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Wheate, Nial Joseph Chemistry Australian Defence Force Academy UNSW. "Platinum anti-cancer complexes." Awarded by:University of New South Wales - Australian Defence Force Academy. School of Chemistry, 2001. http://handle.unsw.edu.au/1959.4/38704.
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[Formulae and special characters can only be approximated here. Please see the pdf version of the Abstract for an accurate reproduction.] Several inert platinum complexes were synthesised: [(en)Pt([special character]-dpzm)2Pt(en)]4+, [{Pt(dien)}2[special character]-dpzm]4+, [{Pt(dien)}2[special character]-H2N-(CH2)6-NH2]4+, cis-[(NH3)2Pt([special character]--dpzm)2Pt(NH3)2]4+, trans-[Pt(NH3)2([special character]-dpzm)2]2+. Three active complexes, all with chloro ligands, were also synthesised: trans-[{Pt(NH3)Cl2}2[special character]-dpzm)], trans-[{Pt(NH3)2Cl}2[special character]-dpzm]2+ (di-Pt) and trans-[trans-{Pt(NH3)2Cl}2{trans-[Pt(NH3)2([special character]-dpzm)2]}]4+ (tri-Pt). 1H NMR established that multi-nuclear platinum complexes will preferentially associate in the DNA minor groove with a preference for A/T sequences, and with a binding constant [special character]-105 M-1, regardless of the charge, linking ligand, length or shape. Using [(en)Pt([special character]-dpzm)2Pt(en)]4+ and the oligonucleotide d(GC)5 it was determined that the metal complex binds G/C rich sequences also in the minor groove, but with a much reduced binding constant, 103 M-1. CD studies showed [(en)Pt([special character]-dpzm)2Pt(en)]4+ was able to induce a DNA conformation change from B-type to what appeared to be a partial Z-type. Transcription assays showed that even though the metal complex does not bind DNA covalently, it is still able to inhibit DNA transcription at particular sites. The complexes di-Pt, tri-Pt, [{Pt(dien)}2[special character]-dpzm]4+ and trans-[Pt(NH3)2([special character]-dpzm)2]2+ were tested for anti-cancer activity in the L1210 murine leukaemia cell line, and gave values of 3.8, 2.5, [special character]200 and 64 [special character]M respectively. In the cisplatin resistant line (L1210/DDP), trans-[Pt(NH3)2([special character]-dpzm)2]2+ showed an increase in activity with a drop to 32 [special character]M, while both di-Pt and tri-Pt showed decreases in activity to values of 8.8 and 3.6 [special character]M. In the human ovarian carcinoma 2008 cell line and its cisplatin resistant derivative C13[special character]5, both complexes showed good activity with values of 2.5 and 20.9 [special character]M respectively, but again both showed decreases in activity in the resistant line with values of 17.8 and 37.7 [special character]M respectively. To help explain the difference between activity of these complexes and the complexes BBR3464 and BBR3005, cell uptake and DNA interstrand cross-linking experiments were performed. The cell uptake studies showed that both di-Pt and tri-Pt are taken up by cells at very high levels, when administered at 100 [special character]M, thus indicating that the difference is unlikely to be due to large differences in cell uptake. The DNA interstrand cross-linking studies showed both complexes readily form interstrand adducts (50% interstrand cross-linking at 12 nM and 22 nM respectively, c.f cisplatin 3 [special character]M). These results suggest that the rigid nature of the dpzm linker may be affecting the DNA adducts formed, with more interstrand links being formed than BBR3464. Possibly, it is this that causes the large differences in cytotoxicity. The DNA binding of di-Pt and tri-Pt was examined with the nucleosides adenosine and guanosine and the dinucleotide d(GpG). Both complexes bound at the N7 of guanosine, but 2-fold slower than cisplatin. In addition, di-Pt bound at the N7 and either the N1 or N3 of adenosine, 7-fold slower than guanosine. Di-Pt forms a large variety of cross-links between two d(GpG) molecules, however it could not be established whether the 1,2-intrastrand adduct could be formed. Di-Pt, however, forms a 1,2-GG interstrand adduct with the oligonucleotide d(ATGCAT)2 resulting in a conformation change away from B-type DNA. The sugar pucker of the G3 nucleoside changes from 2[special character]-endo towards 3[special character]-endo, and the position of the nucleotide relative to the sugar changes from anti to syn. The ability of multi-nuclear platinum complexes to form covalent adducts in the DNA minor groove remains unclear. It appears that di-Pt can form up to 33% minor groove adducts with the oligonucleotide d(AT)5, but when added to the oligonucleotide d(GCCAAATTTCCG)2 no definite minor groove adducts are seen and the major adduct appears to be a 1,2-interstrand cross-link between the two A6's or between the G1 and G11. Finally, a study of the encapsulation of platinum complexes within cucurbit[7]uril (Q7) as a means of reducing drug toxicity was made. For complex A and di-Pt, encapsulation of the linker ligand occurred. The effect of Q7 on the rate of hydrolysis of di-Pt was at least a 3-fold reduction as compared to free di-Pt with guanosine. Studies with [{Pt(dien)}2[special character]-dpzm]4+/Q7 and the oligonucleotide d(CGCGAATTCGCG)2 showed that the metal complex could dissociate from the Q7 and associate with the oligonucleotide, where an equilibrium is achieved with 15 % of the metal complex bound to the oligonucleotide and 75 % encapsulated in Q7. Tests in the L1210 and L1210/DDP cancer cell lines showed that di-Pt/Q7 has almost the same activity compared to free di-Pt.
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McGowan, Geraldine. "Platinum picoline anticancer complexes." Thesis, University of Edinburgh, 2005. http://hdl.handle.net/1842/11119.
