Synthesis, characterization and antiparasitic evaluation of chalcone hybrids
- Authors: Zulu, Ayanda Ignatia
- Date: 2021-10-29
- Subjects: Uncatalogued
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/192853 , vital:45271
- Description: Thesis (PhD) -- Faculty of Science, Chemistry, 2021
- Full Text:
- Date Issued: 2021-10-29
- Authors: Zulu, Ayanda Ignatia
- Date: 2021-10-29
- Subjects: Uncatalogued
- Language: English
- Type: Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/192853 , vital:45271
- Description: Thesis (PhD) -- Faculty of Science, Chemistry, 2021
- Full Text:
- Date Issued: 2021-10-29
Synthesis and evaluation of arylpyrrole-chalcone hybrids as antiplasmodial and antitrypanosomal agents
- Authors: Zulu, Ayanda Ignatia
- Date: 2017
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/65268 , vital:28716
- Description: Expected release date-May 2019
- Full Text:
- Date Issued: 2017
- Authors: Zulu, Ayanda Ignatia
- Date: 2017
- Language: English
- Type: text , Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/65268 , vital:28716
- Description: Expected release date-May 2019
- Full Text:
- Date Issued: 2017
Phototransformation of pollutants using lutetium and zinc phthalocyanines anchored on electrospun polymer fibers
- Authors: Zugle, Ruphino
- Date: 2013
- Subjects: Electrospinning Phthalocyanines Lutetium Zinc Polymers Dysprosium Pollutants Air Pollution Photochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4286 , http://hdl.handle.net/10962/d1002962
- Description: Novel lanthanide phthalocyanines containing dysprosium, erbium and lutetium as central metals were synthesized using phthalonitrile:metal salt ratio of 4:1 or lower phthalonitrile content as well as using unmetallated phthalocyanine. They were characterized using various spectroscopic and elemental analyses. Dysprosium bis-phthalocyanine was obtained while monomers were obtained for erbium and lutetium phthalocyanines. Theopen-shelldysprosiumbis-phthalocyanine and the monomeric complex of the open-shell erbium were neither fluorescent nor showed the ability to generate singlet oxygen. The triplet states of all the lutetium phthalocyanines were found to be populated with high triplet quantum yields and corresponding high singlet oxygen quantum yields. The fluorescence quantum yields of the lutetium phthalocyanines were however found to be very low. The lutetium phthalocyanines together with unsubstituted zinc phthalocyanine and its derivatives were successfully incorporated into electrospun polymer fibers either by covalent linkage or sorption forces. Spectral characteristics of the functionalized electrospun polymer fibers indicated that the phthalocyanines were bound and their integrity maintained within the fiber matrices. Most importantly the fluorescence and photoactivity of the phthalocyanines were equally maintained within the electrospun fibers. The functionalized electrospun polymer fibers especially those containing the zinc phthalocyanines could qualitatively detect nitrogen dioxide, a known environmental air pollutant. Also all the functionalized electrospun polystyrene and polysulfone fibers containing lutetium and zinc phthalocyanines could be applied for the photoconversion of 4-chlorophenol, 4-nitrophenol and methyl orange. Those of polystyrene could be re-used. Polyacrylic acid and polyurethane functionalized electrospun fibers were found not to be suitable for photocatalytic applications in aqueous medium. 4-Chlorophenol was found to be more susceptible to photodegradation while methyl orange very difficult to degrade.
- Full Text:
- Date Issued: 2013
- Authors: Zugle, Ruphino
- Date: 2013
- Subjects: Electrospinning Phthalocyanines Lutetium Zinc Polymers Dysprosium Pollutants Air Pollution Photochemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4286 , http://hdl.handle.net/10962/d1002962
- Description: Novel lanthanide phthalocyanines containing dysprosium, erbium and lutetium as central metals were synthesized using phthalonitrile:metal salt ratio of 4:1 or lower phthalonitrile content as well as using unmetallated phthalocyanine. They were characterized using various spectroscopic and elemental analyses. Dysprosium bis-phthalocyanine was obtained while monomers were obtained for erbium and lutetium phthalocyanines. Theopen-shelldysprosiumbis-phthalocyanine and the monomeric complex of the open-shell erbium were neither fluorescent nor showed the ability to generate singlet oxygen. The triplet states of all the lutetium phthalocyanines were found to be populated with high triplet quantum yields and corresponding high singlet oxygen quantum yields. The fluorescence quantum yields of the lutetium phthalocyanines were however found to be very low. The lutetium phthalocyanines together with unsubstituted zinc phthalocyanine and its derivatives were successfully incorporated into electrospun polymer fibers either by covalent linkage or sorption forces. Spectral characteristics of the functionalized electrospun polymer fibers indicated that the phthalocyanines were bound and their integrity maintained within the fiber matrices. Most importantly the fluorescence and photoactivity of the phthalocyanines were equally maintained within the electrospun fibers. The functionalized electrospun polymer fibers especially those containing the zinc phthalocyanines could qualitatively detect nitrogen dioxide, a known environmental air pollutant. Also all the functionalized electrospun polystyrene and polysulfone fibers containing lutetium and zinc phthalocyanines could be applied for the photoconversion of 4-chlorophenol, 4-nitrophenol and methyl orange. Those of polystyrene could be re-used. Polyacrylic acid and polyurethane functionalized electrospun fibers were found not to be suitable for photocatalytic applications in aqueous medium. 4-Chlorophenol was found to be more susceptible to photodegradation while methyl orange very difficult to degrade.
- Full Text:
- Date Issued: 2013
Synthetic and bioactivity studies of antiplasmodial and antibacterial marine natural products
- Authors: Young, Ryan Mark
- Date: 2012
- Subjects: Antibacterial agents Marine natural products Marine pharmacology Plasmodium falciparum Staphylococcus aureus Isocyanides Imidazoles
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4378 , http://hdl.handle.net/10962/d1005043
- Description: This thesis is divided into two parts, assessing marine and synthetic compounds active firstly against Plasmodium falciparum (Chapter 3 and 4) and secondly active against methicillin resistant Staphylococcus aureus (MRSA, Chapter 5). In Chapter 3 the synthesis of nine new tricyclic podocarpanes (3.203-3.207 and 3.209-3.212) from the diterpene (+)-manool is described. Initial SAR study of synthetic podocarpanes concluded that the most active compound was a C-13 phenyl substituted podocarpane (3.204, IC₅₀ 6.6 μM). By preparing analogues with varying halogenated substituents on the phenyl ring (3.209-3.212) the antiplasmodial activity was improved (IC₅₀ 1.4 μM), while simultaneously decreasing the haemolysis previously reported for this class of compounds. Inspired by the antiplasmodial activity of Wright and Wattanapiromsakul’s tricycle marine isonitriles (2.16-2.21 and 2.24-2.27) an unsuccessfully attempt was made to convert tertiary alcohol moieties to isonitrile functionalities in compounds 3.188, 3.204-3.207 and 3.209-3.212. Over a decade ago Wright et al. proposed a putative antiplasmodial mechanism of action for marine isonitriles (2.4, 2.9, 2.15, 2.19 and 2.35) and isothiocyanate (2.34) which involved interference in haem detoxification by P. falciparum thus inhibiting the growth of the parasite. In Chapter 4 we describe how we successfully managed to scale down Egan’s β-haematin inhibition assay for the analyses of small quantities of marine natural products as potential β-haematin inhibitors. Our modified assay revealed that the most active antiplasmodial marine isonitrile 2.9 (IC₅₀ 13 nM) showed total β-haematin inhibition while 2.15 (IC₅₀ 81 nM) and 2.19 (IC₅₀ 31 nM) showed partial inhibition at three equivalents relative to haem. Using contempary molecular modelling techniques the charge on the isonitrile functionality was more accurately describe and the modified charge data sets was used to explore docking of marine isonitriles to haem using AutoDock. In Chapter 5 we describe how a lead South African marine bisindole MRSA pyruvate kinase inhibitor (5.8) was discovered in collaboration with colleagues at the University of British Columbia (UBC) and how this discovery inspired us to design a synthetic route to the dibrominated bisindole, isobromotopsentin (5.20) in an attempt to increase the bioactivity displayed by 5.8. We devised a fast and high yielding synthetic route using microwave assited organic synthesis. We first tested this synthesis using simple aryl glyoxals (5.27-5.32) as precursors to synthesize biphenylimidazoles (5.21-5.26), which later allowed us to synthesize the ascidian natural product 5.111. This method was sucessfully extended to the synthesis of deoxytopsentin (5.33) from an N-Boc protected indole methyl ketone (5.89). We subsequently were able to effectively remove the carbamate protection via thermal decomposition by heating the protected bisindole imidazole (5.90) in a microwave reactor for 5 min under argon. The synthesis of 5.20 resulted in an inseparable mixture of monoprotected and totally deprotected topsentin products, and due to time constraints we were not able to optimise this synthesis. Nonetheless our synthesis of the marine natural product 5.33 which was faster and higher yielding than previously reported routes could be extended to the synthesis of other topsentin bisindoles (5.138-5.140). Work towards this goal continues in our laboratory.
