEMISTRY: A STUDY ON PARTIALLY REDUCED CFx AS A PRIMARY Li/CFx CELL CATHODE MATERIAL.
Degree: MS, Chemistry, 2011, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10272011-170834/
;
► Conventional primary Li/CFx batteries employ graphite and polyvinylidene fluoride additives in the cathodes. These additives usher in some un-desired side-effects, such as lower battery…
(more)
▼ Conventional primary Li/CFx batteries employ graphite and polyvinylidene fluoride additives in the cathodes. These additives usher in some un-desired side-effects, such as lower battery capacities (mAh/g) and smaller current densities (mA/g).
An innovative pretreatment was developed in this research in which CFx was subject to a solvated electron reduction to obtain a thin layer graphitic carbon coating on the CFx particle surfaces. Resistivity tests revealed that these partially reduced CFx particles have a higher conductivity at comparable graphitic carbon contents. Electrochemical discharge reactions demonstrated that batteries made from the reduced CFx were superior to the conventional batteries with higher current densities and higher capacities achieved. Impedance spectroscopy (EIS) studies found out that the reduced CFx particles have smaller cell reaction resistances, smaller double layer/intercalation capacitances and smaller mass transport resistances.
It appears that use of reduced CFx has the potential to replace the conventional CFx plus additives as a cathode material in Li/CFx batteries.
Advisors/Committee Members: David O. Wipf (chair), Charles U. Pittman, Jr. (chair), Dongmao Zhang (committee member), Andrzej Sygula (committee member).
Subjects/Keywords: primary lithium/CFx battery; cathode material; electrochemical impedance spectroscopy; solvated electron reduction; core-shell morphology
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APA (6th Edition):
Mathews, M. (2011). ADVANCING Li/CFx BATTERY CHEMISTRY: A STUDY ON PARTIALLY REDUCED CFx AS A PRIMARY Li/CFx CELL CATHODE MATERIAL. (Masters Thesis). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-10272011-170834/ ;
Chicago Manual of Style (16th Edition):
Mathews, Martin. “ADVANCING Li/CFx BATTERY CHEMISTRY: A STUDY ON PARTIALLY REDUCED CFx AS A PRIMARY Li/CFx CELL CATHODE MATERIAL.” 2011. Masters Thesis, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-10272011-170834/ ;.
MLA Handbook (7th Edition):
Mathews, Martin. “ADVANCING Li/CFx BATTERY CHEMISTRY: A STUDY ON PARTIALLY REDUCED CFx AS A PRIMARY Li/CFx CELL CATHODE MATERIAL.” 2011. Web. 17 Apr 2021.
Vancouver:
Mathews M. ADVANCING Li/CFx BATTERY CHEMISTRY: A STUDY ON PARTIALLY REDUCED CFx AS A PRIMARY Li/CFx CELL CATHODE MATERIAL. [Internet] [Masters thesis]. Mississippi State University; 2011. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10272011-170834/ ;.
Council of Science Editors:
Mathews M. ADVANCING Li/CFx BATTERY CHEMISTRY: A STUDY ON PARTIALLY REDUCED CFx AS A PRIMARY Li/CFx CELL CATHODE MATERIAL. [Masters Thesis]. Mississippi State University; 2011. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10272011-170834/ ;
14.
Abeyratne Kuragama, Peumie Luckshika.
Design, synthesis, and testing of bis-corannulene receptors for fullerenes based on Klärners tethers.
Degree: PhD, Chemistry, 2015, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10262015-115717/
;
► The discovery of the new allotropic forms of elemental carbon (e.g. fullerenes and carbon nanotubes) introduced a novel motif in supramolecular chemistry based on…
(more)
▼ The discovery of the new allotropic forms of elemental carbon (e.g. fullerenes and carbon nanotubes) introduced a novel motif in supramolecular chemistry based on dispersion interactions of curved networks of sp
2 hybridized carbon atoms. Buckybowls, the curve-shaped polycyclic aromatic hydrocarbons, appear to be ideal candidates for molecular receptors to recognize fullerenes. Corannulene, the smallest and the best studied buckybowl, has been recognized as one of the important pincers in developing molecular receptors for fullerenes. The main goal of our research is to synthesize corannulene-based molecular receptors for fullerenes with high binding affinities with the use of the pincers preorganized on tailor made tethers of proper topology.