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The 2-picoline (2-methylpyridine) complex, cis-[PtCl2(NH3)(2-pic)] (AMD473), is promising new generation platinum antitumour agent currently in clinical trials and highly active cisplatin resistant cell-lines. The antitumour activity of trans platinum complexes has attracted renewed interest since it has been shown that some trans compounds, in particular those possessing planar amine ligands, are anticancer-active. Therefore, three trans isomers, trans-[PtCl2(NH3)(2-pic)] (1), trans-[PtCl2(NH3)(3-pic)] (2) and trans-[PtCl2(NH3)(4-pic)] (3), were synthesised and characterised. The crystal structure of 1 shows steric hindrance induced by the 2-methyl group towards an axial approach to Pt, while its 3-pic (2) and 4-pic (3) analogues are less sterically hindered. Notable however, is that in the solid state complex 1 is less sterically-hindered than its cis isomer. 15N-labelling of complexes 1-3 allowed both the hydrolysis rates and pKa values of the complexes to be determined using 2D[1H, 15N] NMR spectroscopy. Adducts of cis- and trans-(PtCl2(NH3)(2-pic)] with neutral 9-ethylguanine (9-EtGH) and anionic (N1-deprotonated) 9-ethylguanine (9-EtG) were prepared and their structures determined by X-ray crystallography. Platinum is coordinated at the guanine N7 position with a head-to-tail arrangement of the bases in all cases. Two of the complexes exhibited intermolecular triple hydrogen bonding between neutral and deprotonated guanine ligands. In addition, adducts of cis- and trans-[PtCl2(NH3)(2-pic)] with guanosine and 2’-deoxyguanosine were prepared and characterised in solution by NMR spectroscopy and ESI mass spectrometry. The complexes cis-[Pt(NH3)(2-pic)(Guo)2]2+, and cis- and trans-(Pt(NH3)(2-pic)(2’-dGuo)2]2+ were assigned as head-to-tail conformations, on the basis of their NOE cross-peaks. The reaction of cis-[Pt(15NH3)(2-pic)(OH2)2]2+ and guanosine (Guo) was followed by 2D [1H, 15N] NMR spectroscopy and was found to proceed through two mono(guanosine) intermediate species to yield the dominant product cis-[Pt(15NH3)(2-pic)(Guo)2]2+. Initial guanosine substitution trans to 2-picoline was faster than substitution cis to 2-picoline due to steric hindrance, but the rates of the second guanosine substitution were similar. The binding of 15N-labelled-1 to a self-complementary DNA duplex, d(TATGGTACCATA)2, was investigated using 1D 1H and 2D [1H, 15H] NMR spectroscopy. The first aquation step appeared to be the rate-limiting step in the formation of the monofunctional adducts. Several DNA products were observed but could not be identified unambiguously. The rate constants for reactions between 15N-laabelled 1 and guanosine 5’-monophosphate (5’-GMP) were determined via 2D NMR studies, and compared to those previously reported for cis-[PtCl2(NH3)(2-pic)].
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Davies, Sian E. "Novel platinum (O) complexes." Thesis, University of Sussex, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.335049.
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Hindmarsh, Kathryn. "Kinetic studies of platinum complexes." Thesis, University of Canterbury. Chemistry, 1998. http://hdl.handle.net/10092/8647.
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Since the chance discovery, in 1967, of the anti-tumour activity of cisplatin, cis-dichlorodiammineplatinum(II), research has focussed on studying the reactions of this and other related complexes in an effort to elucidate the nature of the biological activity. This thesis presents a study of the aqueous solution chemistry of some platinum(II) and platinum(IV) complexes in order to extend what is known about the simple chemistry of this biologically important class of compounds.
The chloride ion anation of diaqua (cis-[Pt(OH₂)₂(N)₂]²⁺) complexes is investigated as is the bromide ion anation of the bromoaqua (cis-[PtBr(OH₂)(N)₂]⁺) and diaqua (cis-[Pt(OH₂)₂(N)₂]²⁺) species, all in 1.0 M HC1O₄. The kinetics are studied using UV/Vis spectroscopic methods - both conventional and stopped-flow. High-pressure stopped-flow is used for selected reactions to determine the effect of pressure on the anation process. The collective data are used to calculate activation parameters from which conclusions are drawn as to the mechanism of the reaction.
The redox kinetics of the platinum(II)/platinum(IV) couple are investigated using a variety of redox agents. These data provide a basis on which to form mechanistic interpretations for both the oxidation and reduction processes. Extrapolations are made to the biological system for the reduction of anti-tumour active platinum(IV) drugs.
Platinum(IV) complexes are known to be very inert. An investigation into the base hydrolysis of platinum(IV) complexes is presented and a mechanism proposed.
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Mackay, Fiona S. "Photoactive platinum azide anticancer complexes." Thesis, University of Edinburgh, 2006. http://hdl.handle.net/1842/11085.
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Photoactive platinum compounds have the potential to reduce some of the debilitating side-effects associated with conventional chemotherapeutics, such as cisplatin. Stable, inert platinum(IV) compounds which are reduced to active platinum(II) species only upon irradiation, could provide a site-specific treatment. The PtIV azide complexes, cis, trans, cis-[Pt(N3)2(OH)2(NH3)2] and cis, trans-[Pt(en)(N3)2, have previously been shown to be stable in the dark but reduced to PtII upon irradiation. The synthesis and characterisation of new platinum azide compounds, designed to improve important properties such as solubility and wavelength of absorbance are described here. Complexes which have azide ligands in a trans position were synthesised, the general formula is trans, trans, trans-[Pt(N3)2(OH)2(NH3)R] where R is NH3, pyridine, methylamine, ethylamine, thiazole, 2-picoline, 3-picoline, 4-picoline or cyclohexylamine. Several PtIV diazido compounds containing chelating aromatic ligands, such as 2,2’-bipyridine and 1,10-phenanthroline were also prepared. Many of the novel compounds synthesised were characterised by X-ray structure determination. The complexes with trans azides generally showed improved water solubility as well as a shift of the main absorbance band towards the visible region, compared to their cis analogues. A transcription mapping study of a fragment of pSP73KB plasmid DNA treated with cis, trans-[Pt(en)(N3)2(OH)2] and visible light, has shown that platination mainly occurs at consecutive guanine bases. The major binding sites were similar to those of cisplatin. No platination was seen in an identical sample which was not irradiated.
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Shaili, Evyenia. "Photoactivatable platinum (IV) anticancer complexes." Thesis, University of Warwick, 2013. http://wrap.warwick.ac.uk/59800/.