- Full Text:
- Date Issued: 2012
- Authors: Young, Ryan Mark
- Date: 2012
- Subjects: Antibacterial agents Marine natural products Marine pharmacology Plasmodium falciparum Staphylococcus aureus Isocyanides Imidazoles
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4378 , http://hdl.handle.net/10962/d1005043
- Description: This thesis is divided into two parts, assessing marine and synthetic compounds active firstly against Plasmodium falciparum (Chapter 3 and 4) and secondly active against methicillin resistant Staphylococcus aureus (MRSA, Chapter 5). In Chapter 3 the synthesis of nine new tricyclic podocarpanes (3.203-3.207 and 3.209-3.212) from the diterpene (+)-manool is described. Initial SAR study of synthetic podocarpanes concluded that the most active compound was a C-13 phenyl substituted podocarpane (3.204, IC₅₀ 6.6 μM). By preparing analogues with varying halogenated substituents on the phenyl ring (3.209-3.212) the antiplasmodial activity was improved (IC₅₀ 1.4 μM), while simultaneously decreasing the haemolysis previously reported for this class of compounds. Inspired by the antiplasmodial activity of Wright and Wattanapiromsakul’s tricycle marine isonitriles (2.16-2.21 and 2.24-2.27) an unsuccessfully attempt was made to convert tertiary alcohol moieties to isonitrile functionalities in compounds 3.188, 3.204-3.207 and 3.209-3.212. Over a decade ago Wright et al. proposed a putative antiplasmodial mechanism of action for marine isonitriles (2.4, 2.9, 2.15, 2.19 and 2.35) and isothiocyanate (2.34) which involved interference in haem detoxification by P. falciparum thus inhibiting the growth of the parasite. In Chapter 4 we describe how we successfully managed to scale down Egan’s β-haematin inhibition assay for the analyses of small quantities of marine natural products as potential β-haematin inhibitors. Our modified assay revealed that the most active antiplasmodial marine isonitrile 2.9 (IC₅₀ 13 nM) showed total β-haematin inhibition while 2.15 (IC₅₀ 81 nM) and 2.19 (IC₅₀ 31 nM) showed partial inhibition at three equivalents relative to haem. Using contempary molecular modelling techniques the charge on the isonitrile functionality was more accurately describe and the modified charge data sets was used to explore docking of marine isonitriles to haem using AutoDock. In Chapter 5 we describe how a lead South African marine bisindole MRSA pyruvate kinase inhibitor (5.8) was discovered in collaboration with colleagues at the University of British Columbia (UBC) and how this discovery inspired us to design a synthetic route to the dibrominated bisindole, isobromotopsentin (5.20) in an attempt to increase the bioactivity displayed by 5.8. We devised a fast and high yielding synthetic route using microwave assited organic synthesis. We first tested this synthesis using simple aryl glyoxals (5.27-5.32) as precursors to synthesize biphenylimidazoles (5.21-5.26), which later allowed us to synthesize the ascidian natural product 5.111. This method was sucessfully extended to the synthesis of deoxytopsentin (5.33) from an N-Boc protected indole methyl ketone (5.89). We subsequently were able to effectively remove the carbamate protection via thermal decomposition by heating the protected bisindole imidazole (5.90) in a microwave reactor for 5 min under argon. The synthesis of 5.20 resulted in an inseparable mixture of monoprotected and totally deprotected topsentin products, and due to time constraints we were not able to optimise this synthesis. Nonetheless our synthesis of the marine natural product 5.33 which was faster and higher yielding than previously reported routes could be extended to the synthesis of other topsentin bisindoles (5.138-5.140). Work towards this goal continues in our laboratory.
- Full Text:
- Date Issued: 2012
The constituents of the resin of Euryops floribundus. N.E.Br.
- Authors: Woolard, Graham Robert
- Date: 1966
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4510 , http://hdl.handle.net/10962/d1013449
- Description: The aerial portions of the plant Euryops floribundus were extracted and shown to contain Euryopsonol and another sesquiterpenoid for which the name Euryopsol is proposed. An extraction of Euryops tenuissimus contained Euryopsol only. Euryopsonol, of empirical formula C₁₅ H₂₀ O₃, was previously shown to contain a hydroxyl group and a keto-group and to be doubly unsaturated. The hydroxyl group has been shown to be secondary, while the keto-group is ⋉, β, γ, δ-unsaturated, Spectroscopic and Mass spectrosmetric measurements showed euryopsonol to possess a furan ring and to be member of the eremophilane -9 of sesquiterpenoids . These proposals were confirmed by the conversion of euryopsonol to furanoeremophilone -9, thus establishing the stereochemistry at C₄, C₅ and C₁₀. This free hydroxyl group has been placed at C₃, but its stereochemistry is still unknown. Euryopsol, of empirical formula C₁₅ H₂₂ O₄, possesses an unstable furan ring and readily undergoes autoxidation, probably to a more stable ¥-lactone. It contains two vicinal hydroxyl groups, one of which was placed by Mass spectrometry at C₉. If euryopsol possesses the eremophilane skeleton the other hydroxyl group must be at C₁₀.
- Full Text:
- Date Issued: 1966
- Authors: Woolard, Graham Robert
- Date: 1966
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4510 , http://hdl.handle.net/10962/d1013449
- Description: The aerial portions of the plant Euryops floribundus were extracted and shown to contain Euryopsonol and another sesquiterpenoid for which the name Euryopsol is proposed. An extraction of Euryops tenuissimus contained Euryopsol only. Euryopsonol, of empirical formula C₁₅ H₂₀ O₃, was previously shown to contain a hydroxyl group and a keto-group and to be doubly unsaturated. The hydroxyl group has been shown to be secondary, while the keto-group is ⋉, β, γ, δ-unsaturated, Spectroscopic and Mass spectrosmetric measurements showed euryopsonol to possess a furan ring and to be member of the eremophilane -9 of sesquiterpenoids . These proposals were confirmed by the conversion of euryopsonol to furanoeremophilone -9, thus establishing the stereochemistry at C₄, C₅ and C₁₀. This free hydroxyl group has been placed at C₃, but its stereochemistry is still unknown. Euryopsol, of empirical formula C₁₅ H₂₂ O₄, possesses an unstable furan ring and readily undergoes autoxidation, probably to a more stable ¥-lactone. It contains two vicinal hydroxyl groups, one of which was placed by Mass spectrometry at C₉. If euryopsol possesses the eremophilane skeleton the other hydroxyl group must be at C₁₀.
- Full Text:
- Date Issued: 1966
An x-ray investigation of the thermal decomposition of unirradiated and irradiated silver permanganate.
- Authors: Woods, Geoffrey Steward
- Date: 1963
- Subjects: Decomposition (Chemistry) , Materials -- Thermal properties , Solids -- Thermal properties , Permanganates , Silver compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4511 , http://hdl.handle.net/10962/d1013450
- Description: [From Introduction] The first step in the study of the thermal decompositions of solids is an examination of the kinetics, since this casts much light on the mechanism of the reaction. It must be borne in mind, however, that a theoretical expression, derived on the basis of a particular mechanism, even if it fits the observed experimental results, is not conclusive proof of the validity of the mechanism when applied to the decomposition under examination.