This dissertation describes the design, synthesis, and testing of two bis-corannulene receptors with Klärners tethers. First, molecular mechanics (MM) was employed for the assessment of the binding potential of the receptors with fullerenes. Next, the receptors were synthesized by Diels-Alder cycloaddition reactions with isocorannulenofuran and Klärners dienophiles followed by dehydration. Finally, 1H NMR titrations of both molecular tweezers with fullerenes C
60 and C
70 were performed. While the first receptor exhibits the affinity for fullerenes comparable to the previously reported corannulene based receptors, the other with longer, naphthalene based tether, exceeds the performance of the former systems by ca. two orders of magnitude and, in addition, shows an enhanced preference for C
70 over C
60. These results are in line with the predictions based on MM modeling. The x-ray crystal structure of the 1:1 complex of the larger receptor with C60 indicates that the tether not only preorganizes the pincers into a proper topology to accept the host, but also contributes to the dispersion based binding with the fullerene guests.
Fullerenes and their derivatives are frequently used as electron acceptors in polymer based solar cells. By amalgamation of fullerenes with organic receptors, like the ones reported here, the novel surface bound structures can be constructed with potential applications in nanotechnology and material sciences.
Advisors/Committee Members: Andrzej Sygula (committee member), Keith T. Mead (committee member), Todd E. Mlsna (committee member), Dongmao Zhang (committee member), Stephen C. Foster (committee member).
Subjects/Keywords: N/A
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APA (6th Edition):
Abeyratne Kuragama, P. L. (2015). Design, synthesis, and testing of bis-corannulene receptors for fullerenes based on Klärners tethers. (Doctoral Dissertation). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-10262015-115717/ ;
Chicago Manual of Style (16th Edition):
Abeyratne Kuragama, Peumie Luckshika. “Design, synthesis, and testing of bis-corannulene receptors for fullerenes based on Klärners tethers.” 2015. Doctoral Dissertation, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-10262015-115717/ ;.
MLA Handbook (7th Edition):
Abeyratne Kuragama, Peumie Luckshika. “Design, synthesis, and testing of bis-corannulene receptors for fullerenes based on Klärners tethers.” 2015. Web. 17 Apr 2021.
Vancouver:
Abeyratne Kuragama PL. Design, synthesis, and testing of bis-corannulene receptors for fullerenes based on Klärners tethers. [Internet] [Doctoral dissertation]. Mississippi State University; 2015. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10262015-115717/ ;.
Council of Science Editors:
Abeyratne Kuragama PL. Design, synthesis, and testing of bis-corannulene receptors for fullerenes based on Klärners tethers. [Doctoral Dissertation]. Mississippi State University; 2015. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-10262015-115717/ ;
15.
Cebada-Ricalde, Maria Concepcion.
Synthesis and characterization of PANI-coated VGCNFs and evaluation of its use for corrosion inhibition.
Degree: PhD, Chemistry, 2014, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-05012014-201000/
;
► Recently, conductive polymer/carbon nanomaterials have drawn attention for use in corrosion inhibition, sensors, energy storage devices, and coatings for electromagnetic shielding applications due to…
(more)
▼ Recently, conductive polymer/carbon nanomaterials have drawn attention for use in corrosion inhibition, sensors, energy storage devices, and coatings for electromagnetic shielding applications due to their good mechanical properties and electronic conductivity. Therefore, efforts have been made to find fast and facile methods for the synthesis and development of these hybrids that allow control over key parameters, such as the thickness of the conductive polymer coating. In this study, such hybrids were prepared using polyaniline (PANI) as the conductive polymer and vapor-grown carbon nanofibers (VGCNFs) as the carbon nanomaterial or filler by a semi-dilute in situ polymerization method to be evaluated for their effectiveness as corrosion inhibitory additives to alkyd paints.
Spectroscopic, colorimetric, and electric properties of PANI-coated VGCNFs were investigated. The thickness of the PANI coating, along with other parameters, impacts the behavior and mechanisms by which the nanomaterial performs its role in a given application, particularly in the corrosion inhibition processes. Thus, different synthesis conditions, including pretreatment of the nanofibers, the presence of sodium dodecyl sulfate (SDS) surfactant, PreT-VGCNF/ANI ratios (w/w), and polymerization times were tested and their effects on the PANI thickness were microscopically and statistically evaluated. It was found that only different PreT-VGCNF/ANI ratios allowed definite control of the PANI thickness. No clear effect on the thickness was observed after three hours of polymerization. The presence of SDS and pretreatment of VGCNFs displayed a synergistic effect on the appearance and thickness of the PANI film.
