Design and Synthesis of Luminescent Alkynylplatinum (II) Terpyridine Complexes and Their Function as Optical Probes for Biomolecules and Ions

Design and Synthesis of Luminescent Alkynylplatinum (II) Terpyridine Complexes and Their Function as Optical Probes for Biomolecules and Ions
Author: Ching-Lam Margaret Yeung
Publisher: Open Dissertation Press
Total Pages:
Release: 2017-01-27
Genre:
ISBN: 9781361369432
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This dissertation, "Design and Synthesis of Luminescent Alkynylplatinum (II) Terpyridine Complexes and Their Function as Optical Probes for Biomolecules and Ions: From Self-aggregarion, Supramolecular Assembly to Host-guest Chemistry" by Ching-lam, Margaret, Yeung, 楊靖琳, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: A number of cationic water-soluble alkynylplatinum(II) terpyridine complexes, [Pt(tpy){C≡CCH2OC6H3-(CH2OH)2-3,5}]OTf, [Pt(tBu3tpy){C≡CCH2OC6H3- (CH2OH)2-3,5}]Cl, [Pt(tpy){C≡CCH2OC6H4-(CH2OH)-4}]OTf, [Pt(tpy){C≡CC6H3- (CH2OH)2-3,5}]OTf, [Pt(tpy){C≡CC6H4-(CH2OH)-4}]OTf, [Pt(tpy)(C≡C－C≡CH)]OTf and [Pt(tpy){C≡CC6H4(CH2NMe3)-4}](OTf)2, have been synthesized. Phosphate anion derivatives of polyanionic nature, e.g. adenosine triphosphate and tyrosine-containing phosphopeptide, were employed to investigate the induced supramolecular helical assembly behaviors of several of the water-soluble platinum(II) complexes through the study of their UV-vis absorption, emission and circular dichroism (CD) spectroscopies. The extent of such induced self-aggregation properties has been shown to be dependent on the concentration of substrates and capable of screening their respective structurally similar analogues. Two of the complexes were further explored for their use as label-free detection probes for real-time monitoring of the conversion of these phosphate anion derivatives to their metabolic products catalyzed by several biologically important enzymes. Michaelis-Menten analyses have been performed to determine the kinetic parameters. Supramolecular self-assembly and disassembly behaviors of water-soluble platinum(II) complexes have also been explored for their sensing applications for biomacromolecules with quantitative analyses based on UV-vis, emission and CD spectral titration studies. Making use of the selective binding affinity of aptamers towards their target substrates, the extent of self-assembly of the platinum(II) complexes in the presence of lysozyme and thrombin, which arose from their electrostatic interactions with the negatively charged aptamers, could be modulated for the quantification of these substrates. The potential applicability of this probing strategy in real biological environment has been assessed. Other than that, CD spectroscopic studies revealed the formation of supramolecular helical assembly of the platinum(II) complexes upon electrostatic interaction with heparin. Such helical conformation of the heparin-complex mixture together with the distribution of the negatively charged functionalities on the heparin have endowed the complex with high differentiating power for screening possible interfering analogues. Insulin has also been employed as a template for inducing the self-assembly of the platinum(II) complex. Changes in negative surface charge distribution on insulin, brought about by its conformational changes upon conversion to insulin amyloid under destabilizing conditions, have resulted in different extent of induced self-assembly of the metal complex. Spectral changes of the platinum(II) complex has provided a convenient monitoring of insulin amyloid formation, with kinetic parameters determined. A number of platinum(II) complexes with nucleobase-functionalized alkynyl ligands, [Pt(tpy)(C≡CCH2-T-1)]OTf, [Pt(tBu3tpy)(C≡CCH2T-1)]OTf, [Pt(tpy)(C≡C- CH2-A-9)]OTf, [Pt(tpy)(C≡CCH2-C-1)]OTf and [Pt(tpy)(C≡CCH2-G-9)]OTf (T = thymine; A = adenine; C = cytosine; and G = guanine), and amide-functionalized terpyridine ligands, [Pt{tpy-(CONHPh)2}(C≡CPh)]PF6 and [Pt{tpy-(CONHC6H13)

Design and Synthesis of Luminescent Alkynylplatinum (II) Terpyridine Complexes and Their Function As Optical Probes for Biomolecules and Ions