- Full Text:
- Date Issued: 1963
- Authors: Woods, Geoffrey Steward
- Date: 1963
- Subjects: Decomposition (Chemistry) , Materials -- Thermal properties , Solids -- Thermal properties , Permanganates , Silver compounds
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4511 , http://hdl.handle.net/10962/d1013450
- Description: [From Introduction] The first step in the study of the thermal decompositions of solids is an examination of the kinetics, since this casts much light on the mechanism of the reaction. It must be borne in mind, however, that a theoretical expression, derived on the basis of a particular mechanism, even if it fits the observed experimental results, is not conclusive proof of the validity of the mechanism when applied to the decomposition under examination.
- Full Text:
- Date Issued: 1963
Synthetic approaches to marine labdane diterpenes
- Authors: Wisch, Gregory Albert
- Date: 2002 , 2013-05-10
- Subjects: Diterpenes
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4289 , http://hdl.handle.net/10962/d1003131 , Diterpenes
- Description: The work presented in this thesis describes the synthesis of labd-13-en-8ß, 15-diol (46) a stable reduced derivative of an unstable marine natural product aldehyde [8ß-hydroxylabd-13E-en-15-al (6)] isolated by Cimino, et al. from the skin of a Notaspidean mollusc Pleurobranchaea meckelii. The rationale for the synthesis was to provide sufficient 46 for eventual mild oxidation to 6 and investigation of the biological activity of this latter compound. (-)-Sclareol (32), a common diterpene synthetic precursor, was the starting point for the ten step synthesis of 46 described in this thesis. A search of the literature revealed that only one non stereospecific synthesis of 46 had been previously reported. To provide the necessary background to the synthetic component of this thesis, both the occurrence of labdane and ent-labdane in the marine environment and the use of sclareol in the synthesis of marine natural products, was reviewed. The initial step in the synthesis of 46 was the potassium permanganate oxidation of sclareol to give a bisnorlabdane ketone. Reduction of this ketone with lithium aluminium hydride produced a mixture of diols which, through t-butyldimethysilyl triflate protection, afforded a quantitative route to protecting the C-13 ketone in an effort to prevent unwanted intramolecular cyclization reactions. Dehydration of the tertiary alcohol moiety at C-8 with phosphorous oxychloride yielded the Δ⁸·¹⁵ exocyclic alkene required for the next oxidation step. Ozonolysis succeeded in producing the desired C-8 ketone after much deliberation and research into alternative oxidation strategies. Methyl lithium methylation quantitatively afforded the desired a-methyl substitution at C-8, identified at the onset as the key step in the synthesis. Tetra-butylarnmonium fluoride deprotection yielded the 8ß,13-dihydoxylated product, which was in turn subjected to a Swern oxidition to give the desired 8ß-hydroxy-bisnorlabda-13-one. A modified Horner-Wadsworth-Emmons reaction allowed for elaboration at C-13 to yield a to Δ¹³ olefin with a terminal C-15 ethyl ester. Diisobutylaluminium hydride reduction of the ester produced the desired labd-13-en-8ß, 15-diol (46) in a low overall yield of 3.4%. Although opportunities for optimization of at least three steps in the synthesis exist, time constraints prevented both optimization of these steps and an investigation of the oxidation of 46 to 6. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 2002
- Authors: Wisch, Gregory Albert
- Date: 2002 , 2013-05-10
- Subjects: Diterpenes
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4289 , http://hdl.handle.net/10962/d1003131 , Diterpenes
- Description: The work presented in this thesis describes the synthesis of labd-13-en-8ß, 15-diol (46) a stable reduced derivative of an unstable marine natural product aldehyde [8ß-hydroxylabd-13E-en-15-al (6)] isolated by Cimino, et al. from the skin of a Notaspidean mollusc Pleurobranchaea meckelii. The rationale for the synthesis was to provide sufficient 46 for eventual mild oxidation to 6 and investigation of the biological activity of this latter compound. (-)-Sclareol (32), a common diterpene synthetic precursor, was the starting point for the ten step synthesis of 46 described in this thesis. A search of the literature revealed that only one non stereospecific synthesis of 46 had been previously reported. To provide the necessary background to the synthetic component of this thesis, both the occurrence of labdane and ent-labdane in the marine environment and the use of sclareol in the synthesis of marine natural products, was reviewed. The initial step in the synthesis of 46 was the potassium permanganate oxidation of sclareol to give a bisnorlabdane ketone. Reduction of this ketone with lithium aluminium hydride produced a mixture of diols which, through t-butyldimethysilyl triflate protection, afforded a quantitative route to protecting the C-13 ketone in an effort to prevent unwanted intramolecular cyclization reactions. Dehydration of the tertiary alcohol moiety at C-8 with phosphorous oxychloride yielded the Δ⁸·¹⁵ exocyclic alkene required for the next oxidation step. Ozonolysis succeeded in producing the desired C-8 ketone after much deliberation and research into alternative oxidation strategies. Methyl lithium methylation quantitatively afforded the desired a-methyl substitution at C-8, identified at the onset as the key step in the synthesis. Tetra-butylarnmonium fluoride deprotection yielded the 8ß,13-dihydoxylated product, which was in turn subjected to a Swern oxidition to give the desired 8ß-hydroxy-bisnorlabda-13-one. A modified Horner-Wadsworth-Emmons reaction allowed for elaboration at C-13 to yield a to Δ¹³ olefin with a terminal C-15 ethyl ester. Diisobutylaluminium hydride reduction of the ester produced the desired labd-13-en-8ß, 15-diol (46) in a low overall yield of 3.4%. Although opportunities for optimization of at least three steps in the synthesis exist, time constraints prevented both optimization of these steps and an investigation of the oxidation of 46 to 6. , KMBT_363 , Adobe Acrobat 9.54 Paper Capture Plug-in
- Full Text:
- Date Issued: 2002
Some aspects of the chemistry of zirconium compounds relating to their combination with collagen
- Williams-Wynn, David Ernest Arthur
- Authors: Williams-Wynn, David Ernest Arthur
- Date: 1960
- Subjects: Zirconium compounds , Collagen
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4513 , http://hdl.handle.net/10962/d1013456
- Description: [Summary] Some properties of zirconium compounds in aqueous solution have been determined using physico-chemical techniques. Zirconium oxychloride was used as the source of zirconium in all detailed investigations; zirconium sulphate was used in a few cases for comparative purposes. The Stokes diaphragm cell method has been used to determine the diffusion coefficient of zirconium in hydrochloric acid solution. It was found that the diffusion coefficient fell progressively with time, a limiting value being reached 4 to 5 weeks after dissolving the salt, and it was demonstrated that particles in the aged solutions were more homogeneous than in freshly prepared solutions. The limiting values were concentration dependent; dilute solutions had a lower diffusion coefficient than the more concentrated solutions when measured at the natural pH. In the presence of added acid the rate of diffusion was increased until a limiting value was reached in 0.5 M acid. The addition of alkali or complexing acids reduced the rate of diffusion.
- Full Text:
- Date Issued: 1960
- Authors: Williams-Wynn, David Ernest Arthur
- Date: 1960
- Subjects: Zirconium compounds , Collagen
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4513 , http://hdl.handle.net/10962/d1013456
- Description: [Summary] Some properties of zirconium compounds in aqueous solution have been determined using physico-chemical techniques. Zirconium oxychloride was used as the source of zirconium in all detailed investigations; zirconium sulphate was used in a few cases for comparative purposes. The Stokes diaphragm cell method has been used to determine the diffusion coefficient of zirconium in hydrochloric acid solution. It was found that the diffusion coefficient fell progressively with time, a limiting value being reached 4 to 5 weeks after dissolving the salt, and it was demonstrated that particles in the aged solutions were more homogeneous than in freshly prepared solutions. The limiting values were concentration dependent; dilute solutions had a lower diffusion coefficient than the more concentrated solutions when measured at the natural pH. In the presence of added acid the rate of diffusion was increased until a limiting value was reached in 0.5 M acid. The addition of alkali or complexing acids reduced the rate of diffusion.