PANI-coated VGCNF additives, with PANI in the leucoemeraldine base (LEB) and emeraldine base (EB) forms, were synthesized using a PreT-VGCNF/ANI ratio of 0.4 in the presence of SDS. Cold-rolled steel coupons were coated with 20-30 ìm thick alkyd paint coatings, and their electrochemical behavior was investigated by open circuit potential (OCP) and electrochemical impedance (EIS) measurements. The results indicate that, overall, EB/VGCNF additive performed better as a corrosion inhibitor, followed by PreT-VGCNF and LEB/VGCNF additives.
Advisors/Committee Members: David Wipf (chair), Charles U. Pittman, Jr. (committee member), Dongmao Zhang (committee member), Todd E. Mlsna (committee member), Andrzej Sygula (committee member).
Subjects/Keywords: conductivity measurements; colorimetric characterization; TEM; SEM; AFM; UV-vis; ATR-FTIR; Nyquist plots; Bode plots; impedance measurement; open circuit potential measurement
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APA (6th Edition):
Cebada-Ricalde, M. C. (2014). Synthesis and characterization of PANI-coated VGCNFs and evaluation of its use for corrosion inhibition. (Doctoral Dissertation). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-05012014-201000/ ;
Chicago Manual of Style (16th Edition):
Cebada-Ricalde, Maria Concepcion. “Synthesis and characterization of PANI-coated VGCNFs and evaluation of its use for corrosion inhibition.” 2014. Doctoral Dissertation, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-05012014-201000/ ;.
MLA Handbook (7th Edition):
Cebada-Ricalde, Maria Concepcion. “Synthesis and characterization of PANI-coated VGCNFs and evaluation of its use for corrosion inhibition.” 2014. Web. 17 Apr 2021.
Vancouver:
Cebada-Ricalde MC. Synthesis and characterization of PANI-coated VGCNFs and evaluation of its use for corrosion inhibition. [Internet] [Doctoral dissertation]. Mississippi State University; 2014. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-05012014-201000/ ;.
Council of Science Editors:
Cebada-Ricalde MC. Synthesis and characterization of PANI-coated VGCNFs and evaluation of its use for corrosion inhibition. [Doctoral Dissertation]. Mississippi State University; 2014. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-05012014-201000/ ;
Mississippi State University
16.
Wang, Beibei.
DETERMINATION OF ENANTIOMERIC COMPOSITION OF PHARMACEUTICAL COMPOUNDS USING ELECTROSPRAY IONIZATION MASS SPECTROMETRY (ESI-MS).
Degree: MS, Chemistry, 2007, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-02042007-222927/
;
► The work in this thesis has demonstrated the chiral recognition through the adaptation of chromatographically derived chiral recognition systems by electrospray ionization mass spectrometry (ESI-MS).…
(more)
▼ The work in this thesis has demonstrated the chiral recognition through the adaptation of chromatographically derived chiral recognition systems by electrospray ionization mass spectrometry (ESI-MS). Mass-labeled, pseudoenantiomeric chiral selectors (where each pseudoenantiomer had the opposite stereochemistry, but was slightly different in mass due to labeling of one enantiomer) were prepared as soluble analogues of Pirkle type chiral stationary phases. When mixed with a chiral analyte, solutions containing these pseudoenantiomeric selectors afforded selector-analyte complexes in the ESI-MS, and the relative peak intensities of the complexes could be related back to the enantiomeric composition of the analyte. In each case of this study, the complex intensity fraction for either of the selector-analyte complexes in the ESI-MS varies linearly with the enantiomeric composition of the analyte. This linear relationship provides a measure of the extent of enantioselectivity and allows quantitative analysis of the enantiomeric composition of analyte.
Advisors/Committee Members: Stephen C. Foster (committee member), Michael E. Koscho (chair), Andrzej Sygula (committee member).
Subjects/Keywords: enantiomeric composition; chiral stationary phase; chiral selector; ESI-MS; chiral recognition; complex intensity fraction
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APA ·
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APA (6th Edition):
Wang, B. (2007). DETERMINATION OF ENANTIOMERIC COMPOSITION OF PHARMACEUTICAL COMPOUNDS USING ELECTROSPRAY IONIZATION MASS SPECTROMETRY (ESI-MS). (Masters Thesis). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-02042007-222927/ ;
Chicago Manual of Style (16th Edition):
Wang, Beibei. “DETERMINATION OF ENANTIOMERIC COMPOSITION OF PHARMACEUTICAL COMPOUNDS USING ELECTROSPRAY IONIZATION MASS SPECTROMETRY (ESI-MS).” 2007. Masters Thesis, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-02042007-222927/ ;.
