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Reaction of Perrhenate with Phthalocyanine Derivatives in the Presence of Reducing Agents and Rhenium Oxide Nanoparticles in Biomedical Applications

  • Authors: Ntsimango, Songeziwe , Gandidzanwa, Sendibitiyosi , Joseph, Sinelizwi V , Hosten, Eric C , Randall, Marvin , Edkins, Adrienne L , Khene, Samson M , Mashazi, Philani N , Nyokong, Tebello , Abrahams, Abubak’r , Tshentu, Zenixole R
  • Date: 2022
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/300257 , vital:57910 , xlink:href="https://doi.org/10.1002/open.202200037"
  • Description: A novel alternative route to access rhenium(V)−phthalocyanine complexes through direct metalation of metal-free phthalocyanines (H2Pcs) with a rhenium(VII) salt in the presence of various two-electron reducing agents is presented. Direct ion metalation of tetraamino- or tetranitrophthalocyanine with perrhenate (ReO4−) in the presence of triphenylphosphine led to oxidative decomposition of the H2Pcs, giving their respective phthalonitriles. Conversely, treatment of H2Pcs with ReO4− employing sodium metabisulfite yielded the desired ReVO−Pc complex. Finally, reaction of H2Pcs with ReO4− and NaBH4 as reducing agent led to the formation of rhenium oxide (RexOy) nanoparticles (NPs). The NP synthesis was optimised, and the RexOy NPs were capped with folic acid (FA) conjugated with tetraaminophthalocyanine (TAPc) to enhance their cancer cell targeting ability. The cytotoxicity profile of the resultant RexOy−TAPc−FA NPs was assessed and found to be greater than 80 % viability in four cell lines, namely, MDA−MB-231, HCC7, HCC1806 and HEK293T. Non-cytotoxic concentrations were determined and employed in cancer cell localization studies. The particle size effect on localization of NPs was also investigated using confocal fluorescence and transmission electron microscopy. The smaller NPs (≈10 nm) were found to exhibit stronger fluorescence properties than the ≈50 nm NPs and exhibited better cell localization ability than the ≈50 nm NPs.
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Solvent promoted tautomerism in thione-containing tetraazatricyclics: evidence from 1H NMR spectroscopy and transition state studies

  • Authors: Odame, Felix , Tshentu, Zenixole R , Lobb, Kevin A
  • Date: 2022
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/453198 , vital:75230 , xlink:href="https://link.springer.com/article/10.1007/s00894-022-05204-w"
  • Description: Tautomerism in the nitro substituted thione-containing traazatricyclics has been investigated. Evidence from 1 H NMR indicating the existence of the tautomers has been augmented with computational studies providing evidence of the stability or otherwise of these tautomers. The role of water and DMSO in the formation of the tautomers has been explained. The role of the nitro group in assisting in the formation of the tautomers has been discussed.
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Synthesis, characterization, computational studies and DPPH scavenging activity of some triazatetracyclic derivatives

  • Authors: Odame, Felix , Hosten, Eric C , Betz, Richard , Krause, Jason , Frost, Carminita L , Lobb, Kevin A , Tshentu, Zenixole R
  • Date: 2021
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/451186 , vital:75026 , xlink:href="https://doi.org/10.1007/s13738-021-02158-3"
  • Description: Some dihydrobenzo[4,5]imidazo[1,2-c]quinazolines have been synthesized from aldehydes and ketones, using the ketones as both reagents and solvents and tetrahydrofuran (THF) as the solvent for the aldehydes, to yield the triazatetracyclics. The compounds have been characterized with spectroscopy and microanalysis. The crystal structures of 9,9-dimethyl-8,10,17- triazatetracyclo[8.7.02,7.011,16]heptadeca-1(17),2,4,6,11(16),12,14-heptaene (I), 9-butyl-9-methyl-8,10,17-triazatetracyclo[8.7.0.02 , 7 .011,16]heptadeca-(17),2,4,6,11(16),12,14-heptaene (III) and 9-phenyl-8,10,17-triazatetracyclo[8.7.0 02 7.011,16] heptadeca-1(17),2,4,6,11(16),12,14-heptaene (VIII) have been discussed. The computed NMR, IR, molecular electrostatic potential and frontier molecular orbitals of compounds I, III and VIII have been discussed. The M06 functional gave most of its values closest to the experimental values for the bond lengths and bond angles of compounds I and III. For compound VIII, none of the functionals gave values for bond lengths and bond angles that were consistent with the experimental values, but M06 gave values closest to experimental values. The 1,1-diphenyl-2-picrylhydrazyl (DPPH) scavenging activity of the triazatetracyclics showed that compound I exhibits signifcant DPPH scavenging activity with an IC50 of 56.18 µM compared to 2.37 µM for ascorbic acid.
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A novel gold (I)-mediated intramolecular transamidation of benzoyl thiourea derivatives to form benzamides via dethiocyanation