Design and Synthesis of Luminescent Alkynylplatinum (II) Terpyridine Complexes and Their Function As Optical Probes for Biomolecules and Ions
Author: Ching-Lam Margaret Yeung
Publisher:
Total Pages:
Release: 2017-01-27
Genre:
ISBN: 9781361369456
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This dissertation, "Design and Synthesis of Luminescent Alkynylplatinum (II) Terpyridine Complexes and Their Function as Optical Probes for Biomolecules and Ions: From Self-aggregarion, Supramolecular Assembly to Host-guest Chemistry" by Ching-lam, Margaret, Yeung, 楊靖琳, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: A number of cationic water-soluble alkynylplatinum(II) terpyridine complexes, [Pt(tpy){C≡CCH2OC6H3-(CH2OH)2-3,5}]OTf, [Pt(tBu3tpy){C≡CCH2OC6H3- (CH2OH)2-3,5}]Cl, [Pt(tpy){C≡CCH2OC6H4-(CH2OH)-4}]OTf, [Pt(tpy){C≡CC6H3- (CH2OH)2-3,5}]OTf, [Pt(tpy){C≡CC6H4-(CH2OH)-4}]OTf, [Pt(tpy)(C≡C－C≡CH)]OTf and [Pt(tpy){C≡CC6H4(CH2NMe3)-4}](OTf)2, have been synthesized. Phosphate anion derivatives of polyanionic nature, e.g. adenosine triphosphate and tyrosine-containing phosphopeptide, were employed to investigate the induced supramolecular helical assembly behaviors of several of the water-soluble platinum(II) complexes through the study of their UV-vis absorption, emission and circular dichroism (CD) spectroscopies. The extent of such induced self-aggregation properties has been shown to be dependent on the concentration of substrates and capable of screening their respective structurally similar analogues. Two of the complexes were further explored for their use as label-free detection probes for real-time monitoring of the conversion of these phosphate anion derivatives to their metabolic products catalyzed by several biologically important enzymes. Michaelis-Menten analyses have been performed to determine the kinetic parameters. Supramolecular self-assembly and disassembly behaviors of water-soluble platinum(II) complexes have also been explored for their sensing applications for biomacromolecules with quantitative analyses based on UV-vis, emission and CD spectral titration studies. Making use of the selective binding affinity of aptamers towards their target substrates, the extent of self-assembly of the platinum(II) complexes in the presence of lysozyme and thrombin, which arose from their electrostatic interactions with the negatively charged aptamers, could be modulated for the quantification of these substrates. The potential applicability of this probing strategy in real biological environment has been assessed. Other than that, CD spectroscopic studies revealed the formation of supramolecular helical assembly of the platinum(II) complexes upon electrostatic interaction with heparin. Such helical conformation of the heparin-complex mixture together with the distribution of the negatively charged functionalities on the heparin have endowed the complex with high differentiating power for screening possible interfering analogues. Insulin has also been employed as a template for inducing the self-assembly of the platinum(II) complex. Changes in negative surface charge distribution on insulin, brought about by its conformational changes upon conversion to insulin amyloid under destabilizing conditions, have resulted in different extent of induced self-assembly of the metal complex. Spectral changes of the platinum(II) complex has provided a convenient monitoring of insulin amyloid formation, with kinetic parameters determined. A number of platinum(II) complexes with nucleobase-functionalized alkynyl ligands, [Pt(tpy)(C≡CCH2-T-1)]OTf, [Pt(tBu3tpy)(C≡CCH2T-1)]OTf, [Pt(tpy)(C≡C- CH2-A-9)]OTf, [Pt(tpy)(C≡CCH2-C-1)]OTf and [Pt(tpy)(C≡CCH2-G-9)]OTf (T = thymine; A = adenine; C = cytosine; and G = guanine), and amide-functionalized terpyridine ligands, [Pt{tpy-(CONHPh)2}(C≡CPh)]PF6 and [Pt{tpy-(CONHC6H13)

Design and Synthesis of Luminescent Mono- And Dinuclear Platinum(ii) Alkynyl Terpyridine Complexes