- Full Text:
- Date Issued: 1960
Theoretical aspects of the reaction of zirconium compunds and vegetable tannins with the chromium-collagen complex
- Williams-Wynn, David Ernest Arthur
- Authors: Williams-Wynn, David Ernest Arthur
- Date: 1969
- Subjects: Zirconium compounds , Collagen , Chromium compounds , Tannins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4512 , http://hdl.handle.net/10962/d1013455
- Description: Studies have been made of the reactions which take place when zirconium compounds and vegetable tannins react with chromium tanned leather, in order to elucidate the mechanisms of the reactions which occur on retannage. Statistical procedures have been used in all investigations because of the variable nature of the substrate, and computer techniques have been applied to the repetitive statistical computations. Although chromium and vegetable tannages are well understood, further information on the reaction of zirconium with collagen was necessary before attempting to interpret the results of the studies of combination tannages with chromium, and this has been obtained by a comparative study of the reactions of chromium and zirconium with modified collagen. It is concluded that the mechanism of the reaction of basic zirconium sulphate with collagen is multipoint attachment of the tanning material by residual valency forces, although charge effects with basic groups may be supplementary. Zirconyl chloride reacts with carboxyl groups but does not form satisfactory, stable cross-links with collagen. Further evidence for this theory was obtained from the investigation of the reaction of zirconium compounds with chromium tanned collagen. Zirconyl sulphate does not interfere with effective chromium tannage and therefore can have little affinity for the carboxyl groups on the protein, but it displaces chromium complexes loosely held by auxiliary valencies without reducing the shrinkage temperature of the chromium leather Zirconyl chloride, although only fixed to a limited extent, apparently forms co-ordination compounds with the carboxyl groups, disrupting the chromium tannage because there is an over-all loss of hydrothermal stability. There is no evidence that zirconium co-ordinates with, or releases acid from chromium-collagen complexes, since combination chromium/zirconium tanned leathers are stable on storage. Retannage of chromium tanned leather with vegetable tanning materials generally results in loss of strength and a product which tends to deteriorate on ageing. Lower initial strength is probably due to the increased avidity of chromium tanned pelt for vegetable tannins, resulting from the liberation of internally neutralised reactive sites which are not normally available in vegetable tannage, and from the co- ordination of vegetable tannins and non-tannins to the chromium complex with the displacement of sulphate radicals. From a study of the retannage of chromium tanned modified collagen, it appears that basic groups probably play an important part in the rapid absorption of vegetable tannin. These reactions result in overloading of the fibre and an increased number of cross-links, both of which tend to produce weak leather. Deterioration with age is primarily a hydrolytic degradation of the protein which is catalysed by acid liberated from the chromium complexes by the entry of vegetable tannins, those factors which favour the formation of acid causing greater and more rapid deterioration.
- Full Text:
- Date Issued: 1969
- Authors: Williams-Wynn, David Ernest Arthur
- Date: 1969
- Subjects: Zirconium compounds , Collagen , Chromium compounds , Tannins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4512 , http://hdl.handle.net/10962/d1013455
- Description: Studies have been made of the reactions which take place when zirconium compounds and vegetable tannins react with chromium tanned leather, in order to elucidate the mechanisms of the reactions which occur on retannage. Statistical procedures have been used in all investigations because of the variable nature of the substrate, and computer techniques have been applied to the repetitive statistical computations. Although chromium and vegetable tannages are well understood, further information on the reaction of zirconium with collagen was necessary before attempting to interpret the results of the studies of combination tannages with chromium, and this has been obtained by a comparative study of the reactions of chromium and zirconium with modified collagen. It is concluded that the mechanism of the reaction of basic zirconium sulphate with collagen is multipoint attachment of the tanning material by residual valency forces, although charge effects with basic groups may be supplementary. Zirconyl chloride reacts with carboxyl groups but does not form satisfactory, stable cross-links with collagen. Further evidence for this theory was obtained from the investigation of the reaction of zirconium compounds with chromium tanned collagen. Zirconyl sulphate does not interfere with effective chromium tannage and therefore can have little affinity for the carboxyl groups on the protein, but it displaces chromium complexes loosely held by auxiliary valencies without reducing the shrinkage temperature of the chromium leather Zirconyl chloride, although only fixed to a limited extent, apparently forms co-ordination compounds with the carboxyl groups, disrupting the chromium tannage because there is an over-all loss of hydrothermal stability. There is no evidence that zirconium co-ordinates with, or releases acid from chromium-collagen complexes, since combination chromium/zirconium tanned leathers are stable on storage. Retannage of chromium tanned leather with vegetable tanning materials generally results in loss of strength and a product which tends to deteriorate on ageing. Lower initial strength is probably due to the increased avidity of chromium tanned pelt for vegetable tannins, resulting from the liberation of internally neutralised reactive sites which are not normally available in vegetable tannage, and from the co- ordination of vegetable tannins and non-tannins to the chromium complex with the displacement of sulphate radicals. From a study of the retannage of chromium tanned modified collagen, it appears that basic groups probably play an important part in the rapid absorption of vegetable tannin. These reactions result in overloading of the fibre and an increased number of cross-links, both of which tend to produce weak leather. Deterioration with age is primarily a hydrolytic degradation of the protein which is catalysed by acid liberated from the chromium complexes by the entry of vegetable tannins, those factors which favour the formation of acid causing greater and more rapid deterioration.
- Full Text:
- Date Issued: 1969
Improved singlet oxygen generation by a novel bodipy dye and a study of upconverison nanoparticles mixed with a functionalized bodipy compound
- Wildervanck, Martijn Johannes
- Authors: Wildervanck, Martijn Johannes
- Date: 2016
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/3718 , vital:20538
- Description: This research explores the use of the versatile 4,4-difluoro-4-boro-3a,4a-diaza-s-indacene (BODIPY) dyes and the modification of their spectroscopic properties. The synthesis of a tetramethyl-BODIPY bearing a sterically hindered meso-phenyl ring with an ethynyl functional group at the para-position was compared to that of its freely rotating counterpart with no methyl substituents on the BODIPY core, with the fluorescence properties in particular proving to be markedly different. These phenyl-ethynyl-substituted BODIPYs were used as the starting materials for the synthesis of novel BODIPY dyes for sensor applications via Sonogashira coupling reactions at the ethynyl position, but this resulted instead in the serendipitous synthesis of a novel BODIPY dimer in which the para-positions of the meso-phenyl rings are linked by a diethynyl bridge. Following iodination at the 2, 6-positions, the dimer was found to have a singlet oxygen quantum yield of 0.88, compared to the value of 0.86 that was obtained for the analogous monomer. Since the εmax values for the main spectral bands of the dimers are significantly higher, the compounds may be of interest for singlet oxygen generation applications. A second study was carried out on the interaction between methyl ester functionalized BODIPY dyes and upconversion nanoparticles (UCNPs) to explore the possible use of BODIPY-UCNP conjugates in biomedical applications. The singlet oxygen generation properties of the BODIPY were tested following iodination at the 2, 6-positions, a singlet oxygen quantum yield value of 0.86 was obtained. Three sets of oleate capped UCNPs were synthesized with different diameters and were rendered water dispersible with the addition of a silica shell. The necessary scaffolding for conjugation to the BODIPY was provided by amine groups following functionalization of this shell. All of the sets of oleate capped and silica coated UCNPs were characterized by transmission electron microscopy (TEM) and X-ray diffractometry (XRD) and their emission properties were studied upon excitation at 978 nm with a diode laser with a Picoquant Fluotime 300 spectrophotometer that enables the measurement of anti-Stokes emission. The potential utility of UCNP-BODIPY conjugates for singlet oxygen applications, such as PDT, was then assessed.