  • Authors: Odame, Felix , Woodcock, Guillaume , Hosten, Eric C , Lobb, Kevin A , Tshentu, Zenixole R
  • Date: 2020
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/446988 , vital:74575 , xlink:href="https://doi.org/10.1016/j.jorganchem.2020.121359"
  • Description: A novel gold(I)-mediated intramolecular transamidation of thiourea derivatives to yield benzamides via dethiocyanation have been achieved by the reaction of 3-(1,3-benzothiazol-2-yl)-1-(benzoyl)thiourea derivatives in the presence of gold(I) precursors. The compounds have been characterized using IR, NMR, GC-MS and microanalysis. The single crystal XRD of 3-(1,3-benzothiazol-2-yl)-1-(3-bromobenzoyl)thiourea (5), 3-(1,3-benzothiazol-2-yl)-1-(3-methoxybenzoyl)thiourea (6), N-(benzothiazol-2-yl)benzamide (10), N-(benzothiazol-2-yl)-3-chlorobenzamide (11), N-(benzothiazol-2-yl)-4-nitrobenzamide (12), N-(benzothiazol-2-yl)-3-bromobenzamide (14) have been discussed. The novel transformation is thought to proceed by a gold(I)-mediated intramolecular transamidation reaction which releases thiocyanate to yield the benzamide. Density functional theory calculations have been used to support the proposed mechanism for this transformation.
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Synthesis, characterization and biological activity of some Dithiourea Derivatives:

Ultrasound promoted synthesis, characterization and computational studies of some thiourea derivatives

  • Authors: Odame, Felix , Hosten, Eric C , Lobb, Kevin A , Tshentu, Zenixole R
  • Date: 2020
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/451199 , vital:75028 , xlink:href="https://doi.org/10.1016/j.molstruc.2020.128302"
  • Description: Synthesis of some thiourea derivatives have been achieved by using ultrasound, the compounds have been characterised using IR, NMR, GC-MS and elemental analysis. The single crystal X-ray structure of N-[(benzyloxy)methanethioyl]benzamide (IV), 1-benzoyl-3-(2-hydroxyethyl)thiourea (V) and 3-benzoyl-1-(1-benzylpiperidin-4-yl)thiourea (VI) has been presented and the bond lengths and bond angles contrasted with computed results. The HOMO and LUMO energy levels as well as the global chemical reactivity descriptors of the compounds have also been computed and discussed. Two comformers were obtained for compounds IV to VI in the molecular Electrostatic potential and the vibrational frequency computations and these have been discussed.
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Characterization and computational studies of 2-(benzamido) thiazol-5-yl benzoate