Design and Synthesis of Luminescent Mono- And Dinuclear Platinum(ii) Alkynyl Terpyridine Complexes
Author: Hoi-Yiu Chan
Publisher: Open Dissertation Press
Total Pages:
Release: 2017-01-27
Genre:
ISBN: 9781361426180
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This dissertation, "Design and Synthesis of Luminescent Mono- and Dinuclear Platinum(II) Alkynyl Terpyridine Complexes: From Photophysics to Aggregation and Self-assembly" by Hoi-yiu, Chan, 陳凱耀, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Abstract of thesis entitled DESIGN AND SYNTHESIS OF LUMINESCENT MONO- AND DINUCLEAR PLATINUM(II) ALKYNYL TERPYRIDINE COMPLEXES - FROM PHOTOPHYSICS TO AGGREGATION AND SELF-ASSEMBLY submitted by CHAN Hoi Yiu for the degree of Doctor of Philosophy at The University of Hong Kong in August 2006 A series of mononuclear alkynylplatinum(II) terpyridyl complexes, [Pt(trpy)({C{ C} C H )]PF, [Pt(trpy)({C{ C} C H CF -4)]PF, n 6 5 6 n 6 4 3 6 [Pt(trpy)({C{ C} C H CH -4)]PF, and [Pt( Bu trpy)(C{ C C{ C C H )]PF (n = n 6 4 3 6 3 6 5 6 2, 3), have been synthesized. The X-ray crystal structures of the two forms of [Pt(trpy)(C{ C C{ C C H )]PF, [Pt(trpy)(C{ C C{ C C{ C C H CH -4)]PF and 6 5 6 6 4 3 6 [Pt( Bu trpy)(C{ C C{ C C H )]PF have been determined. Dinuclear and 3 6 5 6 trinuclear alkynylplatinum(II) terpyridyl complexes, [1,4- {Pt(trpy)C{ C} C H ](OTf), [1,4-{Pt( Bu trpy)C{ C} C H ](OTf), [2,5- 2 6 4 2 3 2 6 4 2 {Pt(trpy)C{ C} C H S](OTf), [2,5-{Pt( Bu trpy)C{ C} C H S](OTf) and [1,3,5- 2 4 2 2 3 2 4 2 2 {Pt( Bu trpy)C{ C} C H ](OTf) have been successfully synthesized. The X-ray 3 3 6 3 3t crystal structure of [1,4-{Pt( Bu trpy)C{ C} C H ](OTf) has also been 3 2 6 4 2 determined. The luminescence properties of these complexes have been studied and their lowest-lying excited states in fluid solution and in the glass state were tentatively assigned as admixture of MLCT [dS (Pt)ĺ S *(trpy)] and LLCT [S (C{ C)ĺ S *(trpy)] origin, whereas the low-energy emissions in the solid state were attributed to triplet metal metal-to-ligand charge transfer ( MMLCT) phosphorescence, resulting from significant Pt---Pt interactions in the solid state. Besides, a series of luminescent platinum(II) terpyridyl alkynyl complexes with different counter anions, [Pt(trpy)(C{ C C{ C H)]X (X = OTf, PF, ClO, 6 4 BF, BPh ), [Pt(trpy)(C{ C C H )]X (X = OTf, PF, ClO, BF ) and 4 4 6 5 6 4 4 complexes with various substituents on the alkynyl and terpyridyl ligands, [Pt(trpy)(C{ CC H OCH-4)]OTf, [Pt(4'-CH O trpy)(C{ C C H )]OTf, 6 4 3 3 6 5 [Pt( Bu trpy)(C{ C C{ CH)]OTf, [Pt(trpy)(C{ CC H {CH NMe }-4)](OTf), 3 6 4 2 3 2 [Pt(trpy)(C{ C C{ C CH NMe )](OTf) and [Pt(trpy)(C{ C C{ C CH OH)]OTf 2 3 2 2 have been synthesized and their photophysical properties have been stuided. The X-ray crystal structure of [Pt(trpy)(C{ C C H )]ClO and 6 5 4 [Pt( Bu trpy)(C{ C C{ C H)]OTf have been determined. The solid-state absorption and emission spectra showed low-energy bands, which were assigned as derived from MMLCT origin. Solvent-induced aggregation studies of these complexes in solution showed that the color of the aggregates could be very different for different counter-ions, indicating that counter-ions played an important role in governing the degree of aggregation and the extent of interactions within these aggregates. Addition of various anions to solutions of [Pt(trpy)(C{ C C{ C H)]X (X = OTf, PF ) produced anion-induced color 6changes upon solvent-induced aggregation, showing that these complexes might serve as potential colorimetric anion probes. The effect of temperature on the aggregation properties of the complexes has also been explored. New low-energy absorption and emission bands were found upon a reduction of temperature, attributable to the formation o