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In this work, trans-diazido Pt(IV) complexes with general formula [Pt(N3)2(OH)(OCOR)(pyr)2] (where OCOR is a carboxylate axial ligand) and [Pt(N3)2(OH)2(L1)(L2)] (where L1 and L2 are aromatic N-heterocyclic ligands) have been synthesised and characterised. The chemical and photochemical properties of these complexes, as well as their photobiological behaviour, have been studied in order to check their potential as photoactivatable anticancer drugs. Four trans-diazido Pt(IV) complexes with general formula trans, trans, trans- [Pt(N3)2(OH)(OCOR)(pyr)2] (OCOR= succinate, 4-oxo-4-propoxybutanoate, Nmethylisatoate and succinate-(RGD)f peptide ligands) have been obtained by axial derivatisation of one hydroxido ligand from trans, trans, trans- [Pt(N3)2(OH)2(pyr)2]. The crystal structures of three axially-derivatised complexes have been determined by X-ray diffraction. Photoirradiation studies have shown an improved photoactivity of the carboxylate versus the dihydroxido complexes at the longer wavelengths. Release of the axial ligands was observed in the studied complexes. This fact is especially relevant in the case of the Pt(IV)-(cRGD)f complex, where the RGD was incorporated as a tumour cell targeting moiety. DFT-TDDFT calculations performed on the complex trans, trans, trans- [Pt(N3)2(OH)(Succ)(pyr)2] showed dissociative transitions at longer wavelength, which could explain the photolability observed in these carboxylate derivatives. Studies of photoactivation of the diazido Pt(IV) complexes in the presence of 5’- GMP indicate the formation of a mono-GMP Pt(II) adduct as main photoproduct, therefore DNA could be considered a potential target site for these anticancer compounds. Additionally, EPR studies showed that azidyl radical release was observed when complexes bearing the succinate and 4-oxo-4-propoxybutanoate ligands were irradiated with green light. No such result was obtained for the dihydroxo precursor showing that these complexes could be phototoxic with longer wavelength light activation. Seven trans-diazido Pt(IV) complexes, trans, trans, trans- [Pt(N3)2(OH)2(L1)(L2)] (where L1 and L2 are pyridine, 2-picoline, 3-picoline, 4- picoline, thiazole or 1-methylimidazole ligands), have been obtained by oxidation of the corresponding trans-[Pt(N3)2(L1)(L2)] precursor. The X-ray crystal structures have been determined for four Pt(IV) diazido complexes from this family of compounds. Photoirradiation studies indicate that the incorporation of a sterically demanding ligand, e.g. trans, trans, trans-[Pt(N3)2(OH)2(2-pic)(pyr)], greatly enhances the photoactivity in these complexes. DFT-TDDFT calculations are in agreement with these results, since higher intensity transitions were observed for such complex at longer wavelength. Phototoxicity studies carried out on A2780, A2780cis and OE19 cell lines with the trans, trans, trans-[Pt(N3)2(OH)2(pyridine)(n-picoline)] family concluded that steric hindrance close to the platinum centre does not favour phototoxicity. Most of the complexes were equally potent in cisplatin resistance against the ovarian cancer cell line (A2780cis), except [Pt(N3)2(OH)2(3-pic)2] and [Pt(N3)2(OH)2(4-pic)2] which exhibited some cross resistance. All of the complexes tested in both OE19 and A2780 cell lines have shown less sensitivity to OE19 than to A2780. Studies in S. pombe yeast strains (WT and ΔRad3) with trans, trans, trans-[Pt(N3)2(OH)2(pyr)2] suggest that DNA is potentially an important target for this type of compounds, although other targets are not excluded. Furthermore, live-cell confocal microscopy was performed on A2780 cells treated with the complex trans, trans, trans-[Pt(N3)2(OH)2(pyr)2] and irradiated with a low dose of blue light. The cell death, monitored by propidium iodide uptake, was captured occurring 2 h 30 min post activation.
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Chantson, Janine. "Platinum (II) complexes of heteroaromatic derivatives." Pretoria : [s.n.], 2002. http://upetd.up.ac.za/thesis/available/etd-08012005-143742/.
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Aliprandi, Alessandro. "Platinum complexes and their luminescent assemblies." Thesis, Strasbourg, 2015. http://www.theses.fr/2015STRAF041/document.
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Cette thèse porte sur la synthèse et la caractérisation photophysique d'une série de composés neutres luminescents de platine (II) contenant un ligand tridentate dianionique chromophore N-donneur et un ligand auxiliaire monodentate. Les composés montrent un changement notable des propriétés de photoluminescence selon l'auto-assemblage en raison de la formation d'interactions intermoléculaires non covalentes faibles telles que metal-metal et π-π. Nous avons démontré comment les complexes de Pt (II) peuvent être auto-assemblés d'une manière contrôlée et précise en jouant sur les facteurs cinétiques et thermodynamiques, ainsi que la morphologie des différents ensembles étudiés. Ces approches ont conduit à des matériaux avec des propriétés améliorées et uniques tels que le mécano-chromisme, ainsi que l'absorption et l'émission de la lumière polarisée. Les composés étudiés et leurs assemblages sont utiles non seulement pour le développement de nouveaux matériaux fonctionnels supramoléculaires en équilibre et hors- équilibre, mais aussi pour des applications en bio-imagerieThis thesis focuses on the synthesis and the photophysical characterization of a series of luminescent neutral Pt(II) compounds containing a tridentate dianionic N-donor chromophoric ligand and a monodentate ancillary moiety. The compounds exhibited notable change of the photoluminescence properties upon self-assembly due to the establishment of weak non-covalent intermolecular interactions – metal-metal and π-π. We demonstrated how Pt(II) complexes can be self-assembled in a controlled and precise manner by playing with kinetic and thermodynamic factors and the morphology of the different assemblies investigated. Such approaches led to materials with enhanced and unique properties such as mechanochromism and polarized light absorption and emission. The investigated compounds and their assemblies were useful for the development of novel functional supramolecular materials in and out of the equilibrium as well as for bioimaging application
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Moulding, R. P. "Bis(diphenylphosphino)methane complexes of platinum." Thesis, University of Oxford, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.375283.
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Farley, Sarah J. "Platinum complexes as potential photochemotherapeutic agents." Thesis, University of Edinburgh, 2010. http://hdl.handle.net/1842/3769.
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A major challenge of platinum anticancer therapy lies in overcoming the severe side-effects associated with treatment. Photoactivatable PtIV azido complexes, which are stable in the dark and reduced to cytotoxic PtII species upon irradiation, have recently emerged as a potential site-specific treatment. This thesis is concerned with the investigation of PtII and PtIV azido complexes as potential cytotoxic and photochemotherapeutic agents. PtII azido complexes such as [Pt(en)(N3)2] were shown to bind to both 5'-guanosine monophosphate (5'-GMP) and glutathione, at a much reduced rate compared with their PtII chlorido analogues. Interestingly, and unexpectedly, these PtII azido complexes showed moderate cytotoxicity towards the A2780 cancer cell line (IC50 21–47 μM). Binding to 5'-GMP was observed to occur more rapidly upon irradiation with UVA light, although the extent of binding was low and the complexes did not demonstrate phototoxicity towards HaCaT keratinocytes. The pendant hydroxyl group of a PtII azido complex was functionalised with a fluorescent probe; conjugation to one axial hydroxyl ligand of a PtIV azido complex was also achieved. The latter conjugate showed a rapid increase in fluorescence intensity upon irradiation, resulting from loss of the axial ligands upon photoreduction. The functionalisation of quantum dots with PtII complexes was also investigated. Water soluble CdSe-ZnS quantum dots were synthesised and derivatised with an amine ligand to which platinum was bound. Conjugation of apo-transferrin to quantum dots was also achieved, with subsequent platinum binding yielding a conjugate with improved aqueous solubility and fluorescence properties. However, the conjugate was inactive towards the A2780 cancer cell line, likely due to surface modifications preventing cellular internalisation. PtII chlorido and azido conjugates with a porphyrin were synthesised and found to show differing behaviour upon irradiation with visible light; evidence of hydrogen peroxide generation from the chlorido complex was much reduced in the case of the azido complex; it is suggested this may result from quenching of reactive oxygen species by the azide anion released upon irradiation. PtII chlorido and azido complexes of highly coloured azo ligands were synthesised in an attempt to shift the wavelength of activation into the visible region. TD-DFT calculations allowed frontier orbital analysis and assignment of the transitions in the absorption spectra. Irradiation of the PtII azido complexes with UVA or broadband visible light led to their decomposition; one water-soluble complex was found to show moderate cytotoxicity and phototoxicity; in addition, its intense blue colour allowed for visual monitoring of this complex inside cells.