  • Authors: Odame, Felix , Hosten, Eric C , Betz, Richard , Lobb, Kevin A , Tshentu, Zenixole R
  • Date: 2019
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/447003 , vital:74576 , xlink:href="https://doi.org/10.1134/S0022476619010190"
  • Description: Thiazoles have shown a broad range of biological activities and are found in many potent biologically active molecules such as Sulfathiazol (antimicrobial drug), Ritonavir (antiretroviral drug), Abafungin (antifungal drug), and Tiazofurin (antineoplastic drug) [1]. They have exhibited some degree of plant growth regulatory and antifungal activities [2], whilst some thiazoles have shown anti-infective [3] as well as antibacterial activities [4]. The regio-controlled synthesis of 2,5-disubstituted and 2,4,5-trisubstituted thiazoles from ethyl-2-bromo-5-chloro-4-thiazolecarboxylates using sequential palladium-catalyzed coupling reactions has been reported [5]. An efficient general method for the preparation of 2,4-di- and trisubsituted thiazoles is via P–TsOH. H2O-Catalyzed cyclization of trisubstituted propargylic alcohols with thioamides has been accomplished with moderate to excellent product yields under mild and standard conditions [6]. In the presence of triethylamine, (Z)-(2-acetoxyl-1-alkenyl) phenyl-λ3 iodanes reacts with thioureas or thioamides in methanol to afford 2,4- disubstituted thiazoles in good yields. The reaction is thought to proceed by the generation of highly reactive α-λ3 iodanyl ketones through ester exchange of the β-acetoxy group with liberation of methyl acetate, followed by nucleophilic substitutions with thioureas or thioamides [7].
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A New Synthetic Method for Tetraazatricyclic Derivatives and Evaluation of Their Biological Properties

  • Authors: Odame, Felix , Betz, Richard , Hosten, Eric C , Krause, Jason , Isaacs, Michelle , Hoppe, Heinrich C , Khanye, Setshaba D , Sayed, Yasien , Frost, P Carminita , Lobb, Kevin A , Tshentu, Zenixole R
  • Date: 2018
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/123189 , vital:35413 , https://doi.org/10.1002/slct.201802930
  • Description: Herein, we propose novel quinolones incorporating an INH moiety as potential drug templates against TB. The quinolone-based compounds bearing an INH moiety attached via a hydrazide–hydrazone bond were synthesised and evaluated against Mycobacterium tuberculosis H37Rv (MTB). The compounds were also evaluated for cytotoxicity against HeLa cell lines. These compounds showed significant activity (MIC90) against MTB in the range of 0.2–8 μM without any cytotoxic effects. Compounds 10 (MIC90; 0.9 μM), 11 (MIC90; 0.2 μM), 12 (MIC90; 0.8 μM) and compound 15 (MIC90; 0.8 μM), the most active compounds in this series, demonstrate activities on par with INH and superior to those reported for the fluoroquinolones. The SAR analysis suggests that the nature of substituents at positions −1 and −3 of the quinolone nucleus influences anti-MTB activity. Aqueous solubility evaluation and in vitro metabolic stability of compound 12 highlights favourable drug-like properties for this compound class.
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Characterization and computational studies of a co-crystal of 2-aminobenzimidazole and 2-[(benzoylcarbamothioyl) amino] propanoic acid

  • Authors: Odame, Felix , Hosten, Eric C , Betz, Richard , Lobb, Kevin A , Tshentu, Zenixole R
  • Date: 2018
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/447030 , vital:74578 , xlink:href="https://doi.org/10.1134/S0022476618050268"
  • Description: A novel co-crystal of 2-aminobenzimidazole and 2-[(benzoylcarbamothioyl)amino] propanoic acid is synthesized and characterized by spectroscopy, elemental analysis, GC-MS, and single crystal XRD. A computation of the structures involved in the formation of the co-crystal are carried out and their contribution to reactivity is explained.
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Synthesis, characterization and DPPH scavenging activity of some benzimidazole derivatives

  • Authors: Odame, Felix , Krause, Jason , Hosten, Eric C , Betz, Richard , Lobb, Kevin A , Tshentu, Zenixole R , Frost, Carminita L
  • Date: 2018
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/447209 , vital:74592 , xlink:href="https://dx.doi.org/10.4314/bcse.v32i2.8 "
  • Description: A base-catalyzed conversion of aldehydes to benzimidazoles has been achieved. The compounds have been characterized by IR, NMR, micoranalysis, and GC-MS. The reaction for the formation of benzimidazoles has been monitored with 1 H NMR and IR. The crystal structures of two derivatives, 2-(2- chlorophenyl)-1H-benzimidazole and 2-(1H-benzimidazol-2-yl)-4-nitrophenol, are presented. A study of the DPPH scavenging activity of these compounds showed that 2-(1H-benzimidazol-2-yl)phenol (2), 2-p-tolyl-1Hbenzimidazole (3) and 2-(4-methoxyphenyl)-1H-benzimidazole (7) gave IC50 values 1974, 773 and 800 µM.
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Benzimidazole or Diamide From a Reaction of Diamines and Carboxylic Acids or Acid Chlorides: Crystal Structures and Theoretical Studies