MLA Handbook (7th Edition):
Wang, Beibei. “DETERMINATION OF ENANTIOMERIC COMPOSITION OF PHARMACEUTICAL COMPOUNDS USING ELECTROSPRAY IONIZATION MASS SPECTROMETRY (ESI-MS).” 2007. Web. 17 Apr 2021.
Vancouver:
Wang B. DETERMINATION OF ENANTIOMERIC COMPOSITION OF PHARMACEUTICAL COMPOUNDS USING ELECTROSPRAY IONIZATION MASS SPECTROMETRY (ESI-MS). [Internet] [Masters thesis]. Mississippi State University; 2007. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-02042007-222927/ ;.
Council of Science Editors:
Wang B. DETERMINATION OF ENANTIOMERIC COMPOSITION OF PHARMACEUTICAL COMPOUNDS USING ELECTROSPRAY IONIZATION MASS SPECTROMETRY (ESI-MS). [Masters Thesis]. Mississippi State University; 2007. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-02042007-222927/ ;
Mississippi State University
17.
Bachawala, Praveen.
LARGE SCALE SYNTHESIS AND DERIVATIZATION OF CORANNULENE - THE SMALLEST BUCKYBOWL.
Degree: MS, Chemistry, 2006, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-08112006-154307/
;
► The major part of my thesis work includes large scale production of corannulene, C20H10, a bowl-shaped Polycyclic Aromatic Hydrocarbon. Over the road towards corannulene via…
(more)
▼ The major part of my thesis work includes large scale production of corannulene, C20H10, a bowl-shaped Polycyclic Aromatic Hydrocarbon. Over the road towards corannulene via tetramethylfluoranthene, we improved several steps of the existing multistep procedure. These improvements include:
-Nucleophilic displacement of chloride in 2,7-dimethyl-1-chloromethyl- naphthalene with cyanide gave an excellent yield of 2,7-dimethyl-1-naphthalene- acetonitrile when performed in acetonitrile instead of DMSO or acetone/water.
-Oxidation of 3,8-dimethyl-1-acenaphthenone to 3,8-dimethylacenaphthaquinone was successfully achieved with HBr/DMSO instead of selenium dioxide, which usually requires tedious work up.
-Overall yield of 3,8-dimethylacenaphth- aquinone was greatly improved in comparison with the previous reports.
-Palladium catalyzed large scale debromination of tetrabromocorannulene was accomplished within thirty minutes of brief reflux, in contrast to the original Zn/KI method which took weeks for completion.
Alternative palladium catalyzed ring closure methods where tested for synthesis of 1,6,7,10-tetramethylfluroanthene (25), a key intermediate in corannulene production. A structurally similar system, 7,10-dimethylfluoranthene was synthesized by this new approach in low yield. Unfortunately, we did not succeed in the synthesis of 25 using similar methodology, since all our attempts to produce the prerequisite 2,7-dimethyl-1-naphthylboronic acid failed.
Elaboration of the corannulene core by coupling tetrabromocorannulene with p-methoxyphenylboronic acid and p-methoxycarbonylphenylboronic acid under Suzuki conditions resulted in formation of two vital intermediates which can be used to build capsules with corannulene caps.
Advisors/Committee Members: Dr. Michael Koscho (committee member), Dr. Andrzej Sygula (chair), Dr. Stephen C. Foster (committee member).
Subjects/Keywords: CORANNULENE; TETRAMETHYLFLUORANTHENE; FLUORANTHENE
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APA (6th Edition):
Bachawala, P. (2006). LARGE SCALE SYNTHESIS AND DERIVATIZATION OF CORANNULENE - THE SMALLEST BUCKYBOWL. (Masters Thesis). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-08112006-154307/ ;
Chicago Manual of Style (16th Edition):
Bachawala, Praveen. “LARGE SCALE SYNTHESIS AND DERIVATIZATION OF CORANNULENE - THE SMALLEST BUCKYBOWL.” 2006. Masters Thesis, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-08112006-154307/ ;.