- Full Text:
- Date Issued: 2016
- Authors: Wildervanck, Martijn Johannes
- Date: 2016
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/3718 , vital:20538
- Description: This research explores the use of the versatile 4,4-difluoro-4-boro-3a,4a-diaza-s-indacene (BODIPY) dyes and the modification of their spectroscopic properties. The synthesis of a tetramethyl-BODIPY bearing a sterically hindered meso-phenyl ring with an ethynyl functional group at the para-position was compared to that of its freely rotating counterpart with no methyl substituents on the BODIPY core, with the fluorescence properties in particular proving to be markedly different. These phenyl-ethynyl-substituted BODIPYs were used as the starting materials for the synthesis of novel BODIPY dyes for sensor applications via Sonogashira coupling reactions at the ethynyl position, but this resulted instead in the serendipitous synthesis of a novel BODIPY dimer in which the para-positions of the meso-phenyl rings are linked by a diethynyl bridge. Following iodination at the 2, 6-positions, the dimer was found to have a singlet oxygen quantum yield of 0.88, compared to the value of 0.86 that was obtained for the analogous monomer. Since the εmax values for the main spectral bands of the dimers are significantly higher, the compounds may be of interest for singlet oxygen generation applications. A second study was carried out on the interaction between methyl ester functionalized BODIPY dyes and upconversion nanoparticles (UCNPs) to explore the possible use of BODIPY-UCNP conjugates in biomedical applications. The singlet oxygen generation properties of the BODIPY were tested following iodination at the 2, 6-positions, a singlet oxygen quantum yield value of 0.86 was obtained. Three sets of oleate capped UCNPs were synthesized with different diameters and were rendered water dispersible with the addition of a silica shell. The necessary scaffolding for conjugation to the BODIPY was provided by amine groups following functionalization of this shell. All of the sets of oleate capped and silica coated UCNPs were characterized by transmission electron microscopy (TEM) and X-ray diffractometry (XRD) and their emission properties were studied upon excitation at 978 nm with a diode laser with a Picoquant Fluotime 300 spectrophotometer that enables the measurement of anti-Stokes emission. The potential utility of UCNP-BODIPY conjugates for singlet oxygen applications, such as PDT, was then assessed.
- Full Text:
- Date Issued: 2016
Synthetic and spectrometric investigation of 1,4-benzoxazepines
- Authors: Whittal, R D
- Date: 1990
- Subjects: Spectrum analysis , Benzodiazepines
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4381 , http://hdl.handle.net/10962/d1005046
- Description: Flavanone (2,3-dihydro-2-phenyl-4H-benzopyran-4-one) and a series of 4'- and 7-halogeno derivatives were prepared from the corresponding 2'-hydroxychalcones [1-(2-hydroxyphenyl)-3-phenyl-2-propen-l-ones], which, in turn, were synthesized by aldol condensation of substituted 2'-hydroxacetophenones with various benzaldehydes. A series of 2,3-dihydro-2-phenyl-l,4-benzoxazepin-5(4H)-ones were prepared by ring expansion of the corresponding flavanones, via the Schmidt reaction, using trimethylsilylazide and trifluoroacetic acid. A series of tetrazoles {2,3-dihydro-2-phenyl-tetrazolo[1,5-d]-1,4-benzoxazepines} were also isolated as by-products of the Schmidt reaction. Flavanone oxime was synthesized for use in Beckmann reactions, and its molecular structure was determined by x-ray crystallography. Attempts to prepare 1,4-benzoxazepinone or its 1,5-analogue via Beckmann rearrangement of flavanone oxime, with polyphosphoric acid or phosphorus pentachloride catalysts, however, were unsuccessful. Several methods for introducing Δ²-unsaturation into the benzoxazepinone system were also examined. High resolution ¹H n.m.r., computer modelling, and molecular mechanics techniques were used to determine the conformations of the heterocycles of the benzoxazepinones and tetrazoles and results are compared with earlier studies in this field. Certain trends in the fragmentation patterns were observed in the low resolution mass spectra of the benzoxazepinones and tetrazoles, and high resolution mass spectrometric data were used to explore the major fragmentation patterns of these compounds.
- Full Text:
- Date Issued: 1990
- Authors: Whittal, R D
- Date: 1990
- Subjects: Spectrum analysis , Benzodiazepines
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4381 , http://hdl.handle.net/10962/d1005046
- Description: Flavanone (2,3-dihydro-2-phenyl-4H-benzopyran-4-one) and a series of 4'- and 7-halogeno derivatives were prepared from the corresponding 2'-hydroxychalcones [1-(2-hydroxyphenyl)-3-phenyl-2-propen-l-ones], which, in turn, were synthesized by aldol condensation of substituted 2'-hydroxacetophenones with various benzaldehydes. A series of 2,3-dihydro-2-phenyl-l,4-benzoxazepin-5(4H)-ones were prepared by ring expansion of the corresponding flavanones, via the Schmidt reaction, using trimethylsilylazide and trifluoroacetic acid. A series of tetrazoles {2,3-dihydro-2-phenyl-tetrazolo[1,5-d]-1,4-benzoxazepines} were also isolated as by-products of the Schmidt reaction. Flavanone oxime was synthesized for use in Beckmann reactions, and its molecular structure was determined by x-ray crystallography. Attempts to prepare 1,4-benzoxazepinone or its 1,5-analogue via Beckmann rearrangement of flavanone oxime, with polyphosphoric acid or phosphorus pentachloride catalysts, however, were unsuccessful. Several methods for introducing Δ²-unsaturation into the benzoxazepinone system were also examined. High resolution ¹H n.m.r., computer modelling, and molecular mechanics techniques were used to determine the conformations of the heterocycles of the benzoxazepinones and tetrazoles and results are compared with earlier studies in this field. Certain trends in the fragmentation patterns were observed in the low resolution mass spectra of the benzoxazepinones and tetrazoles, and high resolution mass spectrometric data were used to explore the major fragmentation patterns of these compounds.
- Full Text:
- Date Issued: 1990
An investigation of reactions directed towards the synthesis of 2-methyl-2-(methylthio)propanal oxime
- Authors: Whittaker, Ruth Eleanor
- Date: 1995
- Subjects: Pesticides -- Synthesis , Insecticides , Aldicarb -- Synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4322 , http://hdl.handle.net/10962/d1004980 , Pesticides -- Synthesis , Insecticides , Aldicarb -- Synthesis
- Description: The processes leading to the formation of 2-methyl-2-(methylthio)propanal oxime, known industrially as aldicarb oxime, have been studied. The three stages of the synthesis, viz., chlorination, thiomethylation and oximation have been thoroughly investigated, with the aim of optimising the yield and purity of aldicarb oxime. Attention has been focused on the chlorination step, and the effects of altering various conditions have been determined; the reaction has been carried out in the absence and presence of heat, solvent and buffer, and the extent of chlorine addition has also been varied. These studies have led to some improvement in the yield for this step. Several simple and inexpensive methods for purifying contaminated batches of aldicarb oxime have also been examined. Possible aldicarb oxime contaminants, identified by GLC and GC-MS analysis, have been synthesised for use as chromatographic and spectroscopic standards, and confirmation of the presence of a number of these contaminants has been achieved. Aldehyde trimers have been found to be the primary contaminants present in aldicarb oxime and the thermal stability of these trimers, their corresponding monomers and aldicarb oxime itself has been studied using variable temperature ¹H NMR spectroscopy. Novel pyridine derivatives, with potential as aldicarb analogues, have been synthesised and characterised using spectroscopic methods.
- Full Text:
- Date Issued: 1995
- Authors: Whittaker, Ruth Eleanor
- Date: 1995
- Subjects: Pesticides -- Synthesis , Insecticides , Aldicarb -- Synthesis
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4322 , http://hdl.handle.net/10962/d1004980 , Pesticides -- Synthesis , Insecticides , Aldicarb -- Synthesis
- Description: The processes leading to the formation of 2-methyl-2-(methylthio)propanal oxime, known industrially as aldicarb oxime, have been studied. The three stages of the synthesis, viz., chlorination, thiomethylation and oximation have been thoroughly investigated, with the aim of optimising the yield and purity of aldicarb oxime. Attention has been focused on the chlorination step, and the effects of altering various conditions have been determined; the reaction has been carried out in the absence and presence of heat, solvent and buffer, and the extent of chlorine addition has also been varied. These studies have led to some improvement in the yield for this step. Several simple and inexpensive methods for purifying contaminated batches of aldicarb oxime have also been examined. Possible aldicarb oxime contaminants, identified by GLC and GC-MS analysis, have been synthesised for use as chromatographic and spectroscopic standards, and confirmation of the presence of a number of these contaminants has been achieved. Aldehyde trimers have been found to be the primary contaminants present in aldicarb oxime and the thermal stability of these trimers, their corresponding monomers and aldicarb oxime itself has been studied using variable temperature ¹H NMR spectroscopy. Novel pyridine derivatives, with potential as aldicarb analogues, have been synthesised and characterised using spectroscopic methods.