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Cave, Gareth W. V. "Cyclometalation : 2,6-diphenylpyridine complexes of platinum." Thesis, University of Warwick, 1999. http://wrap.warwick.ac.uk/58582/.
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This thesis describes the synthesis and characterisation of novel cycloplatinated 2,6- diphenylpyridine complexes and an interesting platinum carbene complex formed by an unusual intermolecular C-H activation. 2,6-Diphenylpyridine, 2,6-bis(4'-alkoxyphenyl)pyridines, 4-(4-octyloxyphenyl)-2,6- diphenylpyridine and 2,4,6-tris-(4-alkoxyphenyl)-[1,3,5]triazine have all been mono- cycloplatinated to from chloride bridged dimers. These dimers have been cleaved with various ligands including trimethylphosphine, dimethylsulfoxide and carbon monoxide. The synthesis and characterisation of the cyclometalated products of 2- phenylpyridine, and subsequent oxidation to a platinum(IV) complex has been described. A novel high yield synthetic route to the di-cycloplatination of C"N"C type ligands involving a C-H activation induced by water has also been reported. The synthesis of di- cycloplatinated 2,6-diphenylpyridine, 2,6-bis( 4'-alkoxyphenyl)pyridines and 4-(4'- octyloxyphenyl)-2,6-diphenylpyridine ligands has been recorded. The lability of the dimethylsulfoxide ligand used in the di-cyclometalation reaction is demonstrated by its substitution with trimethylphosphine, carbon monoxide and the stilbazole ligand. Thermal analyses of all the ligands and cyclometalated products have been recorded. The mesogenic behaviour of four materials has been described and discussed. This report also includes a synthetic route to a platinum carbene dimer formed from a 2,6-bis(2',4'-alkoxyphenyl)pyridine ligand.
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Spankie, S. A. A. "Ylide complexes of palladium and platinum." Thesis, Heriot-Watt University, 1987. http://hdl.handle.net/10399/1018.
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Wainwright, Julie Ann. "Carbonyl substitution in platinum pentamethylcyclopentadienyl complexes." Thesis, University of Salford, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.245018.
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Peck, Lee Anthony. "Fluoro-complexes of iridium and platinum." Thesis, University of Leicester, 1995. http://hdl.handle.net/2381/33852.
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A range of low-valent iridium and platinum fluoro-complexes have been prepared and characterized by a combination of mass spectrometry, 19F 31P{1H}, 195Pt{1H} and infrared spectroscopies and EXAFS where possible. [Dichlorobis(amine)platinum(II)] complexes of the type [PtCl2(L)2] (L = NMe3, NH3, py; L2 = en, bipy) have been reacted with [XeF2], undergoing oxidative fluorination, to afford various isomers of platinum(IV) amine-fluoride species. The presence of anhydrous hydrofluoric acid (AHF) was observed to influence the nature of the products formed whilst the cis- or trans- stereochemistry of the starting materials was found to determine the number of isomers formed. The first unambiguously characterized difluorobis(phosphine)-platinum(II) complex, cis-[PtF2(PEt3)2] was formed from the reaction of cis-[PtMe2(PEt3)2] and AHF with the elimination of methane gas being the driving force for the reaction. The difluoro-complex, is stable only in AHF or under vacuum, it was characterized by low-temperature 195Pt{1H} NMR spectroscopy. Analogues of Vaska's complex of the type, trans-[IrCl(CO)(PR3)2] (PR3 = PPh3, Pcy3) have been shown to undergo oxidative fluorination reactions with [XeF2] resulting in the formation of cis-, trans-[IrF2Cl(CO)(PR3)2]. Furthermore, the reaction between fluoro-Vaska's trans- [IrF(CO)(PPh3)2] and [XeF2] has been found to afford the novel trifluoro-complex mer-,trans-[IrF3(CO)(PPh3)2]. A series of complexes of the type mer-, [IrF3(CO)(L)2] (L = tertiary phosphine, amine or arsine) have been prepared from the reaction of fac-[IrF3(CO)3] and the appropriate Lewis base. The amine and arsine derivatives represent the first examples of fluoroiridium(III) amine or arsine complexes. X-ray crystal structure determinations for the complexes trans- [PtCl2(NMe3)2], [Pt(C6H4PPh2)(PPh3)2][SbF6], trans-[Ir(C6F5)(CO){PPh2(C6F5)2}2] and [HNEt3][PtCl3(NEt3)] are described.
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Roberts, Yvonne V. "Macrocyclic complexes of platinum group metals." Thesis, University of Edinburgh, 1991. http://hdl.handle.net/1842/11897.
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A series of half-sandwich complexes, [M([9]aneS3)*XY]n+ have been synthesised from MCl2 [M = Pd, Pt,X = Y = Cl-(n = 0), PPh30.5dppm, 0.5dppe,0.5x2, 2'-bipy(n = 2), X = Cl-, Y = PPh3(n&61 1); M = Pd, X = Y = 0.5oxytriphos, 0.5x1, 10-phen(n = 2), X = Cl-, Y = PCy3(n = 1)]. All but one of the crystal structures [M = Pd, X = Y = Cl-, PPh3, 0.5dppm, 0.5oxytriphos, 0.5x2,2'-bipy, 0.5x1,10-phen, X = Cl-, Y&61 PPh3; M = Pt, X = Y&61 PPh3, 0.5dppm] solved show the metal in a square-planar, S2XY co-ordination set, with a long-range apical interaction to the remaining S-atom of [9]aneS3; [Pt([9]aneS3)(PPh3)2]2+ is trigonal bipyramidal. The reductive electrochemistry of the Pd complexes shows the stabilisation of Pd(I) species by bidentate, π-acceptor X,Y ligands. A series of complexes [Ru([9]aneS_3)XYZ]^+ (X-Cl^-, Y = CO or PCy_3, Z&61 H or MeCN; X = H, Y = Z = 0.5x1,5-COD) and [Ru([n]aneS_4)*XY]^m+ (X = Cl^-, Y = PPh_3, n = 12,14,16, m&61 1; X = McCN, Y = PPh_3, n = 12,14, m&61 2; X = Y = McCN, n = 16, m = 2) have also been prepared. The crystral structures of [Ru([9]aneS_3)XYZ]^+ (X = Cl^-, Y = CO, Z&61 McCN; X = H, Y = Z = 0.5x1,5-COD) show the metal to be octahedrally co-ordinated. Such is also the case for [Ru([n]aneS_4)XY]^m+ (n = 14,16, X = Cl^-, Y&61 PPh_3; n = 16, X = Y = MeCN), with the non-macrocyclic ligands mutually cis. A study by nmr spectroscopy of the mechanism of formation of [Ru([9]aneS_3)Cl(PPh_3)(C_4H_3O)H^+ ]^- from [Ru([9]aneS_3)Cl_2(PPh_3)] and Et_2O/THF was undertaken. The former complex, and the dimeric intermediates [Ru([9]aneS_3)(PPh_3)Cl]_2^2+ and [Ru([9]aneS_3(PPh_3)(μ2-Cl)Tl(μ3-Cl)]_2^2+ were characterised by X-ray crystallography. Finally, the novel agostic species [Pd(H[9]aneN_3)Cl_2]_2(PF_6)_2.2([Pd(H[9]aneN_3)Cl_2]_2) is described. The X-ray structure of the dimer shows an unsupported Pd-Pd bond with mutally cis-Cl^- ligands. Only one of the two metal ions in the dimer forms an agostic M-H-N bond. The metal in each of the monomers also forms on M-H-N agostic bond. *[9]aneS_3 = 1,4,7-trithiacyclononane, [14]aneS_4 = 1,4,8,11-tetrathiacyclotetradecane [12]aneS_4 = 1,4,7,10-tetrathiacyclododecane, [16]aneS_4 = 1,5,9,13-tetrathiacyclohexadecane.