Design, Synthesis, Photophysics and Self-Assembly Study of Platinum (II) Terpyridine Complexes and Their Utilization as Stimuli-Responsive Smart Materials and Probes for Molecules and Macromolecules of Biological Interest

Design, Synthesis, Photophysics and Self-Assembly Study of Platinum (II) Terpyridine Complexes and Their Utilization as Stimuli-Responsive Smart Materials and Probes for Molecules and Macromolecules of Biological Interest
Author: Yik-Sham Clive Chung
Publisher: Open Dissertation Press
Total Pages:
Release: 2017-01-27
Genre:
ISBN: 9781361368916
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This dissertation, "Design, Synthesis, Photophysics and Self-assembly Study of Platinum (II) Terpyridine Complexes and Their Utilization as Stimuli-responsive Smart Materials and Probes for Molecules and Macromolecules of Biological Interest" by Yik-sham, Clive, Chung, 鍾亦琛, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: A series of water-soluble platinum(II) terpyridine complexes with functionalized alkynyl ligands and a boronic acid-containing polymer, PAAPBA, have been synthesized and characterized. The photophysical and electrochemical properties of all the platinum(II) complexes have been studied. Some of the complexes have been demonstrated to show ground-state aggregation in organic solvents and aqueous solutions at high concentrations, leading to Pt...Pt and/or π-π interactions and hence the emergence of metal-metal-to-ligand charge transfer (MMLCT) transitions in both the UV-visible and emission spectra. The induced self-assembly of [Pt(tpy)(C≡CC6H4-CH2NMe3-4)](OTf)2 by PAAPBA has been explored for the development of glucose sensing protocols and α-glucosidase assay by monitoring the triplet metal-metal-to-ligand charge transfer (3MMLCT) emission in the near-infrared (NIR) region. [Pt(tpy){C≡CC6H4- {NHC(=NH2])(NH2)}-4}](OTf)2 has been observed to undergo induced aggregation in the presence of citrate, with good selectivity over other mono- and dicarboxylates in the tricarboxylic acid (TCA) cycle. Enzymatic activity of citrate lyase has also been probed by the emission spectral changes of the complex in the NIR region. A series of water-soluble alkynylplatinum(II) terpyridine complexes and water-soluble conjugated polyelectrolytes (CPEs) have been synthesized and characterized. The UV-vis absorption and emission properties of the platinum(II) complexes and CPEs have been investigated in organic solvents and/or aqueous buffer solutions. The electrochemical properties and ground-state aggregation at high concentrations of the platinum(II) complexes have also been examined. Two-component ensembles containing selected platinum(II) complexes and PPE-SO3- have been studied, and Forster resonance energy transfer (FRET) has been demonstrated from the PPE-SO3- donor to the aggregated complexes as acceptors. The ensemble containing PPE-SO3- and [Pt(tpy)(C≡CC6H4CH2NMe3-4)](OTf)2 has been employed for a "proof-of-principle" label-free detection of human serum albumin (HSA) in pH 3 buffer solutions with high selectivity and sensitivity, while another ensemble containing PPE-SO3- and [Pt{tpy(C6H4CH2NMe3-4)-4'}(C≡CC6H5)](OTf)2 has been utilized for selective label-free detection of G-quadruplex structure of the human telomeric DNA in physiological buffer solutions. A series of water-soluble platinum(II) terpyridine complexes with stimuli-responsive alkynyl ligands and a series of water-soluble platinum(II) metallosupramolecular triblock copolymers have been synthesized and characterized. The photophysical and electrochemical properties as well as the ground-state aggregation of the complexes have been investigated. Some of them have been found to show different electronic absorption and emission properties in aqueous solution at different pHs due to aggregation/deaggregation of the complexes. One of the complexes has been employed for live-cell imaging experiments to locate acidic organelles, such as lysosomes, in MDCK cells. The water-soluble platinum(II) metallosupramolecular triblock copolymers have been found to show an increase in 3MMLCT emission intensity in the red-NIR region with temperature, which has been attribu