- Full Text:
- Date Issued: 1995
Studies on achromobacter iophagus and other collagenolytic hide bacteria
- Authors: Welton, Richard Leslie
- Date: 1975
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:21099 , http://hdl.handle.net/10962/6367
- Description: From Introduction: Collagenases are enzymes capable of specifically attacking the native collagen helix under non-denaturing conditions at physiological conditions of pH, temperature and salt concentration. They are active only on collagen or its breakdown products and are without effect on any other fibrous or globular protein. In the laboratory, collagenases are used in investigations of the biosynthesis of collagen and for structural and immunochemical studies of collagens and collagen-like proteins; also they are proving their worth as agents for facilitating tissue transplantation and for cell-dispersion in tissue cultures . Established clinical applications of collagenases include the treatment of burns and dermal lesions; in addition they are being evaluated as agents for the removal of undesirable tissues such as herniated intervertebral discs and the sloughs resulting from cryogenic or cauterizing procedures. Moreover, as human collagenases are implicated in various pathological disorders involving connective tissue degradation, the roles played by these collagenases are being investigated in the hope of finding ways to arrest, control or treat the diseases.
- Full Text:
- Date Issued: 1975
- Authors: Welton, Richard Leslie
- Date: 1975
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:21099 , http://hdl.handle.net/10962/6367
- Description: From Introduction: Collagenases are enzymes capable of specifically attacking the native collagen helix under non-denaturing conditions at physiological conditions of pH, temperature and salt concentration. They are active only on collagen or its breakdown products and are without effect on any other fibrous or globular protein. In the laboratory, collagenases are used in investigations of the biosynthesis of collagen and for structural and immunochemical studies of collagens and collagen-like proteins; also they are proving their worth as agents for facilitating tissue transplantation and for cell-dispersion in tissue cultures . Established clinical applications of collagenases include the treatment of burns and dermal lesions; in addition they are being evaluated as agents for the removal of undesirable tissues such as herniated intervertebral discs and the sloughs resulting from cryogenic or cauterizing procedures. Moreover, as human collagenases are implicated in various pathological disorders involving connective tissue degradation, the roles played by these collagenases are being investigated in the hope of finding ways to arrest, control or treat the diseases.
- Full Text:
- Date Issued: 1975
Synthetic and analytical studies of biomimetic metal complexes
- Authors: Wellington, Kevin Wayne
- Date: 2000
- Subjects: Biomimetics Metal complexes Metalloenzymes Metal ions Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4377 , http://hdl.handle.net/10962/d1005042
- Description: Several series of novel diamido, diamino and diimino ligands containing different spacers and heterocyclic donors have been synthesised. The spacers include the flexible biphenyl, the rigid 1,1 O-phenanthroline and various acyclic moieties, while the heterocyclic donors comprise pyridine, imidazole or benzimidazole groups. These ligands have been designed to complex copper and act as biomimetic models of the active site of the enzyme, tyrosinase, and their complexes with copper, cobalt, nickel and platinum have been analysed using microanalytical, IR, UV-Visible and cyclic voltammetric techniques. Attempted reduction of the biphenyl-based diimino ligands resulted in an unexpected intramolecular cyclisation affording azepine derivatives, the structures of which were elucidated with the aid of single crystal X-ray analysis of cobalt and nickel complexes. Computer modelling methods have been used to explore the conformational options of the copper complexes, and to assess the accessibility of the dinuclear copper site to substrate molecules. Computer modelling has also been used, in conjunction with the available analytical data, to visualise the possible structures of selected ligands and complexes. The copper complexes, although predominantly polymeric, were evaluated as biomimetic catalysts using 3,5-di-t-butylphenol and 3,5-di-t-butylcatechol as substrates. Some of the complexes clearly displayed biomimetic potential, exhibiting both phenolase and catecholase activity.
- Full Text:
- Date Issued: 2000
- Authors: Wellington, Kevin Wayne
- Date: 2000
- Subjects: Biomimetics Metal complexes Metalloenzymes Metal ions Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4377 , http://hdl.handle.net/10962/d1005042
- Description: Several series of novel diamido, diamino and diimino ligands containing different spacers and heterocyclic donors have been synthesised. The spacers include the flexible biphenyl, the rigid 1,1 O-phenanthroline and various acyclic moieties, while the heterocyclic donors comprise pyridine, imidazole or benzimidazole groups. These ligands have been designed to complex copper and act as biomimetic models of the active site of the enzyme, tyrosinase, and their complexes with copper, cobalt, nickel and platinum have been analysed using microanalytical, IR, UV-Visible and cyclic voltammetric techniques. Attempted reduction of the biphenyl-based diimino ligands resulted in an unexpected intramolecular cyclisation affording azepine derivatives, the structures of which were elucidated with the aid of single crystal X-ray analysis of cobalt and nickel complexes. Computer modelling methods have been used to explore the conformational options of the copper complexes, and to assess the accessibility of the dinuclear copper site to substrate molecules. Computer modelling has also been used, in conjunction with the available analytical data, to visualise the possible structures of selected ligands and complexes. The copper complexes, although predominantly polymeric, were evaluated as biomimetic catalysts using 3,5-di-t-butylphenol and 3,5-di-t-butylcatechol as substrates. Some of the complexes clearly displayed biomimetic potential, exhibiting both phenolase and catecholase activity.
- Full Text:
- Date Issued: 2000
Development of a protocol for extracting and quantifying the concentration of thiafentanil in blesbok (Damaliscus pygargus phillipsi) matrices 72-74 hours post administration
- Authors: Webber, Judith Tracy
- Date: 2020
- Subjects: Uncatalogued
- Language: English
- Type: thesis , text , Masters , MSc
- Identifier: http://hdl.handle.net/10962/164738 , vital:41159
- Description: Thesis (MSc)--Rhodes University, Faculty of Science, Chemistry, 2020
- Full Text:
- Date Issued: 2020
- Authors: Webber, Judith Tracy
- Date: 2020
- Subjects: Uncatalogued
- Language: English
- Type: thesis , text , Masters , MSc
- Identifier: http://hdl.handle.net/10962/164738 , vital:41159
- Description: Thesis (MSc)--Rhodes University, Faculty of Science, Chemistry, 2020
- Full Text:
- Date Issued: 2020
Photophysical studies of conjugates of upconversion nanoparticles with aluminium phthalocyanines
- Authors: Watkins, Zane
- Date: 2017
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/4964 , vital:20747
- Description: NaYF4 :Yb/Er/Gd upconversion nanoparticles (UCNP) were synthesised and their photoemission stabilised by embedding these nanoparticles in electrospun fibres. The photophysical behaviour of chloro aluminium tetrasulfo-phthalocyanine chloride (ClAlTSPc) was studied in the presence of UCNPs on mixing the two species in solution. The fluorescence lifetimes for UCNPs were shortened at 658 nm in the presence of ClAlTSPc when the former was embedded in fibre and suspended in a dimethyl sulfoxide solution of the latter. A clear singlet oxygen generation by ClAlTSPc through Forster resonance energy transfer (FRET) was demonstrated using a singlet oxygen quencher, 1,3-diphenylisobenzofuran. UCNP capped with amino groups were then covalently attached to chloro aluminium tetrasulphonated phthalocyanine (ClAlTSPc) and chloro aluminium tetracarboxy phthalocyanine (ClAlTCPc). The conjugates were characterized using different techniques such as infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS) and Transmission electron microscopy (TEM). There was a decrease in fluorescence emission spectra of the UCNPs at 658 nm in the presence of the phthalocyanines. This decrease indicates an energy transfer between the donor UCNP and conjugated accepting phthalocyanine (Pc), due to FRET. Low FRET efficiencies of 18 and 21 % for ClAlTSPc and ClAlTCPc, respectively, were obtained.