MLA Handbook (7th Edition):
Bachawala, Praveen. “LARGE SCALE SYNTHESIS AND DERIVATIZATION OF CORANNULENE - THE SMALLEST BUCKYBOWL.” 2006. Web. 17 Apr 2021.
Vancouver:
Bachawala P. LARGE SCALE SYNTHESIS AND DERIVATIZATION OF CORANNULENE - THE SMALLEST BUCKYBOWL. [Internet] [Masters thesis]. Mississippi State University; 2006. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-08112006-154307/ ;.
Council of Science Editors:
Bachawala P. LARGE SCALE SYNTHESIS AND DERIVATIZATION OF CORANNULENE - THE SMALLEST BUCKYBOWL. [Masters Thesis]. Mississippi State University; 2006. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-08112006-154307/ ;
Mississippi State University
18.
Guo, Hua.
SYNTHESIS AND SELECTED REACTIONS OF 2-ALKENYLTHIAZOLINES.
Degree: MS, Chemistry, 2008, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-07082008-100959/
;
► Three types of 2-alkenylthiazolines were designed and synthesized by a two-step method starting with 2-methylthiazoline and aromatic aldehydes, alkyl aldehydes and alkenyl aldehydes, respectively. Diels-Alder…
(more)
▼ Three types of 2-alkenylthiazolines were designed and synthesized by a two-step method starting with 2-methylthiazoline and aromatic aldehydes, alkyl aldehydes and alkenyl aldehydes, respectively.
Diels-Alder reactions of several 2-styryl-1,3-thiazolines with maleic anhydride in toluene were attempted. Expected Diels-Alder products were not observed or separated. Only starting materials were recovered. Several 2-alkenyl-1,3-thiazolines were successfully reacted with benzoyl chloride to form the N-benzoyl mono-substituted products. This is in sharp contrast with the di-benzoylation of 2-methylthiazoline reported previously by the Pittman group.
2-Methylbenzothiazole was reacted with different folds of aroyl chlorides. However, only di-aroylation products were observed even when a 1:1 2-methylbenzothiazole:aroyl chloride ratio was employed.
Finally, N-methyl cyclic ketene N,O- and N,S-acetals were reacted with different alkylsulfonyl chlorides, respectively. Only di-substituted products were found in the N,O-acetal reacitons and only mono-substituted products were found in the N,S-acetal reactions even when different folds of sulfonyl chloride was employed.
Advisors/Committee Members: Charles U. Pittman, Jr. (chair), Andrzej Sygula (committee member), Stephen C. Foster (committee member).
Subjects/Keywords: acylation; 2-alkenylthiazolines; Organic synthesis
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APA (6th Edition):
Guo, H. (2008). SYNTHESIS AND SELECTED REACTIONS OF 2-ALKENYLTHIAZOLINES. (Masters Thesis). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-07082008-100959/ ;
Chicago Manual of Style (16th Edition):
Guo, Hua. “SYNTHESIS AND SELECTED REACTIONS OF 2-ALKENYLTHIAZOLINES.” 2008. Masters Thesis, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-07082008-100959/ ;.
MLA Handbook (7th Edition):
Guo, Hua. “SYNTHESIS AND SELECTED REACTIONS OF 2-ALKENYLTHIAZOLINES.” 2008. Web. 17 Apr 2021.
Vancouver:
Guo H. SYNTHESIS AND SELECTED REACTIONS OF 2-ALKENYLTHIAZOLINES. [Internet] [Masters thesis]. Mississippi State University; 2008. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-07082008-100959/ ;.
Council of Science Editors:
Guo H. SYNTHESIS AND SELECTED REACTIONS OF 2-ALKENYLTHIAZOLINES. [Masters Thesis]. Mississippi State University; 2008. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-07082008-100959/ ;
Mississippi State University
19.
Zu, Cheng-Li.
ENANTIOMER ANALYSIS USING ELECTROSPRAY IONIZATION MASS SPECTROMETRY.