DESIGN & SYNTHESIS OF LUMINESC

DESIGN & SYNTHESIS OF LUMINESC
Author: Suk-Hang Lam
Publisher: Open Dissertation Press
Total Pages: 292
Release: 2017-01-26
Genre: Science
ISBN: 9781361034019
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This dissertation, "Design and Synthesis of Luminescent Platinum(II) and Gold(III) Complexes With Tridentate Pincer-type Ligands: From Computational Study to Experiments and Application Studies" by Suk-hang, Lam, 林淑恒, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Abstract of thesis entitled DESIGN AND SYNTHESIS OF LUMINESCENT PLATINUM(II) AND GOLD(III) COMPLEXES WITH TRIDENTATE PINCER-TYPE LIGANDS - FROM COMPUTATIONAL STUDY TO EXPERIMENTS AND APPLICATION STUDIES Submitted by LAM Suk Hang for the degree of Doctor of Philosophy at The University of Hong Kong in June 2015 Square planar platinum(II) and gold(III) complexes possess unique spectroscopic and photophysical properties which enable them as promising candidates for many applications such as optoelectronic devices and biological sensors. The understanding of the intrinsic properties of these complexes is therefore essential to optimize their performance as well as provide guidance on the molecular design for specific applications. This thesis aims to provide useful insights for the molecular design strategies with the aid of computational studies to tune the electronic properties of these complexes and electroluminescence studies in the fabrication of organic light-emitting devices (OLEDs). Computational studies have been performed to inspect electronic structures and photophysical properties as well as their correlation with the nature of ancillary ligands in the platinum(II) complexes of 1,3-bis(N-alkylbenzimidazol-2′-yl)benzene, [Pt(bzimb)(C≡C-R)], 1,3-bis-hetero-azolylbenzenes, [Pt(N DEGREESC DEGREESN)(C≡C-R)], and pyridine-based N-heterocyclic carbene, [Pt(NHC)(C≡C-R)] . It was found that the emission of the arylalkynylplatinum(II) complexes with pyridine-based N-heterocyclic carbene ligand was originated from the triplet alkynyl-to-tridentate pincer ligand-to-ligand charge transfer excited state mixed with platinum-to-tridentate pincer metal-to-ligand charge transfer character, and the excited state energy was found to be red-shifted according to the increasing π electron-donating ability of the aryl group attached to the alkynyl ligand. On the other hand, the emission energies of the platinum(II) complexes of 1,3-bis(N-alkylbenzimidazol-2′-yl)benzene and 1,3-bis-hetero-azolylbenzenes were found to be dependent on the different electron-donating substituents on the pincer ligands. Calculations have also been performed on the representative alkynylplatinum(II) + + complexes [Pt(trpy)(C≡C-R)] (trpy = 2,2′ 6′,2′′-terpyridine), [Pt(bzimpy)(C≡C-R)] (bzimpy = 2,6-bis(N-alkylbenzimidazol-2′-yl)pyridine) and [Pt(bzimb)(C≡C-R)] as well as alkynylgold(III) complexes [Au(C DEGREESN DEGREESC)(C≡C-R)] (C DEGREESN DEGREESC = 2,6-diphenylpyridine), [Au{C(Np) DEGREESN DEGREESC(Np)}(C≡C-R)] (C(Np) DEGREESN DEGREESC(Np) = 2,6-di(2-naphthyl)pyridine) and [Au(N DEGREESN DEGREESN)(C≡C-R)] (N DEGREESN DEGREESN = 2,6-bis(1H-benzimidazol-2-yl)pyridine) in order to have a better understanding on their nature of the emissive origins as well as the radiative and nonradiative processes. In particular, factors governing the ordering of the triplet excited states and radiative decay rate constants of the emissive state ( ES) have been examined. Their potential energy profiles for the deactivation process from the ES via triplet metal-centered states have also been explored. This study revealed for the first time the potential energy profiles for the thermal deactivation pathway of square planar platinum(II) and gold(III) complexes. In addition to the computational