- Full Text:
- Date Issued: 2017
- Authors: Watkins, Zane
- Date: 2017
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: http://hdl.handle.net/10962/4964 , vital:20747
- Description: NaYF4 :Yb/Er/Gd upconversion nanoparticles (UCNP) were synthesised and their photoemission stabilised by embedding these nanoparticles in electrospun fibres. The photophysical behaviour of chloro aluminium tetrasulfo-phthalocyanine chloride (ClAlTSPc) was studied in the presence of UCNPs on mixing the two species in solution. The fluorescence lifetimes for UCNPs were shortened at 658 nm in the presence of ClAlTSPc when the former was embedded in fibre and suspended in a dimethyl sulfoxide solution of the latter. A clear singlet oxygen generation by ClAlTSPc through Forster resonance energy transfer (FRET) was demonstrated using a singlet oxygen quencher, 1,3-diphenylisobenzofuran. UCNP capped with amino groups were then covalently attached to chloro aluminium tetrasulphonated phthalocyanine (ClAlTSPc) and chloro aluminium tetracarboxy phthalocyanine (ClAlTCPc). The conjugates were characterized using different techniques such as infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS) and Transmission electron microscopy (TEM). There was a decrease in fluorescence emission spectra of the UCNPs at 658 nm in the presence of the phthalocyanines. This decrease indicates an energy transfer between the donor UCNP and conjugated accepting phthalocyanine (Pc), due to FRET. Low FRET efficiencies of 18 and 21 % for ClAlTSPc and ClAlTCPc, respectively, were obtained.
- Full Text:
- Date Issued: 2017
An investigation into the antidiabetic and catalytic properties of oxovanadium(IV) complexes
- Authors: Walmsley, Ryan Steven
- Date: 2012
- Subjects: Hypoglycemic agents Ligands (Biochemistry) Complex compounds Potentiometry Proton transfer reactions Stability Imidazoles Vanadium catalysts
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4320 , http://hdl.handle.net/10962/d1004978
- Description: In part 1 of this thesis, the antidiabetic activity of a series of novel oxovanadium(IV) complexes was investigated. A range of bidentate N,O-donor ligands, which partially mimic naturally occurring bioligands, were prepared and reacted with the vanadyl ion to form the corresponding bis-coordinated complexes. Initially, 2-(2ˊ-hydroxyphenyl)-1R-imidazoline (where R = H, ethyl and ethanol) ligands were prepared. The aqueous pH-metric chemical speciation was investigated using glass electrode potentiometry which allowed for the determination of protonation and stability constants of the ligands and complexes, respectively. The species distribution diagrams generated from this information gave an indication of how the complexes might behave across the broad pH range experienced in the digestive and circulatory systems. This information was used to create an improved 2nd generation of ligands that were constructed by combining the imidazole and carboxylic acid functionalities. These corresponding bis[(imidazolyl)carboxylato]-oxovanadium(IV) complexes displayed a broader pH-metric stability. Both sets of complexes improved glucose uptake and reduced coagulation in vitro. In part 2 of this thesis, a range of homogeneous and heterogeneous oxovanadium(IV) catalysts were prepared. Firstly, Merrifield beads were functionalized with ligands from Part 1 and then reacted with vanadyl sulfate to afford the corresponding heterogeneous catalysts. These displayed promising catalytic activity for the peroxide facilitated oxidation of thioanisole, styrene and ethylbenzene as well as the oxidative bromination of phenol red. Smaller imidazole-containing beads with higher surface areas than the Merrifield beads were prepared by suspension polymerization. These beads similarly demonstrated excellent catalytic activity for the oxidation of thioanisole and were highly recyclable. In attempt to increase the exposed catalytic surface area, while retaining the ease of separation achieved in the before mentioned systems, micron to nano sized electrospun fibers containing coordinating ligands were fabricated. The corresponding oxovanadium(IV) functionalized fibers were applied to the oxidation of thioanisole using a continuous flow system. The flexible and porous nature of the fiber mats was well suited to this approach. After optimization of the reactant flow rate and catalyst amount, near quantitative (> 99%) oxidation was achieved for an extended period. In addition, leaching of vanadium was mitigated by modification of the attached ligand or polymer material.
- Full Text:
- Date Issued: 2012
- Authors: Walmsley, Ryan Steven
- Date: 2012
- Subjects: Hypoglycemic agents Ligands (Biochemistry) Complex compounds Potentiometry Proton transfer reactions Stability Imidazoles Vanadium catalysts
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4320 , http://hdl.handle.net/10962/d1004978
- Description: In part 1 of this thesis, the antidiabetic activity of a series of novel oxovanadium(IV) complexes was investigated. A range of bidentate N,O-donor ligands, which partially mimic naturally occurring bioligands, were prepared and reacted with the vanadyl ion to form the corresponding bis-coordinated complexes. Initially, 2-(2ˊ-hydroxyphenyl)-1R-imidazoline (where R = H, ethyl and ethanol) ligands were prepared. The aqueous pH-metric chemical speciation was investigated using glass electrode potentiometry which allowed for the determination of protonation and stability constants of the ligands and complexes, respectively. The species distribution diagrams generated from this information gave an indication of how the complexes might behave across the broad pH range experienced in the digestive and circulatory systems. This information was used to create an improved 2nd generation of ligands that were constructed by combining the imidazole and carboxylic acid functionalities. These corresponding bis[(imidazolyl)carboxylato]-oxovanadium(IV) complexes displayed a broader pH-metric stability. Both sets of complexes improved glucose uptake and reduced coagulation in vitro. In part 2 of this thesis, a range of homogeneous and heterogeneous oxovanadium(IV) catalysts were prepared. Firstly, Merrifield beads were functionalized with ligands from Part 1 and then reacted with vanadyl sulfate to afford the corresponding heterogeneous catalysts. These displayed promising catalytic activity for the peroxide facilitated oxidation of thioanisole, styrene and ethylbenzene as well as the oxidative bromination of phenol red. Smaller imidazole-containing beads with higher surface areas than the Merrifield beads were prepared by suspension polymerization. These beads similarly demonstrated excellent catalytic activity for the oxidation of thioanisole and were highly recyclable. In attempt to increase the exposed catalytic surface area, while retaining the ease of separation achieved in the before mentioned systems, micron to nano sized electrospun fibers containing coordinating ligands were fabricated. The corresponding oxovanadium(IV) functionalized fibers were applied to the oxidation of thioanisole using a continuous flow system. The flexible and porous nature of the fiber mats was well suited to this approach. After optimization of the reactant flow rate and catalyst amount, near quantitative (> 99%) oxidation was achieved for an extended period. In addition, leaching of vanadium was mitigated by modification of the attached ligand or polymer material.
- Full Text:
- Date Issued: 2012
Aspects of the resorcinol-formaldehyde condensation
- Waldron, Ronald Augustus Frank
- Authors: Waldron, Ronald Augustus Frank
- Date: 1954
- Subjects: Resorcinol , Formaldehyde
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4514 , http://hdl.handle.net/10962/d1013460
- Description: An attempt was made to producea -β or Ϫ - resorcinyl alcohol from disubstituted resorcinyls. To accomplish this 3,5-dibromo-β-resorcylic acid was reacted with lithium aluminium hybride, a mild reducing agent, in an attempt to reduce the acid group to the alcohol group. This disubstituted resorcinol was recovered unchanged. 3,5-dibromo-β-resorcyl-aldehyde was reduced by lithium aluminium hydride, but, instead of the alcohol forming, resinification took place. 2-methyl- 4-ethylresorcinol and 4,6-diethyrecorinol were reacted with formaldehyde under alkaline and acidic conditions. In each case a resin formed. The above experlments indicated that condensation took place in the meta position of the resorcinol molecule. Trimethylresorcinol was therefore reacted with formaldehyde under alkaline conditions, resulting in a small quantity ot the alcohol derivative. A better yield of the alcohol derivative was obtained by the hydrolysis or the chloromathyl derivative. In pursuing this line, a seres of new compounds and their derivatives were prepared. The condensation of the alcohol derivative with trimethylresorcinol and also with resorcinol was investigated.
- Full Text:
- Date Issued: 1954
- Authors: Waldron, Ronald Augustus Frank
- Date: 1954
- Subjects: Resorcinol , Formaldehyde
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4514 , http://hdl.handle.net/10962/d1013460
- Description: An attempt was made to producea -β or Ϫ - resorcinyl alcohol from disubstituted resorcinyls. To accomplish this 3,5-dibromo-β-resorcylic acid was reacted with lithium aluminium hybride, a mild reducing agent, in an attempt to reduce the acid group to the alcohol group. This disubstituted resorcinol was recovered unchanged. 3,5-dibromo-β-resorcyl-aldehyde was reduced by lithium aluminium hydride, but, instead of the alcohol forming, resinification took place. 2-methyl- 4-ethylresorcinol and 4,6-diethyrecorinol were reacted with formaldehyde under alkaline and acidic conditions. In each case a resin formed. The above experlments indicated that condensation took place in the meta position of the resorcinol molecule. Trimethylresorcinol was therefore reacted with formaldehyde under alkaline conditions, resulting in a small quantity ot the alcohol derivative. A better yield of the alcohol derivative was obtained by the hydrolysis or the chloromathyl derivative. In pursuing this line, a seres of new compounds and their derivatives were prepared. The condensation of the alcohol derivative with trimethylresorcinol and also with resorcinol was investigated.