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Crofts, Rhona D. "Platinum metal complexes of macrocyclic ligands." Thesis, University of Edinburgh, 1995. http://hdl.handle.net/1842/13493.
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Bouché, Mathilde. "Carbene-platinum conjugated : novel anticancer complexes." Thesis, Strasbourg, 2017. http://www.theses.fr/2017STRAE013.
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Bien que les agents anticancéreux à base de platine soient bien établis en clinique, plusieurs paramètres restent à optimiser, notamment leur toxicité et les phénomènes de résistances. La combinaison platine-carbènes N-hétérocycliques (NHCs) a montré des résultats prometteurs dans la lutte antitumorale. Ainsi, afin de développer des agents anticancéreux innovants, ce travail résume les modifications structurales étudiées dans le but d’augmenter la cytotoxicité tout en réduisant les effets secondaires des complexes. Une stratégie développée ici porte sur l’introduction de pnictogènes par échange de ligand pour observer un effet synergétique. Autrement, les efforts se sont concentrés sur les complexes de NHC-platine(IV) de leur synthèse à l’étude de leur stabilité, activité anticancéreuse et mécanisme d’action. Finalement, la combinaison des NHC-Pt à des nanotransporteurs a été étudiée afin d’améliorer leur biocompatibilité et sélectivitéAlthough platinum-based anticancer drugs are well established, several shortcomings have raised concerns, namely their toxicity and resistance mechanisms. Therefore, improved anticancer drugs are strongly awaited to substitute drugs currently used in clinics. Remarkably, the combination of N-Heterocyclic Carbenes (NHCs) to platinum has recently demonstrated very promising results as anticancer agents. In the aim to access novel drugs, this work emphasizes several structural modifications to improve the cytotoxicity and lower side effects. One strategy developed herein focus on the introduction of pnictogens by ligand exchange to access a synergistic effect. Otherwise, efforts mainly focused on NHC-platinum(IV) complexes from their synthesis to stability investigation and anticancer activities and mechanism of action. Finally, the combination of NHC-Pt drugs to nanodelivery devices has been investigated in order to improve both their biocompatibility and selectivity toward cancer cells
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Clarke, Matthew Lee. "Asymmetric catalysis using novel platinum complexes." Thesis, University of Bath, 1999. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.299846.
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Grady, Thomas James. "Platinum(II) Complexes for Biological Applications." Thesis, Curtin University, 2021. http://hdl.handle.net/20.500.11937/82825.
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In this study the synthesis, photophysical properties, and potential biological applications of a range of platinum(II) complexes were investigated. A family of platinum(II) complexes bearing cyclometallated NHC ligands alongside were developed and found to have favourable photophysical properties. Two palladium analogues of platinum(II) complexes were reported and investigated for antimicrobial activity. Finally, the synthesis of a terdentate C^C^N coordinated platinum(II) complexes was investigated, and a number of significant challenges identified.
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Davis, John Christopher. "A Speciation study of the chloro-hydroxo complexes of Pt(II)." Thesis, Nelson Mandela Metropolitan University, 2009. http://hdl.handle.net/10948/1213.
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In this study a method was developed to identify and quantify platinum(II) complexes of the type [PtCl4-n(OH)n]2- and [PtCl4-n(H2O)n]2-n. Separation of the various species was achieved with the aid of a hyphenated reversed phase HPLC-ICP-MS technique coupled with an ion-pairing reagent, HMHDCl2. The adsorption of HMHD2+ onto a C-18 column was investigated by generating a series of breakthrough curves. It was found that the selectivity for high charge density anions originates from its low surface coverage relative to TBA+, which on the other hand could not separate Pt(II) complexes. The peaks in the chromatographic traces were assigned by following the stepwise ligand substitution of [PtCl4]2- in hydroxide medium with UV/Vis spectrophotometry and HPLC-ICP-MS simultaneously. A computer program was written by the author to analyse chromatographic data by deconvoluting the chromatogram into its individual components and calculating the mole fraction of each component. The validity of the consecutive pseudo-first order model was validated by constructing 3D Mauser diagrams with the raw spectrophotometric data (A1 vs A2 vs A3). Additional software was used to simulate the raw spectrophotometric data and processed chromatographic data. The pseudo-first order rate constants obtained in both cases were in agreement with each other. Hence, peaks were assigned to [PtCl4]2-, [PtCl3(OH)]2-, [PtCl2(OH)2]2-, [PtCl3(H2O)]-. The molar extinction coefficient spectra of [PtCl3(OH)]2- and [PtCl2(OH)2]2- were obtained by simulating the spectrophotometric data at wavelengths from 280 to 450 nm. The reaction of [PtCl4]2- with sodium hydroxide was investigated with UV/Vis spectrophotometry at 25 °C. A rate constant consisting of a first and second order term was obtained. The first order term agreed with what has been reported in the literature for aquation of [PtCl4]2- at 25 degrees C. The influence of temperature was established by conducting the experiment at different temperatures. It was found that the reaction proceeds essentially via aquation at elevated temperatures.
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Willis, Richard Ronald. "Synthesis and reactivity of heterobinuclear complexes of ruthenium-platinum and iron-platinum /." The Ohio State University, 1992. http://rave.ohiolink.edu/etdc/view?acc_num=osu1487841548268408.
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Henderson, Steven G. D. "Spectroscopic studies of platinum halo-phosphine complexes." Thesis, University of Edinburgh, 1986. http://hdl.handle.net/1842/28226.
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Fogelström, Ewelina Rebecka [Verfasser]. "Subcellular distribution of platinum complexes / Ewelina Fogelström." Berlin : Freie Universität Berlin, 2013. http://d-nb.info/1033306746/34.
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Chan, Yew Boon Colin. "Synthesis and reactivity of platinum alkynyl complexes." Thesis, Imperial College London, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.395761.
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Dewa, Shaliza Zaini. "Novel 3,3-dialkyldiaziridine platinum and palladium complexes." Thesis, University of Sussex, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.296548.