  • Authors: Odame, Felix , Hosten, Eric C , Betz, Richard , Lobb, Kevin A , Tshentu, Zenixole R
  • Date: 2015
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/447938 , vital:74685 , xlink:href="https://pdfs.semanticscholar.org/bf5a/ce94c9436f40059793eb988e08da8ef09886.pdf"
  • Description: A reaction of an acid chloride with a diamine yielded a diamide. m-Toluic acid was chlorinated to m-toluoyl chloride and subsequently reacted with 4-methyl-o-phenylenediamine in pyridine to obtain 3-methyl-N-[2-(3-methylbenzamido)phenylbenzamide (I). 2-(3-Methylphenyl)-1H-benzimidazole (II) has been obtained upon reacting o-phenylenediamine with m-toluic acid in polyphosphoric acid and toluene. The compounds have been characterized by IR, NMR, microanalyses and GC-MS. The crystal structures of the compounds have been discussed. DFT calculations of the frontier orbitals of the precursor compounds have been carried out to ascertain the groups that contribute to the HOMO and LUMO, and to study their contribution to the reactivity in the formation of the diamides and benzimidazoles. The synthesis of the amide from a diamine was seen to be favoured in the presence of a good leaving group attached to the carbonyl as in the case of acid chloride. However, the synthesis of benzimidazoles was found to be favoured in the presence of an excess of a protonating agent and high temperature.
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Characterization of some amino acid derivatives of benzoyl isothiocyanate: Crystal structures and theoretical prediction of their reactivity

  • Authors: Odame, Felix , Hosten, Eric C , Betz, Richard , Lobb, Kevin A , Tshentu, Zenixole R
  • Date: 2015
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/447952 , vital:74686 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.05.053"
  • Description: The reaction of benzoyl isothiocyanate with L-serine, L-proline, D-methionine and L-alanine gave 2-[(benzoylcarbamothioyl)amino]-3-hydroxypropanoic acid (I), 1-(benzoylcarbamothioyl)pyrrolidine-2-carboxylic acid (II), 2-[(benzoylcarbamothioyl)amino]-4-(methylsulfanyl)butanoic acid (III) and 2-[(benzoylcarbamothioyl)amino]propanoic acid (IV), respectively. The compounds have been characterized by IR, NMR, microanalyses and mass spectrometry. The crystal structures of all the compounds have also been discussed. Compound II showed rotamers in solution. DFT calculations of the frontier orbitals of the compounds have been carried out to ascertain the groups that contribute to the HOMO and LUMO, and to study their contribution to the reactivity of these compounds. The calculations indicated that the carboxylic acid group in these compounds is unreactive hence making the conversion to benzimidazoles via cyclization on the carboxylic acids impractical. This has been further confirmed by the reaction of compounds I–IV, respectively, with o-phenylene diamine which was unsuccessful but gave compound V.
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Synthesis, photophysics and photochemistry of phthalocyanine-ɛ-polylysine conjugates in the presence of metal nanoparticles against Staphylococcus aureus

  • Authors: Nombona, Nolwazi , Antunes, Edith M , Chidawanyika, Wadzanai J U , Kleyi, Phumelele , Tshentu, Zenixole R , Nyokong, Tebello
  • Date: 2015
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/244439 , vital:51257 , xlink:href="https://doi.org/10.1016/j.molstruc.2015.02.040"
  • Description: This work reports on the photodynamic activity of Zn phthalocyanine-ɛ-polylysine conjugates in the presence of gold and silver nanoparticles (NPs) towards the inactivation of Staphylococcus aureus (S. aureus). The conjugates showed high photoinactivation with ∼6% growth at a drug dose of 3 μM and fluence of 39.6 mW/cm2 for 10 min irradiation time in the presence of silver nanoparticles. The presence of silver nanoparticels from the minimal inhibition concentration (MIC50) studies showed remarkable growth inhibition for the tested conjugates even at low concentrations. The MIC50 was lowest for the conjugate of 3 with ɛ-polylysine at concentrations of less than 0.0058 μM in the presence of AgNPs. The lethal photosensitization of microorganisms has emerged as a promising treatment since bacteria have reduced possibilities of developing resistance to photodynamic therapy.
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The development of palladium (II)-specific amine-functionalized silica-based microparticles