Degree: PhD, Chemistry, 2007, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-04092007-103342/
;
► The design, synthesis and evaluation of chiral selectors that allow the determination of enantiomeric composition using electrospray ionization mass spectrometry are detailed herein. The enantiomers…
(more)
▼ The design, synthesis and evaluation of chiral selectors that allow the determination of enantiomeric composition using electrospray ionization mass spectrometry are detailed herein. The enantiomers of the chiral selector were mass labeled at a distant site from the chiral recognition sites of the molecules. The mass-labeled enantiomers were mixed in a one-to-one ratio to form a quasi-racemate. Chiral recognition can be observed by comparing relative abundances of the pseudo-diastereomeric selector-analyte complexes in the mass spectrum. The observed sense of chiral recognition with mass spectrometry was consistent with that observed chromatographically using a corresponding chiral stationary phase in every case. The complex intensity fraction (CIF, intensity of one selector-analyte complex divided by the sum of the intensities for both selector-analyte complexes) is linear with the enantiomeric composition. The slope of this line is an indication of the extent of the enantioselectivity: the larger the slope, the more significant the enantioselectivity. In addition, this line can be used as a calibration curve for the quantitative determination of enantiomeric composition of the same analyte with unkown enantiomeric composition.
Amide derivatives of DNB-amino acids were first used as pseudo-enantiomeric chiral selectors in the presence of added lithium chloride. The enantioselectivity values were smaller than those observed on chiral HPLC using the corresponding chiral stationary phase. The use of deprotonated DNB-amino acids as chiral selectors provides higher enantioselectivities, but with low ion abundances. Tertiary amine appended analogues of the chiral stationary phase DNB-Leucine were prepared. The amine was appended to provide a site for ready ionization (through protonation). The performance of chiral selectors of this type was compared to the original chiral selectors that lack this functional group.
Chiral recognition was also observed in a reciprocal sense using proline-derived pseudo-enantiomeric chiral selectors and analytes similar to DNB-amino acid esters or amides. Optimization of the electrospray ionization conditions provided similar enantioselectivities to those from chiral HPLC.
Libraries of tertiary amine appended derivatives of DNB-dipeptides, which were prepared through combinatorial peptide synthesis, were screened using electrospray ionization mass spectrometry. The use of electrospray ionization mass spectrometry as a discovery tool for new chiral selectors is discussed.
Advisors/Committee Members: Michael E. Koscho (chair), Keith T. Mead (committee member), Alicia M. Beatty (committee member), Andrzej Sygula (committee member), Gloria Thomas (committee member).
Subjects/Keywords: chiral; enantiomer analysis; electrospray ionization mass spectrometry; parrallel combinatorial synthesis; dipeptide chiral selectors
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APA ·
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Export
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Manager
APA (6th Edition):
Zu, C. (2007). ENANTIOMER ANALYSIS USING ELECTROSPRAY IONIZATION MASS SPECTROMETRY. (Doctoral Dissertation). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-04092007-103342/ ;
Chicago Manual of Style (16th Edition):
Zu, Cheng-Li. “ENANTIOMER ANALYSIS USING ELECTROSPRAY IONIZATION MASS SPECTROMETRY.” 2007. Doctoral Dissertation, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-04092007-103342/ ;.
MLA Handbook (7th Edition):
Zu, Cheng-Li. “ENANTIOMER ANALYSIS USING ELECTROSPRAY IONIZATION MASS SPECTROMETRY.” 2007. Web. 17 Apr 2021.
Vancouver:
Zu C. ENANTIOMER ANALYSIS USING ELECTROSPRAY IONIZATION MASS SPECTROMETRY. [Internet] [Doctoral dissertation]. Mississippi State University; 2007. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-04092007-103342/ ;.
Council of Science Editors:
Zu C. ENANTIOMER ANALYSIS USING ELECTROSPRAY IONIZATION MASS SPECTROMETRY. [Doctoral Dissertation]. Mississippi State University; 2007. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-04092007-103342/ ;
Mississippi State University
20.
Ye, Guozhong.
SYNTHESIS AND REACTIONS OF CYCLIC KETENE-N,N-ACETALS.
Degree: PhD, Chemistry, 2008, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-09142008-210135/
;
► Cyclic ketene-<i>N,N</i>-acetal chemistry was explored. 2-Methylimidazoline and 2-methyl-1,4,5,6-tetrahydropyrimidine derivatives were prepared from the condensation reactions of diamines with nitriles under Lewis acid catalysis and used…
(more)
▼ Cyclic ketene-<i>N,N</i>-acetal chemistry was explored. 2-Methylimidazoline and 2-methyl-1,4,5,6-tetrahydropyrimidine derivatives were prepared from the condensation reactions of diamines with nitriles under Lewis acid catalysis and used as the precursors of cyclic ketene-<i>N,N</i>-acetals including the N-methyl and N-acyl cyclic ketene-<i>N,N</i>-acetals.