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Fotheringham, John David. "Heterobimetallic complexes of the platinum group metals." Thesis, University of Edinburgh, 1987. http://hdl.handle.net/1842/10906.
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Muller, Philippe. "Photoactivatable platinum complexes as potential therapeutic agents." Thesis, University of Edinburgh, 2002. http://hdl.handle.net/1842/12698.
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Non-toxic and stable photoactivatable platinum compounds, which can be activated by visible light to toxic anticancer drugs, could strongly reduce the side-effects shown by cisplatin by providing site-specific cancer treatment. In this thesis, the synthesis and characterisation of novel photoactive Pt amine compounds, which can be converted into reactive Pt species by visible light irradiation, are presented and their potential as photoactivatable prodrugs investigated.
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Chan, Danny. "The chemistry of platinum complexes and hydrosilation." Thesis, University of York, 1999. http://etheses.whiterose.ac.uk/14173/.
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This thesis describes the study of a series of platinum complexes, with particular emphasis towards hydrosilation. Platinum bis(phosphine) azodicarbonyl complexes Pt(PRI 3)2(R20CNNCOR2) (RI = Ph, Me; R2 = Ph, Me, OEt, Pri) were synthesised and studied. Multinuclear NMR spectroscopy on Pt(PRI3)2(R20CNNCOR2) revealed that the dicarbonyl substituted azo ligand is co-ordinated asymmetrically, consistent with a five membered, Pt-N-N-C-O ring. The crystal structure of Pt(PPh3)2(Pri02CNNC02Pri) shows that the co-ordination sphere of platinum is essentially square planar and co-planar with the five-membered, Pt(1)-0(1)-C(5)-N(2)-N(1) ring. The Pt(PRI 3)lR20CNNCOR2) complexes show sensitivity towards chlorinated solvents (CH2CI2, CHCI3) under photolysis conditions forming the corresponding platinum bis(phosphine) dichloride complexes; the same products are formed in a slower thermal reaction but only for complexes with azodicarboxylate ligands. Complexes with azodicarboxylate ligands also react photochemically with ethylene in ds-THF yielding Pt(PPh3)2(C2H4) but the azodiacyl analogues are inert in this respect. Azodicarboxylate compounds R02CNNC02R (R = Et, Pri, But) are inhibitors of the catalytic activity of [(Pt {174 _(CH2=CHSiMe2hO }h {.u-( CH2=CHSiMe2)20}] for the hydrosilation reaction. The inhibited species can be decomposed thermally or photoch~mically to give active hydrosilation catalysts. It was found that the bulky azo compound But02CNNC02But was the least effective inhibitor of [(Pt{ 174 - '(CH2=CHSiMe2hO} )2(P-( CH2=CHSiMe2)20)]. The photochemistry of platinum bis(phosphine) malonates and phthalates was found to be limited, and their reactivities were much lower compared to the analogous oxalate complexes. Silyl hydride complexes, cis-Pt(PCY3)2(H)(SiR3), were synthesised from the reaction of Pt(PCY3)2 and the corresponding silane. These complexes were undergo dynamic exchange in solution. Two exchange processes were identified; the first involves mutual phosphine exchange, i.e. positional interchange between the hydride and the silyl ligands. The second process occurs at higher temperatures (above 290 K) and involves the elimination and re-addition of the silane ligand HSiR3. Thermodynamic and activation parameters are obtained for cis-Pt(PCY3)2(SiR3) (R = Ph, SiR3 = SiMe2CH2CH=CH2, SiMe2Et). The reaction of Pt(PCY3)2 with the disilane HSiMe2(l,2-C6~)SiMe2H is thought to form a Pt(IV) bis(silyl) dihydride trigonal bipyramidal species of the form, Pt(PCY3)(H)2[SiMe2(1,2-C6~)SiMe2]' where the hydride ligands are in the axial positions. All of the platinum silyl hydride complexes studied degrade thermally to form trans-Pt(PCY3)2(H)2 at, or above, room temperature.
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Williams, R. Lee. "Ruthenium-Platinum Polypyridyl Complexes: Synthesis and Characterization." Thesis, Virginia Tech, 2001. http://hdl.handle.net/10919/44315.
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A series of bimetallic (RuII, PtII) complexes were synthesized with the general formula [(tpy)RuCl(BL)PtCl2](PF6) (tpy = 2,2':6',2"-terpyridine and BL = bridging ligand) and their spectroscopic, electrochemical, and DNA binding properties studied. The bridging ligands used in these complexes were 2,3-bis(2'-pyridyl)pyrazine (dpp), 2,3-bis(2'-pyridyl)quinoxaline (dpq) and 2,3-bis(2'-pyridyl)benzoquinoxaline (dpb). These complexes combine light-absorbing RuII-polypyridyl chromophores and a cis-PtCl2 structural motif known to bind DNA. The Ru-bound chloride may be substituted, enabling further modification of the spectroscopic properties. The synthesis of [(tpy)RuCl(BL)PtCl2](PF6) utilizes a building block approach that allows modifications to the series of complexes within the general synthetic scheme. This illustrates the applicability of this scheme to the development of new series of complexes.
The lowest-energy absorption for the three complexes is assigned to a Ru(dp)-to-BL(p*) charge transfer transition. This transition shifts to lower energy as the ligand is varied from dpp to dpq to dpb. The first and second reductions are BL(0/-) and BL(-/2-) based and shift to more positive potentials from dpp to dpq to dpb. The Ru(II/III) redox couple remains at a nearly constant potential for the series. All three compounds show DNA binding when incubated with linearized plasmid DNA. Adduct formation was assessed by agarose gel electrophoresis as a retardation of band migration.
when incubated with linearized plasmid DNA. Adduct formation was assessed by agarose gel electrophoresis as a retardation of band migration.Master of Science
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Miyoshi, Emi. "Platinum(II) complexes : studied by diffusion NMR." Thesis, View thesis, 2008. http://handle.uws.edu.au:8081/1959.7/33587.