  • Authors: Fayemi, Omolola E , Ogunlaja, Adeniyi S , Antunes, Edith M , Nyokong, Tebello , Tshentu, Zenixole R
  • Date: 2015
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/241083 , vital:50903 , xlink:href="https://doi.org/10.1080/01496395.2014.978017"
  • Description: The adsorption and separation of platinum(IV) and palladium(II) chlorido species ([PtCl6]2− and [PdCl4]2−) on silica-based microparticles functionalized with ammonium centers based on ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetriamine (TETA) and tris-(2-aminoethyl)amine (TAEA) were investigated. The functionalized sorbent materials were characterized using SEM, XPS, BET, and FTIR. The sorbents were used in the batch and column study for adsorption and selective separation of [PtCl62− and PdCl4]2−. The adsorption model for both [PtCl6]2− and [PdCl4]2− on the different sorbent materials fitted the Freundlich isotherm with R2 values > 0.99. The S-TETA sorbent material was palladium(II) specific. Pd(II) loaded on the silica column was recovered using 3% m/v thiourea solution as the eluting agent. Separation of platinum and palladium was achieved by selective stripping of [PtCl6]2− with 0.5 M of NaClO4 in 1.0 M HCl while Pd(II) was eluted with 0.5 M thiourea in 1.0 M HCl. The separation of palladium (Pd) from a mixture containing platinum (Pt), iridium (Ir), and rhodium (Rh) was successful on silica functionalized with triethylenetriamine (TETA) showing specificity for palladium(II) and a loading capacity of 0.27 mg/g. S-TETA showed potential for use in the recovery of palladium from platinum group metals such as from solutions of worn out automobile emission control catalytic convertors and other secondary sources.
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The development of Palladium(II)-specific amine-functionalized silica-based microparticles : adsorption and column separation studies

  • Authors: Fayemi, Omolola E , Ogunlaja, Adeniyi S , Antunes, Edith M , Nyokong, Tebello , Tshentu, Zenixole R
  • Date: 2015
  • Language: English
  • Type: Article
  • Identifier: vital:7270 , http://hdl.handle.net/10962/d1020285
  • Description: The adsorption and separation of platinum(IV) and palladium(II) chlorido species ([PtCl6]2− and [PdCl4]2−) on silica-based microparticles functionalized with ammonium centers based on ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetriamine (TETA) and tris-(2-aminoethyl)amine (TAEA) were investigated. The functionalized sorbent materials were characterized using SEM, XPS, BET, and FTIR. The sorbents were used in the batch and column study for adsorption and selective separation of [PtCl62− and PdCl4]2−. The adsorption model for both [PtCl6]2− and [PdCl4]2− on the different sorbent materials fitted the Freundlich isotherm with R2 values > 0.99. The S-TETA sorbent material was palladium(II) specific. Pd(II) loaded on the silica column was recovered using 3% m/v thiourea solution as the eluting agent. Separation of platinum and palladium was achieved by selective stripping of [PtCl6]2− with 0.5 M of NaClO4 in 1.0 M HCl while Pd(II) was eluted with 0.5 M thiourea in 1.0 M HCl. The separation of palladium (Pd) from a mixture containing platinum (Pt), iridium (Ir), and rhodium (Rh) was successful on silica functionalized with triethylenetriamine (TETA) showing specificity for palladium(II) and a loading capacity of 0.27 mg/g. S-TETA showed potential for use in the recovery of palladium from platinum group metals such as from solutions of worn out automobile emission control catalytic convertors and other secondary sources. , Original publication is available at http://dx.doi.org/10.1080/01496395.2014.978017
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The Development of Palladium(II)-Specific Amine-Functionalized Silica-Based Microparticles: Adsorption and Column Separation Studies