- Full Text:
- Date Issued: 1954
Catalytic behaviour of metallophthalocyanines towards the detection of nitric oxide
- Authors: Vilakazi, Lea Sibulelo
- Date: 2002
- Subjects: Electrochemistry Nitric oxide
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4418 , http://hdl.handle.net/10962/d1006852
- Description: Electrocatalytic reduction and oxidation of nitric oxide (NO) using cobalt phthalocyanine complexes have been studied and compared to vitamin B₁₂ and other metallophthalocyanine (MPc) complexes. Modifying a glassy carbon electrode with these complexes resulted in improved sensitivity of the electrode allowing detection of NO to 10⁻⁹ mol dm⁻³. The mechanisms of catalysis were studied. Electrocatalysis of NO involves coordination of NO to the MPc complex. Hence catalytic activity is affected by the nature of the metal center. However coordination of NO to the MPc complex has to be reversible to eliminate poisoning of the electrode. Though FePc gave the best sensitivity and lowered the reduction potential more than CoPc, the strong Fe-NO bond resulted in the poisoning of the electrode hence, rendering the electrode unstable. Rate constants for NO coordination to the MPc complexes were studied. These rates were smaller than the studied NO porphyrin coordination rates. Electrocatalytic reduction of NO using MPc complexes involves a transfer of an electron from the metal center to the NO ligand. Hence, substitution of electron-donating grohps on the cobalt pthalocyanine complex resulted in improved sensitivity and catalytic activity. A CoPc modified microelectrode (11μm) was used to monitor NO in human blood components and to detect NO in a rat brain. Detections of NO were also done in aqueous solutions in the presence of interfering species such as dopamine and serotonin. An interaction between NO and serotonin was observed.
- Full Text:
- Date Issued: 2002
- Authors: Vilakazi, Lea Sibulelo
- Date: 2002
- Subjects: Electrochemistry Nitric oxide
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4418 , http://hdl.handle.net/10962/d1006852
- Description: Electrocatalytic reduction and oxidation of nitric oxide (NO) using cobalt phthalocyanine complexes have been studied and compared to vitamin B₁₂ and other metallophthalocyanine (MPc) complexes. Modifying a glassy carbon electrode with these complexes resulted in improved sensitivity of the electrode allowing detection of NO to 10⁻⁹ mol dm⁻³. The mechanisms of catalysis were studied. Electrocatalysis of NO involves coordination of NO to the MPc complex. Hence catalytic activity is affected by the nature of the metal center. However coordination of NO to the MPc complex has to be reversible to eliminate poisoning of the electrode. Though FePc gave the best sensitivity and lowered the reduction potential more than CoPc, the strong Fe-NO bond resulted in the poisoning of the electrode hence, rendering the electrode unstable. Rate constants for NO coordination to the MPc complexes were studied. These rates were smaller than the studied NO porphyrin coordination rates. Electrocatalytic reduction of NO using MPc complexes involves a transfer of an electron from the metal center to the NO ligand. Hence, substitution of electron-donating grohps on the cobalt pthalocyanine complex resulted in improved sensitivity and catalytic activity. A CoPc modified microelectrode (11μm) was used to monitor NO in human blood components and to detect NO in a rat brain. Detections of NO were also done in aqueous solutions in the presence of interfering species such as dopamine and serotonin. An interaction between NO and serotonin was observed.
- Full Text:
- Date Issued: 2002
Reduction of tungsten oxides with carbon and hydrogen
- Authors: Venables, Dean Stuart
- Date: 1996
- Subjects: Oxidation-reduction reaction , Tungsten , Hydrogen , Carbon
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4342 , http://hdl.handle.net/10962/d1005004 , Oxidation-reduction reaction , Tungsten , Hydrogen , Carbon
- Description: The reductions of WO₃ with hydrogen, with CO, and with carbon, as well as the reduction of WO₃/graphite mixtures with hydrogen, were studied using thermogravimetry, evolved gas analysis, X-ray powder diffraction, and scanning electron microscopy. The intermediate phases W₂₀O₅₈, W₁₈O₄₉ and WO₂, were observed in the reductions. The final product of the reductions with hydrogen and carbon was tungsten, and we was formed in the reduction with CO. The reaction paths in the overall processes were determined. The reactant/product gas ratio had a considerable influence on which reactions took place. The morphology of the sample was characterised at different stages of the reduction. The shape of the WO₃ particles was retained during the reduction. Particle growth was observed in the reduction with hydrogen and was attributed to the formation of WO₂(OH)₂(g). The kinetics of the reductions were investigated , and the reaction mechanisms determined. The reduction of WO₃ with CO was studied from 650 to 900°C, and occurred at a phase boundary with an activation energy of 40 kJ mol⁻¹ . The reduction of WO₂, was studied under the same conditions. The reaction also occurred at a phase boundary and had an activation energy of 62 kJ mol⁻¹. The reduction of WO₃ with carbon was studied from 935 to 1100°C and took place via CO and CO₂. Two stages were observed in the reduction . The first stage, which corresponded approximately to the formation of WO₂ had an activation energy of 66 kJ mol⁻¹ and was limited by diffusion through the porous reacting particles. The second stage was first order and had an activation energy of 40 kJ mol⁻¹. The reduction of WO₃ and WO₃ graphite mixtures with hydrogen were studied from 575 to 975 °C. The reactions were controlled by mass-transfer under the conditions investigated. The addition of carbon increased the rate of the reduction process , but did not affect the phases formed in the system. CO₂ was evolved mainly at the start, and CO mainly at the end of the process.
- Full Text:
- Date Issued: 1996
- Authors: Venables, Dean Stuart
- Date: 1996
- Subjects: Oxidation-reduction reaction , Tungsten , Hydrogen , Carbon
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4342 , http://hdl.handle.net/10962/d1005004 , Oxidation-reduction reaction , Tungsten , Hydrogen , Carbon
- Description: The reductions of WO₃ with hydrogen, with CO, and with carbon, as well as the reduction of WO₃/graphite mixtures with hydrogen, were studied using thermogravimetry, evolved gas analysis, X-ray powder diffraction, and scanning electron microscopy. The intermediate phases W₂₀O₅₈, W₁₈O₄₉ and WO₂, were observed in the reductions. The final product of the reductions with hydrogen and carbon was tungsten, and we was formed in the reduction with CO. The reaction paths in the overall processes were determined. The reactant/product gas ratio had a considerable influence on which reactions took place. The morphology of the sample was characterised at different stages of the reduction. The shape of the WO₃ particles was retained during the reduction. Particle growth was observed in the reduction with hydrogen and was attributed to the formation of WO₂(OH)₂(g). The kinetics of the reductions were investigated , and the reaction mechanisms determined. The reduction of WO₃ with CO was studied from 650 to 900°C, and occurred at a phase boundary with an activation energy of 40 kJ mol⁻¹ . The reduction of WO₂, was studied under the same conditions. The reaction also occurred at a phase boundary and had an activation energy of 62 kJ mol⁻¹. The reduction of WO₃ with carbon was studied from 935 to 1100°C and took place via CO and CO₂. Two stages were observed in the reduction . The first stage, which corresponded approximately to the formation of WO₂ had an activation energy of 66 kJ mol⁻¹ and was limited by diffusion through the porous reacting particles. The second stage was first order and had an activation energy of 40 kJ mol⁻¹. The reduction of WO₃ and WO₃ graphite mixtures with hydrogen were studied from 575 to 975 °C. The reactions were controlled by mass-transfer under the conditions investigated. The addition of carbon increased the rate of the reduction process , but did not affect the phases formed in the system. CO₂ was evolved mainly at the start, and CO mainly at the end of the process.
- Full Text:
- Date Issued: 1996