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Six novel platinum(II) intercalators of the form [Pt(AL)(IL)]Cl2, where AL = ethylenediamine (en), 1R,2R-diaminocyclohexane (R,R-dach), or 1S,2S-diaminocyclohexane (S,S-dach) and IL = 4,7-dihydroxy-1,10-phenanthroline (4,7-dhp) or 4,7-dicarboxy-1,10-phenanthroline (4,7-dcp), were synthesised. All complexes were prepared by the addition of the intercalating ligand followed by the addition of the diamine ancillary ligand. The complexes with 4,7-dhp were soluble in DMSO and were characterised by 1H, 13C, and 195Pt NMR, elemental analysis, UV-vis, ESI-MS, and CD. The complexes with 4,7-dcp were only soluble in a highly acidic solution and, therefore, were characterised only by 1H NMR and elemental analysis. The cytotoxicity of the 4,7-dhp complexes was tested in the L1210 murine leukaemia cell line. [Pt(S,S-dach)(4,7-dhp)]Cl2 showed an IC50 value of > 80 μM. The antitumour and antibacterial activities of all six complexes were tested in vitro using the Kirby-Bauer disc diffusion method with Staphylococcus aureus and Agrobacterium tumefaciens. The 4,7-dhp complexes showed no activity to these bacteria strains. The activities of the 4,7-dcp complexes were not able to be tested due to their solubility only in acidic solutions, which itself inhibits cell growth. The diffusion coefficients of the Pt(II) intercalators of the form [Pt(AL)(IL)]Cl2, where AL = en, R,R-dach, or S,S-dach and IL = phen, 4-mp, 4,7-dmp, 4,7-dhp, 4,7-dcp or 3,4,7,8-tmp and various starting materials used during the synthesis of these complexes were measured using pulsed gradient spin-echo (PGSE) NMR. The diffusion coefficients of both 4,7-dcp and [Pt(4,7-dcp)Cl2] were observed to be lower than other compounds with similar molecular weights indicating dimerisation of the compounds. The binding studies of the systems, [Pt(en)(phen)]Cl2 to (i) BSA, (ii) delipidated BSA, and (iii) d(GTCGAC)2 were studied using a simple two-site binding model with diffusion NMR. The binding of [Pt(en)(phen)]Cl2 – BSA was well described by the model giving the values Kd = 0.0021 ± 0.0002 M and n = 5.85 ± 0.31. On the contrary, the binding of [Pt(en)(phen)]Cl2 – delipidated BSA showed a poor fit to the model. From the poor fit of the data, it was speculated that the transverse relaxation of BSA largely affected the system. The binding of [Pt(en)(phen)]Cl2 – d(GTCGAC)2 showed results where the diffusion coefficient decreases as the concentration of the drug increases but an opposite effect was observed from the point where the drug reached equimolar concentrations to d(GTCGAC)2. It was speculated that the drug undergoes allosteric binding to the biomolecule or that a conformational change occurred as the drug concentration increases in the system. A further study of [Pt(en)(phen)]Cl2 and K2PtCl4 using 195Pt diffusion NMR was conducted giving a diffusion coefficient of 3.08 ± 0.04 × 10-10 m2 s-1 for K2PtCl4. The diffusion coefficient of [Pt(en)(phen)]Cl2, however, were unobtainable due to the short transverse relaxation of the Pt complex.
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Miyoshi, Emi. "Platinum(II) complexes studied by diffusion NMR /." View thesis, 2008. http://handle.uws.edu.au:8081/1959.7/33587.
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Thesis (M.Sc.) (Hons)--University of Western Sydney, 2008.A thesis presented to the University of Western Sydney, College of Health and Science, School of Biomedical and Health Sciences, in fulfilment of the requirements for the degree of Master of Science (Honours). Includes bibliographies.
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Al-Resayes, S. I. "Phospha-alkyne complexes of the platinum metals." Thesis, University of Sussex, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.372068.
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Patel, M. K. "Some complexes of platinum and related metals." Thesis, University of Sussex, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.373898.
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Look, Jennifer L. "Mechanistic studies of reactions between molecular oxygen and platinum alkyl and platinum hydrocarbyl hydride complexes /." Thesis, Connect to this title online; UW restricted, 2004. http://hdl.handle.net/1773/11599.
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Butikofer, Jeffrey L. "Synthesis, structure and characterization of dfmp platinum complexes." Laramie, Wyo. : University of Wyoming, 2005. http://proquest.umi.com/pqdweb?did=994234981&sid=1&Fmt=2&clientId=18949&RQT=309&VName=PQD.
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羅政藩 and Chang-fan Lo. "Substitution and redox reactions of some binuclear platinum (II) and platinum (III) complexes." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1989. http://hub.hku.hk/bib/B31231901.
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Lo, Chang-fan. "Substitution and redox reactions of some binuclear platinum (II) and platinum (III) complexes /." [Hong Kong : University of Hong Kong], 1989. http://sunzi.lib.hku.hk/hkuto/record.jsp?B12505304.
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BLUM, THIERRY. "Synthese et reactivite de complexes heterometalliques a ligand (s) phosphure (s)." Université Louis Pasteur (Strasbourg) (1971-2008), 1989. http://www.theses.fr/1989STR13078.
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Louw, Marissa. "New platinum and palladium complexes: their anticancer application." Thesis, Nelson Mandela Metropolitan University, 2010. http://hdl.handle.net/10948/d1016218.
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Novel non-leaving groups were employed in this dissertation to synthesize platinum complexes which can assist in the understanding or improvement of anticancer action. Emphasis was placed on (NS)-chelate and (NN)-chelate platinum complexes. Bidentate (NS)-donor ligands were used as non-leaving ligands in the synthesis of platinum(II) complexes with iodo, chloro, bromo and oxalato groups as leaving groups. These complexes were synthesized and studied since many questions regarding the interaction of sulfur-donors and platinum still exist. These relate to thermodynamic and kinetic factors and their influence on anticancer action. In this dissertation the properties of novel platinum(II) complexes of a bidentate ligand having an aromatic nitrogen-donor atom in combination with a thioethereal sulfur atom capable of forming a five-membered ring with platinum(II) were studied. The general structure of the (NS)-ligands used was 2-((alkylthio)methyl)pyridine. Alkyl groups used were methyl, ethyl, propyl, benzyl and phenyl. Amine complexes of platinum have been studied extensively in the past. However, attention was given to novel aspects of substituted pyridine and imidazole ligands and their corresponding complexes. Amongst these are 2-(2-methylaminoethyl)pyridine, 1-methyl-2-methylaminoethylimidazole and 1-methyl-2-methylaminobenzylimidazole. The leaving groups included chloro, bromo and oxalato. Mononitroplatinum(IV) complexes were prepared using novel synthetic methods. Selected platinum(II) amine complexes were used as starting materials for this synthesis. Some of these compounds exhibit promising anticancer behaviour. (Trans-(R,R)-1,2-diaminocyclohexane)(oxalato)(mononitrochloro)platinum(IV) is a particularly good anticancer agent and has been patented internationally. All these complexes were characterized using mass spectrometry, chromatography, thermogravimetric analysis, kinetic aspects such as ligand exchange rates and finally their anticancer action against three different cancer cell lines was evaluated via cytotoxicity assays. Some of the compounds exhibited particularly good anticancer potential.
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Irwin, Michael J. "Oligomeric and polymeric complexes of gold and platinum." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1997. http://www.collectionscanada.ca/obj/s4/f2/dsk3/ftp04/nq21292.pdf.
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Harding, Nigel Anthony. "β-thia-alkyl complexes of platinum group metals." Thesis, Imperial College London, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.283721.
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尹錦濤 and Kam-to Wan. "Syntheses and photochemistry of monomeric platinum (II) complexes." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1990. http://hub.hku.hk/bib/B31209476.