  • Authors: Fayemi, Omolola E , Ogunlaja, Adeniyi S , Antunes, Edith M , Nyokong, Tebello , Tshentu, Zenixole R
  • Date: 2015
  • Language: English
  • Type: Article
  • Identifier: vital:7269 , http://hdl.handle.net/10962/d1020278
  • Description: The adsorption and separation of platinum(IV) and palladium(II) chlorido species ([PtCl6]2− and [PdCl4]2−) on silica-based microparticles functionalized with ammonium centers based on ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetriamine (TETA) and tris-(2-aminoethyl)amine (TAEA) were investigated. The functionalized sorbent materials were characterized using SEM, XPS, BET, and FTIR. The sorbents were used in the batch and column study for adsorption and selective separation of [PtCl62− and PdCl4]2−. The adsorption model for both [PtCl6]2− and [PdCl4]2− on the different sorbent materials fitted the Freundlich isotherm with R2 values > 0.99. The S-TETA sorbent material was palladium(II) specific. Pd(II) loaded on the silica column was recovered using 3% m/v thiourea solution as the eluting agent. Separation of platinum and palladium was achieved by selective stripping of [PtCl6]2− with 0.5 M of NaClO4 in 1.0 M HCl while Pd(II) was eluted with 0.5 M thiourea in 1.0 M HCl. The separation of palladium (Pd) from a mixture containing platinum (Pt), iridium (Ir), and rhodium (Rh) was successful on silica functionalized with triethylenetriamine (TETA) showing specificity for palladium(II) and a loading capacity of 0.27 mg/g. S-TETA showed potential for use in the recovery of palladium from platinum group metals such as from solutions of worn out automobile emission control catalytic convertors and other secondary sources. , Original publication is available at http://dx.doi.org/10.1080/01496395.2014.978017
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Adsorption and separation of platinum and palladium by polyamine functionalized polystyrene-based beads and nanofibers

  • Authors: Fayemi, Omolola E , Ogunlaja, Adeniyi S , Kempgens, Pierre F M , Antunes, Edith M , Torto, Nelson , Nyokong, Tebello , Tshentu, Zenixole R
  • Date: 2013
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/241694 , vital:50961 , xlink:href="https://doi.org/10.1016/j.mineng.2013.06.006"
  • Description: Adsorption and separation of platinum and palladium chlorido species (PtCl62- and PdCl42-) on polystyrene beads as well as nanofibers functionalized with ammonium centres based on ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA) and tris-(2-aminoethyl)amine (TAEA) are described. The functionalized sorbent materials were characterized by microanalysis, SEM, XPS, BET and FTIR. The surface area of the functionalized fibers was in the range 69–241 m2/g while it was 73–107 m2/g for the beads. The adsorption and loading capacities of the sorption materials were investigated using both the batch and column studies at 1 M HCl concentration. The adsorption studies for both PtCl62- and PdCl42- on the different sorbent materials fit the Langmuir isotherm with R2 values >0.99. The highest loading capacity of Pt and Pd were 7.4 mg/g and 4.3 mg/g respectively for the nanofiber sorbent material based on ethylenediamine (EDA) while the beads with ethylenediamine (EDA) gave 1.0 mg/g and 0.2 mg/g for Pt and Pd respectively. Metals loaded on the sorbent materials were recovered by using 3% m/v thiourea solution as the eluting agent with quantitative desorption efficiency under the selected experimental conditions. Separation of platinum from palladium was partially achieved by selective stripping of PtCl62- with 0.5 M of NaClO4 in 1.0 M HCl while PdCl42- was eluted with 0.5 M thiourea in 1.0 M HCl. Separation of platinum from iridium and rhodium under 1 M HCl concentration was successful on triethylenetriamine (TETA)-functionalized Merrifield beads. This material (M-TETA) showed selectivity for platinum albeit the low loading capacity.
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Catalytic oxidation of thioanisole using oxovanadium (IV)‐functionalized electrospun polybenzimidazole nanofibers