The reactions of 2-methylimidazoline with excess benzoyl chlorides in THF or MeCN in the presence of triethylamine generate <i>N,N'</i>-diacyl-beta-keto-cyclic ketene-<i>N,N</i>-acetals. The corresponding reactions of 1,2-dimethylimidazoline under the same conditions form the ring-opened (Z)-3-((2-benzamidoethyl)(methyl)amino)-3-oxo-1-phenylprop-1-enyl benzoates. The latter reactions feature the formation of carbon-carbon bonds, carbon-nitrogen bonds, and carbon-oxygen bonds in one operation.
The reactions of 2-methyl-1,4,5,6-tetrahydropyrimidine with excess acid chlorides in Et
3N/THF generate <i>N,N</i>-diacyl-cyclic ketene-<i>N,N</i>-acetals, with no further acylation on the exocyclic beta-carbons. In contrast, the reactions of 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine under the same conditions form <i>N</i>-acyl-<i>N'</i>-methyl-beta,beta-diketo-cyclic ketene-<i>N,N</i>-acetals, with the dual acylations on the exocyclic beta-carbons. Significant double bond torsion and elongation were observed by the X-ray analysis of an example compound from the latter reactions.
The reactions of 2-methylimidazoline and 2-methyl-1,4,5,6-tetrahydropyrimidine with 1,3-diacid chlorides, in the presence of Et
3N in refluxing MeCN give highly functionalized potentially bioactive 1,8-naphthyridinetetraones. 2-Methylimidazoline and 2-methyl-1,4,5,6-tetra-hydropyrimidine can be viewed as tridentate nucleophiles which give four consecutive tandem nucleophilic attacks on electrophiles.
The reactions of 1,2-dimethylimidazoline and 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine with isocyanates in refluxing MeCN gave bicyclic pyrimidinediones.
The reactions of <i>N,N'</i>-dimethyl cyclic ketene-<i>N,N</i>-acetals with various isocyanates generated push-pull alkenes which have never been reported. Significant elongations and torsions of the polarized carbon-carbon double bonds in the novel push-pull alkenes were observed using the X-ray crystallography. The stronger pushing effect of the six-membered cyclic ketene acetal portion in a push-pull alkene, versus the five-membered analog, was detected by reactivity differences for the first time.
Advisors/Committee Members: Steven Gwaltney (committee member), Stephen C. Foster (committee member), Keith T. Mead (committee member), Andrzej Sygula (committee member), Charles U. Pittman, Jr. (chair).
Subjects/Keywords: imidazoline; tetrahydropyrimidine; ketene acetals; pyrimidinediones; naphthyridinetetraones; push-pull alkenes
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APA ·
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MLA ·
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CSE |
Export
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Manager
APA (6th Edition):
Ye, G. (2008). SYNTHESIS AND REACTIONS OF CYCLIC KETENE-N,N-ACETALS. (Doctoral Dissertation). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-09142008-210135/ ;
Chicago Manual of Style (16th Edition):
Ye, Guozhong. “SYNTHESIS AND REACTIONS OF CYCLIC KETENE-N,N-ACETALS.” 2008. Doctoral Dissertation, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-09142008-210135/ ;.
MLA Handbook (7th Edition):
Ye, Guozhong. “SYNTHESIS AND REACTIONS OF CYCLIC KETENE-N,N-ACETALS.” 2008. Web. 17 Apr 2021.
Vancouver:
Ye G. SYNTHESIS AND REACTIONS OF CYCLIC KETENE-N,N-ACETALS. [Internet] [Doctoral dissertation]. Mississippi State University; 2008. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-09142008-210135/ ;.
Council of Science Editors:
Ye G. SYNTHESIS AND REACTIONS OF CYCLIC KETENE-N,N-ACETALS. [Doctoral Dissertation]. Mississippi State University; 2008. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-09142008-210135/ ;
Mississippi State University
21.
Collier, Willard Earl.
A COMPUTATIONAL INVESTIGATION OF SOME POLYCALICENES AS NOVEL NONBENZENOID AROMATIC MOLECULES AND THE STRANGE CASE OF THE CYCLOPROPENYL ANION.