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Broadwood-Strong, Gillian. "Novel phosphine complexes of platinum and palladium (0)." Thesis, University of Sussex, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.385600.
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Riley, R. T. "Platinum complexes and their relevance to cancer treament." Thesis, Imperial College London, 1985. http://hdl.handle.net/10044/1/37836.
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Bryant, Mathew James. "Platinum pincer complexes : in pursuit of switchable materials." Thesis, University of Bath, 2016. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.678854.
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The research presented within this thesis is concerned with the design, synthesis, characterisation, and analysis of a series of new compounds of platinum (II), with aims to produce compounds possessing switchable optical properties, and with potential applications as "smart-materials" for use as highly selective sensors.
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Scarpantonio, Luca. "Studies of DNA binding of lanthanide platinum complexes." Thesis, University of Birmingham, 2011. http://etheses.bham.ac.uk//id/eprint/2860/.
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Using supramolecular principles, we have been designing luminescent lanthanide complexes with a defined hairpin bis-interlacator in order to obtain luminescent probes able to recognise DNA. The complexes are comprised of Platinum(II) terpyridine, which acts as a DNA recognition site and is brought together with a "remote" luminescent lanthanide unit. All the synthetic approaches were based on the accessibility of the lanthanide-platinum complexes by the self-assembly of different components in a one pot reaction. Thus, we have been able to isolate a water soluble heterometallic complex based on thiophenal linkage named [LnPt\(_2\)]Cl\(_2\). The complex has a relatively weak lanthanide luminescence, which increases upon addition of DNA. Photophysical and DNA binding properties of the lanthanide-platinum complex were investigated by UV-vis absorption, luminescent studies and circular and linear dichroism. Oligonucleotides of twelve bases were also used to investigate the intercalation [LnPt\(_2\)]Cl\(_2\) and the mono-intercalator AATP used as control compound. Using bidimensional NMR techniques, we investigated the binding site for [LnPt\(_2\)]Cl\(_2\) and AATP upon interaction with Dickerson-Drew sequence. The sulphur lanthanide-platinum linkage in [LnPt\(_2\)]Cl\(_2\) was replaced with an acetylide one in order to introduce new photophysical features. Thus the self-assembly procedures based on DTPA-bis(amido-acetylide) and a platinum(II) terpyridine led us to isolate a new lanthanide-platinum complex named [LnC\(\equiv\)CPt\(_2\)] (CH\(_3\)SO\(_3\))\(_2\). The photophysical properties and the DNA binding properties toward interaction with CT-DNA were investigated. The complex named LnC\(\equiv\)CPt\(_2\)](CH\(_3\)S)\(_3\))\(_2\) exhibited a relatively strong lanthanide luminescence that increased upon addition of DNA. The bi-functional metal complex [EuLPt](PF\(_6\)) (where Pt=platinum-2,2':6'2"-terpyridine and L=assymmetric DTPA bisamide ligand with a thiopheno pendant arm and a quinoline moiety) was synthesised and the interaction of [EuLPt](PF\(_6\)) with CT-DNA was examined by luminescence spectroscopy, linear and circular dichroism studies and thermal denaturation studies. The [EuLPt](PF\(_6\)) retained the ability to increase its luminescence upon the addition of CT-DNA. The binding properties of the complexes were tested toward interaction with plasmid DNA by gel electrophoresis and properties such as the unwinding angle were measured. The bis-intercalators [LnPt\(_2\)]Cl\(_2\) and [LnC\(\equiv\)CPt\(_2\)](CH\(_3\)SO\(_3\))\(_2\) showed the ability to uncoil DNA almost as well as cisplatin and at low concentrations, while almost double the amount of mono-intercalators, such as [EuLPt](PF\(_6\)) is required to observe the same uncoiling effect.
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Phillips, Hazel I. A. "Reaction of photoactive platinum anticancer complexes with biomolecules." Thesis, University of Warwick, 2011. http://wrap.warwick.ac.uk/49155/.
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Photoactive platinum compounds have the potential to reduce some of the debilitating side-effects associated with conventional chemotherapeutics, such as cisplatin. Stable platinum(IV) complexes which are reduced to active platinum(II) species only on irradiation, could provide a site-specific treatment. The photodegradation pathways of the photoactive platinum(IV) diazido complex cis,trans,cis-[Pt(N3)2(OH)2(NH3)2] have been extensively studied. Various photoisomerisation, trans-labilisation and photoreduction pathways were observed, with several unexpected photoproducts including ammonia, oxygen and free azide. The photoreactions of cis,trans,cis-[Pt(N3)2(OH)2(NH3)2] in the presence of two amino acid derivatives, N-acetyl-L-histidine and N-acetyl-L-methionine, and the nitrogen-heterocycle 1-methylimidazole, have also been investigated. In the presence of 1-methylimidazole, surprisingly the major photoproduct was the tetra-substituted PtII complex [PtII(1-MeIm-N3)4]2+, even at a Pt/1-MeIm molar ratio of 1:1. Reactions with the amino acid derivatives identified some unusual di- and tri-substituted platinum(II) photoproducts. This work has involved using a variety of techniques including multinuclear NMR spectroscopy, DFT/TD-DFT calculations and electrospray ionisation-mass spectrometry (ESI-MS). The reaction of cisplatin (cis-[PtCl2(NH3)2]) with the protein ubiquitin was investigated using ion mobility-mass spectrometry (IM-MS), revealing multiple induced protein conformations upon platination. The preferred binding site of cisplatin on the amino acid Met1 was also directly identified for the first time. The primary platination site of cis,trans,cis-[Pt(N3)2(OH)2(NH3)2] and trans,trans,trans-[Pt(N3)2(OH)2(NH3)2] on ubiquitin was also investigated, and found to be Met1. The ESI-MS studies highlight the rapid generation and diverse nature of the photoinduced reactive platinum(II) species after short UVA irradiation times. Insights into the reaction of cis,trans,cis-[Pt(N3)2(OH)2(NH3)2] with cytochrome c are also reported. The antiviral properties of cisplatin (cis-[PtCl2(NH3)2] and the photoinduced activity of cis,trans,cis-[Pt(N3)2(OH)2(NH3)2] and trans,trans,trans-[Pt(N3)2(OH)-2(NH3)2] were assessed against the bacterial virus bacteriophage P1. This work has highlighted the complex and novel speciation of such platinum(IV) complexes upon irradiation, which may lead to new cytotoxic mechanisms in cancer cells.
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Bell, Michael Niall. "Organometallic platinum group metal complexes incorporating macrocyclic ligands." Thesis, University of Edinburgh, 1987. http://hdl.handle.net/1842/13895.
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Marr, Alastair McAlpine. "Studies on difluorophosphine complexes of the platinum metals." Thesis, University of Edinburgh, 1988. http://hdl.handle.net/1842/15270.
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Grove, Levi James. "Synthesis and Characterization of Vapochromic Platinum(II) Complexes." University of Cincinnati / OhioLINK, 2007. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1196030530.
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