  • Authors: Walmsley, Ryan S , Hlangothi, Percy , Litwinski, Christian , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
  • Date: 2013
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/242083 , vital:51000 , xlink:href="https://doi.org/10.1002/app.38067"
  • Description: Polybenzimidazole fibers, with an average diameter of 262 nm, were produced by the process of electrospinning. These fibers were used as a solid support material for the immobilization of oxovanadium(IV) which was achieved via a reaction with vanadyl sulfate. The oxovanadium(IV)-functionalized nanofibers were used as heterogeneous catalysts for the oxidation of thioanisole under both batch and pseudo-continuous flow conditions with great success. Under batch conditions near quantitative oxidation of thioanisole was achieved in under 90 min, even after four successive catalytic reactions. Under continuous conditions, excellent conversion of thioanisole was maintained throughout the period studied at flow rates of up to 2 mLh−1. This study, therefore, proposes that electrospun polybenzimidazole nanofibers, with their small diameters, impressive chemical and thermal stability, as well as coordinating benzimidazole group, may be a desirable support material for immobilization of homogeneous catalysts.
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Oxovanadium (IV)-containing poly (styrene-co-4′-ethenyl-2-hydroxyphenylimidazole) electrospun nanofibers for the catalytic oxidation of thioanisole

  • Authors: Walmsley, Ryan S , Litwinski, Christian , Antunes, Edith M , Hlangothi, Percy , Hosten, Eric C , McCleland, Cedric , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
  • Date: 2013
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/241665 , vital:50959 , xlink:href="https://doi.org/10.1016/j.molcata.2013.07.018"
  • Description: The catalytic fibers have been fabricated by the electrospinning of a copolymer of styrene and 2-(2′-hydroxy-4′-ethenylphenyl)imidazole {p(ST-co-VPIM)} followed by a reaction with a methanolic vanadyl solution to afford the oxovanadium(IV)-containing poly(styrene-co-4′-ethenyl-2-hydroxyphenylimidazole) fibers {p(ST-co-VPIM)-VO fibers}. The relationship between polymer concentration and fiber diameter was investigated, and at high concentration (20 wt%) the fibers were quite large (average diameter of 3.8 μm) but as the concentration was reduced fibers of much lower diameter were produced (0.6 μm using 8 wt%). The BET surface area for p(ST-co-VPIM) fibers (0.6 μm diameter) was 47.9 m2 g−1 and functionalization of p(ST-co-VPIM) with vanadyl resulted in an increase in surface area to 60.7 m2 g−1 for p(ST-co-VPIM)-VO. The presence of vanadyl was confirmed by XPS and EPR. The EPR spectral analyses depicted complex speciation of vanadium within these polymer supports. These catalytic fibers were applied under batch and continuous flow conditions for the catalytic oxidation of thioanisole using hydrogen peroxide. The continuous flow method gave excellent and constant conversion throughout the 10 h period studied. The leaching of vanadium from the fiber support was 4% over the 10 h period indicating a significant stability of the material.
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The development of catalytic oxovanadium (IV)-containing microspheres for the oxidation of various organosulfur compounds

  • Authors: Ogunlaja, Adeniyi S , Khene, Samson M , Antunes, Edith M , Nyokong, Tebello , Torto, Nelson , Tshentu, Zenixole R
  • Date: 2013
  • Subjects: To be catalogued
  • Language: English
  • Type: text , article
  • Identifier: http://hdl.handle.net/10962/241783 , vital:50969 , xlink:href="https://doi.org/10.1016/j.apcata.2013.05.004"
  • Description: The development of poly[allylSB-co-EGDMA] beads containing a tetradentate ligand was achieved via suspension polymerization. The catalyst poly[allylSB-co-EGDMA]-VO was synthesized by reacting VIVOSO4 with poly[allylSB-co-EGDMA]. XPS and EPR were used to confirm the presence of vanadium (V4+) on the beads. The synthesized catalyst (poly[allylSB-co-EGDMA]-VO) was found to have a BET surface area of 22 m2 g−1 and porosity of 135 Å, with the atomic force microscopy (AFM) showing more insight on the porous nature of the beads. Oxidation of thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was carried out using tert-butyl hydroperoxide (t-BuOOH) as oxidant. An overall conversion of 60%, 82%, 98% and 87% was achieved for thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT) and 4,6 dimethyldibenzothiophene (4,6-DMDBT) respectively at higher (t-BuOOH) to substrate ratio and at a temperature of 40 °C. The efficient oxidation of the various organosulfur compounds presents potential for the possible application of this catalyst in oxidative desulfurization (ODS) of crude oil.
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