Degree: PhD, Chemistry, 2009, Mississippi State University
URL: http://sun.library.msstate.edu/ETD-db/theses/available/etd-04022009-213437/
;
► Polycalicenes are novel nonbenzenoid aromatic hydrocarbons made from calicene subunits. A host of related polycalicenes are possible by varying the number of calicenes and…
(more)
▼ Polycalicenes are novel nonbenzenoid aromatic hydrocarbons made from calicene subunits. A host of related polycalicenes are possible by varying the number of calicenes and the bonding motif of the calicenes (e.g. head-to-tail versus head-to-head). Polycalicenes might posses interesting and useful electrical, magnetic, and optical properties. Especially intriguing is that while calicene has never been synthesized, bicalicene 2, where two calicenes are bonded head-to-tail, has been synthesized by Yoshida et al. and found to be aromatic despite having a peripheral 16 ð electron count.
This study details a computational investigation of the aromaticity of some planar polycalicenes using the nucleus independent chemical shift (NICS) criterion of aromaticity. NICS values were calculated with HF/6-31+G(d,p) and B3LYP/6-31+G(d,p). Bicalicene 3, where two calicenes are bonded head-to-head, was shown to have a triplet ground
state which required the calculation of NICS values using UB3LYP/6-31+G(d,p).
Also, the aromaticities of some belted polycalicenes were evaluated using NICS values calculated at 6-31G(d,p). The smaller basis set was used due to the increasing number of basis functions for the larger belted polycalicenes.
In addition, the electronic ground and excited states of the planar polycalicenes were also calculated. The electronic ground states were assigned using HF/6-31+G(d,p) and B3LYP/6-31+G(d,p). CCSD(T)/6-31G(d,p) calculations were used to confirm assignments. The electronic excited states were calculated using time dependent density functional theory (TDDFT) and B3LYP/6-31+G(d,p).
Recently, the reliability of the NICS criterion was questioned when it was claimed NICS found the cyclopropenyl anion to be aromatic. One part of this study details the examination of this claim and concluded that the earlier work was in error. The error was proven to arise from the failure to employ diffuse basis functions in the earlier work.
Advisors/Committee Members: Earl G.Alley (committee member), Charles U. Pittman, Jr. (chair), Steven R. Gwaltney (committee member), Andrzej Sygula (committee member), Stephen C. Foster (committee member).
Subjects/Keywords: aromaticity; NICS; ab initio
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APA (6th Edition):
Collier, W. E. (2009). A COMPUTATIONAL INVESTIGATION OF SOME POLYCALICENES AS NOVEL NONBENZENOID AROMATIC MOLECULES AND THE STRANGE CASE OF THE CYCLOPROPENYL ANION. (Doctoral Dissertation). Mississippi State University. Retrieved from http://sun.library.msstate.edu/ETD-db/theses/available/etd-04022009-213437/ ;
Chicago Manual of Style (16th Edition):
Collier, Willard Earl. “A COMPUTATIONAL INVESTIGATION OF SOME POLYCALICENES AS NOVEL NONBENZENOID AROMATIC MOLECULES AND THE STRANGE CASE OF THE CYCLOPROPENYL ANION.” 2009. Doctoral Dissertation, Mississippi State University. Accessed April 17, 2021.
http://sun.library.msstate.edu/ETD-db/theses/available/etd-04022009-213437/ ;.
MLA Handbook (7th Edition):
Collier, Willard Earl. “A COMPUTATIONAL INVESTIGATION OF SOME POLYCALICENES AS NOVEL NONBENZENOID AROMATIC MOLECULES AND THE STRANGE CASE OF THE CYCLOPROPENYL ANION.” 2009. Web. 17 Apr 2021.
Vancouver:
Collier WE. A COMPUTATIONAL INVESTIGATION OF SOME POLYCALICENES AS NOVEL NONBENZENOID AROMATIC MOLECULES AND THE STRANGE CASE OF THE CYCLOPROPENYL ANION. [Internet] [Doctoral dissertation]. Mississippi State University; 2009. [cited 2021 Apr 17].
Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-04022009-213437/ ;.
Council of Science Editors:
Collier WE. A COMPUTATIONAL INVESTIGATION OF SOME POLYCALICENES AS NOVEL NONBENZENOID AROMATIC MOLECULES AND THE STRANGE CASE OF THE CYCLOPROPENYL ANION. [Doctoral Dissertation]. Mississippi State University; 2009. Available from: http://sun.library.msstate.edu/ETD-db/theses/available/etd-04022009-213437/ ;
. 
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